- Ruhr-Universität Bochum

Abstract: Alloys processed by laser powder-bed fusion show distinct microstructures composed of dislocation cells, dispersed nanoparticles, and columnar grains. Upon post-build annealing, such alloys show sluggish recrystallization kinetics compared to the conventionally processed counterpart. To understand this behavior, AISI 316L stainless steel samples were constructed using the island scan strategy. Rhodonite-like (MnSiO3) nanoparticles and dislocation cells are found within weakly-textured grains in the as-built condition. Upon isothermal annealing at 1150 °C (up to 2880 min), the nucleation of recrystallization occurs along the center of the melt pool, where nuclei sites, high stored elastic energy, and local large misorientation are found in the as-built condition. The low value of the Avrami coefficient (n = 1.16) can be explained based on the non-random distribution of nucleation sites. The local interaction of the recrystallization front with nanoparticles speeds up their coarsening causing the decrease of the Zener-Smith pinning force. This allows the progression of recrystallization in LPBF alloys, although sluggish. These results allow us to understand the progress of recrystallization in LPBF 316L stainless steel, shedding light on the nucleation mechanisms and on the competition between driving and dragging pressures in non-conventional microstructures. They also help to understand the most relevant microstructural aspects applicable for tuning microstructures and designing new LPBF alloys. Graphical abstract: [Figure not available: see fulltext.] © 2022, The Author(s).

Nanomaterials are frequently employed in daily life goods, including health, textile, and food industry. A comprehensive picture is lacking on the role of the capping agents, added ligand molecules, in case of nanoparticle reactions and degradation in aqueous solutions, like surface waters or biofluids. Here, we aim to elucidate the capping agent influence on nanoparticle reactivity probing two commonly employed capping agents citrate and polyvinylpyrrolidone (PVP). Their influence on silver nanoparticle (AgNP) transformation is studied, which is particularly important due to its application as an antimicrobial agent. We induce oxidation and reduction processes of AgNPs in halide solutions and we monitor the associated transformations of particles and capping agents by spectro-electrochemical surface-enhanced Raman spectroscopy (SERS). Raman bands of the capping agents are used here to track chemical changes of the nanoparticles under operando conditions. The sparingly soluble and non-plasmon active silver salts (AgBr and AgCl) are formed under potential bias. In addition, we spectroscopically observe plasmon-mediated structural changes of citrate to cis- or trans-aconitate, while PVP is unaltered. The different behavior of the capping agents implies a change in the physical properties on the surface of AgNPs, in particular with respect to the surface accessibility. Moreover, we showcase that reactions of the capping agents induced by different external stimuli, such as applied bias or laser irradiation, can be assessed. Our results demonstrate how SERS of capping agents can be exploited to operando track nanoparticle conversions in liquid media. This approach is envisaged to provide a more comprehensive understanding of nanoparticle fates in complex liquid environments and varied redox conditions. [Figure not available: see fulltext.] © 2021, The Author(s).

Creating high surface area nanocatalysts that contain stacking faults is a promising strategy to improve catalytic activity. Stacking faults can tune the reactivity of the active sites, leading to improved catalytic performance. The formation of branched metal nanoparticles with control of the stacking fault density is synthetically challenging. In this work, we demonstrate that varying the branch width by altering the size of the seed that the branch grows off is an effective method to precisely tune the stacking fault density in branched Ni nanoparticles. A high density of stacking faults across the Ni branches was found to lower the energy barrier for Ni2+/Ni3+oxidation and result in enhanced activity for electrocatalytic oxidation of 5-hydroxylmethylfurfural. These results show the ability to synthetically control the stacking fault density in branched nanoparticles as a basis for enhanced catalytic activity. © 2022 American Chemical Society. All rights reserved.

Single entity electrochemistry is employed to gain insights into ion solvation in solvent mixtures. To this end, the time required for the oxidation of individual indicator nanoparticles to sparingly soluble products is used to probe ionic diffusion, and hence gain new insights into the solvation properties of solvent mixtures. Herein, water-ethanol or water-methanol mixtures of different compositions are analyzed following this new approach, using silver nanoparticle oxidation in the presence of chloride and iodide as a complementary indicator reaction. For increasing concentrations of the bulkier alcohol molecules in the mixtures with water, an increasing content of alcohol molecules in the halide's solvation shell is detected by the observation of hindered halide diffusion. The extent of this solvent replacement is shown to scale with the charge density of the ions and the experimental results are rationalized with respect to literature-derived thermodynamic data, highlighting the ability of single entity electrochemistry to explore solvation in solvent mixtures. © 2022 The Authors. ChemElectroChem published by Wiley-VCH GmbH.

Aluminum oxides, oxyhydroxides, and hydroxides are important in different fields of application due to their many attractive properties. However, among these materials, tohdite (5Al2O3·H2O) is probably the least known because of the harsh conditions required for its synthesis. Herein, we report a straightforward methodology to synthesize tohdite nanopowders (particle diameter ∼13 nm, specific surface area ∼102 m2g-1) via the mechanochemically induced dehydration of boehmite (γ-AlOOH). High tohdite content (about 80%) is achieved upon mild ball milling (400 rpm for 48 h in a planetary ball mill) without process control agents. The addition of AlF3can promote the crystallization of tohdite by preventing the formation of the most stable α-Al2O3, resulting in the formation of almost phase-pure tohdite. The availability of easily accessible tohdite samples allowed comprehensive characterization by powder X-ray diffraction, total scattering analysis, solid-state NMR (1H and 27Al), N2-sorption, electron microscopy, and simultaneous thermal analysis (TG-DSC). Thermal stability evaluation of the samples combined with structural characterization evidenced a low-temperature transformation sequence: 5Al2O3·H2O → κ-Al2O3→ α-Al2O3. Surface characterization via DRIFTS, ATR-FTIR, D/H exchange experiments, pyridine-FTIR, and NH3-TPD provided further insights into the material properties. © 2022 American Chemical Society. All rights reserved.

Ball milling is growing increasingly important as an alternative synthetic tool to prepare catalytic materials. It was recently observed that supported metal catalysts could be directly obtained upon ball milling from the coarse powders of metal and oxide support. Moreover, when two compatible metal sources are simultaneously subjected to the mechanochemical treatment, bimetallic nanoparticles are obtained. A systematic investigation was extended to different metals and supports to understand better the mechanisms involved in the comminution and alloying of metal nanoparticles. Based on this, a model describing the role of metal-support interactions in the synthesis was developed. The findings will be helpful for the future rational design of supported metal catalysts via dry ball milling. © 2022 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.

Electrochemical analysis relies on precise measurement of electrical signals, yet the distortions caused by potentiostat circuitry and filtering are rarely addressed. Elucidation of these effects is essential for gaining insights behind sensitive low-current and short-duration electrochemical signals, e.g., in single-entity electrochemistry. We present a simulation approach utilizing the Electrical Simulation Program with Integrated Circuit Emphasis (SPICE), which is extensively used in electronic circuit simulations. As a proof-of-concept, we develop a universal electrical circuit model for single nanoparticle impact experiments, incorporating potentiostat and electronic filter circuitry. Considering these alterations, the experimentally observed transients of silver nanoparticle oxidation were consistently shorter and differently shaped than those predicted by established models. This reveals the existence of additional processes, e.g., migration, partial or asymmetric oxidation. These results highlight the SPICE approach's ability to provide valuable insights into processes occurring during single-entity electrochemistry, which can be applied to various electrochemical experiments, where signal distortions are inevitable. © 2022 American Chemical Society. All rights reserved.

Single Pt atom catalysts are key targets because a high exposure of Pt substantially enhances electrocatalytic activity. In addition, PtRu alloy nanoparticles are the most active catalysts for the methanol oxidation reaction. To combine the exceptional activity of single Pt atom catalysts with an active Ru support we must overcome the synthetic challenge of forming single Pt atoms on noble metal nanoparticles. Here we demonstrate a process that grows and spreads Pt islands on Ru branched nanoparticles to create single-Pt-atom-on-Ru catalysts. By following the spreading process by in situ TEM, we found that the formation of a stable single atom structure is thermodynamically driven by the formation of strong Pt–Ru bonds and the lowering of the surface energy of the Pt islands. The stability of the single-Pt-atom-on-Ru structure and its resilience to CO poisoning result in a high current density and mass activity for the methanol oxidation reaction over time. [Figure not available: see fulltext.] © 2022, The Author(s), under exclusive licence to Springer Nature Limited.

The electrical double-layer plays a key role in important interfacial electrochemical processes from catalysis to energy storage and corrosion. Therefore, understanding its structure is crucial for the progress of sustainable technologies. We extract new physico-chemical information on the capacitance and structure of the electrical double-layer of platinum and gold nanoparticles at the molecular level, employing single nanoparticle electrochemistry. The charge storage ability of the solid/liquid interface is larger by one order-of-magnitude than predicted by the traditional mean-field models of the double-layer such as the Gouy–Chapman–Stern model. Performing molecular dynamics simulations, we investigate the possible relationship between the measured high capacitance and adsorption strength of the water adlayer formed at the metal surface. These insights may launch the active tuning of solid–solvent and solvent–solvent interactions as an innovative design strategy to transform energy technologies towards superior performance and sustainability. © 2021 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH

The present review details a chronological description of the events that took place during the development of mesoporous materials, their different synthetic routes and their use as drug delivery systems. The outstanding textural properties of these materials quickly inspired their translation to the nanoscale dimension leading to mesoporous silica nanoparticles (MSNs). The different aspects of introducing pharmaceutical agents into the pores of these nanocarriers, together with their possible biodistribution and clearance routes, would be described here. The development of smart nanocarriers that are able to release a high local concentration of the therapeutic cargo on-demand after the application of certain stimuli would be reviewed here, together with their ability to deliver the therapeutic cargo to precise locations in the body. The huge progress in the design and development of MSNs for biomedical applications, including the potential treatment of different diseases, during the last 20 years will be collated here, together with the required work that still needs to be done to achieve the clinical translation of these materials. This review was conceived to stand out from past reports since it aims to tell the story of the development of mesoporous materials and their use as drug delivery systems by some of the story makers, who could be considered to be among the pioneers in this area. © 2022 The Royal Society of Chemistry

The use of nanoparticles and nanostructured electrodes are abundant in electrocatalysis. These nanometric systems contain elements of nanoconfinement in different degrees, depending on the geometry, which can have a much greater effect on the activity and selectivity than often considered. In this Review, we firstly identify the systems containing different degrees of nanoconfinement and how they can affect the activity and selectivity of electrocatalytic reactions. Then we follow with a fundamental understanding of how electrochemistry and electrocatalysis are affected by nanoconfinement, which is beginning to be uncovered, thanks to the development of new, atomically precise manufacturing and fabrication techniques as well as advances in theoretical modeling. The aim of this Review is to help us look beyond using nanostructuring as just a way to increase surface area, but also as a way to break the scaling relations imposed on electrocatalysis by thermodynamics. © 2022 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.

Single particle electrochemical oxidation of polyvinylpyrrolidone-capped silver nanoparticles at a microdisk electrode is investigated as a function of particle shape (spheres, cubes, and plates) in potassium nitrate and potassium hydroxide solutions. In potassium nitrate, extreme anodic potentials (1500 mV vs Ag/AgCl (3 M KCl)) are necessary to achieve oxidation, while lower anodic potentials are required in potassium hydroxide (900 mV vs Ag/AgCl (saturated KCl)). Upon oxidation, silver oxide is formed, readily catalyzing water oxidation, producing a spike-step current response. The spike duration for each particle is used to probe effects of particle shape on the oxidation mechanism, and is substantially shorter in nitrate solution at the large overpotentials than in hydroxide solution. The integration of current spikes indicates oxidation to a mixed-valence complex. In both electrolytes, the rate of silver oxidation strongly depends on silver content of the nanoparticles, rather than the shape-dependent variable surface area. The step height, which reflects rate of water oxidation, also tracks the silver content more so than shape. The reactivity of less-protected citrate-capped particles toward silver oxidation is also compared with that of the polymer-capped particles under these anodic conditions in the nitrate and hydroxide solutions. © 2022 Electrochemical Society Inc.. All rights reserved.

The three-dimensional (3D) distribution of individual atoms on the surface of catalyst nanoparticles plays a vital role in their activity and stability. Optimising the performance of electrocatalysts requires atomic-scale information, but it is difficult to obtain. Here, we use atom probe tomography to elucidate the 3D structure of 10 nm sized Co2FeO4 and CoFe2O4 nanoparticles during oxygen evolution reaction (OER). We reveal nanoscale spinodal decomposition in pristine Co2FeO4. The interfaces of Co-rich and Fe-rich nanodomains of Co2FeO4 become trapping sites for hydroxyl groups, contributing to a higher OER activity compared to that of CoFe2O4. However, the activity of Co2FeO4 drops considerably due to concurrent irreversible transformation towards CoIVO2 and pronounced Fe dissolution. In contrast, there is negligible elemental redistribution for CoFe2O4 after OER, except for surface structural transformation towards (FeIII, CoIII)2O3. Overall, our study provides a unique 3D compositional distribution of mixed Co-Fe spinel oxides, which gives atomic-scale insights into active sites and the deactivation of electrocatalysts during OER. © 2022, The Author(s).

Deciphering the influence of nanocatalyst morphology on their catalytic activity in the oxygen evolution reaction (OER), the limiting reaction in water splitting process, is essential to develop highly active precious metal-free catalysts, yet poorly understood. The intrinsic OER activity of Co3O4 nanocubes and spheroids is probed at the single particle level to unravel the correlation between exposed facets, (001) vs. (111), and activity. Single cubes with predominant (001) facets show higher activity than multi-faceted spheroids. Density functional theory calculations of different terminations and reaction sites at (001) and (111) surfaces confirm the higher activity of the former, expressed in lower overpotentials. This is rationalized by a change in the active site from octahedral to tetrahedral Co and the potential-determining step from *OH to *O for the cases with lowest overpotentials at the (001) and (111) surfaces, respectively. This approach enables the identification of highly active facets to guide shape-selective syntheses of improved metal oxide nanocatalysts for water oxidation. © 2022 The Authors. Advanced Functional Materials published by Wiley-VCH GmbH.

Co-Ni-Ga shape memory alloys attracted scientific attention as promising candidate materials for damping applications at elevated temperatures, owing to excellent superelastic properties featuring a fully reversible stress-strain response up to temperatures as high as 500 °C. In the present work, the effect of aging treatments conducted in a wide range of aging temperatures and times, i.e. at 300–400 °C for 0.25–8.5 h, was investigated. It is shown that critical features of the martensitic transformation are strongly affected by the heat treatments. In particular, the formation of densely dispersed γ’-nanoparticles has a strong influence on the martensite variant selection and the morphology of martensite during stress-induced martensitic transformation. Relatively large, elongated particles promote irreversibility. In contrast, small spheroidal particles are associated with excellent functional stability during cyclic compression loading of 〈001〉-oriented single crystals. In addition to mechanical experiments, a detailed microstructural analysis was performed using in situ optical microscopy and neutron diffraction. Fundamental differences in microstructural evolution between various material states are documented and the relations between thermal treatment, microstructure and functional properties are explored and rationalized. © 2022 Acta Materialia Inc.

Electrocatalytic oxidation of glycerol (GOR) as the anode reaction in water electrolysis facilitates the production of hydrogen at the cathode at a substantially lower cell voltage compared with the oxygen evolution reaction. It simultaneously provides the basis for the production of value-added compounds at the anode. We investigate earth-abundant transition-metal oxide nanoparticles (Fe, Ni, Mn, Co) embedded in multiwalled carbon nanotubes as GOR catalysts. Out of the four investigated composites, the Ni-based catalyst exhibits the highest catalytic activity toward the GOR according to rotating disk electrode voltammetry, reaching a current density of 10 mA cm–2 already at 1.31 V vs RHE, a potential below the formation of Ni3+. Chronoamperometry conducted in a flow-through cell followed by HPLC analysis is used to identify and quantify the GOR products over time, revealing that the applied potential, electrolyte concentration, and duration of the experiment impact strongly the composition of the products’ mixture. Upon optimization, the GOR is directed toward oxalate production. Moreover, oxalate is not further converted and hence accumulates as a major organic product under the chosen conditions in a concentration ratio of 60:1 with acetate as a minor product after 48 h electrolysis in 7 M KOH, which represents a promising route for the synthesis of this highly valued product. © 2022 American Chemical Society

In this work, a novel in situ auto-reduction strategy was developed to encapsulate uniformly dispersed Pd clusters/nanoparticles in MIL-125-NH2. It is demonstrated that the amino groups in MIL-125-NH2 can react with formaldehyde to form novel reducing groups (-NH[sbnd]CH2OH), which can in situ auto-reduce the encapsulated Pd2+ ions to metallic Pd clusters/nanoparticles. As no additional reductants are required, the strategy limits the aggregation and migration of Pd clusters and the formation of large Pd nanoparticles via controlling the amount of Pd2+ precursor. When applied as catalysts in the hydrogenation of phenol in the aqueous phase, the obtained Pd(1.5)/MIL-125-NH-CH2OH catalyst with highly dispersed Pd clusters/nanoparticles with the size of around 2 nm exhibited 100% of phenol conversion and 100% of cyclohexanone selectivity at 70 °C after 5 h, as well as remarkable reusability for at least five cycles due to the large MOF surface area, the highly dispersed Pd clusters/nanoparticles and their excellent stability within the MIL-125-NH-CH2OH framework. © 2021

The purpose of this study is to find a direct and quantitative correlation of the structure of Co3-xFexO4nanoparticles with catalytic performance in 2-propanol oxidation. Eight nanocrystalline samples with varying iron contents are synthesized, and quantitative information regarding their structure is obtained from nitrogen physisorption, X-ray diffraction (XRD), X-ray absorption near-edge structure (XANES), and extended X-ray absorption fine structure (EXAFS) analyzed by reverse Monte Carlo simulations. The catalytic performance is tested in 2-propanol oxidation in the gas phase. Overall, catalytic conversion data as a function of temperature are deconvoluted to obtain conversion and half-conversion temperatures as quantitative parameters for the different catalytic reaction channels. The crystal structure is described by a spinel structure with interstitial cation defects. These defects result in a reduced electronic state of the nanoparticles. The defect density depends on the cationic composition. We also observe a complex cationic distribution on tetrahedral and octahedral sites, which is strongly influenced by the overall cationic composition. In the catalytic tests, the samples exhibit a low-temperature pathway, which is deactivated in subsequent runs but can be recovered by an oxidative treatment of the catalyst. We find that the frequency of cation pairs CoO-CoOand CoO-CoTof the individual samples correlates directly to their catalytic activity and selectivity. © 2022 American Chemical Society. All rights reserved.

Bimetallic tandem catalysts have emerged as a promising strategy to locally increase the CO flux during electrochemical CO2 reduction, so as to maximize the rate of conversion to C−C-coupled products. Considering this, a novel Cu/C−Ag nanostructured catalyst has been prepared by a redox replacement process, in which the ratio of the two metals can be tuned by the replacement time. An optimum Cu/Ag composition with similarly sized particles showed the highest CO2 conversion to C2+ products compared to non-Ag-modified gas-diffusion electrodes. Gas chromatography and in-situ Raman measurements in a CO2 gas diffusion cell suggest the formation of top-bound linear adsorbed *CO followed by consumption of CO in the successive cascade steps, as evidenced by the increasingνC−H bands. These findings suggest that two mechanisms operate simultaneously towards the production of HCO2H and C−C-coupled products on the Cu/Ag bimetallic surface. © 2022 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.

CO2 methanation using nickel-based catalysts has attracted large interest as a promising power-to-gas route. Ni nanoparticles supported on nitrogen-doped CNTs with Ni loadings in the range from 10 wt% to 50 wt% were synthesized by impregnation, calcination and reduction and characterized by elemental analysis, X-ray powder diffraction, H2 temperature-programmed reduction, CO pulse chemisorption and transmission electron microscopy. The Ni/NCNT catalysts were highly active in CO2 methanation at atmospheric pressure, reaching over 50% CO2 conversion and over 95% CH4 selectivity at 340 °C and a GHSV of 50,000 mL g−1 h−1 under kinetically controlled conditions. The small Ni particle sizes below 10 nm despite the high Ni loading is ascribed to the efficient anchoring on the N-doped CNTs. The optimum loading of 30 wt%–40 wt% Ni was found to result in the highest Ni surface area, the highest degree of conversion and the highest selectivity to methane. A constant TOF of 0.3 s−1 was obtained indicating similar catalytic properties of the Ni nanoparticles in the range from 10 wt% to 50 wt% Ni loading. Long-term experiments showed that the Ni/NCNT catalyst with 30 wt% Ni was highly stable for 100 h time on stream. © 2020 Science Press

In this issue of Matter, Yao et al. report on advanced non-equilibrium high-temperature entropy-controlled synthesis of polyelemental nanoparticles. They achieve extreme mixing of 15 metals, some of them previously immiscible, in the form of a single phase solid solution. The compositionally tunable properties of such atomic scale mixtures within a simple crystal structure makes them highly interesting for the design of new materials, e.g., electrocatalysts. © 2021 Elsevier Inc.

La1−xSrxCoO3 (x=0, 0.1, 0.2, 0.3, 0.4) nanoparticles were prepared by spray-flame synthesis and applied in the liquid-phase oxidation of cyclohexene with molecular O2 as oxidant under mild conditions. The catalysts were systematically characterized by state-of-the-art techniques. With increasing Sr content, the concentration of surface oxygen vacancy defects increases, which is beneficial for cyclohexene oxidation, but the surface concentration of less active Co2+ was also increased. However, Co2+ cations have a superior activity towards peroxide decomposition, which also plays an important role in cyclohexene oxidation. A Sr doping of 20 at. % was found to be the optimum in terms of activity and product selectivity. The catalyst also showed excellent reusability over three catalytic runs; this can be attributed to its highly stable particle size and morphology. Kinetic investigations revealed first-order reaction kinetics for temperatures between 60 and 100 °C and an apparent activation energy of 68 kJ mol−1 for cyclohexene oxidation. Moreover, the reaction was not affected by the applied O2 pressure in the range from 10 to 20 bar. In situ attenuated total reflection infrared spectroscopy was used to monitor the conversion of cyclohexene and the formation of reaction products including the key intermediate cyclohex-2-ene-1-hydroperoxide; spin trap electron paramagnetic resonance spectroscopy provided strong evidence for a radical reaction pathway by identifying the cyclohexenyl alkoxyl radical. © 2021 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH

The formation of nanoparticles by sputtering on ionic liquids could occur at the surface or in the volume of the liquid. To clarify which process occurs, Cu was sputtered in inert and oxidative plasma onto two different ionic liquids. 1-Butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide [Bmim][(Tf)2N] and 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide [Emim][(Tf)2N] were selected for their low solubility of oxygen and their different surface tensions to differentiate the influence of the ionic liquid characteristics on the formation process and characteristics of nanoparticles. The chemical state of nanoparticles in the ionic liquids, metallic or oxidized, was analyzed by X-ray photoelectron spectroscopy. Transmission electron microscopy was performed to acquire nanoparticle size distributions and shapes. The results indicate that nanoparticle formation occurs within the ionic liquid volume, contradicting the prevailing assumption that nanoparticle formation begins at the ionic liquid surface. Nanoparticle size distributions indicate that a higher viscosity of the ionic liquid results in higher nanoparticle diameters. © 2021 The Authors. Published by American Chemical Society.

CoxFe3-xO4nanoparticles (x= 0.4 tox= 2.5) and thin films (x= 0.9 tox= 2.2) are analyzed by Raman, absorption, and photoluminescence spectroscopy to link structural and optical properties to different cobalt to iron (Co/Fe) ratios. Raman spectroscopy shows that with decreasing Co content, the crystal structure changes from a predominantly normal cubic spinel phase to a mixed inverse spinel phase. This finding is supported by absorption spectroscopy that points out that inter valence charge transfer (IVCT) processes between octahedrally coordinated Co2+and Fe3+cations become more prominent with increasing Fe content. Independent of the Co/Fe ratio, CoxFe3-xO4nanoparticles show a broad photoluminescence (PL) band with a maximum at around 510 nm. Time-resolved photoluminescence spectroscopy shows subnanosecond lifetimes and temperature-resolved photoluminescence experiments reveal that the green PL increases with decreasing temperature (300 to 10 K) while showing no temperature-dependent shift in energy. It is proposed that this green PL originates from OH-groups on the particles’ surface. © 2021 The Authors. Published by American Chemical Society

CoxFe3-xO4 nanoparticles (x = 0.4 to x = 2.5) and thin films (x = 0.9 to x = 2.2) are analyzed by Raman, absorption, and photoluminescence spectroscopy to link structural and optical properties to different cobalt to iron (Co/Fe) ratios. Raman spectroscopy shows that with decreasing Co content, the crystal structure changes from a predominantly normal cubic spinel phase to a mixed inverse spinel phase. This finding is supported by absorption spectroscopy that points out that inter valence charge transfer (IVCT) processes between octahedrally coordinated Co2+ and Fe3+ cations become more prominent with increasing Fe content. Independent of the Co/Fe ratio, CoxFe3-xO4 nanoparticles show a broad photoluminescence (PL) band with a maximum at around 510 nm. Time-resolved photoluminescence spectroscopy shows subnanosecond lifetimes and temperature-resolved photoluminescence experiments reveal that the green PL increases with decreasing temperature (300 to 10 K) while showing no temperature-dependent shift in energy. It is proposed that this green PL originates from OH-groups on the particles' surface. © 2021 The Authors. Published by American Chemical Society.

X-ray-based analytics are routinely applied in many fields, including physics, chemistry, materials science, and engineering. The full potential of such techniques in the life sciences and medicine, however, has not yet been fully exploited. We highlight current and upcoming advances in this direction. We describe different X-ray-based methodologies (including those performed at synchrotron light sources and X-ray free-electron lasers) and their potentials for application to investigate the nano-bio interface. The discussion is predominantly guided by asking how such methods could better help to understand and to improve nanoparticle-based drug delivery, though the concepts also apply to nano-bio interactions in general. We discuss current limitations and how they might be overcome, particularly for future use in vivo. ©

Understanding the structure-property relations of non-precious metal heteroatom co-doped carbon electrocatalysts exhibiting high activity as well as long-term durability for both ORR and OER remains challenging but is indispensable for the development of bifunctional ORR/OER electrocatalysts. We propose B-N-co-doped graphitic 2D carbon nanostructures impregnated with controlled amount of transition metals (M-BCN; M=Co, Ni, Fe, Cu) as bifunctional ORR/OER electrocatalysts. Co-BCN outperformed the Ni-, Fe-, Cu-based BCN catalysts exhibiting potential values of 0.87 V and 1.62 V at −1 mA/cm2 and 10 mA/cm2 during ORR and OER, respectively. Importantly, Co-BCN shows bifunctional cyclic stability (Δη; EOER−EORR=0.75 V) of up to 300 cycles in 1 M KOH for a duration of 20 h with total activity loss of only 10.2 % (ORR) and 6.2 % (OER), respectively. A low loading of the metal precursors was used to preserve porosity and to facilitate the formation of metal nanoparticles or M−NxB/C type species embedded in the graphitic carbon layers. The B-N-co-doped graphitic layers also protect the embedded metal nanoparticles explaining the observed long-term stability. © 2021 The Authors. ChemElectroChem published by Wiley-VCH GmbH

Research and development in the field of metal-based additive manufacturing are advancing steadily every year. In order to increase the efficiency of powder bed fusion of metals using a laser beam system (PBF LB/M), machine manufacturers have implemented extensive optimizations with regard to the laser systems and build volumes. However, the optimization of metallic powder materials using nanoparticle additives enables an additional improvement of the laser–material interaction. In this work, tool steel 1.2709 powder was coated with silicon carbide (SiC), few-layer graphene (FLG), and iron oxide black (IOB) on a nanometer scale. Subsequently, the feedstock material and the modified powder materials were analyzed concerning the reflectance of the laser radiation and processed by PBF-LB/M in a systematic and consistent procedure to evaluate the impact of the nano-additivation on the process efficiency and mechanical properties. As a result, an increased build rate is achieved, exhibiting a relative density of 99.9% for FLG/1.2709 due to a decreased reflectance of this modified powder material. Furthermore, FLG/1.2709 provides hardness values after precipitation hardening with only aging comparable to the original 1.2709 material and is higher than the SiC- and IOB-coated material. Additionally, the IOB coating tends to promote oxide‐formation and lack‐of‐fusion defects. © 2021 by the authors. Licensee MDPI, Basel, Switzerland.

In a previous publication, ball milling was introduced as an effective method for the preparation of supported metal catalysts, simply from the coarse powders of the metal and metal oxide support. In this follow-up study, we demonstrate that mixing multiple metal sources can result in supported alloyed nanoparticles, extending the field of application of the method to the synthesis of supported bimetallic catalysts. Ball milling Au and Pd or Au and Cu in a high-energy regime (shaker mill) indeed led to the formation of Au-Pd and Au-Cu nanoparticles, supported on MgO or yttria-stabilized zirconia (YSZ), which were explored as model systems. Powder X-ray diffraction and electron microscopy were the primary means to investigate as-synthesized materials. The catalytic performance in CO oxidation was also investigated to understand better how the synthetic method could affect the features of the final materials as catalysts. © 2021 The Authors. Published by American Chemical Society.

The use of biomolecules as capping and reducing agents in the synthesis of metallic nanoparticles constitutes a promising framework to achieve desired functional properties with minimal toxicity. The system's complexity and the large number of variables involved represent a challenge for theoretical and experimental investigations aiming at devising precise synthesis protocols. In this work, we use L-asparagine (Asn), an amino acid building block of large biomolecular systems, to synthesise gold nanoparticles (AuNPs) in aqueous solution at controlled pH. The use of Asn offers a primary system that allows us to understand the role of biomolecules in synthesising metallic nanoparticles. Our results indicate that AuNPs synthesised in acidic (pH 6) and basic (pH 9) environments exhibit somewhat different morphologies.We investigate these AuNPs via Raman scattering experiments and classical molecular dynamics simulations of zwitterionic and anionic Asn states adsorbing on (111)-, (100)-, (110)-, and (311)-oriented gold surfaces. A combined analysis suggests that the underlying mechanism controlling AuNPs geometry correlates with amine's preferential adsorption over ammonium groups, enhanced upon increasing pH. Our simulations reveal that Asn (both zwitterionic and anionic) adsorption on gold (111) is essentially different from adsorption on more open surfaces. Water molecules strongly interact with the gold face-centred-cubic lattice and create traps, on the more open surfaces, that prevent the Asn from diffusing. These results indicate that pH is a relevant parameter in green-synthesis protocols with the capability to control the nanoparticle's geometry, and pave the way to computational studies exploring the effect of water monolayers on the adsorption of small molecules on wet gold surfaces. © 2021 The Author(s).

The modification of metal alloy powders by coating with nanoparticles offers the possibility to improve additive manufacturing processes, in particular the powder bed fusion of metals with laser beams (PBF/LB-M), from the material side of view. Subsequently, component qualities including mechanical properties and microstructural characteristics could be improved. Furthermore, the modification enables improved energy utilization due to an increase in laser absorption. In this work three commercial additive manufacturing powders, namely stainless steel (1.4404), tool steel (1.2709), and aluminum alloy (3.2381) were coated with three different nanoparticles (Silicon carbide (SiC), few layer graphene (FLG), and iron oxide black (IOB) to increase the laser light absorption in the PBF/LB/M process, mechanical properties, and flowability of the powders. The coating was conducted within a fluidized bed system, resulting in homogeneous coatings. This study demonstrates, that well scalable processes i.e. stirred media milling and fluidized bed coating have the potential to improve the commercial AM powders regarding their bulk density, flowability, and energy absorption, which is a crucial step towards an improvement in the efficiency of the whole PBF process. Overall important information and relations were gathered to transfer them to the real powder deposition process in future work. © 2021

The development of efficient and cost-effective electrocatalytic materials is an important part in scaling up sustainable electrochemical energy devices such as electrolyzers and fuel cells. In particular, the sluggish kinetics of the oxygen evolution reaction (OER) during water splitting renders the need of a catalyst indispensable. However, the development of catalysts is often based on laboratorial trial-and-error approaches and complex synthetic routes. Herein, the facile and systematic synthesis of pentlandite-like FexNi9-xS8 (x=0–9) nanosized particles from its elements with distinct Fe: Ni ratios was achieved using a mechanochemical method. The OER performance is optimized through tailoring the surface properties via altering the catalyst composition. The catalytic activity increases with higher nickel content in the structure, accomplishing an overpotential of 354 and 420 mV for ‘Ni9S8’ to drive 10 and 100 mA cm−2, respectively, with high stability. The in-situ formed nickel oxide/hydroxide species concurrent with sulphur depletion from the pentlandite structure upon OER are more active than NiS, inferring the crucial role of the pentlandite structure in activity. The herein reported simple synthetic approach could bring significant progress in the catalyst material development via rationally screening pentlandites with desired properties for modern energy systems. © 2021 The Authors. ChemElectroChem published by Wiley-VCH GmbH.

Hydrogen production is a key driver for sustainable and clean fuels used to generate electricity, which can be achieved through electrochemical splitting of water in alkaline solutions. However, the hydrogen evolution reaction (HER) is kinetically sluggish in alkaline media. Therefore, it has become imperative to develop inexpensive and highly efficient electrocatalysts that can replace the existing expensive and scarce noble-metal-based catalysts. Herein, we report on the rational design of nonprecious heterostructured electrocatalysts comprising a highly conductive face-centered cubic nickel metal, a nickel sulfide (NiS) phase, and a reduced graphene oxide (rGO) doped with phosphorous (P), sulfur (S), and nitrogen (N) in one ordered heteromaterial named Ni/NiS/P,N,S-rGO. The Ni/NiS/P,N,S-rGO electrode shows the best performance toward HER in 1.0 M KOH media among all materials tested with an overpotential of 155 mV at 10.0 mA cm-2 and a Tafel slope of 135 mV dec-1. The performance is comparable to the herein used Pt/C-20% benchmark catalyst examined under the same experimental conditions. The chronoamperometry and chronopotentiometry measurements have reflected the high durability of the Ni/NiS/P,N,S-rGO electrode for technological applications. At the same time, the current catalyst showed a high robustness and structure retention after long-term HER performance, which is reflected by SEM, XRD, and XPS measurements. ©

Nano-electrochemical tools to assess individual catalyst entities are critical to comprehend single-entity measurements. The intrinsic electrocatalytic activity of an individual well-defined Co3O4 nanoparticle supported on a carbon-based nanoelectrode is determined by employing an efficient SEM-controlled robotic technique for picking and placing a single catalyst particle onto a modified carbon nanoelectrode surface. The stable nanoassembly is microscopically investigated and subsequently electrochemically characterized. The hexagonal-shaped Co3O4 nanoparticles demonstrate size-dependent electrochemical activity and exhibit very high catalytic activity with a current density of up to 11.5 A cm−2 at 1.92 V (vs. RHE), and a turnover frequency of 532±100 s−1 at 1.92 V (vs. RHE) towards catalyzing the oxygen evolution reaction. © 2020 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH

One of the AM processes for direct manufacturing of metallic components is powder bed fusion of metals using a laser beam system (PBF-LB/M), in which metallic powders are molten and solidified in a layer upon layer manner by a focused laser beam. In recent years, the focus has initially been on increasing the efficiency of the systems itself. However, the modification of standard AM metal alloys using nanoparticles offers the possibility to improve the PBF-LB/M-process concerning its process efficiency and actual densification and thermal conductivity. In this work, a methodology for an in-situ investigation of the thermal conductivity as well as the reflectance behavior of metallic powder materials during the PBF-LB/M-process is established. The powder material stainless steel 1.4404 was coated with different nanoparticles (few-layer graphene (FLG), silicon carbide (SiC)) and processed in a standardized build process. As a result, the reflectance rate of all modified materials could be increased. Besides, the thermal conductivity of the material is attested to be a decisive and influencing factor for the quality of the final component. Thus, an improved relative density was achieved using the FLG/1.4404 and SiC/1.4404 (1 vol%) due to the increased thermal conductivity of the material. Also significant defects in the cross section were visible at SiC/1.4404 (4 vol%). © 2021 The Authors

Co3O4 nanocubes are evaluated concerning their intrinsic electrocatalytic activity towards the oxygen evolution reaction (OER) by means of single-entity electrochemistry. Scanning electrochemical cell microscopy (SECCM) provides data on the electrocatalytic OER activity from several individual measurement areas covering one Co3O4 nanocube of a comparatively high number of individual particles with sufficient statistical reproducibility. Single-particle-on-nanoelectrode measurements of Co3O4 nanocubes provide an accelerated stress test at highly alkaline conditions with current densities of up to 5.5 A cm−2, and allows to derive TOF values of up to 2.8×104 s−1 at 1.92 V vs. RHE for surface Co atoms of a single cubic nanoparticle. Obtaining such high current densities combined with identical-location transmission electron microscopy allows monitoring the formation of an oxy(hydroxide) surface layer during electrocatalysis. Combining two independent single-entity electrochemistry techniques provides the basis for elucidating structure–activity relations of single electrocatalyst nanoparticles with well-defined surface structure. © 2021 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH

Single-entity electrochemistry allows for assessing electrocatalytic activities of individual material entities such as nanoparticles (NPs). Thus, it becomes possible to consider intrinsic electrochemical properties of nanocatalysts when researching how activity relates to physical and structural material properties. Conversely, conventional electrochemical techniques provide a normal-ized sum current referring to a huge ensemble of NPs constituting, along with additives (e.g., bind-ers), a complete catalyst-coated electrode. Accordingly, recording electrocatalytic responses of single NPs avoids interferences of ensemble effects and reduces the complexity of electrocatalytic pro-cesses, thus enabling detailed description and modelling. Herein, we present insights into the oxygen evolution catalysis at individual cubic Co3O4 NPs impacting microelectrodes of different support materials. Simulating diffusion at supported nanocubes, measured step current signals can be analyzed, providing edge lengths, corresponding size distributions, and interference-free turnover frequencies. The provided nano-impact investigation of (electro-)catalyst-support effects contra-dicts assumptions on a low number of highly active sites. © 2021 by the authors. Licensee MDPI, Basel, Switzerland.

Photocatalytic selective oxidation of alcohols under mild conditions is an emerging technique to encounter the global challenges of energy source shortages and the green synthesis perspective. Herein, we investigate the solvent effects on heterogeneous photocatalytic anaerobic oxidation of benzyl alcohol with Pt-loaded defective SrTiO3nanoparticles. It is found that the optimal solvent is water mixed with a small amount of dimethylformamide (DMF) or acetonitrile, while the solvent effects on the oxidation of benzyl alcohol are related to the adsorption of benzyl alcohol and benzaldehyde on the photocatalysts in different solvents, in which the adsorption of benzyl alcohol plays a major role, while such positive effect can be significantly offset in case the adsorption of benzaldehyde is leading the effort. This work offers the avenue to improve the photocatalytic oxidation of alcohols by optimizing the reaction solvents in addition to the well-known structure engineering of the photocatalysts. © 2021 American Chemical Society

Traditionally, bandgap materials are a prerequisite to photocatalysis since they can harness a reasonable range of the solar spectrum. However, the high impedance across the bandgap and the low concentration of intrinsic charge carriers have limited their energy conversion. By contrast, metallic nanoparticles possess a sea of free electrons that can effectively promote the transition to the excited state for reactions. Here, an atomic layer of a bimetallic concoction of silver–gold shells is precisely fabricated onto an Au core via a sonochemical dispersion approach to form a core–shell of Au–Ag that exploits the wide availability of excited states of Ag while maintaining an efficient localized surface plasmon resonance (LSPR) of Au. Catalytic results demonstrate that this mix of Ag and Au can convert solar energy to hydrogen at high efficiency with an increase of 112.5% at an optimized potential of −0.5 V when compared to light-off conditions under the electrochemical LSPR. This outperforms the commercial Pt catalysts by 62.1% with a hydrogen production rate of 1870 µmol g−1 h−1 at room temperature. This study opens a new route for tuning the range of light capture of hydrogen evolution reaction catalysts using fabricated core–shell material through the combination of LSPR with electrochemical means. © 2021 Wiley-VCH GmbH

By photodeposition of CrOxon SrTiO3-based semiconductors doped with aliovalent Mg(II) and functionalized with Ni/NiOxcatalytic nanoparticles (economically significantly more viable than commonly used Rh catalysts), an increase in apparent quantum yield (AQYs) from ∼10 to 26% in overall water splitting was obtained. More importantly, deposition of CrOxalso significantly enhances the stability of Ni/NiO nanoparticles in the production of hydrogen, allowing sustained operation, even in intermittent cycles of illumination.In situelemental analysis of the water constituents during or after photocatalysis by inductively coupled plasma mass spectrometry/optical emission spectrometry shows that after CrOxdeposition, dissolution of Ni ions from Ni/NiOx-Mg:SrTiO3is significantly suppressed, in agreement with the stabilizing effect observed, when both Mg dopant and CrOxare present. State-of-the-art electron microscopy and energy-dispersive X-ray spectroscopy (EDX) and electron energy-loss spectroscopy (EELS) analyses demonstrate that upon preparation, CrOxis photodeposited in the vicinity of several, but not all, Ni/NiOxparticles. This implies the formation of a Ni-Cr mixed metal oxide, which is highly effective in water reduction. Inhomogeneities in the interfacial contact, evident from differences in contact angles between Ni/NiOxparticles and the Mg:SrTiO3semiconductor, likely affect the probability of reduction of Cr(VI) species during synthesis by photodeposition, explaining the observed inhomogeneity in the spatial CrOxdistribution. Furthermore, by comparison with undoped SrTiO3, Mg-doping appears essential to provide such favorable interfacial contact and to establish the beneficial effect of CrOx. This study suggests that the performance of semiconductors can be significantly improved if inhomogeneities in interfacial contact between semiconductors and highly effective catalytic nanoparticles can be resolved by (surface) doping and improved synthesis protocols. © 2021 The Authors. Published by American Chemical Society

Understanding structure and function of solid–liquid interfaces is essential for the development of nanomaterials for various applications including heterogeneous catalysis in liquid phase processes and water splitting for storage of renewable electricity. The characteristic anisotropy of crystalline nanoparticles is believed to be essential for their performance but remains poorly understood and difficult to characterize. Dual scale atomic force microscopy is used to measure electrostatic and hydration forces of faceted semiconducting SrTiO3 nanoparticles in aqueous electrolyte at variable pH. The following are demonstrated: the ability to quantify strongly facet-dependent surface charges yielding isoelectric points of the dominant {100} and {110} facets that differ by as much as 2 pH units; facet-dependent accumulation of oppositely charged (SiO2) particles; and that atomic scale defects can be resolved but are in fact rare for the samples investigated. Atomically resolved images and facet-dependent oscillatory hydration forces suggest a microscopic charge generation mechanism that explains colloidal scale electrostatic forces. © 2021 The Authors. Advanced Materials published by Wiley-VCH GmbH

Dry reforming of methane is considered a potential reaction for the utilization of waste greenhouse gases to generate valuable chemicals. However, catalyst deactivation under a harsh reaction condition appears as the main obstacle toward its commercialization. In the present work, a facile hydrothermal synthesis procedure was adopted to prepare a robust Ru-based catalyst. Among the various combinations, a 1% Ru supported over Zr0.5Ce0.5O2 nanorod catalyst showed enhanced coke resistance and almost stable activity during 200 h activity analysis. Promotion of Ru/Zr0.5Ce0.5O2 with an optimum amount of Gd2O3 improved catalyst stability, which was attributed to the strong interaction of Ru with Gd2O3 leading to smaller Ru particle size (∼5 nm) and an improved OSC was inhibiting coke deposition. Promotion with 0.5% Gd2O3 further lowered the apparent activation energy of methane conversion to ∼20.6 kcal/mol without changing the reaction orders significantly. DFT calculation confirmed, due to the orbital similarity, methane cracking is preferred over Ru atoms and CO2 activation occurred on Gd atoms. ©

Scanning electrochemical cell microscopy (SECCM) is increasingly applied to determine the intrinsic catalytic activity of single electrocatalyst particle. This is especially feasible if the catalyst nanoparticles are large enough that they can be found and counted in post-SECCM scanning electron microscopy images. Evidently, this becomes impossible for very small nanoparticles and hence, a catalytic current measured in one landing zone of the SECCM droplet cannot be correlated to the exact number of catalyst particles. We show, that by introducing a ruler method employing a carbon nanoelectrode decorated with a countable number of the same catalyst particles from which the catalytic activity can be determined, the activity determined using SECCM from many spots can be converted in the intrinsic catalytic activity of a certain number of catalyst nanoparticles.[Figure not available: see fulltext.] © 2021, The Author(s).

Antimony doped tin oxide (ATO) supported platinum nanoparticles are considered a more stable replacement for conventional carbon supported platinum materials for the oxygen reduction reaction. However, the interplay of antimony, tin and platinum and its impact on the catalytic activity and durability has only received minor attention. This is partly due to difficulties in the preparation of morphology- and surface-area-controlled antimony-doped tin oxide materials. The presented study sheds light onto catalyst-support interaction on a fundamental level, specifically between platinum as a catalyst and ATO as a support material. By using a previously described hard-templating method, a series of morphology controlled ATO support materials for platinum nanoparticles with different antimony doping concentrations were prepared. Compositional and morphological changes before and during accelerated stress tests are monitored, and underlying principles of deactivation, dissolution and catalytic performance are elaborated. We demonstrate that mobilized antimony species and strong metal support interactions lead to Pt/Sb alloy formation as well as partially blocking of active sites. This has adverse consequences on the accessible platinum surface area, and affects negatively the catalytic performance of platinum. Operando time-resolved dissolution experiments uncover the potential boundary conditions at which antimony dissolution can be effectively suppressed and how platinum influences the dissolution behavior of the support. © 2021 The Author(s). Published on behalf of The Electrochemical Society by IOP Publishing Limited.

Additive manufacturing processes, such as laser powder bed fusion, require steady powder processing but often exhibit poor flowability and low powder bed densities. Reducing the attractive Van-der-Waals force through nanoparticle coating can enhance initially poor flowability. We investigated the effect of dry-coating nanosized SiO2 on gas-atomized CoCrFeNi powders containing different amounts of particles < 20 μm with respect to nanoparticle concentration and mixing time. The dynamic angle of repose of a 0–90 μm powder reduced 50% and bulk powder density increased 30% with nanoparticle concentrations up to 0.153 wt.-%. The granular Bond-number was correlated with the powder flowability and porosity. The effect of mixing time was investigated with mixing two fractions 20–90 μm and 0–90 μm at a constant nominal nanoparticle surface area coverage of 128% for 2 to 1440 min. Short mixing times improved the flowability, while extensive mixing resulted in nanoparticle reagglomeration and deteriorated flow. © 2020

Cu-based catalysts have shown structural instability during the electrochemical CO2reduction reaction (CO2RR). However, studies on monometallic Cu catalysts do not allow a nuanced differentiation between the contribution of the applied potential and the local concentration of CO as the reaction intermediate since both are inevitably linked. We first use bimetallic Ag-core/porous Cu-shell nanoparticles, which utilise nanoconfinement to generate high local CO concentrations at the Ag core at potentials at which the Cu shell is still inactive for the CO2RR. Usingoperandoliquid cell TEM in combination withex situTEM, we can unequivocally confirm that the local CO concentration is the main source for the Cu instability. The local CO concentration is then modulated by replacing the Ag-core with a Pd-core which further confirms the role of high local CO concentrations. Product quantification during CO2RR reveals an inherent trade-off between stability, selectivity and activity in both systems. © The Royal Society of Chemistry 2021.

Bimetallic silver-copper electrocatalysts are promising materials for electrochemical CO2 reduction reaction (CO2RR) to fuels and multi-carbon molecules. Here, we combine Ag core/porous Cu shell particles, which entrap reaction intermediates and thus facilitate the formation of C2+ products at low overpotentials, with gas diffusion electrodes (GDE). Mass transport plays a crucial role in the product selectivity in CO2RR. Conventional H-cell configurations suffer from limited CO2 diffusion to the reaction zone, thus decreasing the rate of the CO2RR. In contrast, in the case of GDE-based cells, the CO2RR takes place under enhanced mass transport conditions. Hence, investigation of the Ag core/porous Cu shell particles at the same potentials under different mass transport regimes reveals: (i) a variation of product distribution including C3 products, and (ii) a significant change in the local OH- activity under operation. © 2021 The Authors. ChemElectroChem published by Wiley-VCH GmbH

Upscaling of nanoparticle fabrication by sputtering into an ionic liquid is shown for the example of Cu. Long-time sputtering (24 h) into a large amount (50 mL) of the ionic liquid 1-butyl-3-methylimidazolium bis-(trifluoromethylsulfonyl)imide [Bmim][(Tf)2 N] yields an amount of approximately 1 g Cu nanoparticles (mean spherical diameter (2.6 ± 1.1) nm), stabilized in ionic liquid without agglomerations. Extraction of Cu nanoparticles from the stabilizing ionic liquid was performed with the capping agent hexadecylamine. Extracted particles could be redispersed in other solvents, thus enabling applications of sputtered nanoparticles beyond ionic liquids. © 2021, The Author(s).

In recent years, the application field of laser powder bed fusion of metals and polymers extends through an increasing variability of powder compositions in the market. New powder formulations such as nanoparticle (NP) additivated powder feedstocks are available today. Interestingly, they behave differently along with the entire laser powder bed fusion (PBF-LB) process chain, from flowability over absorbance and microstructure formation to processability and final part properties. Recent studies show that supporting NPs on metal and polymer powder feedstocks enhances processability, avoids crack formation, refines grain size, increases functionality, and improves as-built part properties. Although several inter-laboratory studies (ILSs) on metal and polymer PBF-LB exist, they mainly focus on mechanical properties and primarily ignore nano-additivated feedstocks or standardized assessment of powder feedstock properties. However, those studies must obtain reliable data to validate each property metric’s repeatability and reproducibility limits related to the PBF-LB process chain. We herein propose the design of a large-scale ILS to quantify the effect of nanoparticle additivation on powder characteristics, process behavior, microstructure, and part properties in PBF-LB. Besides the work and sample flow to organize the ILS, the test methods to measure the NP-additivated metal and polymer powder feedstock properties and resulting part properties are defined. A research data management (RDM) plan is designed to extract scientific results from the vast amount of material, process, and part data. The RDM focuses not only on the repeatability and reproducibility of a metric but also on the FAIR principle to include findable, accessible, interoperable, and reusable data/meta-data in additive manufacturing. The proposed ILS design gives access to principal component analysis (PCA) to compute the correlations between the material–process– microstructure–part properties. © 2021 by the authors. Licensee MDPI, Basel, Switzerland.

Nanoparticles have become increasingly interesting for a wide range of applications because in principle it is possible to tailor their properties by controlling size, shape, and composition. One of these applications is heterogeneous catalysis, and a fundamental understanding of the structural details of the nanoparticles is essential for any knowledge-based improvement of reactivity and selectivity. In this work, we investigate the atomic structure of brass nanoparticles containing up to 5000 atoms as a typical example for a binary alloy consisting of Cu and Zn. As systems of this size are too large for electronic structure calculations, in our simulations, we use a recently parameterized machine learning potential providing close to density functional theory accuracy. This potential is employed for a structural characterization as a function of chemical composition by various types of simulations such as Monte Carlo in the semigrand canonical ensemble and simulated annealing molecular dynamics. Our analysis reveals that the distribution of both elements in the nanoparticles is inhomogeneous, and zinc accumulates in the outermost layer, while the first subsurface layer shows an enrichment of copper. Only for high zinc concentrations, alloying can be found in the interior of the nanoparticles, and regular patterns corresponding to crystalline bulk phases of α-brass can then be observed. The surfaces of the investigated clusters exhibit well-ordered single-crystal facets, which can give rise to grain boundaries inside the clusters. The melting temperature of the nanoparticles is found to decrease with increasing zinc-atom fraction, a trend which is well known also for the bulk phase diagram of brass. © 2021 The Authors. Published by American Chemical Society.

Phase-pure spinel-type magnetic nickel ferrite (NiFe2O4) nanocrystals in the size range of 4 to 11 nm were successfully synthesized by a fast and energy-saving microwave-assisted approach. Size and accessible surface areas can be tuned precisely by the reaction parameters. Our results highlight the correlation between size, degree of inversion, and magnetic characteristics of NiFe2O4 nanoparticles, which enables fine-tuning of these parameters for a particular application without changing the elemental composition. Moreover, the application potential of the synthesized powders for the electrocatalytic oxygen evolution reaction in alkaline media was demonstrated, showing that a low degree of inversion is beneficial for the overall performance. The most active sample reaches an overpotential of 380 mV for water oxidation at 10 mA cm−2 and 38.8 mA cm−2 at 1.7 V vs. RHE, combined with a low Tafel slope of 63 mV dec−1. © 2021 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH

The combination of nanostructured transition metal oxides and carbon materials is a promising approach to obtain inexpensive, highly efficient, and stable bifunctional electrocatalysts for the oxygen reduction (ORR) and the oxygen evolution (OER) reactions. We present a strategy for improving the bifunctional ORR/OER activity of supported FeCoOx nanoparticles by tuning the properties of multi-walled carbon nanotubes (MWCNT) via nitrogen doping during their synthesis in the presence of ammonia and subsequent oxidative functionalization. In-depth structural characterization indicates that oxidative treatment provides fine control of the dispersion and localization of FeCoOx nanoparticles in MWCNT, while the optimal degree of nitrogen doping leads to increased bifunctional activity due to enhanced electrical conductivity as well as improved catalyst stability, in both OER and ORR conditions, for nanoparticles formed by two different synthesis routes. The findings reported can be strategically considered for the design of high-performance reversible ORR/OER electrocatalysts. © 2021 The Authors. ChemElectroChem published by Wiley-VCH GmbH

Li et al. commented that our report claims that methods reported thus far cannot enable the production of high-purity corundum with surface areas greater than 100 m2g-1, and that our obtained material could be porous aggregates rather than nanoparticles. We disagree with both of these suggestions. © 2020 American Association for the Advancement of Science. All rights reserved.

Since nanoparticles are frequently used in commercial applications, there is a huge demand to obtain deeper insights into processes at the nanoscale. Especially, catalysis, chemical and electrochemical reaction dynamics are still poorly understood. Thus, simultaneous and coupled opto-and spectro-electrochemical dark-field microscopy is used to study in situ and operando the electrochemically driven dissolution mechanism of single silver nanoparticles in the presence of nitrate ions as non-complexing counter-ions, herein. Hyperspectral imaging is used to probe the intrinsic localized surface plasmon resonance of individual silver nanospheres before, during and after their electrochemical oxidation on a transparent indium tin oxide (ITO) electrode. Furthermore, optical video imaging was performed for additional information. Based on the complete loss of spectral information and intensity, a dissolution of the particles during the reaction was concluded. This way it is revealed that the dissolution of individual particles proceeds over several seconds, indicating a hindrance by the nitrate ions. Only electrochemical analysis does not provide this insight as the measured current does not allow distinguishing between successive fast dissolution of one particle after another or slow dissolution of several particles in a concerted manner. For comparison, experiments were performed in the presence of chloride ions. It was observed that the silver chloride formation is an instantaneous process. Thus, it is possible to study and define the reaction dynamics on the single nanoparticle level in various electrochemical systems and electrolyte solutions. Accordingly, operando opto- and spectro-electrochemical studies allow us to conclude, that the oxidation of silver to solvated silver cations is a kinetically slow process, while the oxidation to silver chloride is fast. We propose this approach as a new method to study electrocatalyst materials, their transformation and degradation under operando conditions. © Copyright © 2020 Wonner, Rurainsky and Tschulik.

Pd nanoparticles deposited on nitrogen-doped mesoporous carbon are promising catalysts for highly selective and effective catalytic hydrogenation reactions. To design and utilize these novel catalysts, it is essential to understand the effect of N doping on the metal-support interactions. A combined experimental (X-ray photoelectron spectroscopy) and computational (density functional theory) approach is used to identify preferential adsorption sites and to give detailed explanations of the corresponding metal-support interactions. Pyridinic N atoms turned out to be the preferential adsorption sites for Pd nanoparticles on nitrogen-doped mesoporous carbon, interacting through their lone pairs (LPs) with the Pd atoms via N-LP-Pd dσ and N-LP-Pd s and Pd dπ-π∗ charge transfer, which leads to a change in the Pd oxidation state. Our results evidence the existence of bifunctional palladium nanoparticles containing Pd0 and Pd2+ centers. © the Owner Societies.

The electrocatalytic reduction of carbon dioxide (CO2) by means of renewable energies is widely recognized as a promising approach to establish a sustainable closed carbon cycle economy. However, widespread application is hampered by the inherent difficulty in suppressing the hydrogen evolution reaction and controlling the overall process selectivity. Further critical parameters are the limited solubility of CO2 in many electrolytes and its hindered mass transport to the electrodes. Herein we report on a series of nanoparticle Cu electrocatalysts on different carbon supports and their potential to perform the electrochemical CO2 reduction under supercritical conditions (scCO2). Herein, CO2 serves as the reaction medium and reactant alike. By a detailed comparison to ambient conditions we show that scCO2 conditions largely suppress the undesirable hydrogen evolution and favor the production of formic acid by the Cu electrodes. Furthermore, we show that scCO2 conditions significantly prevent Cu nanoparticle agglomeration during electrocatalysis. © 2020 American Chemical Society.

Intensive research is being conducted into highly efficient and cheap nanoscale materials for the electrocatalytic oxidation of water. In this context, we built heterostructures of multilayered CoNi-cyanide bridged coordination (CoNi-CP) nanosheets and graphene oxide (GO) sheets (CoNi-CP/GO) as a source for heterostructured functional electrodes. The layered CoNi-CP/GO hybrid components heated in nitrogen gas (N2) at 450 °C yield CoNi-based carbide (CoNi-C) through thermal decomposition of CoNi-CP, while GO is converted into reduced GO (rGO) to finally form a CoNi-C/rGO-450 composite. The CoNi-C/rGO-450 composite shows a reasonable efficiency for oxygen evolution reaction (OER) through water oxidations in alkaline solution. Meanwhile, regulated annealing of CoNi-CP/GO in N2 with thiourea at 450 and 550 °C produces CoNi-based sulfide (CoNi-S) rather than CoNi-C between rGO sheets co-doped by nitrogen (N) and sulfur (S) heteroatoms (NS-rGO) to form CoNi-S/NS-rGO-450 and CoNi-S/NS-rGO-550 composites, respectively. The CoNi-S/NS-rGO-550 shows the best efficiency for electrocatalytic OER among all electrodes with an overpotential of 290 mV at 10 mA cm-2 and a Tafel slope of 79.5 mV dec-1. By applying the iR compensation to remove resistance of the solution (2.1 ω), the performance is further improved to achieve a current density of 10 mA cm-2 at an overpotential of 274 mV with a Tafel slope of 70.5 mV dec-1. This result is expected to be a promising electrocatalyst compared to the currently used electrocatalysts and a step for fuel cell applications in the future. © 2020 American Chemical Society.

Bimetallic Co-Cu catalysts are widely applied in higher alcohol synthesis (HAS), but the formation of the final active structure has not yet been fully clarified, especially for Co-rich catalysts. We investigated the structural evolution of a Co-Cu catalyst (Co:Cu = 2) from the hydrotalcite precursor containing additional Al3+ and Zn2+ to the final active state after 80 h under reaction conditions at 280 °C and 60 bar. The reconstruction of the bimetallic Co-Cu nanoparticles obtained by H2 reduction was induced by the feed gas consisting of an equimolar H2 and CO syngas mixture resulting in fast phase separation and sintering of metallic Cu0 and Co0 in the first 2 h time on stream (TOS) and a continuous carbidization of Co0 forming Co2C and its sintering until steady state was reached after 40 h TOS. An intergrowth of metallic Cu0 nanoparticles with Co2C nanoparticles was observed to occur under reaction conditions. The high selectivity to oxygenates amounting to 41% compared with 29% to hydrocarbons is ascribed to the multi-functional Co2C/Cu0 interface enabling dissociative CO adsorption, hydrogenation and CO insertion. The formation of hydrogenated carbon species (CxHy) originating from dissociative CO chemisorption is assumed to be favored by hydrogen spillover from Cu0 to Co2C. The adsorption sites for molecular CO provided by both Cu0 and Co2C facilitate its insertion into the CxHy intermediates thus leading to a higher selectivity to alcohols following the Anderson-Schulz-Flory distribution. © 2020 Elsevier Inc.

A strategy to reduce implant-related infections is the inhibition of the initial bacterial implant colonization by biomaterials containing silver (Ag). The antimicrobial efficacy of such biomaterials can be increased by surface enhancement (nanosilver) or by creating a sacrificial anode system for Ag. Such a system will lead to an electrochemically driven enhanced Ag ion release due to the presence of a more noble metal. Here we combined the enlarged surface of nanoparticles (NP) with a possible sacrificial anode effect for Ag induced by the presence of the electrochemically more noble platinum (Pt) in physical mixtures of Ag NP and Pt NP dispersions. These Ag NP/Pt NP mixtures were compared to the same amounts of pure Ag NP in terms of cell biological responses, i.e. the antimicrobial activity against Staphylococcus aureus and Escherichia coli as well as the viability of human mesenchymal stem cells (hMSC). In addition, Ag NP was analyzed by ultraviolet-visible (UV-vis) spectroscopy, cyclic voltammetry, and atomic absorption spectroscopy. It was found that the dissolution rate of Ag NP was enhanced in the presence of Pt NP within the physical mixture compared to a dispersion of pure Ag NP. Dissolution experiments revealed a fourfold increased Ag ion release from physical mixtures due to enhanced electrochemical activity, which resulted in a significantly increased toxicity towards both bacteria and hMSC. Thus, our results provide evidence for an underlying sacrificial anode mechanism induced by the presence of Pt NP within physical mixtures with Ag NP. Such physical mixtures have a high potential for various applications, for example as antimicrobial implant coatings in the biomedicine or as bactericidal systems for water and surface purification in the technical area. © 2019 IOP Publishing Ltd.

Complex solid solution electrocatalysts (often called high-entropy alloys) present a new catalyst class with highly promising features due to the interplay of multi-element active sites. One hurdle is the limited knowledge about structure-activity correlations needed for targeted catalyst design. We prepared Cr-Mn-Fe-Co-Ni nanoparticles by magnetron sputtering a high entropy Cantor alloy target simultaneously into an ionic liquid library. The synthesized nanoparticles have a narrow size distribution but different sizes (from 1.3 ± 0.1 nm up to 2.6 ± 0.3 nm), different crystallinity (amorphous, face-centered cubic or body-centered cubic) and composition (i.e. high Mn versus low Mn content). The Cr-Mn-Fe-Co-Ni complex solid solution nanoparticles possess an unprecedented intrinsic electrocatalytic activity for the oxygen reduction reaction in alkaline media, some of them even surpassing that of Pt. The highest intrinsic activity was obtained for body-centered cubic nanoparticles with a low Mn and Fe content which were synthesized using the ionic liquid 1-etyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide [Emimi][(Tf)2N]. This journal is © The Royal Society of Chemistry.

Spray-flame synthesis was used to produce high-surface-area perovskite electrocatalysts with high phase purity, minimum surface contamination, and high electrochemical stability. In this study, as-prepared LaCo1–xFexO3 perovskite nanoparticles (x=0.2, 0.3, and 0.4) were found to contain a high degree of combustion residuals, and mostly consist of both, stoichiometric and oxygen-deficient perovskite phases. Heating them at moderate temperature (250 °C) in oxygen could remove combustion residuals and increases the content of stoichiometric perovskite while preventing particle growth. A higher surface crystallinity was observed with increasing iron content coming along with a rise in oxygen deficient phases. With heat treatment, OER activity and stability of perovskites improved at 30 and 40 at.% Fe while deteriorating at 20 at.% Fe. This study highlights spray-flame synthesis as a promising technique to synthesize highly active nanoscale perovskite catalysts with improved OER activity. © 2020 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

Phase-pure magnesium ferrite (MgFe2O4) spinel nanocrystals are synthesized by a fast microwave-assisted route. The elemental composition is optimized via the ratio of the precursor mixture and controlled by energy-dispersive X-ray spectroscopy. Fine-tuning of the magnetic properties without changing the overall elemental composition is demonstrated by superconducting quantum interference device (SQUID) magnetometry and Mössbauer spectroscopy. Together with X-ray absorption spectroscopy and X-ray emission spectroscopy, we confirm that the degree of cation inversion is altered by thermal annealing. We can correlate the magnetic properties with both the nanosize influence and the degree of inversion. The resulting nonlinear course of saturation magnetization (Ms) in correlation with the particle diameter allows to decouple crystallite size and saturation magnetization, by this providing a parameter for the production of very small nanoparticles with high Ms with great potential for magnetic applications like ferrofluids or targeted drug delivery. Our results also suggest that the optical band gap of MgFe2O4 is considerably larger than the fundamental electronic band gap because of the d5 electronic configuration of the iron centers. The presented different electronic transitions contributing to the absorption of visible light are the explanation for the large dissent among the band gaps and band potentials found in the literature. © 2020 American Chemical Society.

The elimination of waste and by-product generation and reduced dependence on hazardous chemicals are the key steps towards environmentally sustainable chemical transformations. Heterogeneously catalysed oxidation of cyclohexene with environmentally friendly oxidizing agents such as O2, H2O2 and tert-butyl hydroperoxide (TBHP) has great potential to replace existing processes using stoichiometric oxidants. A series of spray-flame synthesised nanoparticulate LaCo1-xFexO3 catalysts was employed for cyclohexene oxidation, and the comparative results showed that TBHP led to the highest initial activity and allylic selectivity, but O2 resulted in higher conversion for longer reaction times. Furthermore, the influence of Fe substitution was studied, which did not show any beneficial synergistic effects. LaCoO3 was found to be the optimum catalyst for cyclohexene oxidation with O2, following first-order reaction kinetics with an apparent activation energy of 57 kJ mol-1. The catalyst showed good reusability due to its highly stable particle size, morphology and perovskite structure. 7-Oxabicyclo[4.1.0]heptan-2-one was identified to be formed by the oxidation of 2-cyclohexene-1-one with 2-cyclohexene-1-hydroperoxide. © 2020 The Royal Society of Chemistry.

CoFe2O4 nanoparticles (NPs) were synthesized by using a colloidal one-pot synthesis method based on the decomposition of metal acetylacetonates in the presence of oleyl amine. The characterization by X-ray diffraction, transmission electron microscopy and N2 physisorption revealed non-porous spinel phase CoFe2O4 NPs with an average particle size of 4 nm. The unsupported metal oxide NPs were applied in the selective oxidation of 2-propanol in a continuously operated fixed-bed reactor under quasi steady-state conditions using a heating rate of 0.5 k min−1. 2-Propanol was found to be oxidatively dehydrogenated over CoFe2O4 yielding acetone and H2O with high selectivity. Only to a minor extent dehydration to propene and total oxidation to CO2 was observed at higher temperatures. The detected low-temperature reaction pathway with maxima at 430 and 510 K was inhibited after the initial 2-propanol oxidation up to 573 K, but an oxidative treatment in O2 or N2O atmosphere led to full regeneration. No correlation between the desorbing amount or the surface oxygen species investigated by O2 temperature-programmed desorption experiments and the low-temperature activity was observed. The amounts of evolving CO2 during the TPO experiments indicate deactivation due to formation of carbonaceous species. Inhibition experiments with pre-adsorbed reaction intermediates and infrared spectroscopy identified acetate species as reversible poison, whereas carbonates are rather spectators. In addition, carbon deposition was detected by X-ray photoelectron spectroscopy, which also revealed a minor influence of cobalt reduction during the deactivation process as confirmed by X-ray absorption spectroscopy studies. © 2019 Elsevier Inc.

Monometallic Mo and W carbides as well as highly mixed (Mo,W) carbides with various Mo/W ratios were synthesized directly on oxygen-functionalized carbon nanotubes (OCNTs), and used as noble-metal-free electrocatalysts in the hydrogen evolution reaction (HER) under both acidic and alkaline conditions. A purely orthorhombic structure was found in both monometallic and mixed carbide samples by X-ray diffraction. Transmission electron microscopy images showed that the carbide particles were highly dispersed on the OCNTs with well-controlled particle size. The homogeneous distribution of Mo and W in the carbides was confirmed by elemental mapping. (Mo,W)2C/OCNT with a Mo/W ratio of 3 : 1 showed the lowest overpotential to reach a current density of 10 mA/cm2 (87 mV in 0.1 M KOH and 92 mV in 0.5 M H2SO4), and the smallest Tafel slope of 34 mV/dec. Long-term stability under both alkaline and acidic conditions was demonstrated for 24 h. Our results revealed that an optimal amount of W in the mixed carbide can significantly improve its performance in the HER following the Tafel reaction pathway, most likely due to the weakened Mo−Hads bond. © 2020 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

Successful design of reversible oxygen electrocatalysts does not only require to consider their activity towards the oxygen reduction (ORR) and the oxygen evolution reactions (OER), but also their electrochemical stability at alternating ORR and OER operating conditions, which is important for potential applications in reversible electrolyzers/fuel cells or metal/air batteries. We show that the combination of catalyst materials containing stable ORR active sites with those containing stable OER active sites may result in a stable ORR/OER catalyst if each of the active components can satisfy the current demand of their respective reaction. We compare the ORR/OER performances of oxides of Mn (stable ORR active sites), Fe (stable OER active sites), and bimetallic Mn0.5Fe0.5 (reversible ORR/OER catalyst) supported on oxidized multi-walled carbon nanotubes. Despite the instability of Mn and Fe oxide for the OER and the ORR, respectively, Mn0.5Fe0.5 exhibits high stability for both reactions. © 2020, The Author(s).

The interfacial fracture toughness of sintered hybrid silver nanoparticles (AgNPs) on both Au and Cu substrates is studied as a function of sintering temperature. Interfacial microstructure and porosity evolution of Au/AgNPs and Cu/AgNPs are observed to impact the fracture toughness. An Au–Ag interfacial diffusion layer is resolved at the interface of Au/AgNPs interconnects, while an oxide layer is found at the interface of Cu/AgNPs interconnects. Both porosity and pore sizes of the sintered silver interconnects are analyzed across the micro- and macro-length scales and related to the interfacial fracture toughness. The experimental observations can be theoretically described, which permits to predict the fracture toughness of the sintered silver interconnects. © 2019, Springer Science+Business Media, LLC, part of Springer Nature.

Producing stable but active materials is one of the enduring challenges in electrocatalysis and other types of catalysis. Producing branched nanoparticles is one potential solution. Controlling the number of branches and branch size of faceted branched nanoparticles is one of the major synthetic challenges to achieve highly active and stable nanocatalysts. Herein, we use a cubic-core hexagonal-branch mechanism to synthesize branched Ru nanoparticles with control over the size and number of branches. This structural control is the key to achieving high exposure of active {10–11} facets and optimum number of Ru branches that enables improved catalytic activity for oxygen evolution reaction while maintaining high stability. © 2020 Wiley-VCH GmbH

Electrocatalytic nanoparticles that mimic the three-dimensional geometric architecture of enzymes where the reaction occurs down a substrate channel isolated from bulk solution, referred to herein as nanozymes, were used to explore the impact of nano-confinement on electrocatalytic reactions. Surfactant covered Pt-Ni nanozyme nanoparticles, with Ni etched from the nanoparticles, possess a nanoscale channel in which the active sites for electrocatalysis of oxygen reduction are located. Different particle compositions and etching parameters allowed synthesis of nanoparticles with different average substrate channel diameters that have varying amounts of nano-confinement. The results showed that in the kinetically limited regime at low overpotentials, the smaller the substrate channels the higher the specific activity of the electrocatalyst. This is attributed to higher concentrations of protons, relative to bulk solution, required to balance the potential inside the nano-confined channel. However, at higher overpotentials where limitation by mass transport of oxygen becomes important, the nanozymes with larger substrate channels showed higher electrocatalytic activity. A reaction-diffusion model revealed that the higher electrocatalytic activity at low overpotentials with smaller substrate channels can be explained by the higher concentration of protons. The model suggests that the dominant mode of mass transport to achieve these high concentrations is by migration, exemplifying how nano-confinement can be used to enhance reaction rates. Experimental and theoretical data show that under mass transport limiting potentials, the nano-confinement has no effect and the reaction only occurs at the entrance of the substrate channel at the nanoparticle surface. © The Royal Society of Chemistry.

Controlling the formation of nanosized branched nanoparticles with high uniformity is one of the major challenges in synthesizing nanocatalysts with improved activity and stability. Using a cubic-core hexagonal-branch mechanism to form highly monodisperse branched nanoparticles, we vary the length of the nickel branches. Lengthening the nickel branches, with their high coverage of active facets, is shown to improve activity for electrocatalytic oxidation of 5-hydroxymethylfurfural (HMF), as an example for biomass conversion. © 2020 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA

Electrochemical dealloying as a post-Treatment can greatly improve the catalytic activity of nanoparticles. To date, selecting suitable conditions to reach desired porosity, composition and catalytic activity is based on trial-And-error-Attempts, due to insufficient understanding of the electrochemically induced morphological and compositional changes of the nanoparticles. These changes are elucidated here by combining electrochemistry with identical location electron microscopy analyses and linking them to the electrocatalytic properties of the obtained nanocatalysts. Using AgAu alloy nanoparticles and the hydrogen evolution reaction as a model system, the influence of cyclic voltammetry parameters on the catalytic activity upon electrochemical dealloying is investigated. Increasing the number of cycles initially results in a decreased Ag content and a sharp improvement in activity. Additional dealloying increases the nanoparticle porosity, while marginally altering their composition, due to surface motion of atoms. Since this is accompanied by particle aggregation, a decrease in catalytic activity results upon extensive cycling. This transition between porosity formation and particle aggregation marks the optimum for nanocatalyst post-production. The gained insights may aid speeding up the development of new materials by electrochemical dealloying as an easy-To-control post-processing route to tune the properties of existing nanoparticles, instead of having to alter usually delicate synthesis routes as a whole. © The Royal Society of Chemistry.

Discovering precious metal-free electrocatalysts exhibiting high activity and stability toward both the oxygen reduction (ORR) and the oxygen evolution (OER) reactions remains one of the main challenges for the development of reversible oxygen electrodes in rechargeable metal–air batteries and reversible electrolyzer/fuel cell systems. Herein, a highly active OER catalyst, Fe0.3Ni0.7OX supported on oxygen-functionalized multi-walled carbon nanotubes, is substantially activated into a bifunctional ORR/OER catalyst by means of additional incorporation of MnOX. The carbon nanotube-supported trimetallic (Mn-Ni-Fe) oxide catalyst achieves remarkably low ORR and OER overpotentials with a low reversible ORR/OER overvoltage of only 0.73 V, as well as selective reduction of O2 predominantly to OH−. It is shown by means of rotating disk electrode and rotating ring disk electrode voltammetry that the combination of earth-abundant transition metal oxides leads to strong synergistic interactions modulating catalytic activity. The applicability of the prepared catalyst for reversible ORR/OER electrocatalysis is evaluated by means of a four-electrode configuration cell assembly comprising an integrated two-layer bifunctional ORR/OER electrode system with the individual layers dedicated for the ORR and the OER to prevent deactivation of the ORR activity as commonly observed in single-layer bifunctional ORR/OER electrodes after OER polarization. © 2019 The Authors. Published by WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Laser fragmentation in liquids (LFL) allows the synthesis of fully inorganic, ultrasmall gold nanoparticles, usAu NPs (<3 nm). Although the general method is well established, there is a lack of understanding the chemical processes that are triggered by the laser pulses, which may dictate the surface properties that are highly important in heterogeneous oxidation catalytic reactions. We observed the formation of radical oxygen species during LFL, which suggested that LFL is a physicochemical process that leads to particle size reductions and initiates oxidative processes. When the ionic strength in the nanoenvironment was increased, the oxidation of the first atomic layer saturated at 50%, whereby the surface charge density increases continuously. We found a correlation between the surface charge density after synthesis of colloidal nanoparticles and its behavior in catalysis. The properties of the laser-generated nanoparticles in the colloidal state appear to have predetermined the catalytic performance. We found that a smaller surface charge density of the usAu NPs was beneficial for the catalytic activity in CO and ethanol oxidation, while their peroxidase-like activity was affected less. The catalytic activity was 2 times higher for samples prepared by chloride-free LFL after ozone pretreatment compared to samples prepared in pure water. Copyright © 2020 American Chemical Society.

Functionalization of semiconductors by metallic nanoparticle is considered to be one of the most effective procedure to improve photocatalytic hydrogen production. Photodeposition is frequently used for functionalization but particle sizes and dispersions are still difficult to control. Here, Pt functionalization is achieved in a one-pot synthesis. The as-prepared samples are compared to reference materials prepared by conventional photodeposition and our results confirm that small and well-dispersed nanoparticles with superior stability are obtained by one-pot synthesis. The enhanced stability is attributed to a limited leaching of Pt nanoparticles during illumination likely caused by the preferable interaction of small, well dispersed Pt nanoparticles with the TiO2 support material. In addition, our results demonstrate that Na-residues are detrimental for the photocatalytic performance and washing in acidic solution is mandatory to effectively reduce the sodium contamination. © 2019 Elsevier B.V.

Biomass-derived 5-hydroxymethylfurfural (HMF) is regarded as one of the most promising platform chemicals to produce 2,5-dimethylfuran (DMF) as a potential liquid transportation fuel. Pd nanoparticles supported on N-containing and N-free mesoporous carbon materials were prepared, characterized, and applied in the hydrogenolysis of HMF to DMF under mild reaction conditions. Quantitative conversion of HMF to DMF was achieved in the presence of formic acid (FA) and H2 over Pd/NMC within 2 h. The reaction mechanism, especially the multiple roles of FA, was explored through a detailed comparative study by varying hydrogen source, additive, and substrate as well as by applying in situ ATR-IR spectroscopy. The major role of FA is to shift the dominant reaction pathway from the hydrogenation of the aldehyde group to the hydrogenolysis of the hydroxymethyl group via the protonation by FA at the C-OH group, lowering the activation barrier of the C−O bond cleavage and thus significantly enhancing the reaction rate. XPS results and DFT calculations revealed that Pd2+ species interacting with pyridine-like N atoms significantly enhance the selective hydrogenolysis of the C−OH bond in the presence of FA due to their high ability for the activation of FA and the stabilization of H−. © 2020 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH

Bottom-up and top-down approaches are described for the challenging synthesis of Fe/Al nanoparticles (NPs) in ionic liquids (ILs) under mild conditions. The crystalline phase and morphology of the metal nanoparticles synthesized in three different ionic liquids were identified by powder X-ray diffractometry (PXRD), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), selected-area electron diffraction (SAED) and fast Fourier transform (FFT) of high-resolution TEM images. Characterization was completed by scanning electron microscopy with energy dispersive X-ray spectroscopy (SEM-EDX) for the analysis of the element composition of the whole sample consisting of the NPs and the amorphous background. The bottom-up approaches resulted in crystalline FeAl NPs on an amorphous background. The top-down approach revealed small NPs and could be identified as Fe4Al13 NPs which in the IL [OPy][NTf2] yield two absorption bands in the green-blue to green spectral region at 475 and 520 nm which give rise to a complementary red color, akin to appropriate Au NPs. © 2020 The Royal Society of Chemistry.

The synthesis of nanoparticles by combinatorial sputtering in ionic liquids is a versatile approach for discovering new materials. Whereas the influence on nanoparticle formation of different pure ionic liquids has been addressed, the influence of (I) dilution of ionic liquid with solvents and (II) different mixtures of ionic liquids is less known. Therefore, mixtures of the ionic liquid [Bmim][(Tf)2N] with the organic solvent anisole and other ionic liquids ([Bmim][(Pf)2N], [BmPyr][(Tf)2N]) were used as liquid substrates for the sputter synthesis of nanoparticles, in order to investigate the influence of these mixtures on the size of the nanoparticles. First, mixtures of anisole with a suspension of sputtered Ag nanoparticles in [Bmim][(Tf)2N] were prepared in different volumetric steps to investigate if the stabilization of the NPs by the ionic liquid could be reduced by the solvent. However, a continuous reduction in nanoparticle size and amount with increasing anisole volume was observed. Second, Ag, Au and Cu were sputtered on ionic liquid mixtures. Ag nanoparticles in [Bmim][(Tf)2N]/[Bmim][(Pf)2N] mixtures showed a decrease in size with the increasing volumetric fraction of [Bmim][(Tf)2N], whereas all nanoparticles obtained from [Bmim][(Tf)2N]/[BmPyr][(Tf)2N] mixtures showed increasing size and broadening of the size distribution. Maximum sizes of sputtered Ag and Au NPs were reached in mixtures of [Bmim][(Tf)2N] with 20 vol.% and 40 vol.% [BmPyr][(Tf)2N]. The results indicate that ionic liquid mixtures with different portions of cations and anions have the capability of influencing the ionic liquid stabilization characteristics with respect to, e.g., nanoparticle size and size distribution. © 2020 by the authors. Licensee MDPI, Basel, Switzerland.

Binary metal clusters are of high interest for applications in heterogeneous catalysis and have received much attention in recent years. To gain insights into their structure and composition at the atomic scale, computer simulations can provide valuable information if reliable interatomic potentials are available. In this paper we describe the construction of a high-dimensional neural network potential (HDNNP) intended for simulations of large brass nanoparticles with thousands of atoms, which is also applicable to bulk α-brass and its surfaces. The HDNNP, which is based on reference data obtained from density-functional theory calculations, is very accurate with a root-mean-square error of 1.7 meV/atom for total energies and 39 meV Å-1 for the forces of structures not included in the training set. The potential has been thoroughly validated for a wide range of energetic and structural properties of bulk α-brass, its surfaces as well as clusters of different size and composition demonstrating its suitability for large-scale molecular dynamics and Monte Carlo simulations with first-principles accuracy. © 2020 American Chemical Society.

In this study, using a natural and green protein R-phycoerythrin (R-PE) extracted from marine Porphyra yezoensis as the stabilizer and reducer, silver nanoparticles (AgNPs) were synthesized. Based on this, a highly sensitive and selective method for the detection of Cu2+ ions was developed using R-PE-AgNPs as fluorescent probe. The interactions between R-PE-AgNPs and Cu2+ ions were systematically characterized by fluorescence spectroscopy, transmission electron microscopy (TEM), elemental mapping and Fourier transform infrared (FTIR). It was found that Cu2+ ions could cause aggregation of the R-PE-AgNPs, accompanied by the greatly increased particle size. Importantly, the method offered a wide linear detection range from 0 μM to 100.0 μM with a detection limit of 0.0190 μM. Moreover, the proposed method was successfully applied to analyze Cu2+ ions in tap water and lake water samples, acquiring satisfactory recovery between 91.6% and 102.2%. Such a green, fast and cost-effective fluorimetric method of the R-PE-AgNPs probe has great potential for tracing Cu2+ ions in diverse aqueous media. © 2018 Elsevier Inc.

Binary alloy nanoparticles were fabricated by two combinatorial methods: (I) cosputtering from elemental targets into the ionic liquid 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide [Bmim][(Tf)2N] and (II) by mixing elemental nanoparticles after sputtering them separately into [Bmim][(Tf)2N]. Both methods lead to the formation of Au-Cu nanoparticles (2.3 nm for cosputtered, 3.6 nm for mixed), however with different resulting compositions: cosputtered nanoparticles show a composition range of Au80-90Cu20-10; mixing of Au- and Cu-loaded ionic liquids leads to the formation of Au75Cu25 nanoparticles. Annealing the binary nanoparticles at 100 °C shows that the mixed nanoparticles grow to sizes of 4.1 nm, whereas the cosputtered nanoparticles grow only to 3 nm. © 2019 American Chemical Society.

A future widespread application of electrochemical energy conversion and storage technologies strongly depends on the substitution of precious metal-based electrocatalysts for the high-overpotential oxygen reduction and oxygen evolution reactions. We report a novel Co/Co–Fe nanoparticles/N-doped carbon composite electrocatalyst (Co/CoxFey/NC) obtained by pyrolysis of CoFe layered double hydroxide (CoFe LDH) embedded in a film of a bisphenol A and tetraethylenepentamine-based polybenzoxazine poly(BA-tepa). During pyrolysis poly(BA-tepa) forms a highly conductive nitrogen-doped carbon matrix encapsulating Co/Co–Fe nanoparticles, thereby circumventing the need of any additional binder material and conductive additives. Optimization with respect to pyrolysis temperature, the CoFe LDH/BA-tepa ratio, as well as of the gas atmosphere used during the thermal treatment was performed. The optimized Co/CoxFey/NC composite material catalyst exhibits remarkable bifunctional activity towards oxygen reduction (ORR) and oxygen evolution (OER) reactions in 0.1 M KOH represented by a potential difference of only 0.77 V between the potentials at which current densities of −1 mA cm−2 for the ORR and 10 mA cm−2 for the OER were recorded. Moreover, the Co/CoxFey/NC composite material pyrolyzed in ammonia atmosphere exhibits promising stability during both the ORR and the OER. © 2019 Elsevier Ltd

Laser ablation of gold in liquids with nanosecond laser pulses in aqueous solutions of inorganic electrolytes and macromolecular ligands for gold nanoparticle size quenching is probed inside the laser-induced cavitation bubble by in situ X-ray multicontrast imaging with a Hartmann mask (XHI). It is found that (i) the in situ size quenching power of sodium chloride (NaCl) in comparison to the ablation in pure water can be observed by the scattering contrast from XHI already inside the cavitation bubble, while (ii) for polyvinylpyrrolidone (PVP) as a macromolecular model ligand an in situ size quenching cannot be observed. Complementary ex situ characterization confirms the overall size quenching ability of both additive types NaCl and PVP. The macromolecular ligand as well as its monomer N-vinylpyrrolidone (NVP) are mainly effective for growth quenching of larger nanoparticles on later time scales, leading to the conclusion of an alternative interaction mechanism with ablated nanoparticles compared to the electrolyte NaCl, probably outside of the cavitation bubble, in the surrounding liquid phase. While monomer and polymer have similar effects on the particle properties, with the polymer being slightly more efficient, only the polymer is effective against hydrodynamic aggregation. © 2019 American Chemical Society.

The direct growth of Pt islands on lattice mismatched Ni nanoparticles is a major synthetic challenge and a promising strategy to create highly strained Pt atoms for electrocatalysis. By using very mild reaction conditions, Pt islands with tunable strain were formed directly on Ni branched particles. The highly strained 1.9 nm Pt-island on branched Ni nanoparticles exhibited high specific activity and the highest mass activity for hydrogen evolution (HER) in a pH 13 electrolyte. These results show the ability to synthetically tune the size of the Pt islands to control the strain to give higher HER activity. Copyright © 2019 American Chemical Society.

Identifying the intrinsic electrocatalytic activity of nanomaterials is challenging, as their characterization usually requires additives and binders whose contributions are difficult to dissect. Herein, we use nano impact electrochemistry as an additive-free method to overcome this problem. Due to the efficient mass transport at individual catalyst nanoparticles, high current densities can be realized. High-resolution bright-field transmission electron microscopy and selected area diffraction studies of the catalyst particles before and after the experiments provide valuable insights in the transformation of the nanomaterials during harsh oxygen evolution reaction (OER) conditions. We demonstrate this for 4 nm sized CoFe2O4 spinel nanoparticles. It is revealed that these particles retain their size and crystal structure even after OER at current densities as high as several kA·m-2. The steady-state current scales with the particle size distribution and is limited by the diffusion of produced oxygen away from the particle. This versatilely applicable method provides new insights into intrinsic nanocatalyst activities, which is key to the efficient development of improved and precious metal-free catalysts for renewable energy technologies. © 2019 American Chemical Society.

A series of surfactant-free nickel-core and silver-shell (Ni@Ag) nanoparticles encapsulated within the mesopores of SBA-15 were synthesized and tested as catalysts for direct propylene oxidation by molecular oxygen. The influences of temperature, Gas Hour Space Velocity (GHSV) and Ni/Ag ratio on catalytic activity were systematically investigated. Among the prepared samples, Ni1Ag0.4/SBA-15 exhibited the best catalytic performance with selectivity of 70.7% and PO production rate of 4.4 nmol/g/s under 1 bar at 220 °C with GHSV of 192 h−1. High selectivity was attributed to longer Ag-Ag interatomic distance obtained by careful engineering the thickness of Ag shell over preformed Ni nanoparticles. In addition, all prepared new Ni@Ag core-shell catalysts presented excellent stability, which could maintain the conversion and selectivity for at least 10 h. These results suggest that new designs based on Ag surface atoms tailoring might pave the way to highly efficient and robust Ag catalysts for direct propylene oxidation using molecular oxygen as sole oxidant. © 2018 Elsevier B.V.

Fabrication of efficient and cost-effective bifunctional oxygen electrocatalysts for both the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER) remains a challenge for the development of rechargeable metal-air batteries and unitized regenerative fuel cells technologies. Herein, we report high-performance bifunctional ORR/OER electrocatalysts consisting of mixed transition metal (Fe, Co, Ni) oxide nanoparticles supported on oxidized multi-walled carbon nanotubes (MWCNT). Investigation of the ORR and OER activity of samples with different metal compositions showed that trimetallic/MWCNT composites having Fe:Ni:Co = x:x:(1-2x) ratios, with 0.25 ≤ x ≤ 0.4, exhibit highest bifunctional activity in terms of the reversible ORR/OER overvoltage at a given current density. Moreover, the trimetallic catalysts exhibited improved selectivity with respect to the reduction of O 2 to OH − compared to the bimetallic Fe-Ni, Fe-Co and Co-Ni catalysts, thus revealing synergistic interactions among the metal oxide components. Correlation of the electrocatalytic activity with the structure of the composites is discussed for the most representative cases. © 2019 Elsevier B.V.

Manganese oxides are promising catalysts for the oxidation of CO as well as the removal of volatile organic compounds from exhaust gases because of their structural versatility and their ability to reversibly change between various oxidation states. MnO2 nanoparticles doped with Na+ or K+ were synthesized by a semi-continuous precipitation method based on spray drying. Specific surface area, crystallite size, and morphology of these particles were predominantly determined by the spray-drying parameters controlling the quenching of the crystallite growth, whereas thermal stability, reducibility, and phase composition were strongly influenced by the alkali ion doping. Pure α-MnO2 was obtained by K+ doping under alkaline reaction conditions followed by calcination at 450 °C, which revealed a superior catalytic activity in comparison to X-ray amorphous or Mn2O3-containing samples. Thus, the phase composition is identified as a key factor for the catalytic activity of manganese oxides, and it was possible to achieve a similar activation of a K+-doped X-ray amorphous catalyst under reaction conditions resulting in the formation of crystalline α-MnO2. The beneficial effect of K+ doping on the catalytic activity of MnO2 is mainly associated with the stabilizing effect of K+ on the α-MnO2 tunnel structure. © 2019, Springer Nature Switzerland AG.

The impact of individual HAuCl4 nanoreactors is measured electrochemically, which provides operando insights and precise control over the modification of electrodes with functional nanoparticles of well-defined size. Uniformly sized micelles are loaded with a dissolved metal salt. These solution-phase precursor entities are then reduced electrochemically—one by one—to form nanoparticles (NPs). The charge transferred during the reduction of each micelle is measured individually and allows operando sizing of each of the formed nanoparticles. Thus, particles of known number and sizes can be deposited homogenously even on nonplanar electrodes. This is demonstrated for the decoration of cylindrical carbon fibre electrodes with 25±7 nm sized Au particles from HAuCl4-filled micelles. These Au NP-decorated electrodes show great catalyst performance for ORR (oxygen reduction reaction) already at low catalyst loadings. Hence, collisions of individual precursor-filled nanocontainers are presented as a new route to nanoparticle-modified electrodes with high catalyst utilization. © 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

The reduction in noble metal content for efficient oxygen evolution catalysis is a crucial aspect towards the large scale commercialisation of polymer electrolyte membrane electrolyzers. Since catalytic stability and activity are inversely related, long service lifetime still demands large amounts of low-abundant and expensive iridium. In this manuscript we elaborate on the concept of maximizing the utilisation of iridium for the oxygen evolution reaction. By combining different tin oxide based support materials with liquid atomic layer deposition of iridium oxide, new possibilities are opened up to grow thin layers of iridium oxide with tuneable noble metal amounts. In-situ, time- and potential-resolved dissolution experiments reveal how the stability of the substrate and the catalyst layer thickness directly affect the activity and stability of deposited iridium oxide. Based on our results, we elaborate on strategies how to obtain stable and active catalysts with maximized iridium utilisation for the oxygen evolution reaction and demonstrate how the activity and durability can be tailored correspondingly. Our results highlight the potential of utilizing thin noble metal films with earth abundant support materials for future catalytic applications in the energy sector. [Figure not available: see fulltext.]. © 2019, The author(s).

Due to material gaps and synthesis-related cross-correlations in heterogeneous catalysis, chemists and physicists are constantly motivated to develop novel catalyst preparation methods for independent control of morphology, size, and composition. Within this article, advances, opportunities, and the current limits of laser-based catalyst preparation technique, as well as synergies with conventional methods will be reviewed in terms of purity, particle size, morphology, composition, and nanoparticle-support interaction. It will be shown, that the surfactant-free particles represent ideal model materials to validate kinetic models and conduct parametric activity studies by independent adjustment of functional properties like nanoparticle size, composition, and load. Consequently, the importance of transient plasma dynamics tailoring nanoparticle formation will be pointed out, comparing experimental studies with own calculations and novel simulations taken from literature. Finally, perspectives of surfactant-free colloidal nanoparticles for unrevealing active sites in heterogeneous catalysts are presented. © 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Coupling electrochemical generation of hydrogen with the concomitant formation of an industrially valuable product at the anode instead of oxygen can balance the high costs usually associated with water electrolysis. We report the synthesis of a variety of nanoparticulate LaCo1−xFexO3 perovskite materials through a specifically optimized spray-flame nanoparticle synthesis method, using different ratios of La, Co, and Fe precursor compounds. Structural characterization of the resulting materials by XRD, TEM, FTIR, and XPS analysis revealed the formation of mainly perovskite-type materials. The electrocatalytic performance of the formed perovskite-type materials towards the oxygen evolution reaction and the ethanol oxidation reaction was investigated by using rotating disk electrode voltammetry. An increased Fe content in the precursor mixture leads to a decrease in the electrocatalytic activity of the nanoparticles. The selectivity towards alcohol oxidation in alkaline media was assessed by using the ethanol oxidation reaction as a model reaction. Operando electrochemistry/ATR-IR spectroscopy results reveal that acetate and acetaldehyde are the final products, depending on the catalyst composition as well as on the applied potential. © 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Enzymes can perform complex multistep cascade reactions by linking multiple distinct catalytic sites via substrate channeling. We mimic this feature in a generalized approach with an electrocatalytic nanoparticle for the carbon dioxide reduction reaction comprising a Ag core surrounded by a porous Cu shell, providing different active sites in nanoconfined volumes. The architecture of the nanozyme provides the basis for a cascade reaction, which promotes C-C coupling reactions. The first step occurs on the Ag core, and the subsequent steps on the porous copper shell, where a sufficiently high CO concentration due to the nanoconfinement facilitates C-C bond formation. The architecture yields the formation of n-propanol and propionaldehyde at potentials as low as-0.6 V vs RHE. Copyright © 2019 American Chemical Society.

Determination of the intrinsic electrocatalytic activity of nanomaterials by means of macroelectrode techniques is compromised by ensemble and film effects. Here, a unique “particle on a stick” approach is used to grow a single metal–organic framework (MOF; ZIF-67) nanoparticle on a nanoelectrode surface which is pyrolyzed to generate a cobalt/nitrogen-doped carbon (CoN/C) composite nanoparticle that exhibits very high catalytic activity towards the oxygen evolution reaction (OER) with a current density of up to 230 mA cm−2 at 1.77 V (vs. RHE), and a high turnover frequency (TOF) of 29.7 s−1 at 540 mV overpotential. Identical location transmission electron microscopy (IL-TEM) analysis substantiates the “self-sacrificial” template nature of the MOF, while post-electrocatalysis studies reveal agglomeration of Co centers within the CoN/C composite during the OER. “Single-entity” electrochemical analysis allows for deriving the intrinsic electrocatalytic activity and furnishes insight into the transient behavior of the electrocatalyst under reaction conditions. © 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

The production of acetaldehyde through biomass-derived ethanol dehydrogenation is a sustainable alternative compared to the fossil-feedstock based process, for which Cu-based catalysts are considered to be the most efficient. Herein, we modified the surface of silicon carbide (SiC) to alter the properties of the interface from SiO2-rich to C-rich, and we prepared a series of Cu-supported catalysts (Cu/SiC, Cu/SiO2/SiC, and Cu/C/SiC) with the aim of insight into the effect of the interface structure and composition on catalytic dehydrogenation of ethanol. At 280 °C, the Cu/SiO2/SiC catalyst exhibits high ethanol conversion due to the excellent dispersion of Cu nanoparticles promoted by SiO2-rich interface. In contrast, Cu nanoparticles dispersed on C/SiC shows somewhat lower activity but excellent acetaldehyde selectivity with trace amounts of by-products under identical reaction conditions. This difference is attributed to the fast removal of acetaldehyde because of its low affinity for the relatively inert C-rich interface (C/SiC). This work provides an in-depth understanding of Cu−Si−C multi-interfacial structure and the ethanol dehydrogenation behavior, which may shed light on the design of novel catalysts with tailored interfacial structures. © 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Crystalline Co3O4 nanoparticles with a uniform size of 9 nm as shown by X-ray diffraction (XRD) and transmission electron microscopy (TEM) were synthesized by thermal decomposition of cobalt acetylacetonate in oleylamine and applied in the oxidation of 2-propanol after calcination. The catalytic properties were derived under continuous flow conditions as a function of temperature up to 573 K in a fixed-bed reactor at atmospheric pressure. Temperature-programmed oxidation, desorption (TPD), surface reaction (TPSR), and 2-propanol decomposition experiments were performed to study the interaction of 2-propanol and O2 with the exposed spinel surfaces. Co3O4 selectively catalyzes the oxidative dehydrogenation of 2-propanol, yielding acetone and H2O and only to a minor extent the total oxidation to CO2 and H2O at higher temperatures. The high catalytic activity of Co3O4 reaching nearly full conversion with 100% selectivity to acetone at 430 K is attributed to the high amount of active Co3+ species at the catalyst surface as well as surface-bound reactive oxygen species observed in the O2 TPD, 2-propanol TPD, TPSR, and 2-propanol decomposition experiments. Density functional theory calculations with a Hubbard U term support the identification of the 5-fold-coordinated octahedral surface Co5c3+ as the active site, and oxidative dehydrogenation involving adsorbed atomic oxygen was found to be the energetically most favored pathway. The consumption of surface oxygen and reduction of Co3+ to Co2+ during 2-propanol oxidation derived from X-ray absorption spectroscopy and X-ray photoelectron spectroscopy measurements before and after reaction and poisoning by strongly bound carbonaceous species result in the loss of the low-temperature activity, while the high-temperature reaction pathway remained unaffected. © 2019 American Chemical Society.

Complex solid solution (CSS) nanoparticles were recently discovered as efficient electrocatalysts for a variety of reactions. As one of many advantages, they exhibit the potential to replace noble-metal catalysts with multinary combinations of transition metals because they offer formation of new unique and tailorable active sites of multiple elements located next to each other. This Perspective reports on the current state and on challenges of the (combinatorial) synthesis of multinary nanoparticles and advanced electron microscopy characterization techniques for revealing structure-activity correlations on an atomic scale. We discuss what distinguishes this material class from common catalysts to highlight their potential to act as electrocatalysts and rationalize their nontypical electrochemical behavior. We provide an overview about challenges in synthesis, characterization, and electrochemical evaluation and propose guidelines for future design of CSS catalysts to achieve further progress in this research field, which is still in its infancy. © 2019 American Chemical Society.

Bimetallic alloyed silver-platinum nanoparticles (AgPt NP) with different metal composition from Ag10Pt90 to Ag90Pt10 in steps of 20 mol% were synthesized. The biological effects of AgPt NP, including cellular uptake, cell viability, osteogenic differentiation and osteoclastogenesis as well as the antimicrobial activity towards Staphylococcus aureus and Escherichia coli were analyzed in comparison to pure Ag NP and pure Pt NP. The uptake of NP into human mesenchymal stem cells was confirmed by cross-sectional focused-ion beam preparation and observation by scanning and transmission electron microscopy in combination with energy-dispersive x-ray analysis. Lower cytotoxicity and antimicrobial activity were observed for AgPt NP compared to pure Ag NP. Thus, an enhanced Ag ion release due to a possible sacrificial anode effect was not achieved. Nevertheless, a Ag content of at least 50 mol% was sufficient to induce bactericidal effects against both Staphylococcus aureus and Escherichia coli. In addition, a Pt-related (≥50 mol% Pt) osteo-promotive activity on human mesenchymal stem cells was observed by enhanced cell calcification and alkaline phosphatase activity. In contrast, the osteoclastogenesis of rat primary precursor osteoclasts was inhibited. In summary, these results demonstrate a combinatory osteo-promotive and antimicrobial activity of bimetallic Ag50Pt50 NP. © 2019 IOP Publishing Ltd.

The development of bifunctional oxygen electrodes is a key factor for the envisaged application of rechargeable metal-air batteries. In this work, we present a simple procedure based on pyrolysis of polybenzoxazine/metal metalloid nanoparticles composites into efficient bifunctional oxygen reduction and oxygen evolution electrocatalysts. This procedure generates nitrogen-doped carbon with embedded metal metalloid nanoparticles exhibiting high activity towards both, oxygen reduction and oxygen evolution, in 0.1 M KOH with a roundtrip voltage of as low as 0.81 V. Koutecký-Levich analysis coupled with scanning electrochemical microscopy reveals that oxygen is preferentially reduced in a 4e− transfer pathway to hydroxide rather than to hydrogen peroxide. Furthermore, the polybenzoxazine derived carbon matrix allows for stable catalyst fixation on the electrode surface, resulting in unattenuated activity during continuous alternate polarisation between oxygen evolution at 10 mA cm−2 and oxygen reduction at −1.0 mA cm−2. © 2018 Elsevier Ltd

The functional composite of metal nanoparticles (NPs) and defect-engineered metal-organic frameworks (DE-MOFs), NPs@DE-MOFs, is an emerging field of MOF materials chemistry. Herein, we report on a series of novel Pd-NPs@DE-HKUST-1(Cu/Pd) catalysts containing both micro- and mesopores through the incorporation of the defect-generating linker 2,6-pyridyldicarboxylate (pydc). The Pd NPs are formed by partial reduction of the Pd2+ sites of the pristine mixed-metal DE-HKUST-1(Cu/Pd) with methanol. The size regime and the spatial distribution of the Pd NPs can be controlled by the amount of framework-incorporated pydc. The samples exhibit superior catalytic activity in the aerobic oxidation of cinnamyl alcohol as compared to the parent HKUST-1. © 2019 The Royal Society of Chemistry.

Laser ablation in liquid-phase (LAL) has been developed since the 1990s, but the interest in laser synthesis of colloids has emerged in the last decade due to a significant improvement in the production rate, proven comparative advantages in biomedical and catalysis applications, and recent commercialization. However, the method relies on highly transient phenomena, so that the fundamental understanding lacks behind the LAL synthesis refinement research. The complexity of the physics and chemistry involved has led to experimental and theoretical investigations that attempt to provide a basic description of the underlying processes but face the challenge of temporal and spatial resolution as well as non-equilibrium conditions. It appears that the processes occurring at the early time scales, ranging from femtoseconds to several microseconds are critical in the definition of the final product. The review is mainly dedicated to the comprehensive description of the processes occurring at early time scales, which include the description of laser-matter interaction for ultrashort and short laser pulses, plasma formation processes as well as comparison of the measured plasma parameters at these time scales, and subsequent description of the cavitation bubble dynamics. Furthermore, the plasma and cavitation bubble chemistry are addressed, and their impact on the nanoparticle formation is emphasized. © 2019 IOP Publishing Ltd.

Supported catalysts are among the most important classes of catalysts. They are typically prepared by wet-chemical methods, such as impregnation or co-precipitation. Here we disclose that dry ball milling of macroscopic metal powder in the presence of a support oxide leads in many cases to supported catalysts with particles in the nanometer size range. Various supports, including TiO2, Al2O3, Fe2O3, and Co3O4, and different metals, such as Au, Pt, Ag, Cu, and Ni, were studied, and for each of the supports and the metals, highly dispersed nanoparticles on supports could be prepared. The supported catalysts were tested in CO oxidation, where they showed activities in the same range as conventionally prepared catalysts. The method thus provides a simple and cost-effective alternative to the conventionally used impregnation methods. © 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

“Single entity” measurements are central for an improved understanding of the function of nanoparticle-based electrocatalysts without interference arising from mass transfer limitations and local changes of educt concentration or the pH value. We report a scanning electrochemical cell microscopy (SECCM) investigation of zeolitic imidazolate framework (ZIF-67)-derived Co−N-doped C composite particles with respect to the oxygen evolution reaction (OER). Surmounting the surface wetting issues as well as the potential drift through the use of a non-interfering Os complex as free-diffusing internal redox potential standard, SECCM could be successfully applied in alkaline media. SECCM mapping reveals activity differences relative to the number of particles in the wetted area of the droplet landing zone. The turnover frequency (TOF) is 0.25 to 1.5 s−1 at potentials between 1.7 and 1.8 V vs. RHE, respectively, based on the number of Co atoms in each particle. Consistent values at locations with varying number of particles demonstrates OER performance devoid of macroscopic film effects. © 2019 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

Synthesis of silver nanoparticles (Ag NPs) with state-of-the-art chemical or photo-reduction methods generally takes several steps and requires both reducing agents and stabilizers to obtain NPs with narrow size distribution. Herein, we report a novel method to synthesize Ag NPs rapidly in one step, achieving typical particle sizes in the range from 5 to 15 nm. The synthesis steps only involve three chemicals without any reducing agent: AgNO3 as precursor, polyvinylpyrrolidone (PVP) as stabilizer, and AgCl as photocatalyst. The Ag NPs were supported on carbon and showed excellent performance in thermal catalytic p-nitrophenol reduction and nitrobenzene hydrogenation, and as electrocatalyst for the oxygen reduction reaction. © 2019 Science Press and Dalian Institute of Chemical Physics, Chinese Academy of Sciences

Gold nanoparticles supported on reduced TiO2 (110) surfaces are widely used as catalysts for oxidation reactions. Despite extensive studies, the role of oxygen vacancies in such systems remains elusive and is controversially discussed. Combining ab initio molecular dynamics simulations with methods originally developed to describe defects in semiconductor physics we study how the electronic charge originally located at the vacancy modifies the charge on the cluster. Despite differences resulting from the employed level of density functional theory (namely semilocal/GGA, GGA + U, and hybrid functionals), we consistently find that the Au clusters remain either neutral or acquire a positive charge. The intuitively expected electron transfer from the oxygen vacancy to the gold cluster can be safely ruled out. Analyzing these findings, we discuss the role of the oxygen vacancy in the bonding between Au clusters and support and the catalytic activity of the system. © 2019 American Chemical Society.

Metal-nanoparticles (M-NPs) were synthesized in a wet-chemical synthesis route in tunable aryl alkyl ionic liquids (TAAILs) based on the 1-aryl-3-alkyl-substituted imidazolium motif from Ru3(CO)12 and Ir4(CO)12 by microwave-heating induced thermal decomposition. The size and size dispersion of the NPs were determined by transmission electron microscopy (TEM) to an average diameter of 2.2(±0.1) to 3.9(±0.3) nm for Ru-NPs and to an average diameter of 1.4(±0.1) to 2.4(±0.1) nm for Ir-NPs. The TAAILs used contain the same bis(trifluoromethylsulfonyl)imide anion but differ in the substituents on the 1-aryl ring, e.g. 2-methyl-, 4-methoxy- and 2,4-dimethyl groups and in the 3-alkyl chain lengths (C4H9, C5H11, C8H17, C9H19, C11H23). All used TAAILs are suitable for the stabilization of Ru- and Ir-NPs over months in the IL dispersion. Different from all other investigations on M-NP/IL systems which we are aware of the particle separation properties of the TAAILs vary strongly as a function of the aryl substituent. Good NP separation can be achieved with the 4-methoxyphenyl- and 2,4-dimethylphenyl-substituted ILs, irrespective of the 3-alkyl chain lengths. Significant aggregation can be observed for 2-methylphenyl-substituted ILs. The good NP separation can be correlated with a negative electrostatic potential at the 4-methoxyphenyl or 4-methylphenyl substituent that is in the para-position of the aryl ring, whereas the 2-(ortho-)methylphenyl group assumes no negative potential. ϵ-ePC-SAFT calculations were used to validate that the interactions between ILs and the washing agents (required for TEM analyses) do not cause the observed aggregation/separation behaviour of the M-NPs. Ru-NPs were investigated as catalysts for the solvent-free hydrogenation of benzene to cyclohexane under mild conditions (70 °C, 10 bar) with activities up to 760 (mol cyclohexane) (mol Ru)-1 h-1 and over 95% conversion in ten consecutive runs for Ru-NPs. No significant loss of catalytic activity could be observed. This journal is © The Royal Society of Chemistry.

Nowadays, silver nanoparticles are extensively employed in several branches of industry and medicine. Hence, those particles are amongst the most studied class of nanomaterials, yet their reactivity and in particular their reactivity in biological systems is still poorly understood. This discrepancy leads to a huge demand for further insights into the reaction dynamics of electrochemical reactions. For this purpose, coupled opto- and spectro-electrochemical dark-field microscopy is used herein to study the electrochemical oxidation and dissolution process of individual silver nanoparticles in thiocyanate solutions. It is observed, that upon electrochemical oxidation of silver, a silver thiocyanate complex is formed. This is indicated by a change of both the measured plasmon resonance frequency and scattering intensity, simultaneous to the detection of an oxidative current. Subsequently, this silver pseudo-halide is chemically converted to a silver thiocyanate complex with higher solubility in the presence of high thiocyanate concentrations. This follow-up reaction is only detectable thanks to in situ spectroscopy as no current is associated with this chemical conversion but a distinct change in the spectroscopy response of the individual particles is seen. We were thus able to reveal that the total conversion of silver nanoparticles in the presence of thiocyanate is a multi-step process which lasts much longer than the electrochemical response suggests. © 2019 Elsevier Ltd

The effects of the alkali cations Na+ and K+ were investigated in the alkaline electrochemical oxidation of glycerol over Pd nanoparticles (NPs) deposited on functionalized carbon nanotubes (CNTs). The electrocatalytic activity was assessed by cyclic voltammetry revealing a lower overpotential of glycerol oxidation for nitrogen-functionalized Pd/NCNTs compared with oxygen-functionalized Pd/OCNTs. Whereas significantly lower current densities were observed for Pd/OCNT in NaOH than in KOH in agreement with stronger non-covalent interactions on the Pd surface, Pd/NCNT achieved an approximately three-times higher current density in NaOH than in KOH. In situ electrochemistry/IR spectroscopy was applied to unravel the product distribution as a function of the applied potential in NaOH and KOH. The IR spectra exhibited strongly changing band patterns upon varying the potential between 0.77 and 1.17 V vs RHE: at low potentials oxidized C3 species such as mesoxalate and tartronate were formed predominantly, and with increasing potentials C2 and C1 species originating from C-C bond cleavage were identified. The tendency to produce carbonate was found to be less pronounced in KOH. The less favored formation of highly oxidized C3 species and of carbonate is deduced to be the origin of the lower current densities in the cyclic voltammograms (CVs) for Pd/NCNT in KOH. The enhanced current densities in NaOH are rationalized by the presence of Na+ ions bound to the basic nitrogen species in the NCNT support. Adsorbed Na+ ions can form complexes with the organic molecules, presumably enhanced by the chelate effect. In this way, the organic molecules are assumed to be bound more tightly to the NCNT support in close proximity to the Pd NPs facilitating their oxidation. © 2018 Hiltrop et al.

There is intense interest in quantifying the levels of microRNA because of its importance as a blood-borne biomarker. The challenge has been to develop methods that can monitor microRNA expression both over broad concentration ranges and in ultralow amounts directly in a patient’s blood. Here, we show that, through electric-field-induced reconfiguration of a network of gold-coated magnetic nanoparticles modified by probe DNA (DNA–Au@MNPs), it is possible to create a highly sensitive sensor for direct analysis of nucleic acids in samples as complex as whole blood. The sensor is the first to be able to detect concentrations of microRNA from 10 aM to 1 nM in unprocessed blood samples. It can distinguish small variations in microRNA concentrations in blood samples of mice with growing tumours. The ultrasensitive and direct detection of microRNA using an electrically reconfigurable DNA–Au@MNPs network makes the reported device a promising tool for cancer diagnostics. © 2018, The Author(s).

The determination of the intrinsic properties of nanomaterials is essential for their optimization as electrocatalysts, however it poses great challenges from the standpoint of analytical tools and methods. Herein, we report a novel methodology that allows for a binder-free investigation of electrocatalyst nanoparticles. The potential-assisted immobilization of a non-noble metal catalyst, i.e., nickel-iron layered double hydroxide (NiFe LDH) nanoparticles, was employed to directly attach small nanoparticle ensembles from a suspension to the surface of etched carbon nanoelectrodes. The dimensions of this type of electrodes allowed for the immobilization of the catalyst material below the picogram scale and resulted in a high resolution towards the faradaic current response. In addition the effect of the electrochemical aging on the intrinsic activity of the catalyst was investigated in alkaline media by means of continuous cyclic voltammetry. A change in the material properties could be observed, which was accompanied by a substantial decrease in its intrinsic activity. [Figure not available: see fulltext.] © 2018, Tsinghua University Press and Springer-Verlag GmbH Germany, part of Springer Nature.

We present a transparent and flexible self-charging biosupercapacitor based on an optimised mediator- and membrane-free enzymatic glucose/oxygen biofuel cell. Indium tin oxide (ITO) nanoparticles were spray-coated on transparent conducting ITO supports resulting in a flocculent, porous and nanostructured electrode surface. By this, high capacitive currents caused by an increased electrochemical double layer as well as enhanced catalytic currents due to a higher number of immobilised enzyme molecules were obtained. After a chemical pre-treatment with a silane derivative, bilirubin oxidase from Myrothecium verrucaria was immobilized onto the ITO nanostructured electrode surface under formation of a biocathode, while bioanodes were obtained by either immobilisation of cellobiose dehydrogenase from Corynascus thermophilus or soluble PQQ-dependent glucose dehydrogenase from Acinetobacter calcoaceticus. The latter showed a lower apparent KM value for glucose conversion and higher catalytic currents at µM glucose concentrations. Applying the optimised device as a biosupercapacitor in a discontinuous charge/discharge mode led to a generated power output of 0.030 mW/cm2 at 50 µM glucose, simulating the glucose concentration in human tears. This represents an enhancement by a factor of 350 compared to the power density obtained from the continuously operating biofuel cell with a maximum power output of 0.086 µW/cm2 under the same conditions. After 17 h of charging/discharging cycles a remarkable current enhancement was still measured. The entire device was transferred to flexible materials and applied for powering a flexible display showing its potential applicability as an intermittent power source in smart contact lenses. © 2017 Elsevier B.V.

Nano impact electrochemistry is used to measure a transient signal while a nanoparticle (NP) hits an electrode due to its motion in a solution. A variety of information can be obtained from this current pulse, yet its accurate measurement is challenging due to its short duration (μs to s) and small amplitude (≤10 nA). A typically used low bandwidth low-pass filter can improve the signal-to-noise ratio, but it may cost severely in the accuracy of the data. Here, we demonstrate the effects of electronic filters by using generated current impulses with duration from 125 μs to 8 ms. Initially, a system dedicated to measure short and low current impulses was employed. There, an 8th order Bessel filter was used and the effect of varying the cut-off frequency between 50 Hz and 20 kHz on the impulse response is studied. Even though the charge is generally conserved by the filter, amplitude and duration of the pulse vary greatly in dependence of the cut-off frequency. In comparison, the response of widely used potentiostats was tested and significant deviations of the measured signal from the input were detected. Supported by destructive nano impact experiments with Ag NPs in KCl(aq), we show how the filtering affects the experimentally determined size of Ag NPs and Cl− diffusion coefficient, using impact charges and duration, respectively. As a result, we suggest a general guideline to researchers for accurate electrochemical nano impact measurements, in particular with respect to current peak duration analysis. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Materials used for photocatalytic overall water splitting (POWS) are typically composed of light-absorbing semiconductor crystals, functionalized with so-called cocatalytic nanoparticles to improve the kinetics of the hydrogen and/or oxygen evolution reactions. While function, quantity, and protection of such metal(oxide) nanoparticles have been addressed in the literature of photocatalysis, the stability and transients in the active oxidation-state upon illumination have received relatively little attention. In this Perspective, the latest insights in the active state of frequently applied cocatalysts systems, including Pt, Rh/Cr2O3, or Ni/NiOx, will be presented. While the initial morphology and oxidation state of such nanoparticles is a strong function of the applied preparation procedure, significant changes in these properties can occur during water splitting. We discuss these changes in relation to the nature of the cocatalyst/semiconductor interface. We also show how know-how of other disciplines such as heterogeneous catalysis or electro-catalysis and recent advances in analytical methodology can help to determine the active state of cocatalytic nanoparticles in photocatalytic applications. © 2018 American Chemical Society.

Achieving stability with highly active Ru nanoparticles for electrocatalysis is a major challenge for the oxygen evolution reaction. As improved stability of Ru catalysts has been shown for bulk surfaces with low-index facets, there is an opportunity to incorporate these stable facets into Ru nanoparticles. Now, a new solution synthesis is presented in which hexagonal close-packed structured Ru is grown on Au to form nanoparticles with 3D branches. Exposing low-index facets on these 3D branches creates stable reaction kinetics to achieve high activity and the highest stability observed for Ru nanoparticle oxygen evolution reaction catalysts. These design principles provide a synthetic strategy to achieve stable and active electrocatalysts. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Metallic nanostructures have become popular for applications in therapeutics, catalysts, imaging, and gene delivery. Molecular dynamics simulations are gaining influence to predict nanostructure assembly and performance; however, instantaneous polarization effects due to induced charges in the free electron gas are not routinely included. Here we present a simple, compatible, and accurate polarizable potential for gold that consists of a Lennard-Jones potential and a harmonically coupled core-shell charge pair for every metal atom. The model reproduces the classical image potential of adsorbed ions as well as surface, bulk, and aqueous interfacial properties in excellent agreement with experiment. Induced charges affect the adsorption of ions onto gold surfaces in the gas phase at a strength similar to chemical bonds while ions and charged peptides in solution are influenced at a strength similar to intermolecular bonds. The proposed model can be applied to complex gold interfaces, electrode processes, and extended to other metals. © 2018 The Author(s).

The quantitative characterisation of electrocatalytic properties of nanoparticle catalyst materials is so far only performed for layers typically comprising additionally conducting additives and binders. We propose a method enabling the evaluation of intrinsic catalytic activity of nanoparticles based on the diffusion-limited steady-state current. In a step-after-step process, the influence of coverage on kinetic and diffusion limited current is evaluated to highlight the challenges of sub-monolayer electroanalysis. Conclusions are used to point out strategies and their limitations for qualitative and quantitative comparison of intrinsic catalytic properties. Particularly, the impact of coverage, electrode geometry, altered diffusion profile for nanoparticles and the catalyst activity and selectivity are discussed. Fundamental information about electrochemical sub-monolayer nanoparticle analysis is provided. © 2018 The Royal Society of Chemistry.

Bimetallic nanoparticles consisting of silver and platinum were prepared by a modified seeded-growth process in water in the full composition range in steps of 10 mol%. The particles had diameters between 15-25 nm as determined by disc centrifugal sedimentation (DCS) and transmission electron microscopy (TEM). Whereas particles with high platinum content were mostly spherical with a solid silver core/platinum shell structure, mostly hollow alloyed nanoparticles were observed with increasing silver content. The internal structure and the elemental distribution within the particles were elucidated by high-resolution transmission electron microscopy (HRTEM) in combination with energy-dispersive X-ray spectroscopy (EDX). The particles were cytotoxic for human mesenchymal stem cells (hMSC) above 50 mol% silver. This was explained by dissolution experiments where silver was only released at and above 50 mol% silver. In contrast, platinum-rich particles (less than 50 mol% silver) did not release any silver ions. This indicates that the presence of platinum inhibits the oxidative dissolution of silver. © 2018 The Royal Society of Chemistry.

The activity towards the oxygen reduction reaction (ORR) of single silver nanoparticles (AgNP) was quantified by using AgNP impacts on dual-bore carbon nanoelectrodes in highly alkaline media. We found suitable conditions for the particles to adhere sufficiently stably for detailed electrochemical characterization of a single particle. The special electrode design opens the possibility to dose gaseous oxygen to the nanoparticle under study. Deactivation of the catalytic activity of the AgNP upon excessive exposure to oxygen as well as the recovery of catalytic activity under reducing conditions is presumably attributed to hydrogen evolution at the applied low potentials. The proposed approach allows mechanistic parameters for the ORR to be extracted at a single AgNP in highly alkaline media in the absence of any binder materials and under exclusion of averaging ensemble effects. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Surface segregation, restructuring, and sintering phenomena in size-selected copper-nickel nanoparticles (NPs) supported on silicon dioxide substrates were systematically investigated as a function of temperature, chemical state, and reactive gas environment. Using near-ambient pressure (NAP-XPS) and ultrahigh vacuum X-ray photoelectron spectroscopy (XPS), we showed that nickel tends to segregate to the surface of the NPs at elevated temperatures in oxygen- or hydrogen-containing atmospheres. It was found that the NP pretreatment, gaseous environment, and oxide formation free energy are the main driving forces of the restructuring and segregation trends observed, overshadowing the role of the surface free energy. The depth profile of the elemental composition of the particles was determined under operando CO2 hydrogenation conditions by varying the energy of the X-ray beam. The temperature dependence of the chemical state of the two metals was systematically studied, revealing the high stability of nickel oxides on the NPs and the important role of high valence oxidation states in the segregation behavior. Atomic force microscopy (AFM) studies revealed a remarkable stability of the NPs against sintering at temperatures as high as 700 °C. The results provide new insights into the complex interplay of the various factors which affect alloy formation and segregation phenomena in bimetallic NP systems, often in ways different from those previously known for their bulk counterparts. This leads to new routes for tuning the surface composition of nanocatalysts, for example, through plasma and annealing pretreatments. © 2017 American Chemical Society.

By scrutinizing the trajectory of individual nanoparticles (NPs) in solution, NP tracking analysis (NTA) allows sizing individual NPs and providing meaningful complementary information to single NP electrochemistry. Herein, a model is developed to extend NTA to allow dynamic NP sizing and to analyze the kinetics of growth of NPs in solution. Interpreting the NP trajectories as scaled Brownian motion, Monte Carlo simulations produce stochastic trajectories of growing NPs (under diffusion-controlled growth). These trajectories are grounds for determining a strategy to estimate the growth parameters of individual NPs from the time evolution analysis of the mean square displacement (MSD) curves. In particular, we evaluate the accuracy and precision of the parameter estimates from MSD analysis. In addition, the strategy is illustrated to depict the homogeneous electrosynthesis of silver NPs from the oxidation of a sacrificial Ag ultramicroelectrode (UME) in Fe2+ solution. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Controlling the amorphous or crystalline state of multinary Cr-Mn-Fe-Co-Ni alloy nanoparticles with sizes in the range between ~1.7 and ~4.8 nm is achieved using three processing routes. Direct current sputtering from an alloy target in the ionic liquid 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide leads to amorphous nanoparticles as observed by high-resolution transmission electron microscopy. Crystalline nanoparticles can be achieved in situ in a transmission electron microscope by exposure to an electron beam, ex situ by heating in vacuum, or directly during synthesis by using a high-power impulse magnetron sputtering process. Growth of the nanoparticles with respect to the amorphous particles was observed. Furthermore, the crystal structure can be manipulated by the processing conditions. For example, a body-centered cubic structure is formed during in situ electron beam crystallization while longer ex situ annealing induces a face-centered cubic structure. © 2018 by the authors. Licensee MDPI, Basel, Switzerland.

By a combination of electron paramagnetic resonance spectroscopy, finite-temperature ab initio simulations, and electronic structure analyses, the activation of molecular dioxygen at the interface of gold nanoparticles and titania in Au/TiO2 catalysts is explained at the atomic scale by tracing processes down to the molecular orbital picture. Direct evidence is provided that excess electrons in TiO2, for example created by photoexcitation of the semiconductor, migrate to the gold particles and from there to oxygen molecules adsorbed at gold/titania perimeter sites. Superoxide species are formed more efficiently in this way than on the bare TiO2 surface. This catalytic effect of the gold nanoparticles is attributed to a weakening of the internal O-O bond, leading to a preferential splitting of the molecule at shorter bond lengths together with a 70% decrease of the dissociation free energy barrier compared to the non-catalyzed case on bare TiO2. The findings are an important step forward in the clarification of the role of gold in (photo)catalytic processes. © 2018 American Chemical Society.

Pd−Au core-shell nanoparticles with a palladium core (diameter about 5.5 nm) and a gold shell (thickness about 1.7 nm) were wet-chemically synthesized in an easy water-based one-pot synthesis by sequential reduction of Pd2+ and Au3+ with glucose in the presence of poly(N-vinylpyrrolidone) (PVP). The metals are present in about equal amounts (molar ratio Pd:Au about 2:1) with a clear separation between core and shell. The reaction was monitored in-situ by small-angle X-ray scattering (SAXS), showing the initial growth of the palladium seeds, followed by the epitactic formation of the gold shell. The core-shell character of the particles was confirmed by high-resolution scanning transmission electron microscopy (STEM) and energy-dispersive X-ray spectroscopy (EDX). However, X-ray powder diffraction with Rietveld analysis indicated a partial alloying, i. e. a gradual border between the two metals. Cell culture experiments showed no adverse effects on human mesenchymal stem cells (hMSCs) with a Pd−Au nanoparticle concentration (computed as total metal) up to 50 μg mL−1 after 24 h incubation, i. e. the particles can be considered as biologically harmless, even after unintended human exposure. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

For a comparative cytotoxicity study, nanoparticles of the noble metals Rh, Pd, Ag, Pt, and Au (spherical, average diameter 4 to 8 nm) were prepared by reduction in water and colloidally stabilized with poly(N-vinyl pyrrolidone) (PVP). Thus, their shape, size, and surface functionalization were all the same. Size and morphology of the nanoparticles were determined by dynamic light scattering (DLS), analytical disc centrifugation (differential centrifugal sedimentation, DCS), and high-resolution transmission electron microscopy (HRTEM). Cell-biological experiments were performed to determine the effect of particle exposure on the viability of human mesenchymal stem cells (hMSCs). Except for silver, no adverse effect of any of the metal nanoparticles was observed for concentrations up to 50 ppm (50 mg L-1) incubated for 24 h, indicating that noble metal nanoparticles (rhodium, palladium, platinum, gold) that do not release ions are not cytotoxic under these conditions. © 2018 Rostek et al.

Spillover hydrogen species were generated by dissociative H2 adsorption on Pt nanoparticles supported on nitrogen-doped mesoporous carbon. The spillover hydrogen species on the support can migrate back to the Pt nanoparticles and hydrogenate subsequently adsorbed nitrobenzene to aniline at 80 °C, which was detected during temperature-programmed desorption experiments from 80 to 300 °C in pure He. The amount of spillover hydrogen can be tuned mainly by the pre-reduction temperature rather than by other parameters. The absence of aniline formation during nitrobenzene desorption experiments in the presence of CO indicates that hydrogenation occurs exclusively on Pt and that the spillover hydrogen species are present on the carbon support in a chemically inactive state. Most likely, spillover hydrogen is reversibly stored on the carbon support as adsorbed protons on the surface and as electrons in the bulk. These findings provide a new perspective on Pt/C-based hydrogen storage materials and fuel cell catalysts. © 2018

A facile strategy is reported for the synthesis of Fe/Co mixed metal oxide nanoparticles supported on, and embedded inside, high purity oxidized multiwalled carbon nanotubes (MWCNTs) of narrow diameter distribution as effective bifunctional catalysts able to reversibly drive the oxygen evolution reaction (OER) and the oxygen reduction reaction (ORR) in alkaline solutions. Variation of the Fe/Co ratio resulted in a pronounced trend in the bifunctional ORR/OER activity. Controlled synthesis and in-depth characterization enabled the identification of an optimal Fe/Co composition, which afforded a low OER/OER reversible overvoltage of only 0.831 V, taking the OER at 10 mA cm−2 and the ORR at −1 mA cm−2. Importantly, the optimal catalyst with a Fe/Co ratio of 2:3 exhibited very promising long-term stability with no evident change in the potential for both the ORR and the OER after 400 charge/discharge (OER/ORR) cycles at 15 mA cm−2 in 6 m KOH. Moreover, detailed investigation of the structure, size, and phase composition of the mixed Fe/Co oxide nanoparticles, as well as their localization (inside of or on the surface of the MWCNTs) revealed insight of the possible contribution of the individual catalyst components and their synergistic interaction in the catalysis. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Despite the frequent use of silver nanoparticles in consumer products and medical treatments, their reactivity and degradation in aqueous suspensions are still under debate. Here we elucidate this reactivity by an in situ opto- and spectro-electrochemical approach. Using dark-field microscopy coupled to a spectrophotometer and to an electrochemical cell, redox reactions of individual silver nanoparticles are studied in the presence of chloride. The intensity and spectral position of the plasmon resonance of an individual particle are tracked simultaneously in real time during cyclic voltammetry. They both change almost instantaneously with the detected current in a chemically reversible way. Thus, it is evidenced that the intensity decrease of the optical signal at the silver peak position is caused by the reversible formation of silver chloride and not by dissolution of silver. Moreover, at large positive potentials, further transformation to silver oxide or chlorite is revealed spectroscopically, although the electrochemical current is hidden by water and chloride oxidation. Thus, the combination of electrochemistry with dark-field microscopy and hyperspectral imaging is introduced as a new tool for real-time analysis of (electro-)chemical reactions of nanoparticles on a single-entity level. Copyright © 2018 American Chemical Society.

Enzymes are characterized by an active site that is typically embedded deeply within the protein shell thus creating a nanoconfined reaction volume in which high turnover rates occur. We propose nanoparticles with etched substrate channels as a simplified enzyme mimic, denominated nanozymes, for electrocatalysis. We demonstrate increased electrocatalytic activity for the oxygen reduction reaction using PtNi nanoparticles with isolated substrate channels. The PtNi nanoparticles comprise an oleylamine capping layer that blocks the external surface of the nanoparticles participating in the catalytic reaction. Oxygen reduction mainly occurs within the etched channels providing a nanoconfined reaction volume different from the bulk electrolyte conditions. The oxygen reduction reaction activity normalized by the electrochemically active surface area is enhanced by a factor of 3.3 for the nanozymes compared to the unetched nanoparticles and a factor of 2.1 compared to mesoporous PtNi nanoparticles that possess interconnecting pores. © Copyright 2018 American Chemical Society.

The cellular uptake and dissolution of trigonal silver nanoprisms (edge length 42 ± 15 nm, thickness 8 ± 1 nm) and mostly spherical silver nanoparticles (diameter 70 ± 25 nm) in human mesenchymal stem cells (hMSC's) and human keratinocytes (HaCaT cells) were investigated. Both particles are stabilized by polyvinylpyrrolidone (PVP), with the prisms additionally stabilized by citrate. The nanoprisms dissolved slightly in pure water but strongly in isotonic saline or at pH 4, corresponding to the lowest limit for the pH during cellular uptake. The tips of the prisms became rounded within minutes due to their high surface energy. Afterward, the dissolution process slowed down due to the presence of both PVP stabilizing Ag{100} sites and citrate blocking Ag{111} sites. On the contrary, nanospheres, solely stabilized by PVP, dissolved within 24 h. These results correlate with the finding that particles in both cell types have lost >90% of their volume within 24 h. hMSC's took up significantly more Ag from nanoprisms than from nanospheres, whereas HaCaT cells showed no preference for one particle shape. This can be rationalized by the large cellular interaction area of the plateletlike nanoprisms and the bending stiffness of the cell membranes. hMSC's have a highly flexible cell membrane, resulting in an increased uptake of plateletlike particles. HaCaT cells have a membrane with a 3 orders of magnitude higher Young's modulus than for hMSC. Hence, the energy gain due to the larger interaction area of the nanoprisms is compensated for by the higher energy needed for cell membrane deformation compared to that for spheres, leading to no shape preference. © 2017 American Chemical Society.

Spherical bimetallic AgAu nanoparticles in the molar ratios 30:70, 50:50, and 70:30 with diameters of 30 to 40 nm were analyzed together with pure silver and gold nanoparticles of the same size. Dynamic light scattering (DLS) and differential centrifugal sedimentation (DCS) were used for size determination. Cyclic voltammetry (CV) was used to determine the nanoalloy composition, together with atomic absorption spectroscopy (AAS), energy-dispersive X-ray spectroscopy (EDX) and ultraviolet-visible (UV/Vis) spectroscopy. Underpotential deposition (UPD) of lead (Pb) on the particle surface gave information about its spatial elemental distribution and surface area. Scanning electron microscopy (SEM), transmission electron microscopy (TEM), and atomic force microscopy (AFM) were applied to study the shape and the size of the nanoparticles. X-ray powder diffraction gave the crystallite size and the microstrain. The particles form a solid solution (alloy) with an enrichment of silver on the nanoparticle surface, including some silver-rich patches. UPD indicated that the surface only consists of silver atoms. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Martensitic transformations in nanoscaled shape-memory alloys exhibit characteristic features absent for the bulk counterparts. Detailed understanding is required for applications in micro- and nanoelectromechanical systems, and experimental limitations render atomistic simulation an important complementary approach. Using a recently developed, accurate potential we investigate the phase transformation in freestanding Ni-Ti shape-memory nanoparticles with molecular-dynamics simulations. The results confirm that the decrease in the transformation temperature with decreasing particle size is correlated with an overstabilization of the austenitic surface energy over the martensitic surface energy. However, a detailed atomistic analysis of the nucleation and growth behavior reveals an unexpected difference in the mechanisms determining the austenite finish and martensite start temperature. While the austenite finish temperature is directly affected by a contribution of the surface energy difference, the martensite start temperature is mostly affected by the transformation strain, contrary to general expectations. This insight not only explains the reduced transformation temperature but also the reduced thermal hysteresis in freestanding nanoparticles. © 2018 American Physical Society.

In the endeavor of discovering new noble metal–free electrocatalysts for the oxygen reduction reaction, noble metal–free multinary transition metal nanoparticle libraries are investigated. The complexity of such multiple principal element alloys provides access to a large variety of different elemental compositions, each with potentially unique properties. The strategy for efficient identification of novel electrocatalytically active systems comprises combinatorial co-sputtering into an ionic liquid followed by potential-assisted immobilization of the formed nanoparticles at a microelectrode which allows the evaluation of their intrinsic electrocatalytic activity in alkaline media. A surprisingly high intrinsic activity is found for the system Cr–Mn–Fe–Co–Ni, which is at least comparable to Pt under the same conditions, an unexpected result based on the typical properties of its constituents. Systematic removal of each element from the quinary alloy system yields a significant drop in activity for all quaternary alloys, indicating the importance of the synergistic combination of all five elements, likely due to formation of a single solid solution phase with altered properties which enables the limitations of the single elements to be overcome. Multinary transition metal alloys as a novel material class in electrocatalysis with basically unlimited possibilities for catalyst design, targeting the replacement of noble metal–based materials, are suggested. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Decomposition of rare-earth tris(N, N'-diisopropyl-2-methylamidinato)metal(III) complexes [RE(MeC(N(iPr)2))3] (RE(amd)3; RE = Pr(III), Gd(III), Er(III)) and tris(2,2,6,6-tetramethyl-3,5-heptanedionato)europium(III) (Eu(dpm)3) induced by microwave heating in the ionic liquids (ILs) 1-butyl-3-methylimidazolium tetrafluoroborate ([BMIm][BF4]), 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([BMIm][NTf2]) and in propylene carbonate (PC) yield oxide-free rare-earth metal nanoparticles (RE-NPs) in [BMIm][NTf2] and PC for RE = Pr, Gd and Er or rare-earth metal-fluoride nanoparticles (REF3-NPs) in the fluoridedonating IL [BMIm][BF4] for RE = Pr, Eu, Gd and Er. The crystalline phases and the absence of significant oxide impurities in RE-NPs and REF3-NPs were verified by powder X-ray diffraction (PXRD), selected area electron diffraction (SAED) and highresolution X-ray photoelectron spectroscopy (XPS). The size distributions of the nanoparticles were determined by transmission electron microscopy (TEM) and high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) to an average diameter of (11 ± 6) to (38 ± 17) nm for the REF3-NPs from [BMIm][BF4]. The RE-NPs from [BMIm][NTf2] or PC showed diameters of (1.5 ± 0.5) to (5 ± 1) nm. The characterization was completed by energy-dispersive X-ray spectroscopy (EDX). © 2018 Siebels et al.

Diffusion is often the rate-limiting factor of reactions in condensed phase. Thus, knowing the diffusion coefficient is key in numerous aspects ranging from drug release to steering of reactions in both homogeneous liquid phase and electrochemical reactions. Cyclic voltammetry at macro electrodes and chronoamperometry at micro electrodes are well-established methods to determine the diffusion coefficients of redox-active species dissolved in a solution. However, if the formal potentials of the redox species are outside of the potential window of the solvent, then these methods cannot be readily applied. Here we demonstrate a new concept to determine the diffusion coefficient of ions to overcome this limitation. We use their reaction with a well-defined amount of a redox-active indicator substance, which is confined in a nanoparticle suspended in a solution containing the species of interest. Employing transformative nanoparticle impact analysis, the diffusion-limited reaction of an indicator nanoparticle with the species of interest is initiated and followed by chronoamperometry. Measuring the time it takes to fully convert the indicator particle enables the determination of the diffusion coefficient of interest. This concept is demonstrated for variety of (pseudo-)halides in aqueous solution using Ag nanoparticles as redox indicator. Using chloride as an example, is further shown that this new methodology can be applied to study effects of temperature and viscosity on the diffusion coefficients. Given the multitude of nanoparticles that may serve as electrochemical redox indicator, this approach can be used to determine the diffusion coefficients for a large variety of species in different liquid environments. © 2018 Elsevier Ltd

SrTiO3 is a well-known photocatalyst inducing overall water splitting when exposed to UV irradiation of wavelengths <370 nm. However, the apparent quantum efficiency of SrTiO3 is typically low, even when functionalized with nanoparticles of Pt or Ni@NiO. Here, we introduce a simple solid-state preparation method to control the incorporation of magnesium into the perovskite structure of SrTiO3. After deposition of Pt or Ni@NiO, the photocatalytic water-splitting efficiency of the Mg:SrTiOx composites is up to 20 times higher compared to SrTiO3 containing similar catalytic nanoparticles, and an apparent quantum yield (AQY) of 10 % can be obtained in the wavelength range of 300–400 nm. Detailed characterization of the Mg:SrTiOx composites revealed that Mg is likely substituting the tetravalent Ti ion, leading to a favorable surface–space–charge layer. This originates from tuning of the donor density in the cubic SrTiO3 structure by Mg incorporation and enables high oxygen-evolution rates. Nevertheless, interfacing with an appropriate hydrogen evolution catalyst is mandatory and non-trivial to obtain high-performance in water splitting. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Cobalt oxide nanoparticles were deposited on nitrogen-doped carbon nanotubes (NCNTs) through impregnation by using cobalt nitrate as a precursor and subsequent drying and calcination. Co loadings were prepared in the range from 4 to 40 wt%, and hydrogen and ammonia were applied in the thermal post-treatment of the CoOx/NCNT samples. The Co3O4 spinel structure was detected in all samples, while the thermal treatment in ammonia and hydrogen led to the formation of CoO and metallic Co in addition. Treatment in ammonia resulted in the partial reduction of Co3O4 to CoO and nitrogen doping of the oxides, leading to excellent electrocatalytic activity in the oxygen evolution reaction (OER) and stability despite of the lower Co oxidation states compared with the sample calcined in air. In contrast, the sample reduced in hydrogen showed a lower activity and stability in the OER. The high activity of the ammonia-treated sample can be assigned to improved conductivity, favorable surface properties with surface nitrogen improving the hydrophilicity of the catalysts, and the more facile transformation to the OER-active layered cobalt oxyhydroxide phase under anodic conditions. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Single-particle electrochemistry at a nanoelectrode is explored by dark-field optical microscopy. The analysis of the scattered light allows in situ dynamic monitoring of the electrodeposition of single cobalt nanoparticles down to a radius of 65 nm. Larger sub-micrometer particles are directly sized optically by super-localization of the edges and the scattered light contains complementary information concerning the particle redox chemistry. This opto-electrochemical approach is used to derive mechanistic insights about electrocatalysis that are not accessible from single-particle electrochemistry. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

The catalytic hydrogenation of ethyl acetate to ethanol was studied at ambient pressure in the temperature range from 463 K to 513 K using Cu/ZrO2 catalysts obtained by co-precipitation as a function of the Cu loading. The hydrogenation was established as a reproducible probe reaction by determining optimal reaction parameters without deactivation or thermodynamic limitations. Power-law kinetics were determined yielding an apparent activation energy of 74 kJ mol−1 and reaction orders of 0.1–0.3 for H2 and −0.4 to 0.1 for ethyl acetate in the temperature range from 473 K to 503 K. Metallic Cu was found to be essential for the hydrogenation, but the catalytic activity was not proportional to the Cu surface area derived from N2O decomposition and temperature-programmed H2 desorption experiments identifying Cu/ZrO2 as bifunctional catalyst. The acidic sites of the ZrO2 matrix were probed by temperature-programmed experiments with ethyl acetate and NH3. Cu0 is assumed to provide atomic hydrogen by dissociative adsorption and spillover, but the reaction rate is more affected by the tight contact between the embedded Cu nanoparticles and the X-ray amorphous ZrO2 matrix. © 2017 Elsevier Inc.

Due to the layer-by-layer build-up of additively manufactured parts, the deposited material experiences a cyclic re-heating in the form of a sequence of temperature pulses. In the current work, this “intrinsic heat treatment (IHT)” was exploited to induce the precipitation of NiAl nanoparticles in an Fe-19Ni-xAl (at%) model maraging steel, a system known for rapid clustering. We used Laser Metal Deposition (LMD) to synthesize compositionally graded specimens. This allowed for the efficient screening of effects associated with varying Al contents ranging from 0 to 25 at% and for identifying promising concentrations for further studies. Based on the existence of the desired martensitic matrix, an upper bound for the Al concentration of 15 at% was defined. Owing to the presence of NiAl precipitates as observed by Atom Probe Tomography (APT), a lower bound of 3–5 at% Al was established. Within this concentration window, increasing the Al concentration gave rise to an increase in hardness by 225 HV due to an exceptionally high number density of 1025 NiAl precipitates per m3, as measured by APT. This work demonstrates the possibility of exploiting the IHT of the LMD process for the production of samples that are precipitation strengthened during the additive manufacturing process without need for any further heat treatment. © 2017

New catalysts are needed to achieve lower overpotentials and higher faradaic efficiency for desirable products during the electroreduction of CO2. In this study, we explore the size-dependence of monodisperse gold-copper alloy nanoparticles (NPs) synthesized by inverse micelle encapsulation as catalysts for CO2 electroreduction. X-ray spectroscopy revealed that gold-copper alloys were formed and were heavily oxidized in their initial as prepared state. Current density was found to increase significantly for smaller NPs due to the increasing population of strongly binding low coordinated sites on NPs below 5nm. Product analysis showed formation of H2, CO, and CH4, with faradaic selectivity showing a minor dependence on size. The selectivity trends observed are assigned to reaction-induced segregation of gold atoms to the particle surface and altered electronic or geometric properties due to alloying. © 2016.

Manganese oxides are promising electrocatalysts for the oxygen evolution reaction due to their versatile redox properties. Manganese oxide (MnOx) nanoparticles were synthesized on oxygen- and nitrogen-functionalized carbon nanotubes (OCNTs and NCNTs) by calcination in air of Mn-impregnated CNTs with a loading of 10 wt% Mn. The calcined samples were exposed to reducing conditions by thermal treatment in H2 or NH3, and to strongly oxidizing conditions using HNO3 vapor, which enabled us to flexibly tune the oxidation state of Mn from 2+ in MnO to 4+ in MnO2. The samples were characterized by X-ray photoelectron spectroscopy, X-ray diffraction, transmission electron microscopy and temperature-programmed reduction. The oxidation state of Mn was more easily changed in the MnOx/NCNTs samples compared with the MnOx/OCNTs samples. Furthermore, the reduction of MnO2 to MnO occurred in one-step on NCNTs, whereas Mn2O3 intermediate states were observed for OCNTs. STEM and TEM images revealed a smaller and uniform dispersion of the MnOx nanoparticles on NCNTs as compared to OCNTs. Electrocatalytic oxygen evolution tests in 0.1 M KOH showed that Mn in high oxidation states, specifically 4+ as in MnO2 generated by HNO3 vapor treatment, is more active than Mn in lower oxidation states, using the potential at 10 mA cm-2 and the Tafel slopes as the performance metrics. © the Owner Societies 2017.

Developing high-performance non-precious metal catalysts (NPMCs) for the oxygen-reduction reaction (ORR) is of critical importance for sustainable energy conversion. We report a novel NPMC consisting of iron carbide (Fe3C) nanoparticles encapsulated in N-doped bamboo-like carbon nanotubes (b-NCNTs), synthesized by a new metal-organic framework (MOF)-templated assembly approach. The electrocatalyst exhibits excellent ORR activity in 0.1m KOH (0.89V at -1mAcm-2) and in 0.5m H2SO4 (0.73V at -1mAcm-2) with a hydrogen peroxide yield of below 1% in both electrolytes. Due to encapsulation of the Fe3C nanoparticles inside porous b-NCNTs, the reported NPMC retains its high ORR activity after around 70hours in both alkaline and acidic media. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

By a combination of FT-NIR Raman spectroscopy, infrared spectroscopy of CO adsorption under ultrahigh vacuum conditions (UHV-IR) and Raman spectroscopy in the line scanning mode the formation of a reduced titania phase in a commercial Au/TiO2 catalyst and in freshly prepared Au/anatase catalysts was detected. The reduced phase, formed at the Au-TiO2 interface, can serve as nucleation point for the formation of stoichiometric rutile. TinO2n−1 Magnéli phases, structurally resembling the rutile phase, might be involved in this process. The formation of the reduced phase and the rutilization process is clearly linked to the presence of gold nanoparticles and it does not proceed under similar conditions with the pure titania sample. Phase transformations might be both thermally or light induced, however, the colloidal deposition synthesis of the Au/TiO2 catalysts is clearly ruled out as cause for the formation of the reduced phase. © 2017, The Author(s).

Surface functionalization of carbon nanotubes (CNTs) was achieved by a thermal treatment in the presence of pre-adsorbed potassium hydroxide and steam at 350–550 °C. The generated oxygen-containing functional groups were more basic and thermally stable compared with conventional acid-generated groups. The influence of the KOH-steam co-treatment conditions on the functionalization of CNTs was systematically investigated. Residual K species were found to intercalate in the inner graphene layers of the CNTs providing additional Brønsted basicity. Owing to the favorable basic properties and high thermal stability of the generated functional groups, Pd nanoparticles supported on the co-treated CNTs were found to be strongly anchored leading to a high degree of Pd dispersion and a high resistance to sintering. The Pd nanoparticles on the co-treated CNT support produced at 450 °C and 550 °C showed the highest activity and yields of acetic acid in the aerobic oxidation of aqueous ethanol reaching almost full conversion after 5 h in the absence of additional base. In addition, the KOH-steam co-treatment was found to enhance the recyclability of the Pd/CNT catalysts. © 2017 Elsevier Ltd

Prompted by the impact of Ni-based support materials on the intrinsic activity of electrocatalysts, we investigated the influence of partial Co substitution by Ni during the reductive thermal synthesis of cobalt-cobalt phosphide nanoparticles from triphenylphosphine complexes. The obtained catalysts were characterised by X-ray diffraction and electrochemistry. Increasing the amount of Ni in the precursor complexes leads to materials with lower overpotential for the OER at low current densities, and lower Tafel slopes. Co nanoparticles, which are only formed in materials with low Ni content, increase the intrinsic material conductivity and reduce the OER overpotential at high current densities. © 2017

The realization of metal nanoparticles (NPs) with bimetallic character and distinct composition for specific catalytic applications is an intensively studied field. Due to the synergy between metals, most bimetallic particles exhibit unique properties that are hardly provided by the individual monometallic counterparts. However, as small-sized NPs possess high surface energy, agglomeration during catalytic reactions is favored. Sufficient stabilization can be achieved by confinement of NPs in porous support materials. In this sense, metal-organic frameworks (MOFs) in particular have gained a lot of attention during the last years; however, encapsulation of bimetallic species remains challenging. Herein, the exclusive embedding of preformed core-shell PdPt and RuPt NPs into chemically robust Zr-based MOFs is presented. Microstructural characterization manifests partial retention of the core-shell systems after successful encapsulation without harming the crystallinity of the microporous support. The resulting chemically robust NP@UiO-66 materials exhibit enhanced catalytic activity towards the liquid-phase hydrogenation of nitrobenzene, competitive with commercially used Pt on activated carbon, but with superior size-selectivity for sterically varied substrates. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

By doping the TiO2 support with nitrogen, strong metal-support interactions (SMSI) in Pd/TiO2 catalysts can be tailored to obtain high-performance supported Pd nanoparticles (NPs) in nitrobenzene (NB) hydrogenation catalysis. According to the comparative studies by X-ray diffraction, X-ray photoelectron spectroscopy (XPS), and diffuse reflectance CO FTIR (CO-DRIFTS), N-doping induced a structural promoting effect, which is beneficial for the dispersion of Pd species on TiO2. High-angle annular dark-field scanning transmission electron microscopy study of Pd on N-doped TiO2 confirmed a predominant presence of sub-2 nm Pd NPs, which are stable under the applied hydrogenation conditions. XPS and CO-DRIFTS revealed the formation of strongly coupled Pd-N species in Pd/TiO2 with N-doped TiO2 as support. Density functional theory (DFT) calculations over model systems with Pdn (n = 1, 5, or 10) clusters deposited on TiO2(101) surface were performed to verify and supplement the experimental observations. In hydrogenation catalysis using NB as a model molecule, Pd NPs on N-doped TiO2 outperformed those on N-free TiO2 in terms of both catalytic activity and stability, which can be attributed to the presence of highly dispersed Pd NPs providing more active sites, and to the formation of Pd-N species favoring the dissociative adsorption of the reactant NB and the easier desorption of the product aniline. (Figure Presented). © 2016 American Chemical Society.

Oxide-dispersion strengthened materials are important candidates for several high-temperature structural applications in advanced nuclear power plants. Most of the desirable mechanical properties presented by these materials are due to the dispersion of stable nanoparticles in the matrix. Samples of ODS-Eurofer steel were annealed for 4320 h (6 months) at 800 °C. The material was characterized using atom probe tomography in both conditions (prior and after heat treatment). The particles number density, size distribution, and chemical compositions were determined. No significant changes were observed between the two conditions indicating a high thermal stability of the Y-rich nanoparticles at 800 °C. © 2017 Elsevier B.V.

Metal oxides and carbon-based materials are the most promising electrode materials for a wide range of low-cost and highly efficient energy storage and conversion devices. Creating unique nanostructures of metal oxides and carbon materials is imperative to the development of a new generation of electrodes with high energy and power density. Here we report our findings in the development of a novel graphene aerogel assisted method for preparation of metal oxide nanoparticles (NPs) derived from bulk MOFs (Co-based MOF, Co(mIM)2 (mIM = 2-methylimidazole). The presence of cobalt oxide (CoOx) hollow NPs with a uniform size of 35 nm monodispersed in N-doped graphene aerogels (NG-A) was confirmed by microscopic analyses. The evolved structure (denoted as CoOx/NG-A) served as a robust Pt-free electrocatalyst with excellent activity for the oxygen reduction reaction (ORR) in an alkaline electrolyte solution. In addition, when Co was removed, the resulting nitrogen-rich porous carbon-graphene composite electrode (denoted as C/NG-A) displayed exceptional capacitance and rate capability in a supercapacitor. Further, this method is readily applicable to creation of functional metal oxide hollow nanoparticles on the surface of other carbon materials such as graphene and carbon nanotubes, providing a good opportunity to tune their physical or chemical activities. © 2017 American Chemical Society.

The development of reversible oxygen electrodes, able to drive both the oxygen evolution reaction (OER) and the oxygen reduction reaction (ORR), is still a great challenge. We describe a very efficient and stable bifunctional electrocatalytic system for reversible oxygen electrodes obtained by direct CVD growth of nitrogen-doped carbon nanotubes (NCNTs) on the surface of cobalt boride (CoB) nanoparticles. A detailed investigation of the crystalline structure and elemental distribution of CoB before and after NCNT growth reveals that the NCNTs grow on small CoB nanoparticles formed in the CVD process. The resultant CoB/NCNT system exhibited outstanding activity in catalyzing both the OER and the ORR in 0.1 M KOH with an overvoltage difference of only 0.73 V between the ORR at -1 mA cm-2 and the OER at +10 mA cm-2. The proposed CoB/NCNT catalyst showed stable performance during 50 h of OER stability assessment in 0.1 M KOH. Moreover, CoB/NCNT spray-coated on a gas diffusion layer as an air-breathing electrode proved its high durability during 170 galvanostatic charge-discharge (OER/ORR) test cycles (around 30 h) at ±10 mA cm-2 in 6 M KOH, making it an excellent bifunctional catalyst for potential Zn-air battery application. © 2017 The Royal Society of Chemistry.

Oxide-dispersion strengthened (ODS) Eurofer steel is targeted for structural applications in future fusion nuclear reactors. Samples were cold rolled down to 80% reduction in thickness and annealed at 1350 °C up to 8 h. The microstructural characterization was performed using Vickers microhardness testing, electron backscatter diffraction, scanning and scanning transmission electron microscopies. Experimental results provide evidence of coarsening of the Y-rich oxide particles in ODS-Eurofer steel annealed at 1350 °C within delta ferrite phase field. © 2016 Elsevier B.V.

There has been growing interest in the synthesis of efficient reversible oxygen electrodes for both the oxygen reduction reaction (ORR) and the oxygen evolution reactions (OER), for their potential use in a variety of renewable energy technologies, such as regenerative fuel cells and metal-air batteries. Here, a bi-functional electrocatalyst, derived from a novel dicyanamide based nitrogen rich MOF {[Co(bpe)2(N(CN)2)]⋅(N(CN)2)⋅(5 H2O)}n [Co-MOF-1, bpe=1,2-bis(4-pyridyl)ethane, N(CN)2 −=dicyanamide] under different pyrolysis conditions is reported. Pyrolysis of the Co-MOF-1 under Ar atmosphere (at 800 °C) yielded a Co nanoparticle-embedded N-doped carbon nanotube matrix (Co/NCNT-Ar) while pyrolysis under a reductive H2/Ar atmosphere (at 800 °C) and further mild calcination yielded Co3O4@Co core–shell nanoparticle-encapsulated N-doped carbon nanotubes (Co3O4@Co/NCNT). Both catalysts show bi-functional activity towards ORR and OER, however, the core–shell Co3O4@Co/NCNT nanostructure exhibited superior electrocatalytic activity for both the ORR with a potential of 0.88 V at a current density of −1 mA cm−2 and the OER with a potential of 1.61 V at 10 mA cm−2, which is competitive with the most active bi-functional catalysts reported previously. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Chemical vapor synthesis (CVS) is a unique method to prepare well-defined photocatalyst materials with both large specific surface area and a high degree of crystallinity. The obtained β-Ga2O3 nanoparticles were optimized for photocatalysis by reductive photodeposition of the Rh/CrOx co-catalyst system. The influence of the degree of crystallinity and the specific surface area on photocatalytic aqueous methanol reforming and overall water splitting (OWS) was investigated by synthesizing β-Ga2O3 samples in the temperature range from 1000 °C to 1500 °C. With increasing temperature, the specific surface area and the microstrain were found to decrease, whereas the degree of crystallinity and the crystallite size increased. Whereas the photocatalyst with the highest specific surface area showed the highest aqueous methanol reforming activity, the highest OWS activity was that for the sample with an optimum ratio between high degree of crystallinity and specific surface area. Thus, it was possible to show that the facile aqueous methanol reforming and the demanding OWS have different requirements for high photocatalytic activity. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Nanophase segregation of a bicomponent thiol self-assembled monolayer is predicted using atomistic molecular dynamics simulations and experimentally confirmed. The simulations suggest the formation of domains rich in acid-terminated chains, on one hand, and of domains rich in amide-functionalized ethylene glycol oligomers, on the other hand. In particular, within the amide-ethylene glycol oligomers region, a key role is played by the formation of interchain hydrogen bonds. The predicted phase segregation is experimentally confirmed by the synthesis of 35 and 15 nm gold nanoparticles functionalized with several binary mixtures of ligands. An extensive study by transmission electron microscopy and electron tomography, using silica selective heterogeneous nucleation on acid-rich domains to provide electron contrast, supports simulations and highlights patchy nanoparticles with a trend toward Janus nano-objects depending on the nature of the ligands and the particle size. These results validate our computational platform as an effective tool to predict nanophase separation in organic mixtures on a surface and drive further exploration of advanced nanoparticle functionalization. © 2017 American Chemical Society.

As part of an ongoing effort to understand the deactivation and improve the stability of metal oxide-supported Au catalysts in the low-temperature CO oxidation reaction while maintaining their high activity, we have investigated the influence of a mesoporous silica SBA-15 substrate on the activity and stability of Au/TiO2 catalysts, which consist of a SBA-15 support surface modified by a monolayer of TiOx with Au nanoparticles on top. The extent of the TiOx surface modification was systematically increased, while the Au loading and the Au particle sizes were largely kept constant. Employing kinetic measurements at three different temperatures (30 °C, 80 °C, 180 °C) and a number of ex situ methods as well as in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) for catalyst characterization, we found that the activity of these catalysts increases significantly with the Ti concentration and with reaction temperature. The tendency for deactivation remains essentially unchanged. Detailed in situ DRIFTS measurements reveal that the Au nanoparticles are largely formed on the TiOx surface-modified areas of the SBA-15 support and that the tendency for surface carbonate formation is very low. The observed deactivation may at least partly be related to the accumulation of molecularly adsorbed H2O species, in particular at low temperatures (30 °C). These are likely to be formed from surface hydroxyl groups, they may affect the reaction either by blocking of active sites or by blocking the adsorption of reactants on the substrate. Other effects, such as reaction induced changes in the titania layer, must however, play a role as well, both at 80 °C and in particular at 180 °C, where accumulation of adsorbed species is negligible. The mechanistic ideas are supported by reactivation tests subsequent to calcination at 400 °C, which were found to fully restore the initial activity. © 2017 Elsevier Inc.

We detail a mediator- and membrane-free enzymatic glucose/oxygen biofuel cell based on transparent and nanostructured conducting supports. Chemically modified indium tin oxide nanoparticle modified electrodes were used to substantially increase the active surface area without significantly compromising transparency. Two different procedures for surface nanostructuring were employed, viz. spray-coating and drop-coating. The spray-coated biodevice showed superior characteristics as compared to the drop-coated enzymatic fuel cell, as a result of the higher nanostructured surface area as confirmed by electrochemical characterisation, as well as scanning electron and atomic force microscopy. Subsequent chemical modification with silanes, followed by the immobilisation of either cellobiose dehydrogenase from Corynascus thermophiles or bilirubin oxidase from Myrothecium verrucaria, were performed to obtain the bioanodes and biocathodes, respectively. The optimised biodevice exhibited an OCV of 0.67 V and power output of up to 1.4 µW/cm2 at an operating voltage of 0.35 V. This is considered a significant step forward in the field of glucose/oxygen membrane- and mediator-free, transparent enzymatic fuel cells. © 2017 Elsevier B.V.

The growth of metal–organic framework (ZIF-67) nanocrystals on nickel foam (NF), followed by carbonization in diluted H2, leads to a nitrogen-doped carbon-nanotube-grafted cobalt/carbon polyhedra film on NF. The obtained material serves as a highly active binder-free electrocatalyst for both the oxygen evolution reaction (OER) and the hydrogen evolution reaction (HER), enabling high-performance alkaline (0.1 m KOH) water electrolysis with potentials of 1.62 and 0.24 V, respectively, at OER and HER current densities of 10 mA cm−2. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Here we report on an entirely new kind of bioelectronic device – a solar biosupercapacitor, which is built from a dual-feature photobioanode combined with a double-function enzymatic cathode. The self-charging biodevice, based on transparent nanostructured indium tin oxide electrodes modified with biological catalysts, i.e. thylakoid membranes and bilirubin oxidase, is able to capacitively store electricity produced by direct conversion of radiant energy into electric energy. When self-charged during 10 min, using ambient light only, the biosupercapacitor provided a maximum of 6 mW m− 2 at 0.20 V. © 2016 Elsevier B.V.

Single-nanoparticle electrochemistry has been established as a tool to characterize various nanomaterials based on the charge passed during their random impact at an electrode. Here it is demonstrated that the duration and shape of the resulting current peak can be used to quantify the reaction kinetics on a single-particle basis. Both the chemical rate constant and reaction mechanism for oxidation of single nanoparticles in different electrolytes can be determined directly from the duration of the current signal recorded in high-speed, highsensitivity current measurements. Using 29-nm-sized Ag particles in four different electrolytes as a proof of concept for this general approach, hitherto inaccessible insights into single-particle reactivity are provided. While comparable rate constants were measured for the four electrolytes at low overpotentials, transport-limited impacts at high overpotentials were found to depend strongly on the type and quantity of anions present in solution. [Figure not available: see fulltext.] © 2017 Tsinghua University Press and Springer-Verlag GmbH Germany

Magnetic nanoparticles were generated by ultrashort pulsed laser ablation of an iron target in water, methanol, ethanol, acetone and toluene. The relationship between ablation rate, liquid properties and the physical and chemical properties of the nanoparticles was studied. Composition, morphology and magnetic properties were investigated by TEM, XPS and vibrating-sample (VSM) and SQUID magnetometry. The properties of the generated nanoparticle ensembles reflected the influence of the liquid environment on the particle formation process. For example, the composition was strongly dependent on the carbon to oxygen ratio within the molecules of the liquid. In contrast to short pulsed laser ablation in liquids, the nanoparticles generated by ultrashort pulses had a higher level of polycrystallinity. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

The performance of proton-exchange membrane fuel cells (PEMFCs) is defined by the equally important parameters of the intrinsic activity and stability of the electrocatalysts. This work focuses on the stability of carbon supported high surface area oxygen reduction reaction catalysts at potentials and temperatures similar to the operating conditions of PEMFCs. The catalysts used for this investigation consist of Pt nanoparticles of the same particle size supported on two types of carbon support having different textural properties, i.e., Vulcan and Hollow Graphitic Spheres (HGS). A broad toolbox of characterization techniques is utilized at 60 °C in order to resolve the contribution of the different degradation mechanisms, namely nanoparticle coalescence, metal dissolution and the corrosion of carbon support, to the total active surface area loss. The results obtained by investigating the impact of temperature, potential treatment and catalyst layer morphology on the aging behavior lead to a deeper understanding of the aging mechanisms and their interrelation at application-relevant conditions. Moreover, the previously reported improved performance of the Pt/HGS catalyst is confirmed also under higher temperatures. The experimental approach introduced in this work, highlights new challenges for high-temperature degradation investigations with supported PEMFC catalyst. © 2016 Elsevier Ltd

The inhalation of particles and their exposure to the bronchi and alveoli constitute a major public health risk. Chemical as well as particle-related properties are important factors for the biological response but are difficult to separate from each other. Barium sulfate is a completely inert chemical compound, therefore it is ideally suited to separate these two factors. The biological response of rat alveolar macrophages (NR8383) was analyzed after exposure to barium sulfate particles with three different diameters (40 nm, 270 nm, and 1.3 μm, respectively) for 24 h in vitro (particle concentrations from 12.5 to 200 μg mL− 1). The particles were colloidally stabilized as well as fluorescently-labeled by carboxymethylcellulose, conjugated with 6-aminofluorescein. All kinds of barium sulfate particles were efficiently taken up by NR8383 cells and found inside endo-lysosomes, but never in the cell nucleus. Neither an inflammatory nor a cytotoxic response was detected by the ability of dHL-60 and NR8383 cells to migrate towards a chemotactic gradient (conditioned media of NR8383 cells) and by the release of inflammatory mediators (CCL2, TNF-α, IL-6). The particles neither caused apoptosis (up to 200 μg mL− 1) nor necrosis (up to 100 μg mL− 1). As only adverse reaction, necrosis was found at a concentration of 200 μg mL− 1 of the largest barium sulfate particles (1.3 μm). Barium sulfate particles are ideally suited as bioinert control to study size-dependent effects such as uptake mechanisms of intracellular distributions of pure particles, especially in nanotoxicology. © 2016 Informa UK Limited, trading as Taylor & Francis Group.

High sensitivity and high spatial resolution in localized electrochemical measurements are the key advantages of electroanalysis using nanometer-sized electrodes. Due to recent progress in nanoelectrode fabrication and electrochemical instrument development, nanoelectrochemical methods are becoming more widespread. We summarize different protocols for the fabrication of needle-type nanoelectrodes and discuss their properties with regard to various applications. We discuss the limits of conventional theory to describe electrochemistry at the nanoscale and point out technical aspects for characterization and handling of nanometric electrodes. Different applications are highlighted: i) Nanoelectrodes are powerful tools for non-ensemble studies of electrocatalysis at single nanoparticles at high mass transport rates. ii) Electrochemical nanosensors are employed for highly localized non-invasive analysis of single living cells and intracellular detection of neurotransmitters and metabolites. iii) Used in scanning electrochemical probe techniques, nanoprobes afford topographical and truly chemical imaging of samples with high spatial resolution. © 2016 Published by Elsevier B.V.

Individual Ni(OH)2 nanoparticles deposited on carbon nanoelectrodes are investigated in non-ensemble measurements with respect to their energy storage properties and electrocatalysis for the oxygen evolution reaction (OER). Charging by oxidation of Ni(OH)2 is limited by the diffusion of protons into the particle bulk and the OER activity is independent of the particle size. © 2016 The Royal Society of Chemistry.

In spite of their natural and technological importance, the intrinsic electrochemical properties of hematite (α-Fe2O3) nanoparticles are not well understood. In particular, particle agglomeration, the presence of surface impurities, and/or inadequate proton concentrations are major obstacles to uncover the fundamental redox activities of minerals in solution. These are particularly problematic when samples are characterized in common electrochemical analyses such as cyclic voltammetry in which nanoparticles are immobilized on a stationary electrode. In this work, the intrinsic reaction kinetics and thermodynamics of individual hematite nanoparticles are investigated by particle impact chronoamperometry. The particle radius derived from the integrated area of spikes recorded in a chronoamperogram is in excellent agreement with electron microscopy results, indicating that the method provides a quantitative analysis of the reduction of the nanoparticles to the ferrous ion. A key finding is that the suspended individual nanoparticles undergo electrochemical reduction at potentials much more positive than those immobilized on a stationary electrode. The critical importance of the solid/water interface on nanoparticle activity is further illustrated by a kinetic model. It is found that the first electron transfer process is the rate determining step of the reductive dissolution of hematite nanoparticles, while the overall process is strongly affected by the interfacial proton concentration. This article highlights the effects of the interfacial proton and ferrous ion concentrations on the reductive dissolution of hematite nanoparticles and provides a highly effective method that can be readily applied to study a wide range of other mineral nanoparticles. © 2016 The Royal Society of Chemistry.

Many different aerogel materials are known to be accessible via the controlled destabilization of the respective nanoparticle suspensions. Especially for applications in heterogeneous catalysis such materials with high specific surface areas are highly desirable. Here, a facile method to obtain a mixed ZnPd/ZnO aerogel via a reductive treatment of a preformed Pd/ZnO aerogel is presented. Different morphologies of the Pd/ZnO aerogels could be achieved by controlling the destabilization of the ZnO sol. All aerogels show a high CO2 selectivity of up to 96% and a very good activity in methanol steam reforming that delivers hydrogen, which is one of the most important fuels for future energy concepts. The method presented is promising for different transition metal/metal oxide systems and hence opens a path to a huge variety of materials. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Nanoscopic gold particles have gained very high interest because of their promising catalytic activity for various chemicals reactions. Among these reactions, low-temperature CO oxidation is the most extensively studied one due to its practical relevance in environmental applications and the fundamental problems associated with its very high activity at low temperatures. Gold nanoparticles supported on manganese oxide belong to the most active gold catalysts for CO oxidation. Among a variety of manganese oxides, Mn2O3 is considered to be the most favorable support for gold nanoparticles with respect to catalytic activity. Gold on MnO2 has been shown to be significantly less active than gold on Mn2O3 in previous work. In contrast to these previous studies, in a comprehensive study of gold nanoparticles on different manganese oxides, we developed a gold catalyst on MnO2 nanostructures with extremely high activity. Nanosized gold particles (2-3 nm) were supported on α-MnO2 nanowires and mesoporous β-MnO2 nanowire arrays. The materials were extremely active at very low temperature (-80 °C) and also highly stable at 25 °C (70 h) under normal conditions for CO oxidation. The specific reaction rate of 2.8 molCO·h-1·gAu -1 at a temperature as low as -85 °C is almost 30 times higher than that of the most active Au/Mn2O3 catalyst. © 2016 American Chemical Society.

Metal-organic frameworks (MOFs) feature a great possibility for a broad spectrum of applications. Hollow MOF structures with tunable porosity and multifunctionality at the nanoscale with beneficial properties are desired as hosts for catalytically active species. Herein, we demonstrate the formation of well-defined hollow Zn/Co-based zeolitic imidazolate frameworks (ZIFs) by use of epitaxial growth of Zn-MOF (ZIF-8) on preformed Co-MOF (ZIF-67) nanocrystals that involve in situ self-sacrifice/excavation of the Co-MOF. Moreover, any type of metal nanoparticles can be accommodated in Zn/Co-ZIF shells to generate yolk-shell metal@ZIF structures. Transmission electron microscopy and tomography studies revealed the inclusion of these nanoparticles within hollow Zn/Co-ZIF with dominance of the Zn-MOF as shell. Our findings lead to a generalization of such hollow systems that are working effectively to other types of ZIFs. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The formation of silicate nanoaggregates (NAs) at the very early stages of precursor sols and zeolite beta crystallization from silicate nanoparticles (NPs) are investigated in detail using a combination of different analysis methods, including liquid-state29Si,27Al,14N, and1H NMR spectroscopy, mass spectrometry (MS), small-angle X-ray scattering (SAXS), X-ray diffraction (XRD), and transmission electron microscopy at cryogenic temperatures (cryo-TEM). Prior to hydrothermal treatment, silicate NAs are observed if the Si/OH ratio in the reaction mixture is greater than 1. Condensation of oligomers within the NAs then generates NPs. Aluminum doped into the synthesis mixtures is located exclusively in the NPs, and is found exclusively in a state that is fourfold connected to silicate, favoring their condensation and aggregation. These results are in agreement with general trends observed for other systems. Silicate NAs are essential intermediates for zeolite formation and are generated by the aggregation of hydrated oligomers, aluminate, and templating cations. Subsequent further intra-nanoaggregate silicate condensation results in the formation of NPs.1H and14N liquid NMR as well as diffusion ordered spectroscopy (DOSY) experiments provide evidence for weakly restricted rotational and translational mobility of the organic template within NAs as a consequence of specific silicate–template interactions. NAs thus appear as key species in clear sols, and their presence in the precursor sol favors silicate condensation and further crystallization, promoted either by increasing the Si/OH ratio or by heating. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

The manuscript demonstrates the interrogation of immunoassay platforms after enzyme-catalyzed deposition of silver nanoparticles (AgNPs) using scanning electrochemical microscopy (SECM) and surface-enhanced Raman scattering (SERS). We have selected an immunoassay model platform for the determination of residues of the antibiotic sulfapyridine in milk. The assay involves a direct competitive approach with an HRP-labeled antigen analog and selective capture antibodies immobilized on the surface of glassy carbon plates modified with protein G. Interrogation of the modified substrate by SECM and SERS was carried out after enzyme-catalyzed in-situ deposition of AgNPs. The enhanced Raman scattering for proflavine in the presence of AgNPs was used as signalling system. Hexacyanoferrate(III) was applied as the redox probe in SECM; the visualization of the deposited AgNP spots was enabled by using a competition between the SECM tip microelectrode and the modified carbon plate for the oxidation of ferrocyanide. This SECM strategy proved to be an efficient tool for the interrogation of sensing surfaces that were amplified by enzyme-catalyzed silver deposition. [Figure not available: see fulltext.] © 2015, Springer-Verlag Wien.

High-resolution characterization techniques are combined with thermodynamic calculations (CALPHAD) to rationalize microstructural features of single crystal Ni-base superalloys. Considering the chemical compositions of dendritic and interdendritic regions one can explain differences in γ′-volume fractions. Using thermodynamic calculations one can explain, why γ-nanoparticles are observed in the central regions of large cuboidal γ′-particles and why tertiary γ′-nanoparticles form in the γ-channels. The chemical compositions of the γ-channels and of the newly formed γ-particles differ because of the Gibbs–Thomson pressure which acts on the small particles. With increasing size of secondary γ′-particles, their shape changes from spherical to cuboidal. Some general thermodynamic aspects including the temperature dependencies of the Gibbs free energy G, the enthalpy H, and the entropy S and site occupancies in the ordered L12 (γ′) phase are considered. The importance of cooling rate after homogenization is discussed. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Thermodynamically stable shape-selected Pt and Pd nanoparticles (NPs) were synthesized via inverse micelle encapsulation and a subsequent thermal treatment in vacuum above 1000 °C. The majority of the Pd NPs imaged via scanning tunneling microscopy (STM) had a truncated octahedron shape with (111) top and interfacial facets, while the Pt NPs were found to adopt a variety of shapes. For NPs of identical shape for both material systems, the NP-support adhesion energy calculated based on STM data was found to be size-dependent, with large NPs (e.g. ∼6 nm) having lower adhesion energies than smaller NPs (e.g. ∼1 nm). This phenomenon was rationalized based on support-induced strain that for larger NPs favors the formation of lattice dislocations at the interface rather than a lattice distortion that may propagate through the smaller NPs. In addition, identically prepared Pt NPs of the same shape were found to display a lower adhesion energy compared to Pd NPs. While in both cases, a transition from a lattice distortion to interface dislocations is expected to occur with increasing NP size, the higher elastic energy in Pt leads to a lower transition size, which in turn lowers the adhesion energy of Pt NPs compared to Pd. © 2016 The Royal Society of Chemistry.

The influence of silver nanoparticle morphology on the dissolution kinetics in ultrapure water as well as the biological effect on eukaryotic and prokaryotic cells was examined. Silver nanoparticles with different shapes but comparable size and identical surface functionalisation were prepared, i.e. spheres (diameter 40-80 and 120-180 nm; two different samples), platelets (20-60 nm), cubes (140-180 nm), and rods (diameter 80-120 nm, length > 1000 nm). All particles were purified by ultracentrifugation and colloidally stabilized with poly(N-vinyl pyrrolidone) (PVP). Their colloidal dispersion in ultrapure water and cell culture medium was demonstrated by dynamic light scattering. Size, shape, and colloidal stability were analysed by scanning electron microscopy, atomic force microscopy, dynamic light scattering, and differential centrifugal sedimentation. The dissolution in ultrapure water was proportional to the specific surface area of the silver nanoparticles. The averaged release rate for all particle morphologies was 30 ± 13 ng s-1 m-2 in ultrapure water (T = 25 ± 1°C; pH 4.8; oxygen saturation 93%), i.e. about 10-20 times larger than the release of silver from a macroscopic silver bar (1 oz), possibly due to the presence of surface defects in the nanoparticulate state. All particles were taken up by human mesenchymal stem cells and were cytotoxic in concentrations of >12.5 μg mL-1, but there was no significant influence of the particle shape on the cytotoxicity towards the cells. Contrary to that, the toxicity towards bacteria increased with a higher dissolution rate, suggesting that the toxic species against bacteria are dissolved silver ions. © The Royal Society of Chemistry 2016.

Carbon-protected magnetic nanoparticles exhibit long-term stability in acid or alkaline medium, good biocompatibility, and high saturation magnetization. As a result, they hold great promise for magnetic resonance imaging, photothermal therapy, etc. However, since pyrolysis, which is often required to convert the carbon precursors to carbon, typically leads to coalescence of the nanoparticles, the obtained carbon-protected magnetic nanoparticles are usually sintered as a non-dispersible aggregation. We have successfully synthesized discrete, dispersible, and uniform carbon-protected magnetic nanoparticles via a precise surface/interface nano-engineering approach. Remarkably, the nanoparticles possess excellent water-dispersibility, biocompatibility, a high T2 relaxivity coefficient (384 mM–1·s–1), and a high photothermal heating effect. Furthermore, they can be used as multifunctional core components suited for future extended investigation in early diagnosis, detection and therapy, catalysis, separation, and magnetism. [Figure not available: see fulltext.] © 2016, Tsinghua University Press and Springer-Verlag Berlin Heidelberg.

Pd nanoparticles supported on carbon nanotubes were applied in the selective oxidation of ethanol in the liquid phase. The characterization of the surface and bulk properties combined with the catalytic tests indicated the dissolution and redeposition of Pd under the reaction conditions. A dynamic interplay within the Pd life cycle was identified to be responsible for the overall reactivity. Nitrogen-doped carbon nanotubes were found to act as an excellent support for the Pd catalyst system by efficiently stabilizing and recapturing the Pd species, which resulted in high activity and selectivity to acetic acid. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

The recombination of photogenerated electron-hole pairs is one of the main limiting factors of photoelectrocatalysts absorbing in the visible part of the solar spectrum. Especially for BiVO4 the slow electron transport to the back contact facilitates charge recombination. Hence, thin layers have to be used to obtain higher photocurrents which are concomitantly only allow low absorption of the incident light. To address this limitation we have modified FTO substrates with Pt-nanoparticles before electrodepositing BiVO4. The Pt-nanoparticles decrease the overpotential for the electrodeposition of BiVO4, but more importantly they provide the basis for decreased charge recombination. Electrodeposited Mo-doped BiVO4 on Pt-nanoparticle modified FTO exhibits a substantially decreased recombination of photogenerated charge carriers during frontside illumination. Simultaneous co-doping of BiVO4 with two different metals leads to a substantial enhancement of the incident-photon-to-current efficiency (IPCE) during light driven oxygen evolution reaction. Highest IPCE (>30% at 1.2 V vs. RHE) values were obtained for Mo/Zn- and Mo/B-doped BiVO4. © 2016 The Royal Society of Chemistry.

Dry reforming of methane (DRM) has been studied for many years as an attractive option to produce synthesis gas. However, catalyst deactivation by coking over nonprecious-metal catalysts still remains unresolved. Here, we study the influence of structural and compositional properties of nickel catalysts on the catalytic performance and coking propensity in the DRM. A series of bulk catalysts with different Ni contents was synthesized by calcination of hydrotalcite-like precursors NixMg0.67-xAl0.33(OH)2(CO3)0.17·mH2O prepared by constant-pH coprecipitation. The obtained Ni/MgAl oxide catalysts contain Ni nanoparticles with diameters between 7 and 20 nm. High-resolution transmission electron microscopy (HR-TEM) revealed a nickel aluminate overgrowth on the Ni particles, which could be confirmed by Fourier transform infrared (FTIR) spectroscopy. In particular, catalysts with low Ni contents (5 mol %) exhibit predominantly oxidic surfaces dominated by Ni2+ and additionally some isolated Ni0 sites. These properties, which are determined by the overgrowth, effectively diminish the formation of coke during the DRM, while the activity is preserved. A large (TEM) and dynamic (microcalorimetry) metallic Ni surface at high Ni contents (50 mol %) causes significant coke formation during the DRM. © 2016 American Chemical Society.

The role of the stability of surface functional groups in oxygen- and nitrogen-functionalized multi-walled carbon nanotubes (CNTs) applied as support for iron catalysts in high-temperature Fischer-Tropsch synthesis was studied in a fixed-bed U-tube reactor at 340°C and 25 bar with a H2:CO ratio of 1. Iron oxide nanoparticles supported on untreated oxygen-functionalized CNTs (OCNTs) and nitrogen-functionalized CNTs (NCNTs) as well as thermally treated OCNTs were synthesized by the dry impregnation method using ammonium ferric citrate as iron precursor. The properties of all catalysts were examined using X-ray diffraction, temperature-programmed reduction in H2, X-ray photoelectron spectroscopy and temperature-programmed oxidation in O2. The activity loss for iron nanoparticles supported on untreated OCNTs was found to originate from severe sintering and carbon encapsulation of the iron carbide nanoparticles under reaction conditions. Conversely, the sintering of the iron carbide nanoparticles on thermally treated OCNTs and untreated NCNTs during reaction was far less pronounced. The presence of more stable surface functional groups in both thermally treated OCNTs and untreated NCNTs is assumed to be responsible for the less severe sintering of the iron carbide nanoparticles during reaction. As a result, no activity loss for iron nanoparticles supported on thermally treated OCNTs and untreated NCNTs was observed, which even became gradually more active under reaction conditions. © 2015 Published by Elsevier B.V.

Directly manipulating and controlling the size and shape of metal nanoparticles is a key step for their tailored applications. In this work, molecular dynamics simulations were applied to understand the microscopic origin of the asymmetric growth mechanism in gold nanorods. Different factors influencing the growth were selectively included in the models to unravel the role of the surfactants and ions. In the early stage of the growth, when the seed is only a few nanometers large, a dramatic symmetry breaking occurs as the surfactant layer preferentially covers the (100) and (110) facets, leaving the (111) facets unprotected. This anisotropic surfactant layer in turn promotes anisotropic growth with the less protected tips growing faster. When silver salt is added to the growth solution, the asymmetry of the facets is preserved, but the Br−concentration at the interface increases, resulting in increased surface passivation. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

A size-dependent trend was observed for the electrochemical total oxidation of 2-propanol to CO2 over Au nanoparticles (NPs), with increasing activity (increased current density and lower overpotential) for decreasing NP size. Furthermore, an enhanced stability against poisoning by the unreacted acetone intermediate was also obtained for NPs smaller than ∼2 nm. Operando X-ray absorption fine structure (XAFS) measurements provided insight into the dynamic evolution of the NP structure and chemical state under reaction conditions, shedding light on the nature of the most catalytically active species and catalyst deactivation phenomena via chemically driven sintering. © 2016 American Chemical Society.

The development of new catalysts for energy technology and environmental remediation requires a thorough knowledge of how the physical and chemical properties of a catalyst affect its reactivity. For supported metal nanoparticles (NPs), such properties can include the particle size, shape, composition, and chemical state, but a critical parameter which must not be overlooked is the role of the NP support. Here, we highlight the key mechanisms behind support-induced enhancement in the catalytic properties of metal NPs. These include support-induced changes in the NP morphology, stability, electronic structure, and chemical state, as well as changes in the support due to the NPs. Utilizing the support-dependent phenomena described in this Perspective may allow significant breakthroughs in the design and tailoring of the catalytic activity and selectivity of metal nanoparticles. © 2016 American Chemical Society.

The selectivity of heterogeneously catalyzed chemical reactions is well-known to be dependent on nanoscale determinants, such as surface atomic geometry and composition. However, principles to control the selectivity of nanoparticle (NP) catalysts by means of mesoscopic descriptors, such as the interparticle distance, have remained largely unexplored. We used well-defined copper catalysts to deconvolute the effect of NP size and distance on product selectivity during CO2 electroreduction. Corroborated by reaction-diffusion modeling, our results reveal that mesoscale phenomena such as interparticle reactant diffusion and readsorption of intermediates play a defining role in product selectivity. More importantly, this study uncovers general principles of tailoring NP activity and selectivity by carefully engineering size and distance. These principles provide guidance for the rational design of mesoscopic catalyst architectures in order to enhance the production of desired reaction products. © 2015 American Chemical Society.

The increasing interest in producing bimetallic nanoparticles and utilizing them in modern technologies sets the demand for fast and affordable characterization of these materials. To date Scanning Transmission Electron Microscopy (STEM) coupled to energy dispersive X-ray spectroscopy is usually used to determine the size and composition of alloy nanoparticles, which is time-consuming and expensive. Here electrochemical single nanoparticle analysis is presented as an alternative approach to infer the particle size and composition of alloy nanoparticles, directly in a dispersion of these particles. As a proof of concept, 14 nm sized Ag0.73Au0.27 alloy nanoparticles are analyzed using a combination of chronoamperometric single nanoparticle analysis and cyclic voltammetry ensemble studies. It is demonstrated that the size, the alloying and the composition can all be inferred using this approach. Thus, the electrochemical characterization of single bimetallic alloy nanoparticles is suggested here as a powerful and convenient complement or alternative to TEM characterization of alloy nanoparticles. © The Royal Society of Chemistry.

We report a simple, facile, and safe route for preparation of cobalt-cobalt phosphide (Co/Co2P) nanoparticles and demonstrate their application as efficient low-cost catalysts for electrochemical water splitting. The catalyst achieves good performance in catalyzing both the cathode and anode half-cell water-splitting reactions in 1.0 M KOH and the hydrogen evolution reaction in an acidic electrolyte, 0.5 M H2SO4. For the oxygen evolution reaction in 1.0 M KOH, a current of 10 mA cm(-2) was attained at 0.39 V overpotential on a glassy carbon electrode, while an overpotential of 0.19 V was attained at 50 mA cm(-2) when the catalyst was supported on nickel foam.

Photodegradation under UV light irradiation is a major drawback in photocatalytic applications of sulfide semiconductors. ZnS nanoparticles were doped with very low amounts of chloride or cobalt ions in the ppm range and codoped with chloride and cobalt ions during their synthesis by precipitation in aqueous solution followed by calcination. The high-temperature wurtzite phase annealed at 800 °C had a high susceptibility to UV irradiation in water, while the low-temperature zincblende phase annealed at 400 °C was found to be stable. Chlorine doping increased the rate of photocorrosion in water, whereas cobalt doping led to a stabilization of the ZnS nanoparticles. Based on photochemical and spectroscopic investigations applying UV/vis, X-ray photoelectron, and photoluminescence spectroscopy, the increased susceptibility of Cl-doped ZnS is ascribed to a higher number of surface point defects, whereas the stabilization by Co2+ is caused by additional recombination pathways for the charge carriers in the bulk, thus avoiding photocorrosion processes at the surface. Additional doping of Cl-doped ZnS with cobalt ions was found to counteract the detrimental effect of the chloride ions efficiently. © 2016 American Chemical Society.

The cyclic voltammetric responses of individual palladium-coated carbon nanotubes are reported. Upon impact - from the solution phase - with the electrified interface, the nanoparticles act as individual nanoelectrodes catalyzing the hydrogen-oxidation reaction. At high overpotentials the current is shown to reach a quasi-steady-state diffusion limit, allowing determination of the tube length. The electrochemical response of the individual nanotubes also reveals the system to be modulated by the electrical contact between the electrode and carbon nanotube. This modulation presents itself as fluctuations in the recorded Faradaic current. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

A rapid and reliable nanofabrication route produces electrodes with beneficial properties for electrochemistry based on stochastic nanoparticle collision events. Carbon nanoelectrodes are etched to expose conical carbon tips which present an increased surface area for the detection of nanoparticle impacts. The tuneable electrode size as well as the conical geometry allow to increase the observed particle impact frequency while maintaining low background noise. Moreover, anodic particle coulometry for the sizing of silver nanoparticles shows that the detected impacts are representative of the polydisperse particle population. © 2016

Nitrogen-functionalized carbon nanotubes are promising materials in catalysis due to their versatile surface properties involving nitrogen groups, oxygen groups, surface defects and metal impurities. These factors can be used to tune the dispersion, morphology, crystal structure, electronic structure, mobility/stability and finally the catalytic performance of supported metal nanoparticles. This review focuses on selected examples aiming at understanding the interactions between surface groups, defects, and metal species and their impact on the catalytic properties in electrocatalysis and gas-phase redox catalysis. © 2016 The Royal Society of Chemistry.

A simple and scalable method for synthesizing Co3O4nanoparticles supported on the framework of mesoporous carbon (MC) was developed. Benefiting from an ion-exchange process during the preparation, the cobalt precursor is introduced into a mesostructured polymer framework that results in Co3O4nanoparticles (ca. 3 nm) supported on MC (Co3O4/MC) with narrow particle size distribution and homogeneous dispersion after simple reduction/pyrolysis and mild oxidation steps. The as-obtained Co3O4/MC is a highly efficient catalyst for transfer hydrogenation of α,β-unsaturated aldehydes. Selectivities towards unsaturated alcohols are always higher than 95 % at full conversion. In addition, the Co3O4/MC shows high stability under the reaction conditions, it can be recycled at least six times without loss of activity. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Efficient reversible oxygen electrodes for both the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER) are vitally important for various energy conversion devices, such as regenerative fuel cells and metal-air batteries. However, realization of such electrodes is impeded by insufficient activity and instability of electrocatalysts for both water splitting and oxygen reduction. We report highly active bifunctional electrocatalysts for oxygen electrodes comprising core-shell Co@Co3O4 nanoparticles embedded in CNT-grafted N-doped carbon-polyhedra obtained by the pyrolysis of cobalt metal-organic framework (ZIF-67) in a reductive H2 atmosphere and subsequent controlled oxidative calcination. The catalysts afford 0.85 V reversible overvoltage in 0.1 m KOH, surpassing Pt/C, IrO2, and RuO2 and thus ranking them among one of the best non-precious-metal electrocatalysts for reversible oxygen electrodes. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

We provide a microscopic view of the role of halides in controlling the anisotropic growth of gold nanorods through a combined computational and experimental study. Atomistic molecular dynamics simulations unveil that Br- adsorption is not only responsible for surface passivation, but also acts as the driving force for CTAB micelle adsorption and stabilization on the gold surface in a facet-dependent way. The partial replacement of Br- by Cl- decreases the difference between facets and the surfactant density. Finally, in the CTAC solution, no halides or micellar structures protect the gold surface and further gold reduction should be uniformly possible. Experimentally observed nanoparticle's growth in different CTAB/CTAC mixtures is more uniform and faster as the amount of Cl- increases, confirming the picture from the simulations. In addition, the surfactant layer thickness measured on nanorods exposed to CTAB and CTAC quantitatively agrees with the simulation results. © the Owner Societies 2016.

The (1 1 1)-layered perovskite material Ba5Ta4O15 represents a suitable photoabsorber with remarkable photocatalytic activity in overall water splitting. We are the first to demonstrate overall water splitting without the presence of a noble-metal-based co-catalyst over this catalyst. The photocatalytic activity of Ba5Ta4O15 was investigated by overall water splitting after reductive photodeposition of amorphous Cr2O3. The formation of Cr2O3 nanoparticles for water splitting was evidenced by X-ray photoelectron spectroscopy and transmission electron microscopy. The reductive photodeposition of very low amounts of Cr2O3 on Ba5Ta4O15 induces stable rates in overall water splitting up to 465 μmol h-1 H2 and 228 μmol h-1 O2. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Large scale commercialization of direct ethanol fuel cells is hampered by the high cost and scarcity of noble metal electrocatalysts employed at both the anode and cathode. We demonstrate improved utilization of palladium as anode catalyst for ethanol oxidation by exploiting the strong interaction between Pd nanoparticles and nitrogen-doped carbon nanotubes (NCNTs) as support. 0.85 wt% Pd supported on NCNTs achieved a specific current density of 517 A gPd - 1 compared with 421 A gPd - 1 for 0.86 wt% Pd on oxygen-functionalized carbon nanotubes. The electrocatalytic performance deteriorated only gradually and catalysis was sustained for at least 80 h. © 2015 Elsevier B.V. All rights reserved.

Supracrystals are highly symmetrical ordered superstructures built up from nanoparticles (NPs) via self-assembly. While the NP assembly has been intensively investigated, the formation mechanism is still not understood. To shed some light onto the formation mechanism, one of the most common supracrystal morphologies, the trigonal structures, as a model system is being used to investigate the formation process in solution. To explain the formation of the trigonal structures and determining the size of the supracrystal seeds formed in solution, the concept of substrate-affected growth is introduced. Furthermore, the influence of the NP concentration on the seed size is shown and our investigations from Ag toward Au are extended. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

DC and AC electrical properties of hybrid films, consisting of carbon nanotubes and tungsten disulfide nanotubes (and fullerene like nanoparticles) were studied within the 2 - 300 K temperature range and over the 20 Hz - 1 MHz frequency range. The temperature dependences of the resistance R(T) exhibit behavior typical for the fluctuation-induced tunneling model in the intermediate temperature range. Analysis of the dependences of real and imaginary components of the impedance on the frequency (Z'(f) and Z ''(f)) demonstrates the rising role of the contact barriers between carbon nanotubes inside hybrid films, consisting of the carbon nanotubes and inorganic tungsten disulfide nanotubes as the temperature was decreased. The active component of the impedance was found to prevail in the AC electrical properties of the hybrid films, consisting of multi-wall carbon nanotubes and WS2 nanoparticles over the entire available temperature range.

This study focuses on the synthesis and electrochemical performance (i.e, activity and stability) of advanced electrocatalysts for the oxygen reduction reaction (ORR), made of Pt-Ni nanoparticles embedded in hollow graphitic spheres (HGS). The mechanism of the confined space alloying, that is, the controlled alloying of bimetallic precursors with different compositions (i.e., Pt3Ni, PtNi, and PtNi3) within the HGS mesoporous shell, was examined in detail. It was found that the presence of platinum during the reduction step, as well as the application of high annealing temperatures (at least 850°C for 3.5h in Ar), are necessary conditions to achieve the complete encapsulation and the full stability of the catalysts. The evolution of the activity, the electrochemical surface area, and the residual alloy composition of the Pt-Ni@HGS catalysts was thoroughly monitored (at the macro- and nanoscale level) under different degradation conditions. After the initial activation, the embedded Pt-Ni nanoparticles (3-4 nm in size) yield mass activities that are 2- to 3.5-fold higher than that of pure Pt@HGS (depending on the alloy composition). Most importantly, it is demonstrated that under the normal operation range of an ORR catalyst in PEM-FCs (potential excursions between 0.4 and 1.0 VRHE) both the nanoparticle-related degradation pathways (particle agglomeration) and dealloying phenomena are effectively suppressed, irrespectively of the alloy composition. Thus, the initial enhanced activity is completely maintained over an extended degradation protocol. In addition, owing to the peculiar configuration of the catalysts consisting of space-confined nanoparticles, it was possible to elucidate the impact of the dealloying process (as a function of alloy composition and severity of the degradation protocols) separately from other parallel phenomena, providing valuable insight into this elusive degradation mechanism. (Graph Presented). © 2016 American Chemical Society.

Ultrashort pulse laser ablation has become a very important industrial method for highly precise material removal ranging from sensitive thin film processing to drilling and cutting of metals. Over the last decade, a new method to produce pure nanoparticles emerged from this technique: Pulsed Laser Ablation in Liquids (PLAL). By this method, the ablation of material by a laser beam is used to generate a metal vapor within the liquid in order to obtain nanoparticles from its recondensation process. It is well known that the liquid significantly alters the ablation properties of the substrate, in our case iron. For example, the ablation rate and crater morphology differ depending on the used liquid. We present our studies on the efficiency and quality of ablated grooves in water, methanol, acetone, ethanol and toluene. The produced grooves are investigated by means of white-light interferometry, EDX and SEM. © 2016 The Authors.

Hydrodeoxygenation (HDO) is an attractive route for the upgrading of bio-oils produced from lignocellulose. Current catalysts require harsh conditions to effect HDO, decreasing the process efficiency in terms of energy and carbon balance. Herein we report a novel and facile method for synthesizing bimetallic PtCo nanoparticle catalysts (ca. 1.5 nm) highly dispersed in the framework of nitrogen-doped ordered mesoporous carbon (NOMC) for this reaction. We demonstrate that NOMC with either 2D hexagonal (p6m) or 3D cubic (Im3m) structure can be easily synthesized by simply adjusting the polymerization temperature. We also demonstrate that PtCo/NOMC (metal loading: Pt 9.90 wt %; Co 3.31 wt %) is a highly effective catalyst for HDO of phenolic compounds and “real-world” biomass-derived phenolic streams. In the presence of PtCo/NOMC, full deoxygenation of phenolic compounds and a biomass-derived phenolic stream is achieved under conditions of low severity. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

We report the direct solution-phase characterization of individual gold-core silver-shell nanoparticles through an electrochemical means, with selectivity achieved between the core and shell components based on their different redox activities. The electrochemically determined core-shell sizes are in excellent agreement with electron microscopy-based results, successfully demonstrating the electrochemical characterization of individual core-shell nanoparticles. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

We propose a method for the formation of highly active bifunctional oxygen electrocatalysts, by exploiting the unique features of nitrogen-rich metallo-macrocyclic complexes and the structural and electronic properties of few-layer graphene. The precursors of the electrocatalysts were synthesized by sonication of graphite in DMF leading to exfoliation and the formation of few-layer graphene sheets in the presence of a suitable transition metal macrocyclic complex. After pyrolysis and subsequent mild calcination metal oxide nanoparticles as well as metal-nitrogen (MNx) moieties embedded within a N-doped graphitic carbon matrix are obtained. The formation, in-depth characterization and electrochemical performance of two different catalysts derived from Co and Ni containing precursor complexes are demonstrated. © 2016 Elsevier Ltd

Mercury(I) chloride (Hg2Cl2) nanoparticles (NPs) are synthesised for the first time by using two different techniques. First, particles are formed by implosion of a calomel nanolayer, induced by partial electrolysis at a mercury hemisphere microelectrode. The resulting NPs are then characterised by the nanoimpact method, demonstrating the first time metal chloride NPs have been sized by this technique and showing the ability to form and study NPs insitu. Second, Hg2Cl2 NPs are synthesised by using the precipitation reaction of Hg2(NO3)2 with KCl. The NPs are characterised on both mercury and carbon microelectrodes and their size is found to agree with TEM results. Sizable studies: Mercury(I) chloride (Hg2Cl2) nanoparticles (NPs) are synthesised for the first time by using two different techniques. First, particles are formed by implosion of a calomel nanolayer, induced by partial electrolysis at a mercury hemisphere microelectrode. Second, Hg2Cl2 NPs are synthesised by the precipitation reaction between Hg2(NO3)2 and KCl. The NPs are characterised on both mercury and carbon microelectrodes by using the nanoimpact method and their size is found to agree with TEM results. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The interpenetrating 3-dimensional channel system of silica MCM-48 has been selected for the deposition of ZnO nanoparticles. The post-synthetic organometallic route was employed to load the mesoporous silica with ZnO-precursor molecule. Calcination of the composite transformed the organometallic sorbate to the corresponding metal oxide. X-ray powder diffraction, N2-Adsorption and TEM measurement have supported the efficient loading and growth of ZnO particles in the channels of mesoporous silica matrix. EXAFS analysis (ZnK-edges) also complemented the metal uptake. Presence of nano-dispersed and nanosized ZnO particles confined by the mesoporous pore system was established by TEM and EXAFS analysis. © 2015 VBRI Press.

During laser material processing with high laser beam intensities, a laser-induced vapor formation can occur. Due to the shockwave behavior of the vapor plume and the associated rapid cooling, a significant particle formation can be initiated by nucleation. The laser radiation interacts with the particles which can result in a dynamic change of the intensity distribution on the surface. Especially in the field of laser remote processing, the attenuation of laser radiation by nanoparticles can influence the process stability and reduce the processing quality. The presented work is focused on the particle formation at a height of 10 mm above the material surface during the laser welding of stainless steel with a fiber laser. The laser beam intensity on the surface was varied between 1.3 and 5.1 MW/cm2. Transmission electron microscopy images of the nanoparticles and high speed images of the vapor propagation in the ambient atmosphere were analyzed. The attenuation of a probe beam in the vapor plume was evaluated in dependence on the wavelength. The results indicate a linear connection between the laser beam power and the particle formation rate. © 2015 Laser Institute of America.

Enhancing mass transport to electrodes is desired in almost all types of electrochemical sensing, electrocatalysis, and energy storage or conversion. Here, a method of doing so by means of the magnetic gradient force generated at magnetic-nanoparticle-modified electrodes is presented. It is shown using Fe3O4-nanoparticle-modified electrodes that the ultrahigh magnetic gradients (>108 T·m–1) established at the magnetized Fe3O4 nanoparticles speed up the transport of reactants and products at the electrode surface. Using the Fe(III)/Fe(II)-hexacyanoferrate redox couple, it is demonstrated that this mass transport enhancement can conveniently and repeatedly be switched on and off by applying and removing an external magnetic field, owing to the superparamagnetic properties of magnetite nanoparticles. Thus, it is shown for the first time that magnetic nanoparticles can be used to control mass transport in electrochemical systems. Importantly, this approach does not require any means of mechanical agitation and is therefore particularly interesting for application in micro- and nanofluidic systems and devices. [Figure not available: see fulltext.] © 2015, Tsinghua University Press and Springer-Verlag Berlin Heidelberg.

A Fe-Co-Nb thin film materials library was deposited by combinatorial magnetron sputtering and investigated by high-throughput methods to identify new noncubic ferromagnetic phases, indicating that combinatorial experimentation is an efficient method to discover new ferromagnetic phases adequate for permanent magnet applications. Structural analysis indicated the formation of a new magnetic ternary compound (Fe,Co)3Nb with a hexagonal crystal structure (C36) embedded in an FeCo-based matrix. This nanocomposite exhibits characteristics of a two-phase ferromagnetic system, the so-called hard-soft nanocomposites, indicating that the new phase (Fe,Co)3Nb is ferromagnetic. Magnetic hysteresis loops at various angles revealed that the magnetization reversal process is governed by a domain wall pinning mechanism. © 2015 American Chemical Society.

Adsorption of ceruloplasmin (Cp) at a gold electrode modified with ferromagnetic iron nanoparticles encapsulated in carbon (Fe@C Nps) leads to a successful immobilization of the enzyme in its electroactive form. The proper placement of Cp at the electrode surface on top of the nanocapsules containing an iron core allowed a preorientation of the enzyme, hence allowing direct electron transfer between the electrode and the enzyme. Laser ablation coupled with inductively coupled plasma mass spectrometry indicated that Cp was predominantly located at the paramagnetic nanoparticles. Scanning electrochemical microscopy measurements in the sample-generation/tip-collection mode proved that Cp was ferrooxidative inactive if it was immobilized on the bare gold surface and reached the highest activity if it was adsorbed on Fe@C Nps in the presence of a magnetic field. © 2015 American Chemical Society.

Thermal spray processes are widely used for the manufacture of advanced coating systems, e.g. metallic coatings for wear and corrosion protection. The desired coating properties are closely related to the microstructure, which is highly influenced by the processing parameters, such as temperature, size and velocity of the sprayed particles. In this paper, large scale Molecular Dynamics simulations are conducted to investigate the microstructure formation mechanisms during the spraying process of hot nano-particles onto a substrate at room temperature using pure copper as a benchmark material representing for a wider class of face-centered-cubic metals. To evaluate the influence of processing parameters on the coating morphology, a number of simulations are performed in which the initial temperature, size and velocity of copper particles are systematically varied in order to investigate the thermal and microstructural evolution during impaction. Two distinct types of microstructural formation mechanisms, resulting in different coating morphologies, are observed in the present investigation, which are either governed by plastic deformation or by the process of melting and subsequent solidification. Furthermore, a thermodynamically motivated model as a function of the particle temperature and velocity is developed, which predicts the microstructural mechanisms observed in the simulations. The results provide an elementary insight into the microstructure formation mechanisms on an atomistic scale, which can serve as basic input for continuum modeling of thermal spray process. © 2015 Published by Elsevier B.V.

Nanostructure engineering has been demonstrated to improve the electrochemical performance of iron oxide based electrodes in Li-ion batteries (LIBs). However, the synthesis of advanced functional materials often requires multiple steps. Herein, we present a facile one-pot synthesis of carbon-coated nanostructured iron oxide on few-layer graphene through high-pressure pyrolysis of ferrocene in the presence of pristine graphene. The ferrocene precursor supplies both iron and carbon to form the carbon-coated iron oxide, while the graphene acts as a high-surface-area anchor to achieve small metal oxide nanoparticles. When evaluated as a negative-electrode material for LIBs, our composite showed improved electrochemical performance compared to commercial iron oxide nanopowders, especially at fast charge/discharge rates. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Uniform Au nanoparticles (∼2 nm) with narrow size-distribution (standard deviation: 0.5-0.6 nm) supported on both hydroxylated (Fe-OH) and dehydrated iron oxide (Fe-O) have been prepared by either deposition-precipitation (DP) or colloidal-deposition (CD) methods. Different structural and textural characterizations were applied to the dried, calcined and used gold-iron oxide samples. Transmission electron microscopy (TEM) and high-resolution TEM (HRTEM) showed high homogeneity in the supported Au nanoparticles. The ex situ and in situ X-ray absorption fine structure (XAFS) characterization monitored the electronic and short-range local structure of active gold species. The synchrotron-based in situ X-ray diffraction (XRD), together with the corresponding temperature-programmed reduction by hydrogen (H2-TPR), indicated a structural evolution of the iron-oxide supports, correlating to their reducibility. An inverse order of catalytic activity between DP (Au/Fe-OH < Au/Fe-O) and CD (Au/Fe-OH > Au/Fe-O) was observed. Effective gold-support interaction results in a high activity for gold nanoparticles, locally generated by the sintering of dispersed Au atoms on the oxide support in the DP synthesis, while a hydroxylated surface favors the reactivity of externally introduced Au nanoparticles on Fe-OH support for the CD approach. This work reveals why differences in the synthetic protocol translate to differences in the catalytic performance of Au/FeOx catalysts with very similar structural characteristics in CO oxidation. © The Royal Society of Chemistry 2015.

The geometry of quasi-spherical nanoparticles is investigated. The combination of SEM imaging and electrochemical nano-impact experiments is demonstrated to allow sizing and characterization of the geometry of single silver nanoparticles. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Due to their unique properties, nano-sized materials such as nanoparticles and nanowires are receiving considerable attention. However, little data is available about their chemical makeup at the atomic scale, especially in three dimensions (3D). Atom probe tomography is able to answer many important questions about these materials if the challenge of producing a suitable sample can be overcome. In order to achieve this, the nanomaterial needs to be positioned within the end of a tip and fixed there so the sample possesses sufficient structural integrity for analysis. Here we provide a detailed description of various techniques that have been used to position nanoparticles on substrates for atom probe analysis. In some of the approaches, this is combined with deposition techniques to incorporate the particles into a solid matrix, and focused ion beam processing is then used to fabricate atom probe samples from this composite. Using these approaches, data has been achieved from 10-20 nm core-shell nanoparticles that were extracted directly from suspension (i.e. with no chemical modification) with a resolution of better than ±1 nm. © 2015 Elsevier B.V..

Electrochemical corrosion is a major problem for carbon materials used in electrocatalysis. Highly dispersed TiO2 was deposited on O-functionalized and N-doped carbon nanotubes by chemical vapour deposition to tackle the carbon corrosion problem. Very low Ti loadings of about 1 wt% were applied to minimize the negative influence of TiO2 as a semiconductor on the high conductivity of carbon materials. Both N doping and TiO2 coating facilitate strong metal-support interactions and favour the formation of small Pt particles. N doping improved the intrinsic catalytic activity of the carbon support and enhanced the conductivity due to the removal of surface oxygen groups, while the negative effect of TiO2 on conductivity is counterbalanced by its promoting effect on metal-support interactions leading to enhanced overall catalytic performance. Pt/TiO2/NCNTs showed the highest ORR activity, and significantly outperformed Pt/NCNTs in electrochemical stability tests. © the Owner Societies 2015.

We derive approximate expressions for the average number of diffusive impacts/hits of nanoparticles on microdisc and microwire electrodes for the case where the impact leads to the loss of the nanoparticles from solution either via irreversible adsorption or complete electro-dissolution. The theory can also be applied to sub-micrometre size electrodes (nano-electrodes). The resulting equations can be utilised to analyse the number of impacts and its variance in the 'nano-impact' experiment. We also provide analytical expressions for the first passage time of an impact for dilute nanoparticle solutions in the continuum limit of Fickian diffusion. The expressions for the first passage times are used to estimate the lower limit of detection in ultra-dilute nanoparticle solutions for typical nano-impact experiments, and show the advantage of using microwire electrodes in ultra-dilute solutions or solutions containing larger nano-particles. © 2015 Elsevier B.V. All rights reserved.

We provide a comprehensive durability assessment dedicated to a promising class of electrocatalysts for the oxygen reduction reaction (i.e., porous platinum nanoparticles). The stability of these nanoengineered open structures is tested under two accelerated degradation test conditions (ADT), particularly selected to mimic the potential regimes experienced by the catalyst during the operative life of a fuel cell (i.e., load cycles (up to 1.0 VRHE) and start-up cycles (up to 1.4 VRHE)). To understand the evolution of the electrochemical performance, the catalyst properties are investigated by means of fundamental rotating disc electrode studies, identical location-transmission electron microscopy (IL-TEM) coupled with electron energy loss spectroscopy chemical mapping (IL-EELS), and post-use chemical analysis and online highly sensitive potential resolved dissolution concentration monitoring by scanning flow cell inductively coupled plasma-mass spectrometry (SFC-ICP-MS). The experimental results on the nanoporous Pt revealed distinctive degradation mechanisms that could potentially affect a wide range of other nanoengineered open structures. The study concludes that, although providing promising activity performance, under the relevant operational conditions of fuel cells, the nanoporosity is only metastable and subjected to a progressive reorganization toward the minimization of the nanoscale curvature. The rate and pathways of this specific degradation mechanism together with other well-known degradation mechanisms like carbon corrosion and platinum dissolution are strongly dependent on the selected upper limit potential, leading to distinctly different durability performance. © 2015 American Chemical Society.

Core-shell nanoparticles (NPs) are amongst the most promising candidates in the development of new functional materials. Their fabrication and characterization are challenging, in particular when thin and intact shells are needed. To date no technique has been available that differentiates between intact and broken or cracked shells. Here a method is presented to distinguish and quantify these types of shells in a single cyclic voltammetry experiment by using the different electrochemical reactivities of the core and the shell material. A simple comparison of the charge measured during the stripping of the core material before and after the removal of the shell makes it possible to determine the quality of the shells and to estimate their thickness. As a proof-of-concept two multifunctional examples of core-shell NPs, Fe3O4@Au and Au@SnO2, are used. This general and original method can be applied whenever core and shell materials show different redox properties. Because billions of NPs are probed simultaneously and at a low cost, this method is a convenient new screening tool for the development of new multifunctional core-shell materials and is hence a powerful complementary technique or even an alternative to the state-of-the-art characterization of core-shell NPs by TEM. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

We report on a biophotocathode based on photosystem 1 (PS1)-Pt nanoparticle complexes integrated in a redox hydrogel for photoelectrocatalytic H2 evolution at low overpotential. A poly(vinyl)imidazole Os(bispyridine)2Cl polymer serves as conducting matrix to shuttle the electrons from the electrode to the PS1-Pt complexes embedded within the hydrogel. Light induced charge separation at the PS1-Pt complexes results in the generation of photocurrents (4.8 ± 0.4 μA cm-2) when the biophotocathodes are exposed to anaerobic buffer solutions. Under these conditions, the protons are the sole possible electron acceptors, suggesting that the photocurrent generation is associated with H2 evolution. Direct evidence for the latter process is provided by monitoring the H2 production with a Pt microelectrode in scanning electrochemical microscopy configuration over the redox hydrogel film containing the PS1-Pt complexes under illumination. © 2015 American Chemical Society.

We present azimuth- and polarization-dependent infrared spectroscopy results obtained under ultra-high vacuum conditions on surface species formed by the interaction of formic acid with the mixed-terminated ZnO(101¯0) surface. Since there are no previous IRRAS data for formic-acid derived species on any ZnO single crystal surfaces, we have carried out calculations using density function theory to aid the interpretation of the results. From our combined experimental and theoretical data we conclude that two different formate species are formed. The more strongly bound species is a bidentate with the formate molecular plane oriented along the [12¯10] direction. The less strongly bound species is a quasi-bidentate with its molecular plane oriented along the [0001] direction. This second species is characterized by a strong hydrogen bond between a surface OH species and the formate. In addition, IR data were recorded for the same molecule adsorbed on commercial ZnO nanoparticles. The different bands of the powder IR-data are assigned on the basis of the experimental and theoretical results obtained for the single crystal surface. This study demonstrates the importance of the Surface Science approach to heterogeneous catalysis also for ZnO, an important catalyst for the conversion of syngas to methanol. © 2014 Springer Science+Business Media.

The gas-phase photooxidation of 2-propanol over Au/TiO2 and TiO2 was studied by infrared spectroscopy and online mass spectrometry to gain insight into the mechanism and the role of gold. The presence of O2 was found to be essential for the formation of acetone under UV irradiation at room temperature. In the presence of gold nanoparticles the rate of acetone formation was increased compared to pure TiO2. Baseline bending in the ATR-IR spectra was used as a tool to monitor the accumulation of excess electrons. Electron accumulation was absent in the presence of gold and O2 suggesting that the gold nanoparticles act as co-catalysts enhancing the rate of electron transfer from TiO2 to adsorbed O2 species. © the Owner Societies 2015.

The chemical and morphological stability of size- and shape-selected octahedral PtNi nanoparticles (NP) were investigated after different annealing treatments up to a maximum temperature of 700 °C in a vacuum and under 1 bar of CO. Atomic force microscopy was used to examine the mobility of the NPs and their stability against coarsening, and X-ray photoelectron spectroscopy to study the surface composition, chemical state of Pt and Ni in the NPs, and thermally and CO-induced atomic segregation trends. Exposing the samples to 1 bar of CO at room temperature before annealing in a vacuum was found to be effective at enhancing the stability of the NPs against coarsening. In contrast, significant coarsening was observed when the sample was annealed in 1 bar of CO, most likely as a result of Ni(CO)4 formation and their enhanced mobility on the support surface. Sample exposure to CO at room temperature prior to annealing led to the segregation of Pt to the NP surface. Nevertheless, oxidic PtOx and NiOx species still remained at the NP surface, and, irrespective of the initial sample pretreatment, Ni surface segregation was observed upon annealing in a vacuum at moderate temperature (T < 300 °C). Interestingly, a distinct atomic segregation trend was detected between 300 and 500 °C for the sample pre-exposed to CO; namely, Ni surface segregation was partially hindered. This might be attributed to the higher bonding energy of CO to Pt as compared to Ni. Annealing in the presence of 1 bar CO also resulted in the initial surface segregation of Ni (T < 400 °C) as long as PtOx and NiOx species were available on the surface as a result of the higher affinity of Ni for oxygen. Above 500 °C, and regardless of the sample pretreatment, the diffusion of Pt atoms to the NP surface and the formation of a Ni-Pt alloy are observed. © 2015 American Chemical Society.

Capping agents, key for nanoparticle stability, may hugely influence chemical behaviour. We show that differently capped gold nanoparticles, with either citrate or cetyl trimethylammonium bromide (CTAB) capping agents, show qualitatively different electron transfer properties. Specifically through cyclic voltammetry and nanoimpact studies the CTAB promoted dissolution of gold nanoparticles is shown, highlighting the active role which capping agents can play in charge transfer. This journal is © the Owner Societies.

Bimetallic silver-gold nanoparticles were prepared by co-reduction using citrate and tannic acid in aqueous solution and colloidally stabilized with poly(N-vinylpyrrolidone) (PVP). The full composition range of silver:gold from 0:100 to 100:0 (n:n) was prepared with steps of 10 mol%. The nanoparticles were spherical, monodispersed, and had a diameter of ∼6 nm, except for Ag:Au 90:10 nanoparticles and pure Ag nanoparticles which were slightly larger. The size of the nanoalloys was determined by differential centrifugal sedimentation (DCS) and transmission electron microscopy (TEM). By means of X-ray powder diffraction (XRD) together with Rietveld refinement, precise lattice parameters, crystallite size and microstrain were determined. Scanning transmission electron microscopy (STEM) combined with energy-dispersive X-ray spectroscopy (EDX) and electron energy loss spectroscopy (EELS) showed that the particles consisted of a gold-rich core and a silver-rich shell. XRD and DCS indicated that the nanoparticles were not twinned, except for pure Ag and Ag:Au 90:10, although different domains were visible in the TEM. A remarkable negative deviation from Vegard's linear rule of alloy mixtures was observed (isotropic contraction of the cubic unit cell with a minimum at a 50:50 composition). This effect was also found for Ag:Au bulk alloys, but it was much more pronounced for the nanoalloys. Notably, it was much less pronounced for pure silver and gold nanoparticles. The microstrain was increased along with the contraction of the unit cell with a broad maximum at a 50:50 composition. The synthesis is based on aqueous solvents and can be easily scaled up to a yield of several mg of a well dispersed nanoalloy with application potential due to its tuneable antibacterial action (silver) and its optical properties for bioimaging. © The Royal Society of Chemistry 2015.

Electrostatic interactions between surface-charged nanoparticles (NPs) and electrodes studied using existing techniques unavoidably and significantly alter the system being analyzed. Here we present a methodology that allows the probing of unperturbed electrostatic interactions between individual NPs and charged surfaces. The uniqueness of this approach is that stochastic NP impact events are used as the probe. During a single impact, only an attomole of the redox species reacts and is released at the interface during each sensing event. As an example, the effect of electrostatic screening on the reduction of negatively charged indigo NPs at a mercury microelectrode is explored at potentials positive and negative of the potential of zero charge. At suitable overpotentials fully driven electron transfer is seen for all but very low (<0.005M) ionic strengths. The loss of charge transfer in such dilute electrolytes is unambiguously shown to arise from a reduced driving force for the reaction rather than a reduced population of NPs near the electrode, contradicting popular perceptions. Electrostatics were found not to significantly affect the reactivity of the studied NPs. Importantly, the presented technique is general and can be applied to a wide variety of NPs, including metals, metal oxides and organic compounds. Not what you might think: A new and non-invasive technique to probe the electrostatic interaction between surface-charged nanoparticles and a charged metal/solution interface shows that electrostatic effects are insignificant in all but very dilute electrolytes. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A proof-of-concept for the electrochemical detection of single Escherichia coli bacteria decorated with silver nanoparticles is reported. Impacts of bacteria with an electrode - held at a suitably oxidizing potential - lead to an accompanying burst of current with each collision event. The frequency of impacts scales with the concentration of bacteria and the charge indicates the extent of decoration. © The Royal Society of Chemistry.

Despite extensive work on the controlled surface modification of carbon with redox moieties, to date almost all available methodologies involve complex chemistry and are prone to the formation of polymerized multi-layer surface structures. Herein, the facile bifunctional redox tagging of carbon nanoparticles (diameter 27 nm) and its characterization is undertaken using the industrial dye Reactive Blue 2. The modification route is demonstrated to be via exceptionally strong physisorption. The modified carbon is found to exhibit both well-defined oxidative and reductive voltammetric redox features which are quantitatively interpreted. The method provides a generic approach to monolayer modifications of carbon and carbon nanoparticle surfaces. © The Royal Society of Chemistry 2015.

Abstract Transition metal oxides are regarded as promising anode materials for lithium-ion batteries because of their high theoretical capacities compared with commercial graphite. Unfortunately, the implementation of such novel anodes is hampered by their large volume changes during the Li+ insertion and extraction process and their low electric conductivities. Herein, we report a specifically designed anode architecture to overcome such problems, that is, mesoporous peapod-like Co3O4@carbon nanotube arrays, which are constructed through a controllable nanocasting process. Co3O4 nanoparticles are confined exclusively in the intratubular pores of the nanotube arrays. The pores between the nanotubes are open, and thus render the Co3O4 nanoparticles accessible for effective electrolyte diffusion. Moreover, the carbon nanotubes act as a conductive network. As a result, the peapod-like Co3O4@carbon nanotube electrode shows a high specific capacity, excellent rate capacity, and very good cycling performance. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A catalyst consisting of copper nanoparticles (15-20 nm in size) supported on ordered mesoporous cobalt monoxide was synthesized by the one-step reduction of ethanol from nanocast copper cobalt spinel oxides. The small-angle X-ray scattering patterns showed that the ordered mesostructure was maintained after post-treatment, and the cross-section scanning electron microscopy images showed that the Cu nanoparticles were distributed homogeneously throughout the mesoporous CoO framework. The materials were tested as noble-metal-free catalysts for the oxidation of glycerol under alkaline conditions. The catalytic data showed that the presence of Cu nanoparticles greatly enhanced the catalytic performance. Nothing noble: A catalyst consisting of copper nanoparticles (NPs, 15-20 nm in size) supported on ordered mesoporous cobalt monoxide is synthesized by the one-step reduction with ethanol from nanocast copper cobalt spinel oxides. As a noble-metal-free catalyst for the oxidation of glycerol, the presence of Cu NPs greatly enhances the catalytic performance. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Colloidal chemistry, in combination with nanoparticle (NP)/support epitaxial interactions is used here to synthesize shape-selected and thermodynamically stable metallic NPs over a broad range of NP sizes. The morphology of three-dimensional palladium and platinum NPs supported on TiO2(110) was investigated using scanning tunneling microscopy. Well-defined Pd and Pt NPs were synthesized via inverse micelle encapsulation. The initially spherical NPs were found to become faceted and form an epitaxial relationship with the support after high-temperature annealing (e.g., 1100 °C). Shape selection was achieved for almost all Pd NPs, namely, a truncated octahedron shape with (111) top and interfacial facets. The Pt NPs were however found to adopt a variety of shapes. The epitaxial relationship of the NPs with the support was evidenced by the alignment of the cluster's edges with TiO2(110)-[001] atomic rows and was found to be responsible for the shape control. The ability of synthesizing thermally stable shape-selected metal NPs demonstrated here is expected to be of relevance for applications in the field of catalysis, since the activity and selectivity of NP catalysts has been shown to strongly depend on the NP shape. © 2015 American Chemical Society.

An efficient two-step gas-phase method was developed for the synthesis of Co3O4-MnO2-CNT hybrids used as electrocatalysts in the oxygen evolution reaction (OER). Spinel Co-Mn oxide was used for the catalytic growth of multiwalled carbon nanotubes (CNTs) and the amount of metal species remaining in the CNTs was adjusted by varying the growth time. Gas-phase treatment in HNO3 vapor at 200 °C was performed to 1)open the CNTs, 2)oxidize encapsulated Co nanoparticles to Co3O4 as well as MnO nanoparticles to MnO2, and 3)to create oxygen functional groups on carbon. The hybrid demonstrated excellent OER activity and stability up to 37.5h under alkaline conditions, with longer exposure to HNO3 vapor up to 72h beneficial for improved electrocatalytic properties. The excellent OER performance can be assigned to the high oxidation states of the oxide nanoparticles, the strong electrical coupling between these oxides and the CNTs as well as favorable surface properties rendering the hybrids a promising alternative to noble metal based OER catalysts. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Titania exhibits unique photophysical and -chemical properties and can be used for potential applications in the field of photocatalysis. The control of TiO2 in terms of phase, shape, morphology, and especially nanoscale synthesis of TiO2 particles still remains a challenge. Ti-containing metal-organic frameworks (MOFs), such as MIL-125, can be used as sacrificial precursors to obtain TiO2 materials with diverse phase compositions, morphologies, sizes, and surface areas. MIL-125 is composed of Ti/O clusters as the secondary building units (SBUs) bridged by 1,4-benzenedicarboxylate (bdc). In this study, preformed and surfactant-stabilized gold nanoparticles (GNPs) were deposited onto the surface of amino functionalized NH2-MIL-125 during solvothermal synthesis. Targeted gold/titania nanocomposites, GNP/TiO2, were fabricated through the pyrolysis of GNP/NH2-MIL-125 nanocrystals. The modification of TiO2 with GNPs significantly increased the photocatalytic activity of the MOF derived TiO2 material for the reduction of CO2 to CH4 as compared to TiO2 reference samples such as P-25 and AUROlite (Au/TiO2). The new materials GNP/TiO2 and TiO2 derived by the MOF precursor route were thoroughly characterized by PXRD, FTIR and Raman, TEM, and N2 adsorption studies. © 2015 American Chemical Society.

Nanoparticles are prone to clustering either via aggregation (irreversible) or agglomeration (reversible) processes. It is exceedingly difficult to distinguish the two via conventional techniques such as dynamic light scattering (DLS), nanoparticle tracking analysis (NTA), or electron microscopy imaging (scanning electron microscopy (SEM), transmission electron microscopy (TEM)) as such techniques only generally confirm the presence of large particle clusters. Herein we develop a joint approach to tackle the issue of distinguishing between nanoparticle aggregation vs agglomeration by characterizing a colloidal system of Ag NPs using DLS, NTA, SEM imaging and the electrochemical nanoimpacts technique. In contrast to the conventional techniques which all reveal the presence of large clusters of particles, electrochemical nanoimpacts provide information regarding individual nanoparticles in the solution phase and reveal the presence of small nanoparticles (<30 nm) even in high ionic strength (above 0.5 M KCl) and allow a more complete analysis. The detection of small nanoparticles in high ionic strength media evidence the clustering to be a reversible process. As a result it is concluded that agglomeration rather than irreversible aggregation takes place. This observation is of general importance for all colloids as it provides a feasible analysis technique for a wide range of systems with an ability to distinguish subtly different processes. © 2015 American Chemical Society.

Anatase TiO2 nanoparticles with a specific surface area of 100 m2 g-1 and 300 m2 g-1 have been investigated as negative insertion electrode material for lithium-ion batteries. Galvanostatic intermittent titration (GITT) and electrochemical impedance spectroscopy (EIS) were used to investigate the effect of the specific surface area on the performance of the material. GITT was performed at C/10 rate, followed by an EIS measurement after each relaxation step. Separation of kinetic and thermodynamic contributions to the overpotential of the phase transformation on Li+ (de-)insertion allowed revealing a dependency of both terms on the specific surface area. The material with higher surface area undergoes intrinsic transformation during the initial cycles affecting the thermodynamics of (de-)insertion while the sample with lower surface area shows large and asymmetric kinetic hindrances. For the material with 15 nm particles, Li+ de-insertion appears to have a higher resistance than lithium insertion. © 2015, Elsevier B.V. All rights reserved.

Silver nanoparticles offer highly attractive properties for many applications, however concern has been raised over the possible toxicity of this material in environmental systems. While it is thought that the release of Ag+ can play a crucial role in this toxicity, the mechanism by which the oxidative dissolution of nano-silver occurs is not yet understood. Here we address this through the electrochemical analysis of gold-core silver-shell nanoparticles in various solutions. This novel method allows the direct quantification of silver dissolution by normalisation to the gold core signal. This is shown to be highly effective at discriminating between silver dissolution and the loss of nanoparticles from the electrode surface. We evidence through this rigorous approach that the reduction of O2 drives the dissolution of nano-silver, while in the presence of Cl- this dissolution is greatly inhibited. This work is extended to the single nanoparticle level using nano-impact experiments. © The Royal Society of Chemistry.

Cu-Co-based catalysts were synthesized by co-precipitation using Cu, Co, Zn and Al nitrates and applied in higher alcohol synthesis (HAS) at 280 °C, 60 bar and a ratio of H2/CO = 1. The catalyst exhibiting a Cu/Co ratio of 2.5 was found to provide the best trade-off between product distribution and degree of CO conversion. After activation and 40 h time on stream reaching steady-state conditions the bulk and surface properties of the catalyst were thoroughly investigated without exposing it to air during the transfer and the measurements. The conditions during activation and HAS led to a significant enrichment of Zn in the surface composition of the catalysts. The XRD pattern of the catalyst after reaction compared with the reduced catalyst revealed further sintering of the metallic Cu nanoparticles and the growth of crystalline ZnO nanoparticles, but there were no indications for the presence of bulk metallic Co or for bulk alloying. With increasing time on stream the product distribution shifted favorably towards higher alcohols presumably due to an increased intimate interface contact between the large metallic Cu0 particles detected by XRD and the X-ray amorphous metallic Co surface species probed by XPS. © 2015 Elsevier B.V.

Capping agent-controlled stability of nanoparticles tailors them for different applications, but the associated particle-solvent dynamics are poorly understood. Herein, previously unseen capping agent-gated nanoparticle redox activity is observed for poly(ethylene glycol)-coated silver nanoparticles. This is revealed by stochastic nanoparticle stripping, probing one individual nanoparticle at a time, from an ensemble of surface-immobilized nanoparticles. Thus, new and previously inaccessible understanding is gained on the crucial role of capping agent dynamics on nanoparticle reactivity. © 2015 American Chemical Society.

Partially blocked electrodes (PBEs) are important; many applications use non-conductive nanoparticles (NPs) to introduce new electrode functionalities. As aggregation is a problem in NP immobilization, developing an in situ method to detect aggregation is vital to characterise such modified electrodes. We present chronoamperometry as a method for detection of NP surface aggregation and semi-quantitative sizing of the formed aggregates, based on the diffusion limited current measured at PBEs as compared with the values calculated numerically for different blocking feature sizes. In contrast to voltammetry, no approximations on electrode kinetics are needed, making chronoamperometry a more general and reliable method. Sizing is shown for two modification methods. Upon drop casting, significant aggregation is observed, while it is minimized in electrophoretic NP deposition. The aggregate sizes determined are in semi-quantitative agreement with ex situ microscopic analysis of the PBEs. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The recent surge in investigating electrocatalysts for the H2 evolution reaction is based on finding a cheap alternative to Pt. However platinum's excellent catalytic activity means very little catalyst needs to be used. The present study combines model experiments with numerical modeling to determine exactly how little catalyst is needed. Specifically we investigate ultra-low Pt loadings for use in photoelectrochemical H2 evolution using TiO2-Ti-pn+Si photocathodes. At a current density of 10 mA cm-2, we photocathodically evolve H2 at +465, +450, +350 and +270 mV vs., RHE at Pt loadings of 1000, 200, 50, and 10 ng cm-2 corresponding to HER overpotentials of η1000ng = 32 mV, η200ng = 46 mV, η50ng = 142 mV, and η10ng = 231 mV. To put this in perspective, if 30% of the world's current annual Pt production was used for H2 evolution catalysis, using a loading of 100 ng cm-2 and a current of 10 mA cm-2 would produce 1 TWaverage of H2. The photoelectrochemical data matched the modeling calculations implying that we were near the fundamental maximum in performance for our system. Furthermore modeling indicated that the overpotentials were dominated by mass transfer effects, rather than catalysis unless catalyst loadings were less than 1000 ng cm-2. © The Royal Society of Chemistry.

A study of particle size effects during the catalytic CO2 electroreduction on size-controlled Cu nanoparticles (NPs) is presented. Cu NP catalysts in the 2-15 nm mean size range were prepared, and their catalytic activity and selectivity during CO2 electroreduction were analyzed and compared to a bulk Cu electrode. A dramatic increase in the catalytic activity and selectivity for H2 and CO was observed with decreasing Cu particle size, in particular, for NPs below 5 nm. Hydrocarbon (methane and ethylene) selectivity was increasingly suppressed for nanoscale Cu surfaces. The size dependence of the surface atomic coordination of model spherical Cu particles was used to rationalize the experimental results. Changes in the population of low-coordinated surface sites and their stronger chemisorption were linked to surging H2 and CO selectivities, higher catalytic activity, and smaller hydrocarbon selectivity. The presented activity-selectivity-size relations provide novel insights in the CO2 electroreduction reaction on nanoscale surfaces. Our smallest nanoparticles (∼2 nm) enter the ab initio computationally accessible size regime, and therefore, the results obtained lend themselves well to density functional theory (DFT) evaluation and reaction mechanism verification. © 2014 American Chemical Society.

Platinum and Pt alloy nanoparticles supported on carbon are the state of the art electrocatalysts in proton exchange membrane fuel cells. To develop a better understanding on how material design can influence the degradation processes on the nanoscale, three specific Pt/C catalysts with different structural characteristics were investigated in depth: a conventional Pt/Vulcan catalyst with a particle size of 3-4 nm and two Pt@HGS catalysts with different particle size, 1-2 nm and 3-4 nm. Specifically, Pt@HGS corresponds to platinum nanoparticles incorporated and confined within the pore structure of the nanostructured carbon support, i.e., hollow graphitic spheres (HGS). All three materials are characterized by the same platinum loading, so that the differences in their performance can be correlated to the structural characteristics of each material. The comparison of the activity and stability behavior of the three catalysts, as obtained from thin film rotating disk electrode measurements and identical location electron microscopy, is also extended to commercial materials and used as a basis for a discussion of general fuel cell catalyst design principles. Namely, the effects of particle size, inter-particle distance, certain support characteristics and thermal treatment on the catalyst performance and in particular the catalyst stability are evaluated. Based on our results, a set of design criteria for more stable and active Pt/C and Pt-alloy/C materials is suggested.& copy 2014 Meier et al.

In this paper we report on the first example of Fe2O3/CuO composites fabricated by a two-step vapor-phase synthetic strategy. The target route is based on the CVD of Fe2O3 nanorod arrays on Si(100) at 400°C starting from Fe(hfa)2TMEDA (hfa=1,1,1,5,5,5-hexafluoro-2,4-pentanedionate; TMEDA=N,N,N',N'-tetramethylethylenediamine), followed by radio frequency (RF) copper sputtering for various process durations, and final ex-situ annealing in air. The combined use of complementary structural, morphological, and chemical analyses give evidence of the formation of pure nanocomposite systems, characterized by the presence of the sole ε-Fe2O3 and CuO phases. The unique features of the adopted approach enable an efficient surface decoration of ε-Fe2O3 rods by CuO nanoparticles a few nm in diameter, resulting in an intimate contact between the two oxides, and a CuO content tunable through variations of the sole sputtering time. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

This paper focuses on the investigation of the ageing behaviour of silver nanoparticle containing polytetrafluoroethylene thin films during exposure to phosphate buffer solution (pH = 7.5). In order to investigate the effect of the electrical connection between the silver nanoparticles via a conductive substrate, two kinds of composite films were compared. One model where the nanoparticles are directly deposited on an inert conducting substrate and then covered by an ultra-thin polytetrafluoroethylene like film. In the second case a polytetrafluoroethylene/silver nanoparticle/polytetrafluoroethylene sandwich film was prepared on the same substrate to prevent electrical connection of the silver nanoparticles. Degradation was followed in-situ by means of the combination of ultraviolet-visible spectroscopy and electrochemical impedance spectroscopy. In the case of electrically connected nanoparticles electrochemical Ostwald ripening took place, while this process was not observed for the insulated nanoparticles. The electrochemical impedance spectroscopy studies allowed for the parallel study of the correlated loss of barrier properties. Transmission electron microscopy images of both composite films confirmed the results obtained by means of the in situ electrochemical ultraviolet-visible studies. © 2014 Elsevier B.V.

New opportunity to improve a sensetivity of a label-free biomolecule detection in sensing systems based on microcavity evanescent wave optical sensors has been recently found and is being under intensive development. Novel technique based on combination of optical resonance on microring structures with plasmon resonance. Recently developed tools based on neural network data processing can realize real-Time identification of biological agents. So combining advantages of plasmon enhancing optical microcavity resonance with identification tools can give a new platform for ulta sensitive label-free biomedical sensor. Our developed technique used standard glass and polymer microspheres as sensetive elements. They are fixed in the solution flow by adhesive layer on the surface being in the field of evanescence wave. Sensitive layer have been treated by gold nanoparticel (GN) solution. Another technique used thin film gold layers deposited on the substrate below adhesive. The light from a tuneable diode laser is coupled into the microsphere through a prism and was sharply focussed on the single microsphere. Images were recorded by CMOS camera. Normalized by free spectral range resonance shift of whispering gallery mode (WGM) and a relative efficiency of their excitation were used as input data for biomolecule classification. Both biomolecules and NP injection was obtained caused WGM spectra modification. But after NP treatment spectral shift and intensity of WGM resonances in biomolecule solutions increased. WGM resonances in microspheres fixed on substrate with gold layer with optimized layer thickness in biomolecule solutions also had higher intensity and spectra modification then without gold layer. © 2014 SPIE.

The immobilisation of nanoparticles from solution at a solid surface followed by anodic stripping voltammetry is a simple technique allowing the analysis of nanoparticle concentrations and identity. We report that the modification of gold electrodes with meso-2,3-dimercaptosuccinic acid (DMSA) shows a useful increase in the adsorption rate of silver nanoparticles on a gold substrate showing that the chemical modification of the electrode is analytically advantageous. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The electrocatalytic reduction of CO2 to industrial chemicals and fuels is a promising pathway to sustainable electrical energy storage and to an artificial carbon cycle, but it is currently hindered by the low energy efficiency and low activity displayed by traditional electrode materials. We report here the size-dependent catalytic activity of micelle-synthesized Au nanoparticles (NPs) in the size range of ∼1-8 nm for the electroreduction of CO2 to CO in 0.1 M KHCO3. A drastic increase in current density was observed with decreasing NP size, along with a decrease in Faradaic selectivity toward CO. Density functional theory calculations showed that these trends are related to the increase in the number of low-coordinated sites on small NPs, which favor the evolution of H2 over CO2 reduction to CO. We show here that the H2/CO product ratio can be specifically tailored for different industrial processes by tuning the size of the catalyst particles. © 2014 American Chemical Society.

CO2 hydrogenation to short-chain hydrocarbons was investigated over iron catalysts supported on oxygen- and nitrogen-functionalized multi-walled carbon nanotubes (CNTs) and on silica, which were synthesized by the dry impregnation method using ammonium ferric citrate as precursor. The reduction of the calcined catalysts was examined in detail using temperature-programmed reduction in H2 and in situ X-ray absorption near-edge structure (XANES) analysis. The XANES results revealed that the mixture of hematite and magnetite was gradually transformed into wustite and metallic iron during heating in H2. Iron oxide nanoparticles supported on nitrogen-functionalized CNTs were easier to reduce compared to those on oxygen-functionalized CNTs indicating a promoting effect of the nitrogen functional groups. The interaction between iron oxide and silica was found to be much stronger inhibiting the reduction to metallic iron. As a result, the catalytic activity of iron nanoparticles supported on CNTs in CO2 hydrogenation at 360 °C, 25 bar and a H2:CO 2 ratio of 3 was almost twofold higher compared with iron supported on silica. CO2 was converted into C1-C5 hydrocarbons with CO and methane as major products over all catalysts. The Fe/NCNT catalyst achieved the highest olefin selectivity of 11% in the hydrocarbons range of C2-C5. In contrast, mostly paraffins were formed over the Fe/SiO2 catalyst. © 2014 Elsevier B.V.

We report the use of homemade disposable gold electrodes fabricated from commercial recordable CDs for the detection and quantification of silver nanoparticles from a consumer product in a seawater sample. The "CDtrode" is immersed in a seawater sample containing silver nanoparticles for a certain amount of time during which the silver nanoparticles adsorb onto the CDtrode surface under open circuit conditions. The CDtrode is then transferred to an aqueous electrolyte and oxidative stripping is used to determine the amount of silver nanoparticles that have become stuck to the electrode surface. Depending on immersion time and silver nanoparticle concentration, up to a full monolayer coverage of silver nanoparticles on the CDtrode surface has been achieved. © 2014 Elsevier B.V.

Quantum Confined Stark Effect in hybrid of CdTe quantum dot with superparamagnetic iron oxide nanoparticles in both nonporous and mesoporous silica matrix has been realized. The observed QCSE is due to the local electric field induced by charge dispersion at SiO2/polar solvent interface. Enhanced Stark shift of 89.5 meV is observed in case of mesoporous hybrid structure and the corresponding local electric field has been evaluated as 4.38×104 V/cm. The enhancement is assumed to be caused by greater density of charge in the mesoporous hybrid. The conjugation of superparamagnetic nanoparticles in this tailored hybrid microstructure has not imparted any alteration to the Stark shift, but has added multifunctional attribute. The present study on the local electric field induced enhanced QCSE with wavelength modulation towards red end paves the way of developing magneto-fluorescent hybrid systems for biomedical imaging application. © 2014 Elsevier Ltd.

The catalytic performance of a Ni/MgAlOx catalyst was investigated in the high temperature CO2 reforming of CH4. The catalyst was developed using a Ni, Mg, Al hydrotalcite-like precursor obtained by co-precipitation. Despite the high Ni loading of 55 wt%, the synthesized Ni/MgAlOx catalyst possessed a thermally stable microstructure up to 900 °C with Ni nanoparticles of 9 nm. This stability is attributed to the embedding nature of the oxide matrix, and allows increasing the reaction temperature without losing active Ni surface area. To evaluate the effect of the reaction temperature on the reforming performance and the coking behavior, two different reaction temperatures (800 and 900 °C) were investigated. At both temperatures the prepared catalyst showed high rates of CH4 consumption. The higher temperature promotes the stability of the catalyst performance due to mitigation of the carbon formation. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The interaction between citrate capped silver nanoparticles and two different thiols, mercaptohexanol (MH) and cysteine, was investigated. The thiols interacted with silver nanoparticles in a significantly contrasting manner. With MH, a sparingly soluble silver(I) thiolate complex AgSRm (Rm = -(CH2)6OH) was formed on the silver nanoparticle surface. Cyclic voltammograms and UV-vis spectra were used to infer that the AgSRm complex on the nanoparticle surface undergoes a phase transition to give a mixture of AgSRm and Ag2S-like complexes. In contrast, when silver nanoparticles were exposed to cysteine, the citrate capping agent on the silver nanoparticles was replaced by cysteine to give cysteine capped nanoparticles. As cysteine capped nanoparticles form, the electrochemical data displayed a decrease in oxidative peak charge but the UV-vis spectra showed a constant signal. Therefore, cysteine capped nanoparticles were suggested to have either inactivated the silver surface or else promoted detachment from the electrode surface. © 2014 Science China Press and Springer-Verlag Berlin Heidelberg.

Silver ions and silver nanoparticles have a well-known biological effect that typically occurs in biological or environmental media of complex composition. Silver nanoparticles release silver ions if oxidizing species like molecular oxygen or hydrogen peroxide are present. The presence of glucose as a model for reducing sugars has only a small effect on the dissolution rate. In the presence of chloride ions, precipitation of silver chloride nanoparticles occurs. At physiological salt concentrations, no precipitation of silver phosphate occurs as the precipitation of silver chloride always occurs first. If the surface of a silver nanoparticle is passivated by cysteine, the dissolution is quantitatively inhibited. Upon immersion of silver nanoparticles in pure water for 8 months, leading to about 50% dissolution, no change in the surface was observed by transmission electron microscopy. A model for the dissolution was derived from immersion and dissolution experiments in different media and from high-resolution transmission electron microscopy. A literature survey on the available data on the dissolution of silver nanoparticles showed that only qualitative trends can be identified as the nature of the nanoparticles and of the immersion medium are practically never comparable. The dissolution effects were confirmed by cell culture experiments (human mesenchymal stem cells and neutrophil granulocytes) where silver nanoparticles that were stored under argon had a clearly lower cytotoxicity than those stored under air. They also led to a less formation of reactive oxygen species (ROS). This underscores that silver ions are the toxic species. © The Royal Society of Chemistry 2014.

The efficiency of polymer electrolyte membrane fuel cells is strongly depending on the electrocatalyst performance, that is, its activity and stability. We have designed a catalyst material that combines both, the high activity for the decisive cathodic oxygen reduction reaction associated with nanoscale Pt alloys, and the excellent durability of an advanced nano-structured support. Owing to the high specific activity and large active surface area, the catalyst shows extraordinary mass activity values of 1.0 AmgPt -1. Moreover, the material retains its initial active surface area and intrinsic activity during an extended accelerated aging test within the typical operation range. This excellent performance is achieved by confined space alloying of the nanoparticles in a controlled manner in the pores of the support. © 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Materials libraries of binary alloy nanoparticles (NPs) are synthesized by combinatorial co-sputter deposition of Cu and Au into the ionic liquid (IL) 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([C 1C4im][Tf2N]), which is contained in a micromachined cavity array substrate. The resulting NPs and NP-suspensions are investigated by transmission electron microscopy (TEM), X-ray diffraction (XRD), UV-Vis measurements (UV-Vis), and attenuated total reflection Fourier transformed infrared (ATR-FTIR) spectroscopy. Whereas the NPs can be directly observed in the IL using TEM, for XRD measurements the NP concentration is too low to lead to satisfactory results. Thus, a new NP isolation process involving capping agents is developed which enables separation of NPs from the IL without changing their size, morphology, composition, and state of aggregation. The results of the NP characterization show that next to the unary Cu and Au NPs, both stoichiometric and non-stoichiometric Cu-Au NPs smaller than 7 nm can be readily obtained. Whereas the size and shape of the alloy NPs change with alloy composition, for a fixed composition the NPs have a small size distribution. The measured lattice constants of all capped NPs show unexpected increased values, which could be related to the NP/surfactant interactions. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Insufficient electrochemical stability is a major challenge for carbon materials in oxygen reduction reaction (ORR) due to carbon corrosion and insufficient metal-support interactions. In this work, titania is explored as an alternative support for Pt catalysts. Oxygen deficient titania samples including TiO2-x and TiO2-xNy were obtained by thermal treatment of anatase TiO2 under flowing H2 and NH3, respectively. Pt nanoparticles were deposited on the titania by a modified ethylene glycol method. The samples were characterized by N2-physisorption, X-ray diffraction and X-ray photoelectron spectroscopy. The ORR activity and long-term stability of supported Pt catalysts were evaluated using linear sweep voltammetry and chronoamperometry in 0.1 mol/L HClO4. Pt/TiO2-x and Pt/TiO2-xNy showed higher ORR activities than Pt/TiO2 as indicated by higher onset potentials. Oxygen deficiency in TiO2-x and TiO2-xNy contributed to the high ORR activity due to enhanced charge transfer, as disclosed by electrochemical impedance spectroscopy studies. Electrochemical stability studies revealed that Pt/TiO2-x exhibited a higher stability with a lower current decay rate than commercial Pt/C, which can be attributed to the stable oxide support and strong interaction between Pt nanoparticles and the oxygen-deficient TiO2-x support. © 2014 Dalian Institute of Chemical Physics, the Chinese Academy of Sciences. Published by Elsevier B.V. All rights reserved.

Gaining experimental insight into the intrinsic properties of nanoparticles (NPs) represents a scientific challenge due to the difficulty of deconvoluting these properties from various environmental effects such as the presence of adsorbates or a support. A synergistic combination of experimental and theoretical tools, including X-ray absorption fine-structure spectroscopy, scanning transmission electron microscopy, atomic force microscopy, and density functional theory was used in this study to investigate the structure and electronic properties of small (∼1-4 nm) Au NPs synthesized by an inverse micelle encapsulation method. Metallic Au NPs encapsulated by polystyrene 2-vinylpiridine (PS-P2VP) were studied in the solution phase (dispersed in toluene) as well as after deposition on γ-Al2O3. Our experimental data revealed a size-dependent contraction of the interatomic distances of the ligand-protected NPs with decreasing NP size. These findings are in good agreement with the results from DFT calculations of unsupported Au NPs surrounded by P2VP, as well as those obtained for pure (ligand-free) Au clusters of analogous sizes. A comparison of the experimental and theoretical results supports the conclusion that the P2VP ligands employed to stabilize the gold NPs do not lead to strong distortions in the average interatomic spacing. The changes in the electronic structure of the Au-P2VP NPs were found to originate mainly from finite size effects and not from charge transfer between the NPs and their environment (e.g., Au-ligand interactions). In addition, the isolated ligand-protected experimental NPs only display a weak interaction with the support, making them an ideal model system for the investigation of size-dependent physical and chemical properties of structurally well-defined nanomaterials. © 2014 American Chemical Society.

The application of naive Koutecky-Levich analysis to micro- and nano-particle modified rotating disk electrodes of partially covered and non-planar geometry is critically analysed. Assuming strong overlap of the diffusion fields of the particles such that transport to the entire surface is time-independent and one-dimensional, the observed voltammetric response reflects an apparent electrochemical rate constant kapp o, equal to the true rate constant k o describing the redox reaction of interest on the surface of the nanoparticles and the ratio, ψ, of the total electroactive surface area to the geometric area of the rotating disk surface. It is demonstrated that Koutecky-Levich analysis is applicable and yields the expected plots of I -1 versus ω -1 where I is the current and ω is the rotation speed but that the values of the electrochemical rate constants inferred are thereof kapp o, not k o. Thus, for ψ > 1 apparent electrocatalysis might be naively but wrongly inferred whereas for ψ < 1 the deduced electrochemical rate constant will be less than k o. Moreover, the effect of ψ on the observed rotating disk electrode voltammograms is significant, signalling the need for care in the overly simplistic application of Koutecky-Levich analysis to modified rotating electrodes, as is commonly applied for example in the analysis of possible oxygen reduction catalysts. [Figure not available: see fulltext.] © 2014 Tsinghua University Press and Springer-Verlag Berlin Heidelberg.

Electrochemical impact experiments can be used to detect and size single nanoparticles in suspension and at low concentrations. This is generally performed using a micro-disc working electrode; however, for the first time we report the use of cylindrical micro-wire electrodes for nanoparticle impact experiments. These electrodes provide much enhanced detection limits; specifically decreasing the concentration of nanoparticles measurable by over two orders of magnitude. In addition, the use of micro-wire electrodes reduces the shielding effect due to absorption of particles to the insulating sheath that surrounds a micro-disc electrode. Micro-wire electrodes are fabricated and their electrochemical response analysed via cyclic voltammetry experiments using molecular species. This provides a theoretical framework which is used to calculate the reduced concentration of nanoparticles required for an impact experiment at a micro-cylinder electrode in comparison to the micro-disc. Experimentally, it is demonstrated that impact experiments on the micro-cylinder electrodes can indeed be used for accurate characterisation of ultra-low concentrations (≈0.1 pM) of silver nanoparticles. © 2014 Elsevier B.V.

Metal-organic frameworks are promising materials for manifold applications. This Minireview highlights approaches for the fine-tuning of specific sorption properties (e.g. capacity, selectivity, and breathing behavior) of this interesting class of materials. Central aspects covered are the control over the crystal morphology, the targeted tuning of sorption properties by judicious choice of metal centers and linkers, and the preparation of host-guest systems. We want to introduce the reader to these topics on the basis of the manipulation of a handful of outstanding prototypical metal-organic frameworks. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The electron transfer kinetics associated with both the reduction of oxygen and of protons to form hydrogen at gold nanoparticles are shown to display strong retardation when studied at citrate capped ultra small (2 nm) gold nanoparticles. Negative nanocatalysis in the hydrogen evolution reaction (HER) is reported for the first time. This journal is © the Partner Organisations 2014.

The structure and chemical state of size-selected Pt nanoparticles (NPs) supported on γ-Al2O3 were studied during the oxidation of NO using X-ray absorption near-edge spectroscopy and extended X-ray absorption fine-structure spectroscopy measurements under operando conditions. The data revealed the formation of PtOx species in the course of the reaction that remained present at the maximum temperature studied, 350 °C. The PtOx species were found in all samples, but those with the smallest NPs showed the highest degree of oxidation. Moreover, NO-induced nanoparticle redispersion was observed at temperatures below 150 °C for all catalysts studied. Catalytic tests showed activity toward the oxidation of NO for all samples. Nevertheless, the catalyst with the smallest NPs was found to be the least active, which is explained by a more extensive formation of PtOx species in this catalyst and their detrimental contribution to the oxidation of NO. © 2014 American Chemical Society.

Colloid-based chemical synthesis methods of bimetallic alloy nanoparticles (NPs) provide good monodispersity, yet generally show a strong variation of the resulting mean particle size with alloy composition. This severely compromises accurate correlation between composition of alloy particles and their size-dependent properties. To address this issue, a general CO adsorption-assisted capping ligand-free solvothermal synthesis method is reported which provides homogeneous bimetallic NPs with almost perfectly constant particle size over an unusually wide compositional range. Using Pt-Ni alloy NPs as an example, we show that variation of the reaction temperature between 160 and 240 °C allows for precise control of the resulting alloy particle bulk composition between 15 and 70 atomic % Ni, coupled with a constant mean particle size of ∼4 nm. The size-confining and Ni content-controlling role of CO during the nucleation and growth processes are investigated and discussed. Data suggest that size-dependent CO surface chemisorption and reversible Ni-carbonyl formation are key factors for the achievement of a constant particle size and temperature-controlled Ni content. To demonstrate the usefulness of the independent control of size and composition, size-deconvoluted relations between composition and electrocatalytic properties are established. Refining earlier reports, we uncover intrinsic monotonic relations between catalytic activity and initial Ni content, as expected from theoretical considerations. © 2014 American Chemical Society.

NiTi was investigated as a model system for a binary alloy where the properties strongly depend on the relative proportion of the two elements and on the grain size. The NiTi nanoparticles were generated by laser ablation in water. For the analysis of the particle size distribution, we used transmission electron microscopy and dynamic light scattering. Here, we found a broad particle size distribution (10-200 nm). Furthermore, the temperature-resolved x-ray powder diffraction and differential scanning calorimetry (DSC) were used to evaluate the phase transition behavior of the generated NiTi nanoparticles. Here, we found an interesting effect. During the heating by DSC, an austenite phase transition and a weak martensite phase transition in the NiTi nanoparticles appeared. Moreover, the phase transformation temperature was about 40 K lower than that of the bulk target. © 2014 ASM International.

Citrate-capped gold nanoparticles (AuNPs) of 5 nm in diameter are synthesized via wet chemistry and deposited on a glassy carbon electrode through electrophoresis. The kinetics of the oxygen reduction reaction (ORR) on the modified electrode is determined quantitatively in oxygen-saturated 0.5 M sulphuric acid solution by modelling the cathode as an array of interactive nanoelectrodes. Quantitative analysis of the cyclic voltammetry shows that no apparent ORR electrocatalysis takes place, the kinetics on AuNPs being effectively the same as on bulk gold. Contrasting with the above, a strong ORR catalysis is found when Pb2+ is added to the oxygen saturated solution or when the modified electrode is cycled in lead alkaline solution such that lead dioxide is repeatedly electrodeposited and stripped off on the nanoparticles. In both cases, the underpotential deposition of lead on the gold nanoparticles is found to be related to the catalysis. This journal is © the Owner Societies 2014.

Reversible interconversion of water into H2 and O2, and the recombination of H2 and O2 to H2O thereby harnessing the energy of the reaction provides a completely green cycle for sustainable energy conversion and storage. The realization of this goal is however hampered by the lack of efficient catalysts for water splitting and oxygen reduction. We report exceptionally active bifunctional catalysts for oxygen electrodes comprising Mn3O4 and Co 3O4 nanoparticles embedded in nitrogen-doped carbon, obtained by selective pyrolysis and subsequent mild calcination of manganese and cobalt N4 macrocyclic complexes. Intimate interaction was observed between the metals and nitrogen suggesting residual M-Nx coordination in the catalysts. The catalysts afford remarkably lower reversible overpotentials in KOH (0.1M) than those for RuO2, IrO2, Pt, NiO, Mn3O4, and Co3O4, thus placing them among the best non-precious-metal catalysts for reversible oxygen electrodes reported to date. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Experimental data on detection and identification of variety of biochemical agents, such as proteins, microelements, antibiotic of different generation etc. in both single and multi component solutions under varied in wide range concentration analyzed on the light scattering parameters of whispering gallery mode optical resonance based sensor are represented. Multiplexing on parameters and components has been realized using developed fluidic sensor cell with fixed in adhesive layer dielectric microspheres and data processing. Biochemical component identification has been performed by developed network analysis techniques. Developed approach is demonstrated to be applicable both for single agent and for multi component biochemical analysis. Novel technique based on optical resonance on microring structures, plasmon resonance and identification tools has been developed. To improve a sensitivity of microring structures microspheres fixed by adhesive had been treated previously by gold nanoparticle solution. Another technique used thin film gold layers deposited on the substrate below adhesive. Both biomolecule and nanoparticle injections caused considerable changes of optical resonance spectra. Plasmonic gold layers under optimized thickness also improve parameters of optical resonance spectra. Biochemical component identification has been also performed by developed network analysis techniques both for single and for multi component solution. So advantages of plasmon enhancing optical microcavity resonance with multiparameter identification tools is used for development of a new platform for ultra sensitive label-free biomedical sensor. © 2014 SPIE.

This perspective summarises four different electrochemical techniques that have been established and frequently used to characterize various properties of silver nanoparticles. These are based on drop casting (I), in situ nanoparticle sticking and stripping (II), transfer sticking and stripping (III) or nanoparticle impacts (IV). The specific characteristics of the different methodologies are explained and contrasted with each other with the focus being on the respective benefits and limitations together with essential insights for experimentalists. © 2014 the Owner Societies.

We report the controllable synthesis of Pd aerogels with high surface area and porosity by destabilizing colloidal solutions of Pd nanoparticles with variable concentrations of calcium ions. Enzyme electrodes based on Pd aerogels co-immobilized with glucose oxidase show high activity toward glucose oxidation and are promising materials for applications in bioelectronics. © 2014 American Chemical Society.

The present work reveals the structural and magnetic properties of iron oxide (FexOy) nanoparticles (NPs) prepared by femtosecond laser ablation. The FexOy-NPs were produced in solutions consisting of different ratios of water and acetone. Laser ablation in water yields agglomerates and that in acetone yields chain structures whereas that in water/acetone show a mixture of both. We observe significant fabrication dependent properties such as different crystallinities and magnetic behaviors. The structural characterization shows a change from iron (Fe) to a Fe xOy state of the NPs which depends on the solution composition. Furthermore, transmission electron microscopy measurements exhibit a broad particle size distribution in all samples but with significant differences in the mean sizes. Using magnetic measurements we show that nanoparticles fabricated in pure acetone have lower coercive fields which come along with a smaller mean particle size and therefore increasing superparamagnetic behavior. © 2014 SPIE.

PVP-capped silver nanoparticles with a diameter of the metallic core of 70 nm, a hydrodynamic diameter of 120 nm and a zeta potential of -20 mV were prepared and investigated with regard to their biological activity. This review summarizes the physicochemical properties (dissolution, protein adsorption, dispersability) of these nanoparticles and the cellular consequences of the exposure of a broad range of biological test systems to this defined type of silver nanoparticles. Silver nanoparticles dissolve in water in the presence of oxygen. In addition, in biological media (i.e., in the presence of proteins) the surface of silver nanoparticles is rapidly coated by a protein corona that influences their physicochemical and biological properties including cellular uptake. Silver nanoparticles are taken up by cell-type specific endocytosis pathways as demonstrated for hMSC, primary T-cells, primary monocytes, and astrocytes. A visualization of particles inside cells is possible by X-ray microscopy, fluorescence microscopy, and combined FIB/SEM analysis. By staining organelles, their localization inside the cell can be additionally determined. While primary brain astrocytes are shown to be fairly tolerant toward silver nanoparticles, silver nanoparticles induce the formation of DNA double-strand-breaks (DSB) and lead to chromosomal aberrations and sister-chromatid exchanges in Chinese hamster fibroblast cell lines (CHO9, K1, V79B). An exposure of rats to silver nanoparticles in vivo induced a moderate pulmonary toxicity, however, only at rather high concentrations. The same was found in precision-cut lung slices of rats in which silver nanoparticles remained mainly at the tissue surface. In a human 3D triple-cell culture model consisting of three cell types (alveolar epithelial cells, macrophages, and dendritic cells), adverse effects were also only found at high silver concentrations. The silver ions that are released from silver nanoparticles may be harmful to skin with disrupted barrier (e.g., wounds) and induce oxidative stress in skin cells (HaCaT). In conclusion, the data obtained on the effects of this well-defined type of silver nanoparticles on various biological systems clearly demonstrate that cell-type specific properties as well as experimental conditions determine the biocompatibility of and the cellular responses to an exposure with silver nanoparticles. © 2014 Ahlberg et al.

Anodic stripping voltammetry is a much-utilised method for trace metal analysis. We provide a simple proof-of-concept technique to improve the sensitivity of the method, which is illustrated by the detection of silver cations. This approach requires an electrode pre-treatment, which involves drop casting a metal nanoparticle suspension and oxidising the nanoparticles, leaving small metal nuclei on the electrode surface. In turn, the small metal nuclei act as nucleation sites for subsequent metal deposition when used to interrogate target solutions. In particular, the pre-treatment increases the amount of deposited metal in a given amount of time. Silver nitrate concentrations from 30 nM to 1 μM were tested and at silver ion concentration of 300 nM, the pre-treated electrode gave a signal, which was 40 times larger than the untreated electrode. The larger signal leads to the enhancement of sensitivity and a lowering of the detection limit of anodic stripping voltammetry without introducing other organic molecules, metals or impurities. © 2013 Elsevier B.V.

Typical urinary iodide concentrations range from 0.3 μM to 6.0 μM. The conventional analytical method is based on the Sandell-Kolthoff reaction. It involves the toxic reagent, arsenic acid, and a waiting time of 30 minutes for the iodide ions to reduce the cerium(iv) ions. In the presented work, an alternative fast electrochemical method based on a silver nanoparticle modified electrode is proposed. Cyclic voltammetry was performed with a freshly modified electrode in presence of iodide ions and the voltammetric peaks corresponding to the oxidation of silver to silver iodide and the reverse reaction were recorded. The peak height of the reduction signal of silver iodide was used to plot a calibration line for the iodide ions. Two calibration plots for the iodide ions were obtained, one in 0.1 M sodium nitrate (a chloride-ion free environment to circumvent any interference from the other halides) and another in synthetic urine (which contains 0.2 M KCl). In both of the calibration plots, linear relationships were found between the reduction peak height and the iodide ion concentration of 0.3 μM to 6.0 μM. A slope of 1.46 × 10-2 A M-1 and a R2 value of 0.999 were obtained for the iodide detection in sodium nitrate. For the synthetic urine experiments, a slope of 3.58 × 10-3 A M-1 and a R2 value of 0.942 were measured. A robust iodide sensor with the potential to be developed into a point-of-care system has been validated. This journal is © the Partner Organisations 2014.

Nanostructured, porous metals are of great interest for material scientists since they combine high surface area, gas permeability, electrical conductivity, plasmonic behavior, and size-enhanced catalytic reactivity. Here we present the formation of multimetallic porous three-dimensional networks by a template-free self-assembly process. Nanochains are formed by the controlled coalescence of Au, Ag, Pt, and Pd nanoparticles in aqueous media, and their interconnection and interpenetration leads to the formation of a self-supporting network. The resulting noble-metal-gels are transformed into solid aerogels by the supercritical drying technique. Compared to previously reported results, the technique is facilitated by exclusion of additional destabilizers. Moreover, temperature control is demonstrated as a powerful tool, allowing acceleration of the gelation process as well as improvement of its reproducibility and applicability. Electron microscopy shows the nanostructuring of the network and its high porosity. XRD and EDX STEM are used to investigate the alloying behavior of the bimetallic aerogels and prove the control of the alloying state by temperature induced phase modifications. Furthermore, the resulting multimetallic aerogels show an extremely low relative density (<0.2%) and a very high surface area (>50 m2/g) compared to porous noble metals obtained by other approaches. Electrically conductive thin films as well as hybrid materials with organic polymers are depicted to underline the processability of the materials, which is a key factor regarding handling of the fragile structures and integration into device architectures. Owing to their exceptional and tunable properties, multimetallic aerogels are very promising materials for applications in heterogeneous catalysis and electrocatalysis, hydrogen storage, and sensor systems but also in surface enhanced Raman spectroscopy (SERS) and the preparation of transparent conductive substrates. © 2013 American Chemical Society.

Individual fullerene nanoparticles are detected and sized in a non-aqueous solution via cathodic particle coulometry where the direct, quantitative reduction of single nanoparticles is achieved upon collision with a potentiostated gold electrode. This is the first time that the nanoparticle impact technique has been shown to work in a non-aqueous electrolyte and utilized to coulometrically size carbonaceous nanoparticles. Contrast is drawn between single-nanoparticle electrochemistry and that seen using nanoparticle ensembles via modified electrodes. © 2014 American Chemical Society.

The interaction between the vapor plume and the incident laser radiation affects remote laser welding. Relating to laser systems with an emitted wavelength around 1 μm, a significant loss mechanism can be traced back to the extinction by laser-induced particle formation. Due to the tight coupling between the particle formation and the evaporation rate inside the keyhole, the particle formation shows a strong dependence on the keyhole geometry and thus on process parameters (e.g. feed rate and laser beam power). In order to verify the relationship between particle formation and process parameters, the beam of a broadband LED was guided through the vapor plume during the welding processes with a fiber laser. The attenuated probe beam was analyzed in dependence on the wavelength. In addition, the propagation of the vapor plume was investigated by using high speed imaging. © 2014 The Authors. Published by Elsevier B.V.

The photocatalytic reduction of CO2 by water vapor to produce light hydrocarbons was studied over a series of catalysts consisting of variable loading of Ti incorporated in TUD-1 mesoporous silica, either modified by ZnO nanoparticles or isolated Cr-sites. Unexpectedly, the performance of ZnO-Ti-TUD-1 and Cr-Ti-TUD-1 was inferior to the parent Ti-TUD-1. An explanation can be found in experiments on the photocatalytic degradation of a mixture of hydrocarbons (i.e., CH4, C2H4, C 2H6, C3H6, and C3H 8) under the same illumination conditions. Ti-TUD-1 exhibits the poorest activity in hydrocarbon degradation, while ZnO-Ti-TUD-1 and Cr-Ti-TUD-1 showed very significant degradation rates. This study clearly demonstrates the importance of evaluating hydrocarbon conversion over photocatalysts active in converting CO2 to hydrocarbons (in batch reactors). © 2013 American Chemical Society.

The notorious instability of non-precious-metal catalysts for oxygen reduction and evolution is by far the single unresolved impediment for their practical applications. We have designed highly stable and active bifunctional catalysts for reversible oxygen electrodes by oxidative thermal scission, where we concurrently rupture nitrogen-doped carbon nanotubes and oxidize Co and Mn nanoparticles buried inside them to form spinel Mn-Co oxide nanoparticles partially embedded in the nanotubes. Impressively high dual activity for oxygen reduction and evolution is achieved using these catalysts, surpassing those of Pt/C, RuO2, and IrO2 and thus raising the prospect of functional low-cost, non-precious-metal bifunctional catalysts in metal-air batteries and reversible fuel cells, among others, for a sustainable and green energy future. © 2014 American Chemical Society.

We report the detection and characterisation of polymer nanoparticles using electrochemistry using poly(N-vinylcarbazole) nanoparticles (PVK NPs) as a model system. These were synthesised using the reprecipitation method. The number of electrons (n=2) transferred per PVK monomer was characterised by drop-casting method. Sticking and sensing experiments were then conducted, which involve PVK nanoparticle immobilisation on the electrode surface and subsequent oxidative sensing, to enable rapid detection of polymer nanoparticles in aqueous solution. It is shown for the first time, that using this "stick and sense" method, polymer nanoparticles in aqueous solution can be immobilised, preconcentrated and quantified. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Understanding the interaction of hydrogen with subnanometer platinum nanoparticles (NPs) under industrially relevant conditions is of great importance to heterogeneous catalysis. In this work, we investigate the pressure-dependent changes in hydrogen coverage on size- and shape-selected Pt/γ-Al2O3 NPs by in situ X-ray absorption near-edge structure (XANES) analysis. Difference XANES calculations revealed an increase in the H/Pt ratio from 1.9 to 2.5 upon increasing the hydrogen pressure from 1 to 21 bar at room temperature (1 bar=100 kPa). In addition, extended X-ray absorption fine structure measurements of the local geometrical structure showed changes in Pt - Pt bond length and coordination number, revealing a morphological transformation in the NPs from a 2 D to a 3 D shape under increasing H2 pressure at room temperature. Such shape evolution leads to a decrease in the NP-support contact area and is thus expected to affect the NP stability against coarsening. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

We describe a solid polyphenylene support that serves as an excellent platform for metal-catalyzed reactions that are normally carried out under homogeneous conditions. The catalyst is synthesized by palladium-catalyzed Suzuki coupling which directly results in formation of palladium nanoparticles confined to a porous polyphenylene network. The composite solid is in turn highly active for further Suzuki coupling reactions, including non-activated substrates that are challenging even for molecular catalysts. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The oxidation of AgNPs at a thin-film gold electrode is simultaneously investigated via digital holography and electrochemistry. The use of holography allows, for the first time, the 3D visualization of the electrochemical interfacial region at a relatively high acquisition rate. It is demonstrated how the coupling of these two techniques provides complementary chemical information. The ensemble response of the oxidation of surface-adsorbed silver nanoparticles to AgCl is monitored electrochemically, whereas this process is difficult to observe optically. Conversely, the subsequent chemical dissolution of individual AgCl nanocrystals can be tracked optically due to the associated decrease in the scattered light intensity. © 2014 Elsevier B.V. All rights reserved.

This study illustrates the effect of nanoparticle (NP) shape on the reactivity of size-selected Pt/γ-Al2O3 nanocatalysts for 2-butanol oxidation. Nanoparticles similar in size [transmission electron microscopy (TEM) diameter of ∼1 nm] but with different shapes were prepared via encapsulation in inverse micelles. The NP shape was resolved by combining information extracted from extended X-ray absorption fine structure spectroscopy (EXAFS) data, TEM, and modeling. A correlation was observed between the average first nearest neighbor coordination number of atoms at the NP surface and their catalytic activity. In particular, the NPs with the largest number of weakly coordinated surface atoms (i.e., edges and corners) were found to be the least active for the total oxidation of 2-butanol. This result highlights that not only size but also shape control must be achieved to tailor the catalytic properties of nanoscale materials. © 2013 American Chemical Society.

Hydrogenation of CO2 to hydrocarbons over iron nanoparticles supported on oxygen-functionalized multi-walled carbon nanotubes was studied in a fixed-bed U-tube reactor at 25 bar with a H2:CO2 ratio of 3. Conversion of CO2 was approximately 35% yielding C 1-C5 products at 360°C with methane and CO as major products. The CO2 equilibrium conversion for temperatures in the range of 320° to 420°C was analysed by using CHEMCAD simulation software. Comparison between experimental and simulated degrees of CO 2 conversion shows that reverse water gas shift equilibrium had been achieved in the investigated temperature range and that less than 47% of CO 2 can be converted to CO at 420°C. © 2014 Indian Academy of Sciences.

The type and the amount of functional groups on the surface of carbon nanotubes (CNTs) were tuned to improve the activity of supported Co nanoparticles in hydrogenation catalysis. Surface nitrogen species on CNTs significantly promoted the decomposition of the cobalt precursor and the reduction of cobalt oxide, and improved the resistance of metallic Co against oxidation in ambient atmosphere. In the selective hydrogenation of nitrobenzene in the gas phase, Co supported on CNTs with the highest surface nitrogen content showed the highest activity, which is ascribed to the higher reducibility and the lower oxidation state of the Co nanoparticles under reaction conditions. For Co nanoparticles supported on CNTs with a smaller amount of surface nitrogen groups, a repeated reduction at 350 °C was essential to achieve a comparable high catalytic activity reaching 90% conversion at 250 °C, pointing to the importance of nitrogen species for the supported Co nanoparticles in nitrobenzene hydrogenation. © 2014 American Chemical Society.

Atom probe tomography (APT) has been used to characterize commercially prepared Pt, Pt/Co alloy, and Ir@Pt core-shell nanoparticles supported on high-surface-area carbon black. Concentration profiles and 3D atom maps revealing the detailed internal structures and compositions of Pt, Pt/Co alloy, and Ir@Pt core-shell particles have been generated, and the distribution of trace impurity elements, including Na and Cl, has been examined. The observation of retained Na on the support, especially in the Pt nanoparticle system, indicates a more rigorous washing procedure is required. In the Pt/Co alloyed carbon-supported nanoparticle system, a marked variation in both compositions and particle sizes is observed. In the case of Ir@Pt, significant intermixing of the Ir core and Pt shell atoms takes place, which would be very difficult to measure by other techniques. All such observations will likely impact the catalytic performance of these materials. We envisage that the single nanoparticle analysis capability of APT, providing atomic-scale structures and chemical mapping, can also act as a means of quality control, identifying differences in the final product compared with the intended specification. Although the catalytic activity of these nanoparticles was not part of current study, the detailed information offered by such studies will permit knowledge-based improvements in nanoscale catalyst preparation methods and will also provide new ways of investigating structure and activity relationships at the nanometer scale. © 2014 American Chemical Society.

The kinetics of the proton reduction reaction is studied on a variety of gold surfaces including both macro (r0 = 1.0 mm) and micro (r 0 = 4.6 μm) electrodes, as well as gold nanoparticles (r NP = ∼10 nm). For the gold nanoparticles, two complementary methodologies of study are used. First the particles are investigated as part of an ensemble response in an array (k0 ∼ 7 × 10-8 m s-1). Second, the rate is recorded stochastically at individually impacting nanoparticles (k0 ∼2 × 10-9 m s -1). This apparent decrease in reaction rates on transitioning from the ensemble to individual nanoparticles is understood in terms of the differing connectivity of the nanoparticles to the electrode surface. During the course of the individual catalytic impacts, or "pulses", the recorded current is found to be highly variable; this variability is interpreted as originating from the nanoscopic motion of the particle above the electrode interface. © 2014 American Chemical Society.

The electrochemical detection of organic capped CdSe nanoparticles is achieved down to the highly dilute concentration of 15 pM. Herein, electrode modification is undertaken either via a simple and fast adsorption methodology, or by direct dropcasting of the material. Importantly, the adsorption of the CdSe nanoparticles is evidenced at higher surface coverages by the direct measurement of the cadmium reduction signal. A lower analytical detection limit for the CdSe nanoparticles is enabled by the enhancement of the diffusional borax reduction signal on a gold electrode modified with the quantum dots. The presence of a non-electroactive layer on an electrode has been shown to alter the apparent electrochemical rate constant via modifying the solubility and mass-transport of an electroactive species adjacent to the electrochemical interface. In the present case the origin of the enhanced rate of reduction for borax is ascribed as being due to the presence of the non-electroactive organic capping agent. Hence, due to the ubiquitous nature of capping agents within the field of nano-chemistry, the methodology represents a facile and generally applicable detection route. © 2014 Elsevier B.V.

Laser remote processing is used in a wide field of industrial applications. Among other things, it is characterized by flexible beam guidance in combination with high processing velocities. But in most cases process gas support in the interaction zone is omitted. Consequently, interaction mechanism between the vapor plume and the incident laser radiation can dynamically affect the process stability. Referring to remote welding with high brilliant laser sources having a wavelength around 1 μm, the interaction between the incident laser radiation and formed particles plays an important role. The presented work shows results of the investigation of the laser-induced particle formation during the laser welding of stainless steel with a 2 kW fiber laser under remote conditions. It is therefore concentrated on the dynamical behavior of the laser-induced particle formation and the dependence of the particle formation on the laser beam power. TEM images of formed particles were analyzed. In addition, the radiation of a LED was directed through the vapor plume. On the one hand, the dynamic of the attenuation was considered. On the other hand, the Rayleigh approximation was used in order to evaluate the detected signals. © 2014 SPIE.

We theoretically and experimentally investigate the influence of partial surface blocking on the electrochemistry of nanoparticles impacting at an electrode. To this end, we introduce an analytical model for the adsorption of single blocking molecules on the electrode and calculate the resulting fractional electrode coverage. We find that even small amounts of adsorbed molecules can fully suppress detection of impacts of nanoparticles while the electrode characteristics in the detection of electroactive molecules hardly change. Our findings are supported by experimental data on the indigo nanoparticle electroreduction at a carbon microelectrode (radius 5.5μm) in aqueous solution. We find that nanoimpacts are fully suppressed in the presence of acetone at concentrations of 250nm, which have a negligible effect on the electrode kinetics of the Fe(CN)3-/4- 6 couple. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Superparamagnetic nanoparticles (NPs) are used in a variety of magnetic field-assisted chemical and medical applications, yet little of their fate during magnetic field interrogation is known. Here, fundamental and new insights in this are gained by cathodic particle coulometry. This methodology is used to study individual Fe3O4 NPs in the presence and absence of a magnetic field. It is first noticed that no major NP agglomeration occurs in the absence of a magnetic field even in a suspension of high ionic strength. In contrast, a significant magnetic field-induced agglomeration of NPs is observed in a magnetic field. A second new finding is that the dissolution of Fe 3O4 NPs is strongly inhibited in a magnetic field. This is explained as a result of the magnetic field gradient force trapping the released Fe2+ ions near the surface of a magnetized Fe 3O4 NP and thus hindering the mass-transport controlled NP dissolution. Consequently, fundamental magnetic field effects are measured and quantified on both the single NP scale and in suspension and two novel effects are discovered. This journal is © the Partner Organisations 2014.

The thermal and chemical stability of micelle-synthesized size-selected Pt nanoparticles (NPs) supported on thin SiO2 (20 nm) films was monitored in situ via transmission electron microscopy (TEM) under pure hydrogen and pure oxygen environments. The coarsening treatment was performed for 30 min at each temperature (1 Torr of either O2 or H2), while the TEM measurements were carried out at 1 Torr of H2 and 0.5 Torr of O2. Surprisingly, the NPs were found to be stable against sintering under both gaseous atmospheres up to 650 °C. Nevertheless, drastic sintering via diffusion-coalescence was observed upon annealing in H2 at 800 °C. In contrast, an identically prepared sample demonstrated lack of agglomeration at the same temperature under O2. The latter observation is ascribed to a strengthened chemical bond at the NP/support interface due to the formation of PtOx species at low temperature. Subsequently, oxidative NP redispersion-associated with some loss of Pt due to the formation of volatile PtOx species-is inferred from the behavior in O2 at/above 650 °C. In contrast, SiO2 reduction catalyzed by the presence of the Pt NPs and Pt silicide formation was found in H2 at 800 °C, which might play a role in the enhanced coarsening observed. Subsequent exposure of the PtSi NPs to oxygen led to the formation of Pt-SiO2 core-shell structures. Our findings highlight the dynamic structural transformations that nanoscale materials experience under different environments and the important role played by their initial size, size distribution and dispersion on their stability against sintering. © the Partner Organisations 2014.

Anatase TiO2 nanoparticles with a diameter of 5 nm have been investigated as a negative intercalation electrode material for Li-ion batteries. The focus was on the stability upon cycling within four different potential ranges, namely from 1.5, 1.2, 1.0 and 0.7 V vs. Li/Li+ as the lower potential limit to 3.0 V vs. Li/Li+ as the upper potential limit. While a lower cut-off potential allows for a higher amount of charge stored, the irreversible processes induce a faster fading of the specific charge. Galvanostatic cycling (GC), electrochemical impedance spectroscopy (EIS) and scanning electron microscopy (SEM) experiments suggest that SEI formation has a negligible contribution to the irreversible processes. It appears more plausible that an irreversible degradation of the bulk phase occurs, leading to a decrease in the amount of active sites. Moreover, it has been observed that this degradation appears as an anodic shift of the thermodynamic potential of (de-)intercalation of Li-ions in the TiO2 structure. The shift is caused by a change in the activity of Li-ions in the solid phase, which is driven by changes in the ionic atmosphere of the crystal. © 2014 the Partner Organisations.

We have investigated the behaviour of silver ions in biologically relevant concentrations (10 to 100 ppm) in different media, from physiological salt solution over phosphate-buffered saline solution to protein-containing cell culture media. The results show that the initially present silver ions are bound as silver chloride due to the presence of chloride. Only in the absence of chloride, glucose is able to reduce Ag+ to Ag0. The precipitation of silver phosphate was not observed in any case. We conclude that the predominant silver species in biological media is dispersed nanoscopic silver chloride, surrounded by a protein corona which prevents the growth of the crystals and leads to colloidal stabilization. Therefore, in cell culture experiments where dissolved silver ions are studied in the upper ppm range, in fact the effect of colloidally dispersed silver chloride is observed. We have confirmed this by cell culture experiments (human mesenchymal stem cells; T-cells; monocytes) and bacteria (S. aureus) where the cells were incubated with synthetically prepared silver chloride nanoparticles (diameter ca. 100 nm). These were easily taken up by eukaryotic cells and showed the same toxic effect at the same silver concentration as ionic silver (as silver acetate). Therefore, nanoscopic silver chloride and not free ionic silver is the primary toxic species in biological media. © 2014 the Partner Organisations.

Background: Silver nanoparticles (Ag-NP) are one of the fastest growing products in nano-medicine due to their enhanced antibacterial activity at the nanoscale level. In biomedicine, hundreds of products have been coated with Ag-NP. For example, various medical devices include silver, such as surgical instruments, bone implants and wound dressings. After the degradation of these materials, or depending on the coating technique, silver in nanoparticle or ion form can be released and may come into close contact with tissues and cells. Despite incorporation of Ag-NP as an antibacterial agent in different products, the toxicological and biological effects of silver in the human body after long-term and low-concentration exposure are not well understood. In the current study, we investigated the effects of both ionic and nanoparticulate silver on the differentiation of human mesenchymal stem cells (hMSCs) into adipogenic, osteogenic and chondrogenic lineages and on the secretion of the respective differentiation markers adiponectin, osteocalcin and aggrecan. Results: As shown through laser scanning microscopy, Ag-NP with a size of 80 nm (hydrodynamic diameter) were taken up into hMSCs as nanoparticulate material. After 24 h of incubation, these Ag-NP were mainly found in the endo-lysosomal cell compartment as agglomerated material. Cytotoxicity was observed for differentiated or undifferentiated hMSCs treated with high silver concentrations (≥20 μg·mL-1 Ag-NP; ≥1.5 μg·mL-1 Ag+ ions) but not with low-concentration treatments (≤10 μg·mL-1 Ag-NP; ≤1.0 μg·mL-1 Ag+ ions). Subtoxic concentrations of Ag-NP and Ag+ ions impaired the adipogenic and osteogenic differentiation of hMSCs in a concentration-dependent manner, whereas chondrogenic differentiation was unaffected after 21 d of incubation. In contrast to aggrecan, the inhibitory effect of adipogenic and osteogenic differentiation was confirmed by a decrease in the secretion of specific biomarkers, including adiponectin (adipocytes) and osteocalcin (osteoblasts). Conclusion: Aside from the well-studied antibacterial effect of silver, little is known about the influence of nano-silver on cell differentiation processes. Our results demonstrate that ionic or nanoparticulate silver attenuates the adipogenic and osteogenic differentiation of hMSCs even at non-toxic concentrations. Therefore, more studies are needed to investigate the effects of silver species on cells at low concentrations during long-term treatment. © 2014 Sengstock et al.

The synthesis of 2,5-dimethylfuran (DMF) from 5-hydroxymethylfurfural (HMF) is a highly attractive route to a renewable fuel. However, achieving high yields in this reaction is a substantial challenge. Here it is described how PtCo bimetallic nanoparticles with diameters of 3.6 ± 0.7 nm can solve this problem. Over PtCo catalysts the conversion of HMF was 100% within 10 min and the yield to DMF reached 98% after 2 h, which substantially exceeds the best results reported in the literature. Moreover, the synthetic method can be generalized to other bimetallic nanoparticles encapsulated in hollow carbon spheres. © 2014 Macmillan Publishers Limited.

An investigation of the thermal stability of size-selected Au nanoparticles (NPs) synthesized via inverse micelle encapsulation and deposited on SiO 2(4 nm)/Si(100) is presented. The size and mobility of individual Au NPs after annealing at elevated temperatures in ultrahigh vacuum (UHV) was monitored via atomic force microscopy (AFM). An enhanced thermal stability against coarsening and lack of NP mobility was observed up to 1343 K. In addition, a drastic decrease in the average NP height was detected with increasing annealing temperature, which was not accompanied by the sublimation of Au atoms/clusters in UHV. The apparent decrease in the Au NP height observed is assigned to their ability to dig vertical channels in the underlying SiO 2 support. More specifically, a progressive reduction in the thickness of the SiO2 support underneath and in the immediate vicinity of the NPs was evidenced, leading to NPs partially sinking into the SiO2 substrate. The complete removal of silicon oxide in small patches was observed to take place around the Au NPs after annealing at 1343 K in UHV. These results reveal a Au-assisted oxygen desorption from the support via reverse oxygen spillover to the NPs. © 2013 American Chemical Society.

Anodic particle coulometry (APC) is a recently established method of sizing individual metal nanoparticles by oxidising them during their impact on a micro electrode. Here it is demonstrated that the application of APC can be extended to sizing of metal oxide nanoparticles, such as Fe3O4 magnetite nanoparticles. Additionally, a new route to electrochemical nanoparticle sizing is introduced-cathodic particle coulometry (CPC). This method uses the reduction of impacting nanoparticles, e.g., metal oxide nanoparticles, and is demonstrated to yield correct size information for Fe3O4 nanoparticles. The combination of these two independent electrochemical methods of nanoparticle sizing, allows for purely electrochemical sizing of single nanoparticles and simultaneous verification of the obtained results. © 2013 Tsinghua University Press and Springer-Verlag Berlin Heidelberg.

Kinetic and mechanistic studies of the oxygen reduction reaction (ORR) in oxygen saturated 0.5 M sulfuric acid at 298 K at a gold macroelectrode and at an electrodeposited gold nanoparticle-modified glassy carbon electrode are reported. The conditions of electrodeposition are optimized to obtain small nanoparticles of diameter from 17 nm to 40 nm. The mechanism and kinetics of ORR on the gold macroelectrode are investigated and compared with those obtained for nanoparticle-modified electrodes. The mechanism for this system includes two electron and two proton transfers and hydrogen peroxide as the final product. The first electron transfer step corresponding to the reduction of O2 to O2 - is defined as the rate determining step. No significant changes are found for the nanoparticles here employed: electron transfer rate constant (k0) is k0,bulk = 0.30 cm s -1 on the bulk material and k0,nano = 0.21 cm s -1 on nanoparticles; transfer coefficient (α) changes from αbulk = 0.45 on macro-scale to αnano = 0.37 at the nano-scale. © The Royal Society of Chemistry 2013.

The rational design of nanocomposite structures with specific functions in energy storage applications is a key requisite to increase energy and power density in electrical storage systems. Nanoscale characterisation tools are essential to achieve controlled syntheses of such well-defined interface structures in order to reveal structure-property relationships in functional nanocomposites. In the following, we report on the synthesis of iron (hydr)oxide nanoparticles homogeneously embedded into the walls of the three dimensional carbon network of mesoporous carbon CMK-3 via a mild one-step redox functionalisation. Depth profile Auger electron spectroscopy (DP-AES) and energy filtered transmission electron microscopy (EF-TEM) are applied to analyse elemental distribution profiles and location of the active components. The combination of the two analytical techniques provides a highly resolved spatial distribution of transition metal (hydr)oxide nanoparticles inside the carbon network. Functionalised porous carbon nanocomposites were tested for supercapacitor applications and the highest energy density of an iron oxide carbon composite is demonstrated. The iron (hydr)oxide contributes with a pseudocapacitance of 357 F g-1 to the porous nanocomposite in a 6 M KOH electrolyte. An overall doubling of the specific capacitance of the active electrode material compared to the pristine CMK-3 is achieved. © The Royal Society of Chemistry 2013.

Gold catalysis: Experimental and theoretical data demonstrated consistently that the interfacial sites on a Au/TiO2 catalyst show both high reactivity and selectivity for low-temperature methanol oxidation with O 2 to give formaldehyde. The microscopic mechanism of this complex reaction has been unraveled in full molecular detail (see picture, gold cluster on TiO2 surface). Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Magnetite nanoparticles have been prepared by one-pot thermal decomposition process using iron (III) acetylacetonate in stearic acid in ambient environment. In this process, stearic acid acts as solvent as well as capping agent for the particles. These as-prepared hydrophobic magnetite nanoparticles have been converted into a hydrophilic form using tetramethylammonium hydroxide. This controlled surface functionalization approach limits microstructural and phase alteration due to the ligand exchange. A detailed investigation was carried out on the microstructural characteristics of these nanoparticles with the aid of X-ray diffraction, infrared spectroscopy, XPS and transmission electron microscopy. The hydrophilic superparamagnetic magnetite particles posses extraordinary transverse relaxivity and contrast property, making them potential T2 contrast agent in clinical magnetic resonance imaging. © 2013 Elsevier B.V.

A pure ZnO sample and a sample containing 3 mol% Al were prepared by (co)-precipitation as model materials for the oxidic support phase in Cu/ZnO/Al2O3 methanol synthesis catalysts. The samples were characterized with respect to their crystal, defect and micro-structure using various methods (XRD, TEM, XPS, UV-vis spectroscopy, EPR, NMR). It was found that a significant fraction of the Al is incorporated into the ZnO lattice and enhances the defect chemistry of the material. The defect structure, however, was not stable under reducing conditions as applied in catalytic reactions. Al ions migrated towards the surface of the ZnO nanoparticles leading to formation of an Al-rich shell and an Al-depleted core. This process proceeds during the first 10-20 hours on stream and is associated with strong modification of the optical bandgap energy and the EPR signal of donor sites present in ZnO. © 2013 the Owner Societies.

Nanoparticles (NPs) of cobalt are synthesized in shallow layers of polyimide using 40 keV implantation of Co+ ions with a few different fluences at various ion current densities. Nucleation of individual NPs at low fluencies and their percolation at high fluencies are crucial processes governing the electrical and magnetic properties of the metal/polymer nanocomposites that can be controlled by the implantation regimes. In particular, one can tune the magnetoresistance between negative and positive through appropriate choice of ion fluence and current density. The found non-monotonous dependence of the magnetoresistance on the applied magnetic field allows suggestion of spin-dependent domain wall scattering affecting the electron transport. The samples implanted with low fluencies demonstrate superparamagnetic behavior down to very low blocking temperatures. For high fluence (1.25 × 1017 cm-2) the transition to ferromagnetic ordering is observed that is related to the increased magnetic interaction of NPs. Nanoparticles of cobalt are synthesized in shallow layers of polyimide using low-energy implantation of cobalt ions. Nucleation of individual particles and their percolation are crucial processes governing the electrical and magnetic properties of the metal/polymer nanocomposites. By tuning the implantation regimes magnetoresistance and transitions between the superparamagnetic and ferromagnenic behavior can be controlled. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Fluid pumping cell for plasmonic - photonic microcavity sensor for label-free biomolecule detection and identification has been developed and tested with drug and gold nanoparticle solutions including additional gold layer. Resonant spectra parameters have being analyzed. © 2013 IEEE.

The strong influence of the support properties on the activity of gold catalysts has been observed in many publications. The most studied reaction in this respect seems to be CO-oxidation, for which gold catalysts have outstanding activity. However, since in most studies the support properties are also important in influencing the nature of the gold particles deposited on them by co-precipitation or deposition-precipitation, it is difficult to study the support effect alone. We have in a series of studies used colloidal impregnation of preformed gold particles approximately 3nm in size on different supports in order to decouple the gold particle formation from the deposition process, in order to isolate the support effect. Even for such similarly prepared catalysts very strong differences between different supports were observed. The analysis of the data, also in the light of literature data, suggests that there is no unique factor explaining the high activity of gold catalysts, but rather a combination of effects, which act in different proportion for different catalysts. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

One of the technologically most important requirements for the application of supported metal nanoparticles (NPs) to the field of heterogeneous catalysis is the achievement of thermally and chemically stable systems under reaction conditions. For this purpose, a thorough understanding of the different pathways underlying coarsening phenomena is needed. In particular, in depth knowledge must be achieved on the role of the NP synthesis method, geometrical features of the NPs (size and shape), initial NP dispersion on the support (interparticle distance), support pre-treatment (affecting its morphology and chemical state), and reaction environment (gaseous or liquid medium, pressure, temperature). This study provides examples of the stability and sintering behavior of nanoscale systems monitored ex situ, in situ, and under operando conditions via transmission electron microscopy, atomic force microscopy, scanning tunneling microscopy, and X-ray absorption fine-structure spectroscopy. Experimental data corresponding to physical-vapor-deposited and micelle-synthesized metal (Pt, Au) NPs supported on TiO2, SiO2 and Al2O 3 will be used to illustrate Ostwald-ripening and diffusion coalescence processes. In addition, the role of the annealing environment (H2, O2, water vapor) on the stability of NPs will be discussed. © 2013 Springer Science+Business Media New York.

We have investigated the structure and chemical state of size-selected platinum nanoparticles (NPs) prepared by micelle encapsulation and supported on γ-Al2O3 during the oxidation of methanol under oxygen-rich reaction conditions following both oxidative and reductive pretreatments. X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine-structure (EXAFS) spectroscopy measurements reveal that in both cases, the catalyst is substantially oxidized under reaction conditions at room temperature and becomes partially reduced when the reactor temperature is raised to 50 C. Reactivity tests show that at low temperatures, the preoxidized catalyst, in which a larger degree of oxidation was observed, is more active than the prereduced catalyst. We conclude that the differences in reactivity can be linked to the formation and stabilization of distinct active oxide species during the pretreatment. © 2013 American Chemical Society.

We use molecular dynamics simulations in order to understand the microscopic origin of the asymmetric growth mechanism in gold nanorods. We provide the first atomistic model of different surfaces on gold nanoparticles in a growing electrolyte solution, and we describe the interaction of the metal with the surfactants, namely, cetyltrimethylammonium bromide (CTAB) and the ions. An innovative aspect is the inclusion of the role of the surfactants, which are explicitly modeled. We find that on all the investigated surfaces, namely, (111), (110), and (100), CTAB forms a layer of distorted cylindrical micelles where channels among micelles provide direct ion access to the surface. In particular, we show how AuCl2- ions, which are found in the growth solution, can freely diffuse from the bulk solution to the gold surface. We also find that the (111) surface exhibits a higher CTAB packing density and a higher electrostatic potential. Both elements would favor the growth of gold nanoparticles along the (111) direction. These findings are in agreement with the growth mechanisms proposed by the experimental groups of Murphy and Mulvaney. © 2013 American Chemical Society.

Over the last decade many papers dedicated to the generation of nanoparticles in liquids using la-ser ablation have been published. They have shown that the nanoparticles size distribution is de-pendent of the laser fluence and shifts towards smaller sizes when the surfactant concentration is in-creased. In this paper an alternative approach is presented that permits the control of the size distri-bution of gold nanoparticles during laser ablation in aqueous solutions containing different surfactant molecules with different shapes and size.

Gold nanoparticles have been efficiently photodeposited onto titanate-loaded SBA-15 (Ti(x)/SBA-15) with different titania coordination. Transmission electron microscopy shows that relatively large Au nanoparticles are photodeposited on the outer surface of the Ti(x)/SBA-15 materials and that TiOx tends to form agglomerates in close proximity to the Au nanoparticles, often forming core-shell Au/TiOx structures. This behavior resembles typical processes observed due to strong-metal support interactions. In the presence of gold, the formation of hydrogen on Ti(x)/SBA-15 during the photodeposition process and the performance in the hydroxylation of terephthalic acid is greatly enhanced. The activity of the Au/Ti(x)/SBA-15 materials is found to depend on the TiOx loading, increasing with a larger amount of initially isolated TiO4 tetrahedra. Samples with initially clustered TiOx species show lower photocatalytic activities. When isolated zinc oxide (ZnOx) species are present on Ti(x)/SBA-15, gold nanoparticles are smaller and well dispersed within the pores. Agglomeration of TiOx species and the formation of Au/TiO x structures is negligible. The dispersion of gold and the formation of Au/TiOx in the SBA-15 matrix seem to depend on the mobility of the TiOx species. The mobility is determined by the initial degree of agglomeration of TiOx. Effective hydrogen evolution requires Au/TiOx core-shell composites as in Au/Ti(x)/SBA-15, whereas hydroxylation of terephthalic acid can also be performed with Au/ZnO x/TiOx/SBA-15 materials. However, isolated TiOx species have to be grafted onto the support prior to the zinc oxide species, providing strong evidence for the necessity of Ti-O-Si bridges for high photocatalytic activity in terephthalic acid hydroxylation. © 2013 American Chemical Society.

The selective oxidation of aqueous ethanol solutions with air over two commercial 1.5 and 1wt% Au/TiO2 catalysts was investigated in six stirred mini-autoclaves operated in parallel. The catalysts were characterised by various techniques including elemental analysis, N2 physisorption, X-ray diffraction and transmission electron microscopy (TEM). Temperature, pressure, ethanol concentration, catalyst concentration and reaction time were varied in the batch experiments to study the reaction kinetics. It was possible to confirm the generally accepted mechanism of primary alcohol oxidation, in which acetaldehyde is a primary product of the oxidation that quickly undergoes further transformation to acetic acid. In presence of both acetic acid and ethanol the formation of ethyl acetate takes place until equilibrium conditions are reached. The high yields of acetic acid can be rationalised by the inhibited total oxidation of acetic acid under the applied reaction conditions. Improper storage of the gold catalysts in air exposed to light was found to lead to an irreversible change of the performance, which cannot be restored by means of recalcination. Sintering and blocking of surface sites by deposits were ruled out as possible causes for the deactivation. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The influence of the residual growth catalyst on the reducibility and catalytic activity of Pt nanoparticles supported on oxygen- and nitrogen-functionalized CNTs (OCNTs and NCNTs) was systematically investigated. It was found that the presence of the residual growth catalyst significantly influenced the oxygen and nitrogen functionalization of CNTs, which consequently altered the reducibility of the supported Pt nanoparticles. Pt nanoparticles on NCNTs showed a higher stability against sintering in reducing atmosphere at 200 C and 400 C than those on OCNTs. On NCNTs, Pt was in a higher oxidation state and was not as easily reducible as on OCNTs. In hydrogenation catalysis, removing the residual growth catalyst is essential for the supported Pt catalyst to achieve a better performance. Compared with Pt on OCNTs, Pt on NCNTs was less active, but more selective in olefin hydrogenation due to the poisoning effect of the surface nitrogen species. © 2013 Elsevier Inc. All rights reserved.

Photodeposition of Au nanoparticles was found to enhance the rate of photocatalytic CO2 reduction to short hydrocarbons over titanate species in SBA-15. Product formation from contaminants was ruled out experimentally by a thorough pre-cleaning of the samples and the leak-tight design of the fully metal-sealed gas-phase photoreactor. Without Au, an active carbon pool was observed to accumulate on the catalyst, and higher hydrocarbons were formed. Infrared spectroscopy was used to identify formaldehyde/ paraformaldehyde as major compounds of the carbon pool. The results obtained in the absence of gas-phase water indicate that adsorbed water in the mesopores is sufficient to achieve CO2 reduction and convert CO2 mainly to methane. These results contribute to the knowledge-based improvement of photocatalysts for CO2 reduction. © 2013 Elsevier Inc. All rights reserved.

Analytical expressions for the anodic stripping voltammetry of metallic nanoparticles from an electrode are provided. First, for reversible electron transfer, two limits are studied: that of diffusionally independent nanoparticles and the regime where the diffusion layers originating from each particle overlap strongly. Second, an analytical expression for the voltammetric response under conditions of irreversible electron transfer kinetics is also derived. These equations demonstrate how the peak potential for the stripping process is expected to occur at values negative of the formal potential for the redox process in which the surface immobilised nanoparticles are oxidised to the corresponding metal cation in the solution phase. This work is further developed by considering the surface energies of the nanoparticles and its effect on the formal potential for the oxidation. The change in the formal potential is modelled in accordance with the equations provided by Plieth [J. Phys. Chem., 1982, 86, 3166-3170]. The new analytical expressions are used to investigate the stripping of silver nanoparticles from a glassy carbon electrode. The relative invariance of the stripping peak potential at low surface coverages of silver is shown to be directly related to the surface agglomeration of the nanoparticles. © 2013 The Royal Society of Chemistry.

New developments and characteristics of high brilliant laser sources have led to new applications in the field of laser remote processing. Due to high particle formation rates within the vapor plume, a significant influence of the interaction between laser radiation and nanoparticles on the process may occur. The presented work shows results of the investigation of the dynamical formation of nanoparticles within the vapor plume during the welding of stainless steel with a 2 kW Multi-Mode fiber laser under laser remote conditions. The particle size distribution is measured by the evaluation of TEM-images, whereas, the plasma temperature and particle density are analyzed in dependence of the irradiation time. © 2013 The Authors.

A high-performance Pd catalyst for selective olefin hydrogenation was synthesized by supporting Pd nanoparticles on nitrogen-doped carbon nanotubes (NCNTs). X-ray diffraction, hydrogen chemisorption, transmission electron microscopy and X-ray photoelectron spectroscopy (XPS) were used to characterize Pd supported on NCNTs and nitrogen-free oxygen-functionalized CNTs (OCNTs). The Pd nanoparticles were stabilized on NCNTs with narrower size distribution compared with OCNTs. The XPS analysis revealed that the nitrogen functional groups favor the reduction of Pd on CNTs suggesting an electronic promoter effect. The Pd/NCNT catalyst showed extraordinary catalytic performance in terms of activity, selectivity and stability in the selective hydrogenation of cyclooctadiene, which is related to the structural and electronic promoting effect of the NCNT support. © 2013 The Royal Society of Chemistry.

The electrocatalytic activity for oxygen reduction reaction (ORR) at neutral pH of citrate-capped silver nanoparticles (diameter = 18 nm) supported on glassy carbon (GC) is investigated voltammetrically. Novelly, the modification of the substrate by nanoparticles sticking to form a random nanoparticle array and the voltammetric experiments are carried out simultaneously by immersion of the GC electrode in an air-saturated 0.1 M NaClO4 solution (pH = 5.8) containing chemically-synthesized nanoparticles. The experimental voltammograms of the resulting nanoparticle array are simulated with homemade programs according to the two-proton, two-electron reduction of oxygen to hydrogen peroxide where the first electron transfer is rate determining. In the case of silver electrodes, the hydrogen peroxide generated is partially further reduced to water via heterogeneous decomposition. Comparison of the results obtained on a silver macroelectrode and silver nanoparticles indicates that, for the silver nanoparticles and particle coverages (0.035%-0.457%) employed in this study, the ORR electrode kinetics is slower and the production of hydrogen peroxide larger on the glassy carbon-supported nanoparticles than on bulk silver. [Figure not available: see fulltext.] © 2013 Tsinghua University Press and Springer-Verlag Berlin Heidelberg.

Improved electrocatalytic activity and selectivity for the reduction of H2O2 were obtained by electrodepositing Pd-Pt and Pd-Au on spectrographic graphite from solutions containing salts of the two metals at varying ratio. The electrocatalytic activity of the resulting binary codeposits for H2O2 reduction was evaluated by means of the redox-competition mode of scanning electrochemical microscopy (SECM) and voltammetric methods. In a potential range from 0 to-600 mV (vs. Ag/AgCl/3 M KCl) at pH 7.0 in 0.1 M phosphate citrate buffer, the electrocatalytic activity of both Pd-Pt and Pd-Au codeposits was substantially improved as compared with the identically deposited single metals suggesting an electrocatalytic synergy of the codeposits. Pd-Pt and Pd-Au codeposits were characterized by X-ray diffraction (XRD) analysis and scanning electron microscopy (SEM). Codepositing with Au caused a change of hedgehog-like shaped Pd nanoparticles into cauliflower-like nanoparticles with the particle size decreasing with increasing Au concentration. Codepositing Pd with Pt caused the formation of oblong structures with the size initially increasing with increasing Pt content. However, the particle size decreases with further increase in Pt concentration. The improved electrocatalytic capability for H2O2 reduction of the Pd-Pt electrodeposits on graphite was further demonstrated by immobilizing glucose oxidase as a basis for the development of an interference-free amperometric glucose biosensor. © 2013 American Chemical Society.

This article highlights the fundamental role of mass-transport for interfacial reactions. First, the dissolution of particulate CaCO3 is discussed demonstrating how the dimensions of the dissolving particle can 'switch' the reaction mechanism from being diffusion to surface controlled. Second, the influence of mass-transoprt on electrochemical reactions is considered, specifically considering how electrode modification can alter the observed voltammetric response in the absence of changing the electrochemical mechanism or the rate of electron transfer. Finally, these observations on the chemically controlling role of mass-transport are concluded by considering nanoparticle toxicity and how 'size effects' may be exhibited even in the absence of altered thermodynamics or interfacial kinetics of the reactions involved.

We have studied the effect of Cr capping on the magnetic properties of Co nanoparticles (NPs). The NPs have an average diameter of 2.2 nm. The blocking temperature TB of the bare Co particles is 13.2 K. By capping with a thin Cr layer up to a thickness of tCr = 0.52 nm, we first observe a decrease of TB up to tCr = 0.14 nm, followed by an increase of TB for larger thicknesses 0.14 nm ≤ tCr ≤ 0.52 nm. X-ray magnetic circular dichroism measurements at the resonant Co and Cr L3 edges confirm a magnetic polarization of Cr which is opposite to the magnetization of Co. The antiparallel alignment of Co and Cr spins at the Co/Cr interface can explain the decrease at low capping layer thickness. However, for larger Cr capping layer thicknesses, the Cr film bridges the Co NPs, mediating interparticle exchange coupling and enhancing dipolar coupling that leads to an increase of the blocking temperature. © 2013 AIP Publishing LLC.

Mixed metal-semiconductor nanocrystal aerogels are fabricated, which are light-emitting and highly porous macroscopic monoliths. Thiol-stabilized CdTe and Au nanoparticles from aqueous synthesis act as building blocks for the hybrid material. The Au colloids undergo a surface-modification to enhance the particle stability and achieve thiol functionalities. A photochemical treatment is applied for the gelation process which is found to be reversible by subsequent addition of thiol molecules. Via supercritical drying aerogels are formed. The variation of the initial CdTe to Au nanoparticle ratio permits a facile tuning of the content and the properties of the resulting aerogels. The obtained structures were characterized by means of optical spectroscopy, electron microscopy, elemental analysis, and nitrogen physisorption. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The ability to perform efficient and affordable field detection and quantification of nanoparticles in aquatic environmental systems remains a significant technical challenge. Recently we reported a proof of concept of using 'sticky' electrodes for the detection of silver nanoparticles (Tschulik et al 2013 Nanotechnology 29 295502). Now a disposable electrode for detection and quantification of commercial Ag nanoparticles in natural seawater is presented. A disposable screen printed electrode is modified with cysteine and characterized by sticking and stripping experiments, with silver nanoparticle immobilization on the electrode surface and subsequent oxidative stripping, yielding a quantitative determination of the amount of Ag nanoparticles adhering to the electrode surface. The modified electrode was applied to natural seawater to mimic field-based environmental monitoring of Ag NPs present in seawater. The results demonstrated that commercial Ag NPs in natural seawater can be immobilized, enriched and quantified within short time period using the disposable electrodes without any need for elaborate experiments. © 2013 IOP Publishing Ltd.

The electrochemistry of silver nanoparticles contained in a consumer product has been studied. The redox properties of silver particles in a commercially available disinfectant cleaning spray were investigated via cyclic voltammetry before particle-impact voltammetry was used to detect single particles in both a typical aqueous electrolyte and authentic seawater media. We show that particle-impact voltammetry is a promising method for the detection of nanoparticles that have leached into the environment from consumer products, which is an important development for the determination of risks associated with the incorporation of nanotechnology into everyday products. © 2013 IOP Publishing Ltd.

Cystic fibrosis is a common disease which has an associated characteristic symptom of high sweat chloride content. Thus, chloride ion quantification in sweat is important towards the screening of cystic fibrosis. Electrochemical methods, being cost effective and convenient, can be exploited for this. The electrochemical oxidation of silver nanoparticles in the absence of chloride ions gives one voltammetric signal related to the oxidation of silver to silver ions. The presence of chloride ions in the solution causes the appearance of an additional signal at a lower potential which is related to the oxidation of silver to silver chloride. This signal has a peak height which correlates linearly with the concentration of chloride ions from 2 mM to 40 mM when the electrochemical experiments are performed on silver nanoparticle modified screen printed electrodes. Thus, reliable quantification was found to be achievable. Furthermore, chloride ion levels of diluted synthetic sweat samples are measured accurately with the modified electrodes. Thus, the detection of the chloride ion concentration with a silver nanoparticle modified electrode provides a proof-of-concept for a point-of-care system for preliminary screening of cystic fibrosis. © 2013 The Royal Society of Chemistry.

A study of the morphological and chemical stability of shape-selected octahedral Pt0.5Ni0.5 nanoparticles (NPs) supported on highly oriented pyrolytic graphite (HOPG) is presented. Ex situ atomic force microscopy (AFM) and in situ X-ray photoelectron spectroscopy (XPS) measurements were used to monitor the mobility of Pt0.5Ni0.5 NPs and to study long-range atomic segregation and alloy formation phenomena under vacuum, H2, and O2 environments. The chemical state of the NPs was found to play a pivotal role in their surface composition after different thermal treatments. In particular, for these ex situ synthesized NPs, Ni segregation to the NP surface was observed in all environments as long as PtOx species were present. In the presence of oxygen, an enhanced Ni surface segregation was observed at all temperatures. In contrast, in hydrogen and vacuum, the Ni outward segregation occurs only at low temperature (< 200-270 C), while PtOx species are still present. At higher temperatures, the reduction of the Pt oxide species results in Pt diffusion toward the NP surface and the formation of a Ni-Pt alloy. A consistent correlation between the NP surface composition and its electrocatalytic CO oxidation activity was established. © 2013 American Chemical Society.

We studied the magnetic and transport properties of Co nanoparticles (NPs) being capped with varying amounts of Pt. Beside field and temperature dependent magnetization measurements, we performed δΜ measurements to study the magnetic interactions between the Co NPs. We observe a transition from demagnetizing towards magnetizing interactions between the particles for an increasing amount of Pt capping. Resistivity measurements show a crossover from giant magnetoresistance towards anisotropic magnetoresistance. © 2013 American Institute of Physics.

Detection and quantification of nanoparticles in environmental systems is a task that requires reliable and affordable analytical methods. Here an approach using a cysteine-modified 'sticky' glassy carbon electrode is presented. The electrode is immersed in a silver nanoparticle containing electrolyte and left in this suspension without an applied potential, i.e. under open circuit condition, for a variable amount of time. The amount of silver nanoparticles immobilized on the electrode within this sticking time is then determined by oxidative stripping, yielding the anodic charge and thus the amount of Ag nanoparticles sticking to the electrode surface. When using a cysteine-modified glassy carbon electrode, significant and reproducible amounts of silver nanoparticles stick to the surface, which is not the case for unmodified glassy carbon surfaces. Additionally, proof-of-concept experiments are performed on real seawater samples. These demonstrate that also under simulated environmental conditions an increased immobilization and hence improved detection of silver nanoparticles on cysteine-modified glassy carbon electrodes is achieved, while no inhibitive interference with this complex matrix is observed. © 2013 IOP Publishing Ltd.

The power of spray-dried TiO2 in LIBs: TiO2(B)/ anatase is synthesized by spray drying and investigated as negative electrode material in Li-ion batteries. It exhibits excellent Li-ion storage performances, especially at high charge/discharge rates. The presence of the β phase of TiO2 improves Li-ion diffusivity. Additionally, the scalable synthesis method also allows for Nb-doping, which assists in the maintenance of the electronic conductivity as the thickness of film increases. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Quantitative analytical detection and sizing of silver nanoparticles is achieved by applying the new electrochemical method nanoparticle coulometry. For the first time, tri-sodium citrate is used as both an electrolyte and a nanoparticle stabilizing agent, allowing the individual particles to be addressed. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The structural and magnetic properties of ultrathin near-stoichiometric Fe3Si layers on GaAs(001) are investigated after using scanning tunneling microscopy (STM) analysis to optimize the deposition process. This includes atomic resolution imaging of the surface as measured by STM revealing the atomic ordering and characteristic defects in the topmost layers. Emphasis is laid on connections between the layer morphology and its magnetic properties, which are analysed by in situ MOKE, FMR, and SQUID magnetometry. Upon nucleation, the Fe3Si islands behave like superparamagnetic nanoparticles where we find a quantitative agreement between the size of the nanoparticles and their superspin. At higher coverage, the Fe3Si layers show ferromagnetic behaviour. Here, we investigate the superposition of the magnetocrystalline and the uniaxial anisotropies where the latter can be excluded to be caused by shape anisotropy. Furthermore, an unexpected increase of the magnetic moment towards low coverage can be observed which apart from an increased orbital moment can be attributed to an increased step density. © 2013 American Institute of Physics.

Carbide-derived carbons (CDC) with incorporated transition metal nanoparticles (∼2.5 nm) were prepared using a microemulsion approach. Time-consuming post synthesis functionalization of the carbon support material can thus be avoided and nanoparticle sizes can be controlled by changing the microemulsion composition. This synthesis strategy is a technique for the preparation of highly porous carbon materials with a catalytically active component. In particular we investigated the integration of ruthenium, palladium, and platinum in a concentration ranging from 4.45 to 12 wt.%. It was found that the transition metal has a considerable influence on sorption properties of resulting nanoparticle-CDC composite materials. Depending on the used metal salt additive the surface area and the pore volume ranges from 1480 m 2/g and 1.25 cm 3/g for Pt to 2480 m 2/g and 2.0 cm 3/g for Ru doped carbons. Moreover, members of this material class show impressive properties as heterogeneous catalysts. The liquid phase oxidation of tetralin and the partial oxidation of methane were studied, and electrochemical applications were also investigated. Primarily Pt doped CDCs are highly active in the oxygen reduction reaction, which is of great importance in present day fuel cell research. © 2012 Elsevier Ltd. All rights reserved.

Tailoring the surface and understanding the surface characteristics is necessary for biomedical applications of superparamagnetic nanoparticles. In this paper, superparamagnetic iron oxide nanoparticles (SPIONs) were prepared by thermal decomposition of iron nitrate in presence of stearic acid as surfactant. Due to the multilayer organization of surfactant molecules over the nanoparticle surface, the surface potential can be tuned by pH changes and hence the nanoparticles can be made dispersible in nonpolar as well as in polar solvents. We have presented a simple, facile procedure for controlled replacement of stearic acid from maghemite surface and subsequent derivatization by biocompatible dimercaptosuccinic acid (DMSA) to obtain ultrastable hydrophilic nanoparticles with unaltered morphology, phase and properties. The surface chemistry of the functionalized SPIONs was analyzed by Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA) and X-ray photoelectron spectroscopy (XPS) revealing the presence of bound and unbound thiol groups and disulfides, leading to its prolonged stability in aqueous medium. The consequence of spatially selective functionalization on the stability and solubility of surface hydrophilic SPION has also been realized. © 2012 Elsevier B.V.

A hierarchical carbon-fiber composite was synthesized based on carbon cloth (CC) modified with primary carbon microfibers (CMF) and subsequently secondary carbon nanotubes (CNT), thus forming a three-dimensional hierarchical structure with high BET surface area. The primary CMFs and the secondary CNTs are grown with electrodeposited iron nanoparticles as catalysts from methane and ethylene, respectively. After deposition of Pt nanoparticles by chemical vapor deposition from (trimethyl)cyclopentadienylplatinum, the resulting hierarchical composite was used as catalyst in the electrocatalytic oxygen reduction (oxygen reduction reaction, ORR) as specific test reaction. The modification of the CC with CMFs and CNTs improved the electrochemical properties of the carbon composite as revealed by electrochemical impedance measurements evidencing a low charge transfer resistance for redox mediators at the modified CC. X-ray photoelectron spectroscopy measurements were carried out to identify the chemical state and the surface atomic concentration of the Pt catalysts deposited on the hierarchical carbon composites. The ORR activity of Pt supported on different composites was investigated using rotating disk electrode measurements and scanning electrochemical microscopy. These electrochemical studies revealed that the obtained structured catalyst support is very promising for electrochemical applications, e.g. fuel cells. © 2012 Elsevier Ltd. All rights reserved.

This study presents a systematic detailed experimental and theoretical investigation of the electronic properties of size-controlled free and γ-Al 2O 3-supported Pt nanoparticles (NPs) and their evolution with decreasing NP size and adsorbate (H 2) coverage. A combination of in situ X-ray absorption near-edge structure (XANES) and density functional theory (DFT) calculations revealed changes in the electronic characteristics of the NPs due to size, shape, NP-adsorbate (H 2) and NP-support interactions. A correlation between the NP size, number of surface atoms and coordination of such atoms, and the maximum hydrogen coverage stabilized at a given temperature is established, with H/Pt ratios exceeding the 1:1 ratio previously reported for bulk Pt surfaces. © 2012 the Owner Societies.

We have gained insight into the internal degree of atomic disorder in isolated size-selected Fe nanoparticles (NPs) (∼2-6 nm in size) supported on SiO 2/Si(111) and Al 2O 3(0001) from precise measurements of the low-energy (low-E) part of the phonon density of states [PDOS, g(E)] via 57Fe nuclear resonant inelastic x-ray scattering (NRIXS) combined with transmission electron microscopy (TEM) measurements. An intriguing size-dependent trend was observed, namely, an increase of the low-E excess density of phonon states (as compared to the PDOS of bulk bcc Fe) with increasing NP size. This is unexpected, since usually the enhancement of the density of low-E phonon modes is attributed to low-coordinated atoms at the NP surface, whose relative content increases with decreasing NP size due to the increase in the surface-to-volume ratio. Our NPs are covered by a Ti-coating layer, which essentially restores the local neighborhood of surface Fe atoms towards bulk-like coordination, reducing the surface effect. Our data can be qualitatively explained by the existence of low-coordinated Fe atoms located at grain boundaries or other defects with structural disorder in the interior of the large NPs (∼3-6 nm), while our small NPs (∼2 nm) are single grain and, therefore, characterized by a higher degree of structural order. This conclusion is corroborated by the observation of Debye behavior at low energy [g(E) ∼ En with n ∼ 2] for the small NPs, but non-Debye behavior (with n ∼ 1.4) for the large NPs. The PDOS was used to determine thermodynamic properties of the Fe NPs. Finally, our results demonstrate that, in combination with TEM, NRIXS is a suitable technique to investigate atomic disorder/defects in NPs. We anticipate that our findings are universal for similar NPs with bcc structure. © 2012 American Physical Society.

Noble-metal-free functional oxides are active catalysts for CO oxidation at low temperatures. Spinel-type cobalt oxide (Co 3O 4) nanoparticles can be easily synthesized by impregnation of activated carbon with concentrated cobalt nitrate and successive carbon burn off. Mean size and particle size distribution can be tuned by adding small amounts of silica to the carbon precursor, as witnessed by whole powder pattern modeling of the X-ray powder diffraction data. The catalytic tests performed after silica removal show a significant influence of the mean domain size and of size distribution on the CO oxidation activity of the individual Co 3O 4 specimens, whereas defects play a less important role in the present case. © 2012 American Chemical Society.

Cheers for titania: An N-doped composite of carbon nanotubes (CNTs) and mesoporous TiO 2 is used as support for Pt nanoparticles applied in the oxygen reduction reaction. The composite Pt/N-TiO 2-CNT shows a higher stability than Pt particles on carbon black or N-doped CNTs, as indicated by accelerated stress tests of up to 2000 cycles. The enhanced stability is attributed to strong interactions between TiO 2 and Pt and a higher corrosion resistance of TiO 2 as well as CNTs. © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The stability of Pt nanoparticles (NPs) supported on ultrathin SiO 2 films on Si(111) was investigated in situ under H2 and O2 (0.5 Torr) by high-pressure X-ray photoelectron spectroscopy (HP-XPS) and ex situ by atomic force microscopy (AFM). No indication of sintering was observed up to 600 C in both reducing and oxidizing environments for size-selected Pt NPs synthesized by inverse micelle encapsulation. However, HP-XPS revealed a competing effect of volatile PtOx desorption from the Pt NPs (∼2 and ∼4 nm NP sizes) at temperatures above 450 C in the presence of 0.5 Torr of O2. Under oxidizing conditions, the entire NPs were oxidized, although with no indication of a PtO2 phase, with XPS binding energies better matching PtO. The stability of catalytic NPs in hydrogenation and oxidation reactions is of great importance due to the strong structure sensitivity observed in a number of catalytic processes of industrial relevance. An optimum must be found between the maximization of the surface active sites and metal loading (i.e., minimization of the NP size), combined with the maximization of their stability, which, as it will be shown here, is strongly dependent on the reaction environment. © 2012 American Chemical Society.

Label-free electrochemical detection of DNA hybridization with high selectivity and sensitivity is only achievable if the properties of DNA at an electrified interface are understood in depth. After a short summary of concepts of electrochemical DNA detection as well as initial attempts towards label-free DNA assays the review discusses the physico-chemical properties and differences between single-stranded and double-stranded DNA immobilized at electrode surfaces in the light of their persistence lengths, structural conformation, impact of the charge screening by ion condensation and the electric field generated upon polarization of the electrode. Electrochemical impedance spectroscopy as a tool for label-free elucidation of DNA hybridization is reviewed and the necessity for an in-depth understanding of the interfacial properties is highlighted. Our major aim is to demonstrate the advantageous application of specifically designed intercalating compounds for the design of label-free detection of DNA hybridization. This journal is © 2012 the Owner Societies.

Metallic copper nanoparticles have been efficiently dispersed and stabilized on nitrogen-doped carbon nanotubes. They are about 8-10 nm in diameter and highly resistant against bulk oxidation. Their catalytic activity and recyclability have been investigated in A 3-type coupling reactions for the synthesis of propargylamines. It was easily possible to prepare diastereomerically pure derivatives of proline and to efficiently recover and reuse the supported catalyst several times. © 2012 Elsevier B.V. All rights reserved.

The gasification of carbon with CO 2 was applied to examine the role of the residual iron growth catalyst in multi-walled carbon nanotubes (CNTs), which were pre-treated either by refluxing in nitric acid at 120 °C or by nitric acid vapor at 200 °C. Temperature-programmed desorption (TPD) and surface reaction (TPSR) experiments were performed in He and CO 2, respectively. The Fe nanoparticles were retained after the treatment in HNO 3 vapor, whereas the liquid HNO 3 treatment was able to remove the accessible residual Fe catalyst. The exposed Fe nanoparticles were found to catalyze the gasification of CNTs with CO 2 according to the reverse Boudouard reaction C + CO 2 = 2CO. In case of the CNTs pretreated in HNO 3 vapor, evolving CO 2 formed due to the decomposition of oxygen-containing functional groups during the TPD experiments was fully converted above 750 °C into desorbing CO, and the addition of 2000 ppm CO 2 in the feed gas during the TPSR experiments resulted in full conversion at 1000 °C. X-ray photoelectron spectroscopy studies show that the treatment in HNO 3 vapor at 200 °C favors the formation of oxygen species doubly bound to carbon (CO groups). During the TPSR experiments, CO 2 as a weak oxidant partially oxidized the CNTs leading to the formation of CO groups, and a much higher amount of these groups was detected on HNO 3 vapor-treated CNTs with residual Fe catalyst. Their presence suggests that CO groups are reaction intermediates of the CNT gasification with CO 2, which is considered an effective test reaction for the presence of residual catalytically active nanoparticles. © 2012 Elsevier B.V.

Adsorption and oxidation of CO on Au/ZnO catalysts were studied by Fourier transform infrared (FTIR) spectroscopy using a novel ultra-high-vacuum (UHV) system. The high-quality UHV-FTIRS data provide detailed insight into the catalytic mechanism of low-temperature CO oxidation on differently pretreated Au/ZnO catalysts. For the samples without O 2 pretreatment, negatively charged Au nanoparticles are identified which exhibit high reactivity to CO oxidation at 110 K, yielding CO 2 as well as carbonate species bound to various ZnO facets. O 2 pretreatment leads to formation of neutral Au nanoparticles where CO is activated on the low-coordinated Au sites at the interface. Activation of impinging O 2 occurs at the Au/ZnO interface and is promoted by preadsorbed CO forming an OC-O 2 intermediate complex, accompanied by charge transfer from Au/ZnO substrate to O 2. The CO molecules adsorbed on ZnO serve as a reservoir for reactants and are mobile enough at 110 K to reach the Au/ZnO interface where they react with activated oxygen yielding CO 2. Different carbonate species are further produced via interaction of formed CO 2 with surface oxygen atoms on ZnO. It was found that the active interface sites are slowly blocked at 110 K by the inert carbonate species, thus causing a gradual decrease of the catalytic activity. © 2012 American Chemical Society.

We present a first-principles density functional theory study of domain wall structures in tetragonal BaTiO 3 and its nanoparticles. For the bulk material the domain wall profiles, their width and their formation energy are computed and preliminary investigations on thin BaTiO 3 films up to 4 monolayers and small nanoparticles of 15.8 have been performed. While the 180 wall is atomically sharp, we find a lower bond for the 90 wall width of 16.5 . Although, no ferroelectric state can be stabilized neither in films nor in the nanoparticles of this small size, a large local polarization exits in both cases. © Taylor & Francis Group, LLC.

Gold nanoparticles supported on transition metal oxides are found to exhibit a pronounced particle size effect in CO oxidation. However, the preparation of comparable supported gold nanoparticles with different sizes remains challenging, since the catalytic behavior of these materials is very sensitive to the preparation conditions. To overcome this difficulty, Au, @ZrO 2 catalysts with gold core sizes between 5 and 15 nm were prepared by partial leaching of gold in an ex-post manner. The material obtained offers a unique comparability for particle size effect studies in CO oxidation. No effect of gold particle size was observed in the studied size range. © 2012 Elsevier Inc. All rights reserved.

Experimental evidence has shown that composites comprised Si and Sn nanoparticles embedded inside a matrix are the most promising next generation anodes for Li-ion batteries. This is due to the ability of the matrix material to constrain/buffer the up to 300 volume expansion that Sn and Si undergo upon the formation of lithium rich alloys. Damage still occurs at the nanoparticle/matrix interface, and hence further materials design is required in order to commercialize such anodes. Initial theoretical works have predicted that low volume fractions and high aspect ratios of the nanoparticles result in a greater mechanical stability and hence better capacity retention. The most important design parameters, however, such as particle size and spacing have not been considered theoretically. In the present study, therefore, a gradient enhanced damage model will be employed to predict that damage during Li-insertion, is negligible when the particle size is 20 nm, and the interparticle half-spacing greater then 1.5 times the particle diameter. Furthermore, from the matrix materials considered herein graphene is predicted to be the most promising matrix, which is consistent with recent experimental data. © 2012 Elsevier B.V. All rights reserved.

The durability of electrode materials is a limiting parameter for many electrochemical energy conversion systems. In particular, electrocatalysts for the essential oxygen reduction reaction (ORR) present some of the most challenging instability issues shortening their practical lifetime. Here, we report a mesostructured graphitic carbon support, Hollow Graphitic Spheres (HGS) with a specific surface area exceeding 1000 m2 g-1 and precisely controlled pore structure, that was specifically developed to overcome the long-term catalyst degradation, while still sustaining high activity. The synthetic pathway leads to platinum nanoparticles of approximately 3 to 4 nm size encapsulated in the HGS pore structure that are stable at 850 C and, more importantly, during simulated accelerated electrochemical aging. Moreover, the high stability of the cathode electrocatalyst is also retained in a fully assembled polymer electrolyte membrane fuel cell (PEMFC). Identical location scanning and scanning transmission electron microscopy (IL-SEM and IL-STEM) conclusively proved that during electrochemical cycling the encapsulation significantly suppresses detachment and agglomeration of Pt nanoparticles, two of the major degradation mechanisms in fuel cell catalysts of this particle size. Thus, beyond providing an improved electrocatalyst, this study describes the blueprint for targeted improvement of fuel cell catalysts by design of the carbon support. © 2012 American Chemical Society.

The formation of double-stranded DNA (dsDNA) at gold electrodes decorated with a monolayer of gold nanoparticles bound through a self-assembled dithiol monolayer is detected via specific intercalation of proflavine. Hybridization as well as sequential built-up of the electrode architecture is monitored using Faradaic electrochemical impedance spectroscopy (EIS) as well as surface enhanced Raman scattering (SERS). The adsorption of secondary gold nanoparticles allow for amplified detection of the dsDNA integrated intercalator in a vertical gap mode configuration. The experimental design thus allows probing presence of the intercalator inside the dsDNA. © 2012 Elsevier B.V. All rights reserved.

High-energy-resolution fluorescence-detected X-ray absorption spectroscopy (HERFD-XAS) has been applied to study the chemical state of ∼1.2 nm size-selected Pt nanoparticles (NPs) in an electrochemical environment under potential control. Spectral features due to chemisorbed hydrogen, chemisorbed O/OH, and platinum oxides can be distinguished with increasing potential. Pt electro-oxidation follows two competitive pathways involving both oxide formation and Pt dissolution. © 2012 American Chemical Society.

Nanostructures as catalysts: Pd aerogels modified with α-, β-, and γ-cyclodextrins can be obtained by the spontaneous self-assembly of in situ generated Pd nanoparticles. The Pd aerogels show excellent electrocatalytic activity for the oxidation of ethanol. The catalytic activity is believed to arise from the nonsupported nanometer-scale structure of the aerogel network and the interactions of ethanol with the cyclodextrin. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

One of the technologically most important requirements for the application of oxide-supported metal nanoparticles (NPs) in the fields of molecular electronics, plasmonics, and catalysis is the achievement of thermally stable systems. For this purpose, a thorough understanding of the different pathways underlying thermally-driven coarsening phenomena, and the effect of the nanoparticle synthesis method, support morphology, and degree of support reduction on NP sintering is needed. In this study, the sintering of supported metal NPs has been monitored via scanning tunneling microscopy combined with simulations following the Ostwald ripening and diffusion-coalescence models. Modifications were introduced to the diffusion-coalescence model to incorporate the correct temperature dependence and energetics. Such methods were applied to describe coarsening phenomena of physical-vapor deposited (PVD) and micellar Pt NPs supported on TiO 2(110). The TiO 2(110) substrates were exposed to different pre-treatments, leading to reduced, oxidized and polymer-modified TiO 2 surfaces. Such pre-treatments were found to affect the coarsening behavior of the NPs. No coarsening was observed for the micellar Pt NPs, maintaining their as-prepared size of ~ 3 nm after annealing in UHV at 1060 °C. Regardless of the initial substrate pre-treatment, the average size of the PVD-grown NPs was found to increase after identical thermal cycles, namely, from 0.5 ± 0.2 nm to 1.0 ± 0.3 nm for pristine TiO 2, and from 0.8 ± 0.3 nm to 1.3 ± 0.6 nm for polymer-coated TiO 2 after identical thermal treatments. Although no direct real-time in situ microscopic evidence is available to determine the dominant coarsening mechanism of the PVD NPs unequivocally, our simulations following the diffusion-coalescence coarsening route were in significantly better agreement with the experimental data as compared to those based on the Ostwald-ripening model. The enhanced thermal stability of the micellar NPs as compared to the PVD clusters might be related to their initial larger NP size, narrower size distribution, and larger interparticle distances. © 2012 Elsevier B.V. All rights reserved.

The synthesis of bimetallic nanoparticles (NPs) with well-defined morphology and a size of <5 nm remains an ongoing challenge. Here, we developed a facile and efficient approach to the design of bimetallic nanostructures by the galvanic replacement reaction facilitated by high-intensity ultrasound (100 W, 20 kHz) at low temperatures. As a model system, Pt-Cu NPs deposited on nitrogen-doped carbon nanotubes (NCNTs) were synthesized and characterized by spectroscopic and microscopic techniques. Transmission electron microscopy (TEM) inspection shows that the mean diameter of Pt-Cu NPs can be as low as ≈2.8 nm, regardless of the much larger initial Cu particle size, and that a significant increase in particle number density by a factor of 35 had occurred during the replacement process. The concentration of the Pt precursor solution as well as of the size of the seed particles were found to control the size of the bimetallic NPs. Energy dispersive X-ray spectroscopy performed in the scanning TEM mode confirmed the alloyed nature of the Pt-Cu NPs. Electrochemical oxygen reduction measurements demonstrated that the resulting Pt-Cu/NCNT catalysts exhibit an approximately 2-fold enhancement in both mass- and area-related activities compared with a commercial Pt/C catalyst. © 2012 American Chemical Society.

The sintering of iron nanoparticles on carbon nanotubes (CNTs) under different atmospheres was investigated. CNTs were first treated with HNO3 vapor at 200°C to obtain O-functionalized CNTs (OCNTs). The OCNTs were treated in ammonia at 400°C to obtain N-doped CNTs (NCNTs). Highly dispersed FeOx nanoparticles were subsequently deposited by chemical vapor deposition from ferrocene under oxidizing conditions. The obtained FeOx/OCNT and FeOx/NCNT samples were allowed to sinter at 500°C under flowing helium, hydrogen, or ammonia. The samples were studied by X-ray diffraction, transmission electron microscopy, and X-ray photoelectron spectroscopy. A significant increase in particle size and a decrease in Fe surface atomic concentration were observed in all the sintered samples. The sintering on OCNTs was more severe than on NCNTs, which can be attributed to stronger metal-substrate interactions and a higher amount of surface defects on NCNTs. The applied gas atmosphere had a substantial influence on the sintering behavior of the nanoparticles: treatment in helium led to the growth of particles and a significant widening of particle size distributions, whereas treatment in hydrogen or ammonia resulted in the growth of particles, but not in the widening of particle size distributions. © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Nonhydrolytic/non-sol-gel pyrolytic synthesis technique, as a convenient method, was applied to synthesize zirconium oxide nanoparticles (ZrO2 NPs). Pyrolysis of either the mononuclear keto ester/alkoxide complex zirconium bis(isopropoxide)bis(tert-butylacetoacetate) [Zr(OiPr) 2(tbaoac)2] (I) or the oligonuclear oxocluster compound [Zr6(OH)4O4(OMc)12] (II, Mc = methacrylate) generated ZrO2 NPs at moderate conditions of 300-400 °C. Trioctylamine, stearic acid, and/or oleic acid, which act as both solvents and stabilizing agents, were used. Under the adopted process conditions, the stabilizing agent oleic acid plays a vital role in determining the phase of as-synthesized colloidal ZrO2 nanoparticles, which yield the high-temperature tetragonal phase at moderate conditions of 335 °C. Those as-synthesized samples that contained both monoclinic and tetragonal ZrO2 phases (depending on the choice of the surfactant) were transformed into pure tetragonal phase at 1000 °C. An unambiguous phase determination of ZrO2 nanoparticles was carried out by the combination of powder X-ray diffraction (XRD) and Raman spectroscopy. Furthermore, the samples were analyzed by transmission electron microscopy (TEM), ultraviolet-visible (UV-vis) and photoluminescence (PL) spectroscopy, dynamic light scattering (DLS), and Fourier transform infrared (FT-IR) spectroscopy to elucidate the structure, chemical composition, and morphology of the obtained nanoparticles. Also, the phase transformations of the as-synthesized ZrO2 nanoparticles upon annealing were followed via Raman spectroscopy. © 2012 American Chemical Society.

Stearate@Cu/ZnO nanocomposite particles with molar ratios of ZnOCu = 2 and 5 are synthesized by reduction of the metal-organic Cu precursor [Cu{(OCH(CH 3)CH 2N(CH 3) 2)} 2] in the presence of stearate@ZnO nanoparticles. In the case of ZnOCu = 5, high-angle annular dark field-scanning transmission electron microscopy (HAADF-STEM) combined with electron-energy-loss-spectroscopy (EELS) as well as attenuated total reflection Fourier transform infrared (ATR-IR) spectroscopy are used to localize the small amount of Cu deposited on the surface of 3-5 nm sized stearate@ZnO particles. For ZnOCu = 2, the microstructure of the nanocomposites after catalytic activity testing is characterized by HAADF-STEM techniques. This reveals the construction of large Cu nanoparticles (20-50 nm) decorated by small ZnO nanoparticles (3-5 nm). The catalytic activity of both composites for the synthesis of methanol from syn gas is evaluated. © 2012 the Owner Societies.

Herein, we describe the design, fabrication and gas sensing tests of p-Co 3O 4/n-ZnO nanocomposites. Specifically, arrays of 〈001〉 oriented ZnO nanoparticles were grown on alumina substrates by plasma enhanced-chemical vapor deposition (PECVD) and used as templates for the subsequent PECVD of Co 3O 4 nanograins. Structural, morphological and compositional analyses evidenced the successful formation of pure and high-area nanocomposites with a tailored overdispersion of Co 3O 4 particles on ZnO and an intimate contact between the two oxides. Preliminary functional tests for the detection of flammable/toxic analytes (CH 3COCH 3, CH 3CH 2OH, NO 2) indicated promising sensing responses and the possibility of discriminating between reducing and oxidizing species as a function of the operating temperature. © 2012 American Chemical Society.

Solid-state approaches to quantum information technology are attractive because they are scalable. The coherent transport of quantum information over large distances is a requirement for any practical quantum computer and has been demonstrated by coupling super-conducting qubits to photons. Single electrons have also been transferred between distant quantum dots in times shorter than their spin coherence time. However, until now, there have been no demonstrations of scalable 'flying qubit' architectures - systems in which it is possible to perform quantum operations on qubits while they are being coherently transferred - in solid-state systems. These architectures allow for control over qubit separation and for non-local entanglement, which makes them more amenable to integration and scaling than static qubit approaches. Here, we report the transport and manipulation of qubits over distances of 6 μm within 40 ps, in an Aharonov - Bohm ring connected to two-channel wires that have a tunable tunnel coupling between channels. The flying qubit state is defined by the presence of a travelling electron in either channel of the wire, and can be controlled without a magnetic field. Our device has shorter quantum gates (< μm), longer coherence lengths (∼86 μm at 70 mK) and higher operating frequencies (∼100 GHz) than other solid-state implementations of flying qubits. © 2012 Macmillan Publishers Limited. All rights reserved.

This work reports the preparation of polymer/TiO 2 nanocomposite by adding TiO 2 nanoparticles to the polymer matrices. TiO 2 nanoparticles can be effectively dispersed into the polymer. The refractive index of the nanocomposites can be tuned by increasing the concentration of TiO 2 nanoparticles. The prepared samples exhibit excellent optical transparency in the Vis-NIR region, i.e. at two-photon polymerization (TPP) processing wavelength, and can be used to write threedimensional structures by means of TPP. Structures with high refractive index have been produced with the novel ultrahigh resolution technology based on TPP processing of polymer/TiO 2 nanocomposites. © 2012 SPIE.

High-temperature Fischer-Tropsch synthesis for the production of short-chain olefins over iron catalysts supported on multiwalled carbon nanotubes (CNTs) was investigated under industrially relevant conditions (340°C, 25bar, H 2/CO=1) to elucidate the influence of nitrogen and oxygen functionalization of the CNTs on the activity, selectivity, and long-term stability. Surface functionalization of the CNTs was achieved by means of a gas-phase treatment using nitric acid vapor at 200°C for oxygen functionalization (O-CNTs) and ammonia at 400°C for the subsequent nitrogen doping (N-CNTs). Ammonium iron citrate impregnation followed by calcination was applied for the deposition of iron nanoparticles with particle sizes below 9nm. Subsequent to reduction in pure H 2 at 380°C, the Fe/N-CNT and Fe/O-CNT catalysts were applied in Fischer-Tropsch synthesis, in which they showed comparable initial conversion values with an excellent olefin selectivity [S(C 3-C 6)>85%] and low chain growth probability (α≤0.5). TEM analysis of the used catalysts detected particle sizes of 23 and 26nm on O-CNTs and N-CNTs, respectively, and Fe 5C 2 was identified as the major phase by using XRD, with only traces of Fe 3O 4. After 50h time on stream under steady-state conditions, an almost twofold higher activity compared to the Fe/O-CNT catalysts had been maintained by the Fe/N-CNT catalysts, which are considered excellent Fischer-Tropsch catalysts for the production of short-chain olefins owing to their high activity, high selectivity to olefins, low chain growth probability, and superior long-term stability. © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The thermal stability of inverse micelle prepared Pt nanoparticles (NPs) supported on nanocrystalline γ-Al 2O 3 was monitored in situ under different chemical environments (H 2, O 2, H 2O) via extended X-ray absorption fine-structure spectroscopy (EXAFS) and ex situ via scanning transmission electron microscopy (STEM). Drastic differences in the stability of identically synthesized NP samples were observed upon exposure to two different pre-treatments. In particular, exposure to O 2 at 400°C before high temperature annealing in H 2 (800°C) was found to result in the stabilization of the inverse micelle prepared Pt NPs, reaching a maximum overall size after moderate coarsening of ∼1 nm. Interestingly, when an analogous sample was pre-treated in H 2 at ∼400°C, a final size of ∼5 nm was reached at 800°C. The beneficial role of oxygen in the stabilization of small Pt NPs was also observed in situ during annealing treatments in O 2 at 450°C for several hours. In particular, while NPs of 0.5 ± 0.1 nm initial average size did not display any significant sintering (0.6 ± 0.2 nm final size), an analogous thermal treatment in hydrogen leads to NP coarsening (1.2 ± 0.3 nm). The same sample pre-dosed and annealed in an atmosphere containing water only displayed moderate sintering (0.8 ± 0.3 nm). Our data suggest that PtO x species, possibly modifying the NP/support interface, play a role in the stabilization of small Pt NPs. Our study reveals the enhanced thermal stability of inverse micelle prepared Pt NPs and the importance of the sample pre-treatment and annealing environment in the minimization of undesired sintering processes affecting the catalytic performance of nanosized particles. © 2012 the Owner Societies.

In this paper, we will review our studies of large cadmium chalcogenide nanoparticles and present some new results on cadmium telluride systems. All calculations have been performed using density-functional based methods. The studies deal with the structural properties of saturated and unsaturated nanoparticles where the surfactants generally are hydrogen atoms or thiol groups. We have focused on the investigation of the density of states, the Mulliken charges, the eigenvalue spectra, and the spatial distributions of the frontier orbitals. Optical excitation spectra of pure CdS and CdSe/CdS core-shell systems have been calculated using a linear-response formalism. The reviewed studies are compared to the state of the art of modeling large cadmium chalcogenide particles.

The structure and flow of droplets on solid surfaces is investigated with imaging and scattering techniques and compared to simulations. To access nanostructures at the liquid-solid interface advanced scattering techniques such as grazing incidence small-angle x-ray scattering (GISAXS) with micro-and nanometer-sized beams, GISAXS and insitu imaging ellipsometry and GISAXS tomography are used. Using gold nanoparticle suspensions, structures observed in the wetting area due to deposition are probed insitu during the drying of the droplets. After drying, nanostructures in the wetting area and inside the dried droplets are monitored. In addition to drying, a macroscopic movement of droplets is caused by body forces acting on an inclined substrate. The complexity of the solid surfaces is increased from simple silicon substrates to binary polymer brushes, which undergo a switching due to the liquid in the droplet. Nanostructures introduced in the polymer brush due to the movement of droplets are observed. © 2011 IOP Publishing Ltd.

The shape of platinum and gold nanoparticles (NPs) synthesized via inverse micelle encapsulation and supported on TiO 2(110) has been resolved by scanning tunneling microscopy. Annealing these systems at high temperature (∼1000 °C) and subsequent cooling to room temperature produced ordered arrays of well-separated three-dimensional faceted NPs in their equilibrium state. The observed shapes differ from the kinetically limited shapes of conventional physical vapor deposited NPs, which normally form two-dimensional flat islands upon annealing at elevated temperatures. The initial NP volume was found to provide a means to control the final NP shape. Despite the liquid-phase ex situ synthesis of the micellar particles, the in situ removal of the encapsulating ligands and subsequent annealing consistently lead to the development of a well-defined epitaxial relationship of the metal NPs with the oxide support. The observed epitaxial relationships could be explained in terms of the best overlap between the interfacial Pt (or Au) and TiO 2 lattices. In most cases, the ratio of {100}/{111} facets obtained for the NP shapes resolved clearly deviates from that of conventional bulklike Wulff structures. © 2011 American Chemical Society.

An industrially applicable cobalt-based catalyst was optimized for the production of multiwalled carbon nanotubes (CNTs) from ethene in a hot-wall reactor. A series of highly active Co-Mn-Al-Mg spinel-type oxides with systematically varied Co: Mn ratios was synthesized by precipitation and calcined at different temperatures. The addition of Mn drastically enhanced the catalytic activity of the Co nanoparticles resulting in an extraordinarily high CNTyield of up to 249 g CNT/gcat. All quaternary catalysts possessed an excellent selectivity towards the growth of CNTs. The detailed characterization of the obtained CNTs by electron microscopy, Raman spectroscopy and thermogravimetry demonstrated that a higher Mn content results in a narrower CNT diameter distribution, while the morphology of the CNTs and their oxidation resistance remains rather similar. The temperature- programmed reduction of the calcined precursors as well as in situ X-ray absorption spectroscopy investigations during the growth revealed that the remarkable promoting effect of the Mn is due to the presence of monovalent Mn (II) oxide in the working catalyst, which enhances the catalytic activity of the metallic Co nanoparticles by strong metal-oxide interactions. The observed correlations between the added Mn promoter and the catalytic performance are of high relevance for the production of CNTs on an industrial scale. © 2011 Elsevier Ltd. All rights reserved.

A new class of CeO2/Pt nanostructures containing highly porous carbide-derived carbon composites was obtained for the first time using a polymer precursor strategy and subsequent ceramization. The catalytic transition metal compounds were incorporated into polymeric polycarbosilane structures using an inverse microemulsion method in precisely tunable nanoscale particle sizes. Porous ceramic and carbon composites were obtained by pyrolysis and subsequent chlorination processes. The adsorption properties of nonoxidic ceramic intermediates can be adjusted by the pyrolysis temperatures from mainly microporous to meso- and macroporous materials, respectively. These pore structures remain during the chlorination process confirmed by comparative nitrogen physisorption and small-angle X-ray scattering investigations. The specific surface areas significantly increase up to 1774 m2/g after selective silicon removal. In comparison to unsupported CeO2/Pt nanoparticle structures, the particle sizes and dispersion of the active metal compounds of composite structures remain during pyrolysis and chlorination process studied by electron microscopy methods. Ceramic and carbonaceous composites show catalytic activity and stability in selective methane oxidation. In contrast to the SiC composites, the CDC materials promote the formation of carbon monoxide and hydrogen in reforming reactions at higher temperatures, a conversion pathway important for the generation of synthetic fuels. © 2010 American Chemical Society.

This paper reports on a novel miniaturized deposition technique based on micro-hotplates which are used as microevaporation sources (MES) for a localized deposition of thin films and nanoparticles. The feasibility of this small-scale deposition technique and its general properties are shown for depositions of Ag on unpatterned and microstructured substrates. The deposited films are rotationally symmetric and show a distinct lateral thickness change. We take advantage of this latter effect, as, e.g., all stages of film condensation can be observed within one experiment on one sample, in a size suitable for transmission electron microscopy investigations. For realizing the most laterally confined depositions, a micro-Knudsen cell was used. It is shown that the use of MES is also very suitable for the fabrication and deposition of nanoparticles. © 2011 IEEE.

Silver nanoparticles (Ag-NP) are increasingly used in biomedical applications because of their remarkable antimicrobial activity. In biomedicine, Ag-NP are coated onto or embedded in wound dressings, surgical instruments and bone substitute biomaterials, such as silver-containing calcium phosphate cements. Free Ag-NP and silver ions are released from these coatings or after the degradation of a biomaterial, and may come into close contact with blood cells. Despite the widespread use of Ag-NP as an antimicrobial agent, there is a serious lack of information on the biological effects of Ag-NP on human blood cells. In this study, the uptake of Ag-NP by peripheral monocytes and lymphocytes (T-cells) was analyzed, and the influence of nanosilver on cell biological functions (proliferation, the expression of adhesion molecules, cytokine release and the generation of reactive oxygen species) was studied. After cell culture in the presence of monodispersed Ag-NP (5-30 μg ml -1 silver concentration), agglomerates of nanoparticles were detected within monocytes (CD14+) but not in T-cells (CD3+) by light microscopy, flow cytometry and combined focused ion beam/scanning electron microscopy. The uptake rate of nanoparticles was concentration dependent, and the silver agglomerates were typically found in the cytoplasm. Furthermore, a concentration-dependent activation (e.g. an increased expression of adhesion molecule CD54) of monocytes at Ag-NP concentrations of 10-15 μg ml -1 was observed, and cytotoxicity of Ag-NP-treated monocytes was observed at Ag-NP levels of 25 μg ml -1 and higher. However, no modulation of T-cell proliferation was observed in the presence of Ag-NP. Taken together, our results provide the first evidence for a cell-type-specific uptake of Ag-NP by peripheral blood mononuclear cells (PBMC) and the resultant cellular responses after exposure. © 2011 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

The use of nanostructured yolk-shell materials offers a way to discriminate support and particle-size effects for mechanistic studies in heterogeneous catalysis. Herein, gold yolk-shell materials have been synthesized and used as model catalysts for the investigation of support effects in CO oxidation. Carbon has been selected as catalytically inert support to study the intrinsic activity of the gold nanoparticles, and for comparison, zirconia has been used as oxidic support. Au, @C materials have been synthesized through nanocasting using two different nonporous-core@mesoporous-shell exotemplates: Au@SiO 2@ZrO2 and Au@SiO2@m-SiO2. The catalytic activity of Au, @C with a gold core of about 14nm has been evaluated and compared with Au, @ZrO2 of the same gold core size. The strong positive effect of metal oxide as support material on the activity of gold has been proved. Additionally, size effects were investigated using carbon as support to determine only the contribution of the nanoparticle size on the catalytic activity of gold. Therefore, Au, @C with a gold core of about 7nm was studied showing a less pronounced positive effect on the activity than the metal oxide support effect. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

An in-depth understanding of the fundamental structure of catalysts during operation is indispensable for tailoring future efficient and selective catalysts. We report the evolution of the structure and oxidation state of ZrO2-supported Pd nanocatalysts (∼5 nm) during the in situ reduction of NO with H2 using X-ray absorption fine-structure spectroscopy and X-ray photoelectron spectroscopy. Prior to the onset of the reaction (≤120 °C), a NO-induced redispersion of our initial metallic Pd nanoparticles over the ZrO2 support was observed, and Pd δ+ species were detected. This process parallels the high production of N2O observed at the onset of the reaction (>120 °C), while at higher temperatures (≥150 °C) the selectivity shifts mainly toward N2 (∼80%). Concomitant with the onset of N 2 production, the Pd atoms aggregate again into large (6.5 nm) metallic Pd nanoparticles, which were found to constitute the active phase for the H2-reduction of NO. Throughout the entire reaction cycle, the formation and stabilization of PdOx was not detected. Our results highlight the importance of in situ reactivity studies to unravel the microscopic processes governing catalytic reactivity. © 2011 American Chemical Society.

Recent advances in the synthesis of collidal metal nanoparticles of controlled sizes and shapes that are relevant for catalyst design are reviewed. Three main methods, based on colloid chemistry techniques in solution, i.e., chemical reduction of metal salt precursors, electrochemical synthesis, and controlled decomposition of organometallic compounds and metal-surfactant complexes, are used to synthesize metal nanoparticles. Their catalytic activity and selectivity depend on the shape, size and composition of the metal nanoparticles, and the support effect, as shown for many reactions in quasi-homogeneous and heterogeneous catalysis. A specially designed type of thermally stable catalysts - "embedded" metal catalysts, in which metal nanoparticles are isolated by porous support shells so that metal sintering is effectively avoided at high temperatures, are also introduced. The ultilization of pre-prepared colloidal metal nanoparticles with tuned size, shape and composition as components of designed catalysts opens up new field in catalysis. © 2011 the Owner Societies.

We report about a combined structural and magnetometric characterization of self-assembled magnetic nanoparticle arrays. Monodisperse iron oxide nanoparticles with a diameter of 20nm were synthesized by thermal decomposition. The nanoparticle suspension was spin-coated on Si substrates to achieve self-organized arrays of particles and subsequently annealed at various conditions. The samples were characterized by x-ray diffraction, and bright and dark field high resolution transmission electron microscopy. The structural analysis is compared to magnetization measurements obtained by superconducting quantum interference device magnetometry. We can identify either multi-phase FexO/γ-Fe2O3 or multi-phase Fe xO/Fe3O4 nanoparticles. The Fe xO/γ-Fe2O3 system shows a pronounced exchange bias effect which explains the peculiar magnetization data found for this system. © 2011 IOP Publishing Ltd.

We show that by capping Co nanoparticles (NPs) with small amounts of Pt, strong changes of the magnetic properties can be induced. The Co NPs have a mean diameter of 2.7 nm. From magnetometry measurements we find that for zero and for small amounts of Pt (nominal thickness t Pt < 0.7 nm) the NPs behave superparamagnetic- (SPM)-like. With increasing t Pt the blocking temperature is enhanced from 16 up to 108 K. Capping with Pd yields comparable results. However, for values t Pt > 1 nm a strongly coupled state is encountered resembling a ferromagnet (FM) with a T c ∼ 400 K. © 2011 American Physical Society.

The interaction of CO with differently modified polycrystalline ZnO has been studied by FTIR spectroscopy under ultrahigh vacuum conditions (UHV-FTIRS). After exposing the clean, adsorbate-free ZnO nanoparticles to CO at 110 K we observe an intense vibrational band at 2187 cm-1 which is assigned to a majority of CO species bound to the Zn2+ sites on the mixed-terminated ZnO(101̄0) surface. After the exposure of CO 2-pretreated ZnO nanoparticles to CO at 110 K, a new CO band is observed at 2215 cm-1, which originates from CO species adsorbed on the "free" Zn sites embedded within the (2 × 1) tridentate carbonate structure on the ZnO(101̄0) surface. UHV-FTIRS data recorded at different sample temperatures demonstrate that the binding energy of CO on polycrystalline ZnO is substantially increased in the presence of pre-adsorbed CO2. The presence of hydroxyl species on the ZnO powder particles does not lead to substantial changes of the CO vibrational bands detected at 110 K under UHV conditions. © 2010 Elsevier B.V. All rights reserved.

High-temperature, stable core-shell catalysts for ammonia decomposition have been synthesized. The highly active catalysts, which were found to be also excellent model systems for fundamental studies, are based on α-Fe 2O 3 nanoparticles coated by porous silica shells. In a bottom-up approach, hematite nanoparticles were firstly obtained from the hydrothermal reaction of ferric chlorides, L-lysine, and water with adjustable average sizes of 35, 47, and 75nm. Secondly, particles of each size could be coated by a porous silica shell by means of the base-catalyzed hydrolysis of tetraethylorthosilicate (TEOS) with cetyltetramethylammonium bromide (CTABr) as porogen. After calcination, TEM, high-resolution scanning electron microscopy (HR-SEM), energy-dispersive X-ray (EDX), XRD, and nitrogen sorption studies confirmed the successful encapsulation of hematite nanoparticles inside porous silica shells with a thickness of 20nm, thereby leading to composites with surface areas of approximately 380 m 2g -1 and iron contents between 10.5 and 12.2wt%. The obtained catalysts were tested in ammonia decomposition. The influence of temperature, iron oxide core size, possible diffusion limitations, and dilution effects of the reagent gas stream with noble gases were studied. The catalysts are highly stable at 750°C with a space velocity of 120000 cm 3 g cat -1h -1 and maintained conversions of around 80% for the testing period time of 33 h. On the basis of the excellent stability under reaction conditions up to 800°C, the system was investigated by in situ XRD, in which body-centered iron was determined, in addition to FeN x, as the crystalline phase under reaction conditions above 650deg;C. © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

We report on the probing of the Pt surface for oxygen reduction reaction (ORR) by insertion of Ag. Therefore, PtAg bimetallic nanoparticles were prepared by pulse electrodeposition. In a second step, Ag was electro-dissolved in acidic media from the particles under formation of Pt skeleton. The ORR activity of these Pt skeleton depends on two factors: (1) on the surface properties of the Pt-shell and (2) on the electronic as well as geometric influences of the remaining Ag in the particle core. By varying the conditioning procedure prior to measuring the ORR activity, we were able to differentiate between these two effects. © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The changes induced in the structure and chemical state of size-selected Pt nanoparticles (NPs) supported on ultrathin SiO2 films upon exposure to oxygen have been investigated by atomic force microscopy (AFM), transmission electron microscopy (TEM), in situ X-ray photoelectron spectroscopy (XPS), and temperature-programmed desorption (TPD). For low atomic oxygen exposures, chemisorbed oxygen species were detected on all samples. Exposure to higher atomic oxygen coverages at room temperature leads to the formation and stabilization of PtOx species (PtO2 and PtO). On all samples, a two-step thermal decomposition process was observed upon annealing in ultrahigh vacuum: PtO2 → PtO → Pt. For NPs in the 2-6 nm range, the NP size was found to affect the strength of the O binding. Contrary to the case of Pt(111), where no oxides were detected above 700 K, 10-20% PtO was detected on the NP samples via XPS at the same temperature, suggesting the presence of strongly bound oxygen species. In addition, for identical atomic oxygen exposures, decreasing the NP size was found to favor their ability to form oxides. Interestingly, regardless of whether the desorption of chemisorbed oxygen species or that of oxygen in PtOx species was considered, our TPD data revealed higher O2-desorption temperatures for the Pt NPs as compared with the Pt(111) surface. Furthermore, a clear size-dependent trend was observed, with an increase in the strength of the oxygen bonding with decreasing NP size. © 2011 American Chemical Society.

Nb-doped TiO2 nanoparticles were prepared by a continuous spray drying process using ammonium niobate (V) oxalate and titanium oxysulfate as water-soluble precursors. The structural and electronic properties were investigated using thermogravimetric analysis, X-ray diffraction, X-ray photoelectron spectroscopy and Raman spectroscopy. Nb was found to be mainly incorporated as Nb5+ into the TiO2 lattice resulting in a charge compensation by Ti vacancies. The characterization results indicate that Nb was homogeneously distributed within the titania lattice, and that the surface segregation of Nb, which is commonly observed for Nb-doped TiO 2, was significantly less pronounced. The high homogeneity and the lower extent of surface segregation originate from the efficient atomization of homogeneous precursor solutions and the fast evaporation of the solvent in the spray drying process. As a result, the ion mobility is diminished and spheres of well-mixed precursor materials are formed. Using the continuous spray drying process followed by a controlled heat treatment, the phase composition, the crystal size and the surface area of the Nb-doped TiO2 nanoparticles are easily adjustable. © The Royal Society of Chemistry 2011.

Formic acid (HCOOH) has great potential as an in situ source of hydrogen for fuel cells, because it offers high energy density, is non-toxic and can be safely handled in aqueous solution. So far, there has been a lack of solid catalysts that are sufficiently active and/or selective for hydrogen production from formic acid at room temperature. Here, we report that Ag nanoparticles coated with a thin layer of Pd atoms can significantly enhance the production of H 2 from formic acid at ambient temperature. Atom probe tomography confirmed that the nanoparticles have a core-shell configuration, with the shell containing between 1 and 10 layers of Pd atoms. The Pd shell contains terrace sites and is electronically promoted by the Ag core, leading to significantly enhanced catalytic properties. Our nanocatalysts could be used in the development of micro polymer electrolyte membrane fuel cells for portable devices and could also be applied in the promotion of other catalytic reactions under mild conditions. © 2011 Macmillan Publishers. All rights reserved.

α-Fe2O3 nanoparticles have wide-ranging applications such as in catalysis, sensoring, painting, etc. This is the reason to study their controlled synthesis. Here we have investigated the synthesis of uniform α-Fe2O3 nanoparticles using amino acids as morphology control agents. The products were characterized by transmission electron microscopy (TEM), X-ray diffraction (XRD), thermogravimetry (TG) and differential thermal analysis (DTA). It was found that the type and the amount of amino acids as well as the reaction temperatures have significant influence on the shape and size of the obtained α-Fe2O3 nanoparticles. The use of acidic amino acids (always contain C=O in the side chain) typically leads to the formation of α-Fe2O3 nanoparticles with spindle shape. However, rhombohedrally shaped α-Fe 2O3 nanoparticles were formed in presence of basic amino acids (always contain -NH2 in the side chain). Increasing the amount of amino acid generally results in α-Fe2O3 nanoparticles with decreasing particle sizes. © 2011 World Scientific Publishing Company.

Emulsion separation is of high relevance for filtration applications, liquid-liquid-partitioning of biomolecules like proteins and recovery of products from droplet microreactors. Selective interaction of various components of an emulsion with substrates is used to design microfluidic flow chambers for efficient separation of emulsions into their individual components. Our lab-on-a-chip device consists of an emulsion separation cell with an integrated silicon sensor chip, the latter allowing the detection of liquid motion via the field-effect signal. Thus, within our lab-on-a-chip device, emulsions can be separated while the separation process is monitored simultaneously. For emulsion separation a surface energy step gradient, namely a sharp interface between the hydrophobic and hydrophilic parts of the separation chamber, is used. The key component of the lab-on-a-chip system is a multilayer and multifunctional nanofilm structure which not only provides the surface energy step gradient for emulsion separation but also constitutes the functional parts of the field-effect transistors. The proof-of-principle was performed using a model emulsion consisting of immiscible aqueous and organic solvent components. Droplet coalescence was identified as a key aspect influencing the separation process, with quite different effects during separation on open surfaces as compared to slit geometry. For a detailed description of this observation, an analytical model was derived and lattice Boltzmann computer simulations were performed. By use of grazing incidence small angle x-ray scattering (GISAXS) interfacial nanostructures during gold nanoparticle deposition in a flow field were probed to demonstrate the potential of GISAXS for insitu investigations during flow. © 2011 IOP Publishing Ltd.

A 3D metal ion assisted assembly of nanoparticles has been developed. The approach relies on the efficient complexation of cadmium ions and 5-mercaptomethyltetrazole employed as the stabilizer of both colloidal CdTe and Au nanoparticles. It enables in a facile way the formation of hybrid metal-semiconductor 3D structures with controllable and tunable composition in aqueous media. By means of critical point drying, these assemblies form highly porous aerogels. The hybrid architectures obtained are characterized by electron microscopy, nitrogen adsorption, and optical spectroscopy methods. © 2011 American Chemical Society.

In this study, the authors first review the previously developed, thermodynamics-based theory for size dependency of the cohesion energy of free-standing spherically shaped Al nanoparticles. Then, this model is extrapolated to the cubic and truncated octahedron Al nanoparticle shapes. A series of computations for Al nanoparticles with these two new shapes are presented for particles in the range of 1-100 nm. The thermodynamics computational results reveal that there is a second critical size around 1.62 and 1 nm for cubes and truncated octahedrons, respectively. Below this critical size, particles behave as if they consisted only of surface-energy-state atoms. A molecular dynamics simulation is used to verify this second critical size for Al nanoparticles in the range of 1-5 nm. MD simulation for cube and truncated octahedron shapes shows the second critical point to be around 1.63 and 1.14 nm, respectively. According to the modeling and simulation results, this second critical size seems to be a material property characteristic rather than a shape-dependent feature.

This study presents a systematic investigation of the thermodynamic properties of free and γ-Al 2O 3-supported size-controlled Pt nanoparticles (NPs) and their evolution with decreasing NP size. A combination of in situ extended x-ray absorption fine-structure spectroscopy (EXAFS), ex situ transmission electron microscopy (TEM) measurements, and NP shape modeling revealed (i) a cross over from positive to negative thermal expansion with decreasing particle size, (ii) size- and shape-dependent changes in the mean square bond-projected bond-length fluctuations, and (iii) enhanced Debye temperatures (Θ D, relative to bulk Pt) with a bimodal size-dependence for NPs in the size range of ∼0.8-5.4 nm. For large NP sizes (diameter d >1.5 nm) Θ D was found to decrease toward Θ D of bulk Pt with increasing NP size. For NPs ≤ 1 nm, a monotonic decrease of Θ D was observed with decreasing NP size and increasing number of low-coordinated surface atoms. Our density functional theory calculations confirm the size- and shape-dependence of the vibrational properties of our smallest NPs and show how their behavior may be tuned by H desorption from the NPs. The experimental results can be partly attributed to thermally induced changes in the coverage of the adsorbate (H 2) used during the EXAFS measurements, bearing in mind that the interaction of the Pt NPs with the stiff, high-melting temperature γ-Al 2O 3 support may also play a role. The calculations also provide good qualitative agreement with the trends in the mean square bond-projected bond-length fluctuations measured via EXAFS. Furthermore, they revealed that part of the Θ D enhancement observed experimentally for the smallest NPs (d ≤ 1 nm) might be assigned to the specific sensitivity of EXAFS, which is intrinsically limited to bond-projected bond-length fluctuations. © 2011 American Physical Society.

Herein we reported the PEGylated hollow mesoporous silica (HMS-PEG) nanoparticles as drug vehicles for drug delivery. Hollow mesoporous silica (HMS) nanoparticles with the diameter of ca. 100 nm were synthesized using the colloidal carbon spheres as templates, and HMS-PEG nanoparticles were successfully prepared by covalently grafting poly(oxyethylene)bis(amine) on amino-group modified HMS nanoparticles with p-phenylene diisothiocyanate (DITC) as a cross linker. HMS-PEG nanoparticles exhibited much better dispersity and stability in aqueous solution than HMS nanoparticles. In vitro cytotoxicity and cell uptake of HMS-PEG nanoparticles to Hela and NIH3T3 cells were evaluated. HMS-PEG nanoparticles have little in vitro cytotoxicity up to a concentration of 150 μg/ml, and the uptake amount of HMS-PEG nanoparticles is approximately two times than that of HMS nanoparticles in Hela and NIH3T3 cells. Doxorubicin hydrochloride (DOX), an anticancer drug, was loaded into HMS-PEG nanoparticles, and the DOX-loaded HMS-PEG nanoparticles had a sustained release property. Furthermore, the DOX-loaded HMS-PEG nanoparticles exhibited higher cytotoxicity than the DOX-loaded HMS nanoparticles against Hela and NIH3T3 cells. Therefore, the PEGylation of HMS nanoparticles is a promising strategy toward their potential application as drug delivery vehicles. © 2010 Elsevier Inc. All rights reserved.

PtAg bimetallic nanoparticles for oxygen reduction reaction (ORR) in alkaline media were prepared by pulse electrodeposition (PED). During PED the reduction of Ag + ions predominates, thus an increased Ag content in the co-deposit is accomplished. The mechanism for this anomalous co-deposition was elucidated by potential pulse experiments, which revealed that nuclei formation mainly occurs via the reduction of Pt 2+ ions. The growth of the particles is diffusion controlled leading to the formation of a Ag shell covering a PtAg alloyed region. However, the shell is not growing homogeneously on the PtAg alloy. Hence, regions of the PtAg alloy are exposed, which exhibit an enhanced ORR activity compared to a pure Ag surface. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The activation of CO 2 on clean and hydroxylated ZnO nanoparticles has been studied by ultrahigh vacuum FTIR spectroscopy (UHV-FTIRS). Exposing the clean ZnO powder samples to CO 2 at 300 K leads to the formation of a number of carbonate-related bands. A detailed assignment of these bands was carried out using isotope-substitution experiments with C 18O 2. On the basis of vibrational and thermal stability data for ZnO single crystal surfaces, a consistent description of the interaction of CO 2 with ZnO powder particles can be provided: (1) on the mixed-terminated ZnO(101?0) facets, a tridentate carbonate is formed; (2) on the polar, O-terminated (0001?) facets, a bidentate carbonate species is formed via CO 2 activation at oxygen vacancy sites; and (3) additional monodentate or polydentate carbonate species are formed at defect sites such as steps, edges, kinks, and vacancies. The formation of carbonate-related vibrational bands is observed at an exposure temperature as low as 100 K, thus demonstrating the high activity of ZnO nanoparticles with regard to CO 2 activation. © 2010 American Chemical Society.

Silver nanoparticles (Ag-NP) are widely used due to their well-known antibacterial effects. In medicine Ag-NP have found applications as wound dressings, surgical instruments and bone substitute biomaterials, e.g. silver-containing calcium phosphate cements. Depending on the coating technique, during resorption of a biomaterial Ag-NP may come into close contact with body tissues, including human mesenchymal stem cells (hMSC). Despite the widespread uses of Ag-NP, there is a serious lack of information concerning their biological effects on human cells. In this study the uptake of Ag-NP into hMSC has been analyzed and the intracellular distribution of Ag-NP after exposure determined. Non-agglomerated (dispersed) Ag-NP from the cell culture medium were detected as agglomerates of nanoparticles within the hMSC by combined focused ion beam/scanning electron microscopy. The silver agglomerates were typically located in the perinuclear region, as determined by light microscopy. Specific staining of cellular structures (endo-lysosomes, nuclei, Golgi complex and endoplasmatic reticulum) using fluorescent probes showed that the silver nanoparticles occurred mainly within endo-lysosomal structures, not in the cell nucleus, endoplasmic reticulum or Golgi complex. Quantitative determination of the uptake of Ag-NP by flow cytometry (scattergram analysis) revealed a concentration-dependent uptake of the particles which was significantly inhibited by chlorpromazine and wortmannin but not by nystatin, indicating clathrin-dependent endocytosis and macropinocytosis as the primary uptake mechanisms. © 2010 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

In this paper, we present the excitation spectra of fully saturated CdSe/CdS and CdS/CdSe core shell nanoparticles with a size distribution ranging from 100 to 650 atoms. The spectra have been calculated using linear-response theory and a density-functional tight-binding method. We have investigated their dependence with respect to the size of the core and the shell as well as the underlying crystal structure (zincblende and wurtzite). The influence of the size of the material with the lower band gap (CdSe) is clearly visible in the spectra. Moreover, the frontier orbitals are localized in either the core or the shell part, leading to a moderate overlap only. In contrast, the influence of the symmetry reduction from cubic zincblende to hexagonal wurtzite is rather small and results in a splitting of the excitation peaks.

Unraveling the complex interaction between catalysts and reactants under operando conditions is a key step toward gaining fundamental insight in catalysis. We report the evolution of the structure and chemical composition of size-selected micellar Pt nanoparticles (∼1 nm) supported on nanocrystalline γ-Al2O3 during the catalytic oxidation of 2-propanol using X-ray absorption fine-structure spectroscopy. Platinum oxides were found to be the active species for the partial oxidation of 2-propanol (< 140 °C), while the complete oxidation (>140 °C) is initially catalyzed by oxygen-covered metallic Pt nanoparticles, which were found to regrow a thin surface oxide layer above 200 °C. The intermediate reaction regime, where the partial and complete oxidation pathways coexist, is characterized by the decomposition of the Pt oxide species due to the production of reducing intermediates and the blocking of O2 adsorption sites on the nanoparticle surface. The high catalytic activity and low onset reaction temperature displayed by our small Pt particles for the oxidation of 2-propanol is attributed to the large amount of edge and corner sites available, which facilitate the formation of reactive surface oxides. Our findings highlight the decisive role of the nanoparticle structure and chemical state in oxidation catalytic reactions. © 2011 American Chemical Society.

Electrochemically-assisted deposition of sol-gel materials can be locally confined at Pt nanoparticles. Pt nanoparticles have been locally deposited on glassy carbon surfaces by pulse electrodeposition using a droplet cell. Upon applying a potential for electrochemically-assisted deposition, the formed sol-gel film mirrors the region of the glassy carbon surface previously modified with Pt nanoparticles. © 2011 Elsevier B.V. All rights reserved.

This article presents a systematic study of the formation and thermal stability of Pt oxide species on sizeselected Pt nanoparticles (NPs) supported on SiO2, ZrO2, and TiO2 thin films. The studies were carried out in ultrahigh vacuum (UHV) by temperature-dependent X-ray photoelectron spectroscopy (XPS) measurements and ex situ transmission electron microscopy and atomic force microscopy. The NPs were synthesized by inverse micelle encapsulation and oxidized in UHV at room temperature by an oxygen plasma treatment. For a given particle size distribution, the role played by the NP support on the stability of Pt oxides was analyzed. PtO2 species are formed on all supports investigated after O2-plasma exposure. A two-step thermal decomposition (PtO2 → PtO → Pt) is observed from 300 to 600 K upon annealing in UHV. The stability of oxidized Pt species was found to be enhanced on ZrO2 under annealing treatments in O2. Strong NP/support interactions and the formation of Pt-Ti-O alloys are detected for Pt/TiO2 upon annealing in UHV above 550 K but not under an identical treatment in O2. Furthermore, thermal treatments in both environments above 700 K lead to the encapsulation of Pt by TiOx. The final shape of the micellar Pt NPs is influenced by the type of underlying support as well as by the post-deposition treatment. Spherical Pt NPs are stable on SiO2, ZrO2, and TiO 2 after in situ ligand removal with atomic oxygen at RT. However, annealing in UHV at 1000 K leads to NP flattening on ZrO2 and to the diffusion of Pt NPs into TiO2. The stronger the nature of the NP/support interaction, the more dramatic is the change in the NP shape (TiO2 > ZrO2 > SiO2). © 2010 American Chemical Society.

Magnetic Γ-Fe 2O 3 nanoparticles with a mean diameter of 20 nm and size distribution of 7% were chemically synthesized and spin-coated on top of a Si-substrate. As a result, the particles self-assembled into a mono layer with hexagonal close-packed order. Subsequently, the nanoparticle array was coated with a Co layer of 20 nm thickness. The magnetic properties of this composite nanopar-ticle/thin film system were investigated by magnetometry and related to high-resolution transmission electron microscopy studies. Herein three systems were compared: i.e. a reference sample with only the particle monolayer, a composite system where the particle array was ion-milled prior to the deposition of a thin Co film on top, and a similar composite system but without ion-milling. The nanoparticle array showed a collective super-spin behavior due to dipolar interparticle coupling. In the composite system, we observed a decoupling into two nanoparticle subsystems. In the ion-milled system, the nanoparticle layer served as a magnetic flux guide as observed by magnetic force microscopy. Moreover, an exchange bias effect was found, which is likely to be due to oxygen exchange between the iron oxide and the Co layer, and thus forming of an antiferromagnetic CoO layer at the Γ-Fe 2O 3/Co interface. © 2010 Confalonieri et al.

(Figure Presented) The colloidal deposition method was used to prepare Au/Mg(OH)2 (0.7 wt % gold) catalysts with gold particle sizes between 1.5 to 5 nm which exhibited very high activity for CO oxidation with specific rates higher than 3.7 molCO·h-1·g Au-1 even at temperatures as low as -89° C. © 2010 American Chemical Society.

Exciting new opportunities are emerging in the field of catalysis based on nanotechnology approaches. A new understanding and mastery of catalysis could have broad societal impacts, since about 80% of the processes in the chemical industry depend on catalysts to work efficiently. Efforts in surface science have led to the discovery of new heterogeneous catalysts, however, until recently the only way to develop new or improved catalysts was by empirical testing in trial-and-error experiments. This time-consuming and costly procedure is now rapidly being replaced by rational design methods that utilize fundamental knowledge of catalysts at the nanoscale. The advent of nanoscience and nanotechnology is providing the ability to create controlled structures and geometries to investigate and optimize a broad range of catalytic processes. As a result, researchers are obtaining fundamental insight into key features that influence the activity, selectivity, and lifetime of nanocatalysts. This review article examines several new findings as well as current challenges in the field of nanoparticle based catalysis, including the role played by the particle structure and morphology (size and shape), its chemical composition and oxidation state, and the effect of the cluster support. © 2010 Elsevier B.V. All rights reserved.

Uniform and highly dispersed γ-Fe 2O 3 nanoparticles with a diameter of ∼6 nm supported on CMK-5 carbons and C/SBA-15 composites were prepared via simple impregnation and thermal treatment. The nanostructures of these materials were characterized by XRD, Mössbauer spectroscopy, XPS, SEM, TEM, and nitrogen sorption. Due to the confinement effect of the mesoporous ordered matrices, γ-Fe 2O 3 nanoparticles were fully immobilized within the channels of the supports. Even at high Fe-loadings (up to about 12 wt %) on CMK-5 carbon no iron species were detected on the external surface of the carbon support by XPS analysis and electron microscopy. Fe 2O 3/CMK-5 showed the highest ammonia decomposition activity of all previously described Fe-based catalysts in this reaction. Complete ammonia decomposition was achieved at 700 °C and space velocities as high as 60 000 cm 3 g cat -1 h -1. At a space velocity of 7500 cm 3 g cat -1 h -1, complete ammonia conversion was maintained at 600 °C for 20 h. After the reaction, the immobilized γ-Fe 2O 3 nanoparticles were found to be converted to much smaller nanoparticles (γ-Fe 2O 3 and a small fraction of nitride), which were still embedded within the carbon matrix. The Fe 2O 3/CMK-5 catalyst is much more active than the benchmark NiO/Al 2O 3 catalyst at high space velocity, due to its highly developed mesoporosity. γ-Fe 2O 3 nanoparticles supported on carbon-silica composites are structurally much more stable over extended periods of time but less active than those supported on carbon. TEM observation reveals that iron-based nanoparticles penetrate through the carbon layer and then are anchored on the silica walls, thus preventing them from moving and sintering. In this way, the stability of the carbon-silica catalyst is improved. Comparison with the silica supported iron oxide catalyst reveals that the presence of a thin layer of carbon is essential for increased catalytic activity. © 2010 American Chemical Society.

The adsorption of methanol on pure ZnO and A--u-decorated ZnO nanoparticles and its thermal decomposition monitored by temperature-programmed desorption (TPD) experiments and by diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), both applied under continuous flow conditions in fixed bed reactors, is reported. Two distinguishable methoxy species are formed during methanol adsorption on ZnO differing in the C-O stretching bands. During the subsequent TPD experiments two different H2peaks are observed, indicating the conversion of methoxy into formate species. By applying different heating rates, activation energies of 109 kJmol-1 and 127 kJmol-1 for the selective oxidation of the two methoxy species are derived. Correspondingly, the methoxy decomposition results in two distinguishable formate species, which are identified by the asymmetric and symmetric OCO stretching bands on pure ZnO and Au/ZnO. Based on the decreased intensities of the OH bands during methanol adsorption, which are specific for the various ZnO single crystal surfaces, on the different reactivities of these surfaces, and on the formate FTIR bands observed on ZnO single crystal surfaces, the two methoxy and the corresponding formate species are identified to be adsorbed on the exposed less reactive non-polar ZnO(101̄0) surface and on the highly reactive polar ZnO(0001̄) surface. The simultaneous formation of H2, CO, and CO2 at about 550-600 K during the TPD experiments indicate the decomposition of adsorbed formate species. The CO/CO2 ratio decreases with increasing Au loading, and a broad band due to electronic transitions from donor sites to the conduction band is observed in the DRIFT spectra for the Au-decorated ZnO nanoparticles. Thus, the presence of the Au nanoparticles results in an enhanced reducibility of ZnO facilitating the generation of oxygen vacancies. © 2010 Wiley-VCH Verlag GmbH& Co. KGaA, Weinheim.

Methods and instrumentation based on resonance frequency dependence of dielectric micro resonators on the surrounding medium is being developed as a real-time one-way disposable sensor for a number of parameters of nano particles and modeling blood in situ. © 2010 IEEE.

Electroluminescence from as-prepared silicon nanoparticles, fabricated by gas phase synthesis, is demonstrated. The particles are embedded between an n-doped GaAs substrate and a semitransparent indium tin oxide top electrode. The total electroluminescence intensity of the Si nanoparticles is more than a factor of three higher than the corresponding signal from the epitaxial III-V semiconductor. This, together with the low threshold voltage for electroluminescence, shows the good optical properties of these untreated particles and the efficient electrical injection into the device. Impact ionization by electrons emitted from the top electrode is identified as the origin of the electrically driven light emission. © 2010 IOP Publishing Ltd.

Highly loaded copper catalysts supported on alumina are synthesized applying the cyclic two-step CVD of the precursor copper(II)diethylamino-2- propoxide in a fluidized-bed reactor. Copper/zinc oxide/alumina composites are synthesized by either the CVD of the precursor bis[bis (trimethylsilyl) amido]zinc on Cu/Al2O3, or the CVD of the Cu precursor on Zn-pretreated alumina, impregnating with diethyl zinc in addition. The composites are extensively characterized by atomic absorption spectroscopy (AAS), elemental analysis (EA), mass spectrometry (MS), N2 physisorption, N2O reactive frontal chromatography (RFC), and X-ray diffraction (XRD). The Cu and ZnO nanoparticles originating from the efficient two-step procedure, consisting of adsorption and subsequent decomposition of the adsorbed species in two separated steps, are highly dispersed, X-ray amorphous, and, in the case of the Cu-containing catalysts, have high specific Cu surface areas. The catalytic activities are determined both in methanol synthesis, to judge the contact between the deposited Cu and ZnO nanoparticles, and in the steam reforming of methanol (SRM) to probe the stability of the Cu particles. The turn-over frequencies (TOF) in methanol synthesis of these Cu/ZnO/Al 2O3 catalysts are higher than that of a commercial ternary catalyst. The varied sequence of the CVD of Cu and ZnO on alumina leads to catalysts with similar activities in the case of similar specific Cu areas. © 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The Dark Crystal: A hybrid material is reported that is comprised of 1-2 nm sized gold nanoparticles, accessible only through zeolite micropores in a silicalite-1 crystal, as shown by three-dimensional TEM tomography (see picture). Calcination experiments indicate that the embedded nanoparticles are highly stable towards sintering. Figure Equation Present. © 2010 Wiley-VCH Verlag GmbH & Co. KGaA.

Carbon nanotube (CNT) supported sulfided Rh catalysts were prepared applying three different routes: deposition-precipitation (DP), grafting of colloidal Rh nanoparticles, and polythiophene-assisted synthesis. The catalysts (1.4-1.8 wt%) prepared by DP were synthesized on CNTs from RhCl3 using hydrogen peroxide and subsequent exposure to on-line generated H 2S followed by heat treatment. The Rh particles were found to be highly dispersed on the CNT surface. Alternatively, RhSx/Rh nanoparticles with four different loadings (4.3-21.9 wt%) grafted on carbon nanotubes were prepared through a functionalization of CNTs with short chain thiols and subsequent binding of colloidal Rh nanoparticles onto the thiolated CNTs. All steps of the synthesis were monitored by XPS. Finally, polythiophene/CNT composites were prepared and employed in the preparation of Rh17S15/Rh nanoparticles supported on CNTs. The CNTs with the highest polythiophene loading yielded the highest amount of Rh 17S15 after Rh deposition and thermal treatment. The activity and stability of the prepared catalysts were studied towards the oxygen reduction reaction. © 2010 Elsevier B.V. All rights reserved.

Exposing ZnO nanoparticles to atomic and molecular hydrogen at room temperature decreases the transmission coefficient, which demonstrates that diffusion of hydrogen atoms to subsurface and bulk ZnO sites already occurs at these fairly low temperatures (see figure). The interstitial hydrogen atoms act as n-type shallow donors, which increase the density of electrons in the conduction band. © 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Nanoactuators made from nanoparticulate NiTi shape memory alloy show potential in the mechanical stimulation of bone tissue formation from stem cells. We demonstrate the fabrication of Ni, Ti, and NiTi shape memory alloy nanoparticles and their biocompatibility to human adipose-derived stem cells. The stoichiometry and phase transformation property of the bulk alloy is preserved during attrition by femtosecond laser ablation in liquid, giving access to colloidal nanoactuators. No adverse effect on cell growth and attachment is observed in proliferation assay and environmental electron scanning microscopy, making this material attractive for mechanical stimulation of stem cells.

Nanoscale copper was selectively photodeposited onto the surface of hexadecylamine (HDA) stabilized (monodispersed not agglomerated) ZnO nanoparticles (NPs) of a diameter of 2-5 nm, which leads to HDA-stabilized Cu/ZnO NPs of varied Cu loading. The particles are soluble in non-polar organic solvents. The line broadening and the red shift of the surface plasmon band of Cu/ZnO NPs relative to HDA-stabilized Cu NPs, the profound decrease of the Cu/ZnO NPs visible photoluminescence at 525 nm, the increase of the UV emission intensity at 365 nm and the enhancement of the Raman scattering (RS) intensity in comparison to the parent ZnO NPs confirmed the interfacial contact between the Cu and ZnO phase. © 2010 the Owner Societies.

A novel electrochemical method to prepare platinum shells around carbon-supported metal nanoparticles (Ru and Au) by pulsed electrodeposition from solutions containing Pt ions is presented. Shell formation is confirmed by characteristic changes in the cyclic voltammograms, and is further evidenced by monitoring particle growth by transmission electron microscopy as well as by energy-dispersive analysis of X rays (EDX). Scanning electrochemical microscopy and EDX measurements indicate a selective Pt deposition on the metal/carbon catalyst, but not on the glassy carbon substrate. The thus prepared carbon-supported core-shell nanoparticles are investigated with regard to their activity in electrocatalytic oxygen reduction, which demonstrates the applicability of these materials in electrocatalysis or sensors. © 2010 Wiley-VCH Verlag GmbH& Co. KGaA, Weinheim.

Binding of gold nanoparticles (Au-NP) at amine-functionalised multi-walled carbon nanotubes (MWNTs) is proposed. The MWNTs are functionalised with acylchloride groups, which further react with ethylenediamine to form amine-functionalised MWCNTs. These amines are able to bind preformed colloidal Au-NPs. The Au/MWNT composite material facilitates electron-transfer reactions with free-diffusing redox compounds. © 2010 Elsevier B.V. All rights reserved.

Rhodium-rhodium sulfide nanoparticles supported on multi-walled carbon nanotubes (CNTs) were synthesized via a multi-step colloid route. The CNTs were first exposed to nitric acid to generate oxygen-containing functional groups, and then treated with thionyl chloride to generate acyl chloride groups. The grafting of thiol groups was subsequently carried out by reaction with 4-aminothiophenol. Colloidal rhodium nanoparticles were synthesized using rhodium chloride as metal source, sodium citrate as stabilizer, and sodium borohydride as reducing agent. The immobilization of the generated colloidal rhodium nanoparticles was achieved by adding the thiolated CNTs to the colloidal suspension. All these steps were monitored by X-ray photoelectron spectroscopy, which disclosed the presence of rhodium sulfide, whereas metallic rhodium was detected by X-ray diffraction, suggesting that the nanoparticles probably consist of a metallic Rh core covered by a sulfide layer. Scanning and transmission electron microscopy studies showed that the diameter of the catalyst particles was about 7 nm even at high Rh loadings. Rotating disc electrode measurements and cyclic voltammetry were employed to test the electrocatalytic activity in the oxygen reduction reaction in hydrochloric acid. Among all the synthesized catalysts with different rhodium loadings (4.3-21.9%), the 16.1% rhodium catalyst was found to be the most active catalyst. In comparison to the commercial E-TEK Pt/C catalyst, the 16.1% catalyst displayed a higher electrochemical stability in the highly corrosive electrolyte, as determined by stability tests with frequent current interruptions. © 2010 The Royal Society of Chemistry.

Despite the advances in high throughput experimentation in recent years the synthesis of realistic catalyst libraries especially gradient catalyst libraries remains as a challenge in material science. Recently, we have developed a method for the synthesis of gradient catalyst libraries consisting of nanoparticles supported on high surface area porous substrates. Chemical vapor deposition (CVD) was employed as a gas-phase method for the synthesis. The method made use of the lateral concentration profile of the precursor-loaded carrier gas stream during CVD, resulting in concentration profile of the deposits on porous substrates. In this report, high surface area materials of both powders (e.g., silica) and bulk composites (e.g., hierarchical carbon structures) were successfully employed as substrates for the deposition of single metal or bimetallic catalyst libraries. The synthesis was achieved by controlling the flow behavior of the effluent precursor stream. The resulting effusion cone led to a radial deposition gradient on the substrate. Different from thin film-type model catalyst libraries, the obtained catalysts can be tested under realistic reaction conditions. Methanol oxidation was studied as a test reaction using scanning mass spectrometry. Copyright © 2010 American Scientific Publishers.

Tailoring the chemical reactivity of nanomaterials at the atomic level is one of the most important challenges in catalysis research. In order to achieve this elusive goal, fundamental understanding of the geometric and electronic structure of these complex systems at the atomic level must be obtained. This article reports the influence of the nanoparticle shape on the reactivity of Pt nanocatalysts supported on γ-Al2O3. Nanoparticles with analogous average size distributions (∼0.8-1 nm), but with different shapes, synthesized by inverse micelle encapsulation, were found to display distinct reactivities for the oxidation of 2-propanol. A correlation between the number of undercoordinated atoms at the nanoparticle surface and the onset temperature for 2-propanol oxidation was observed, demonstrating that catalytic properties can be controlled through shape-selective synthesis. © 2010 American Chemical Society.

(Figure Presented) The shape of gold: The title catalyst has been prepared through a colloidal deposition method. Scanning transmission electron microscopy studies confirmed that for the catalyst, gold clusters with a bilayer structure and a diameter of about 0.5 nm are not mandatory to achieve the high activity (see image). © 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Anomalous lattice dynamics and thermal behavior have been observed for ligand-free, size-, and shape-selected Pt nanoparticles (NPs) supported on nanocrystalline γ -Al2 O3 via extended x-ray absorption fine-structure spectroscopy. Several major differences were observed for the NPs with respect to bulk Pt: (i) a contraction in the interatomic distances, (ii) a reduction in the dynamic (temperature-dependent) bond-length disorder and associated increase in the Debye temperature (θD), and (iii) an overall decrease in the bond-length expansion coefficient coupled with NP stiffening. The increase in the Debye temperature is explained in terms of the NP size, shape, support interactions, and adsorbate effects. For a similar average size, we observe a striking correlation between the shapes of the NPs and their θD values. © 2010 The American Physical Society.

A novel emerging technique for the label-free analysis of nano particles including biomolecules using optical micro cavity resonance is being developed. Various schemes based on a mechanically fixed microspheres as well as microspheres melted by laser on the tip of a standard single mode fiber have been investigated to make further development for microbial application. Water solutions of ethanol, HCl, glucose, vitamin C and biotin have been used to test refractive index changes by monitoring the magnitude of the whispering gallery modes spectral shift. Particular efforts were made for effective fixing of the micro spheres in the water flow, an optimal geometry for micro resonance observation and material of microsphere the most appropriate for microbial application. Optical resonance in free micro spheres from PMMA fixed in micro channels produced by photolithography has been observed under the laser power of less then 1 microwatt. Resonance shifts of C reactive protein water solutions as well as albumin solutions in pure water and with HCl modelling blood have been investigated. Introducing controlled amount of glass gel nano particles into sensor microsphere surrounding were accompanied by both correlative resonance shift (400 nm in diameter) and total reconstruct of resonance spectra (57 nm in diameter). Developed schemes have been demonstrated to be a promising technology platform for sensitive, lab-on-chip type sensor of diagnostic tools for different biological molecules, e.g. proteins, oligonucleotides, oligosaccharides, lipids, small molecules, viral particles, cells as well as in different experimental contexts e.g. proteomics, genomics, drug discovery, and membrane studies. © 2010 SPIE.

In this study, we provide a simple and reproducible method for the preparation of highly active and recyclable colloidal acid catalysts. First, 16-heptadecenoic acid-functionalized magnetite nanoparticles were encapsulated in monodisperse cross-linked polymer spheres. This was achieved by emulsion copolymerization technique in an aqueous phase of styrene and divinylbenzene (DVB). Different ratios of styrene and DVB were used to tune the structural stability and surface morphology of the composites. With increase in DVB content, the surfaces of the colloidal composites become increasingly rougher. The obtained colloids were functionalized with sulfonic acid groups to obtain magnetically recyclable catalysts with H+ contents in the range of 2.2-2.5 mmol g-1 and surface areas of 45-120 m2 g -1. For the condensation reaction of benzaldehyde and ethylene glycol, magnetic acid catalyst prepared only from DVB precursor was found to be active and with high selectivity and long-term stability. © 2010 American Chemical Society.

The gold-zirconia yolk-shell system is an interesting catalyst for CO oxidation. The size distribution of the gold nanoparticles is very narrow, and they are well separated from each other also after treatment at high temperature, which is due to their encapsulation in crystalline zirconia hollow spheres. Because this allows thermal and chemical treatment without affecting the size distribution, different defect structures of the gold nanoparticles can be induced, and the effect on catalytic activity can be investigated. Line profile analysis of the powder diffraction data based on the whole powder pattern modeling approach was used to determine the domain size distribution and lattice defects present in this two-phase system. The influence of different diffractometer setups on the results of the line profile analysis was also investigated. Variation of the chemical and thermal treatment procedures allowed altering the microstructure of the system. The resulting catalysts showed substantial variation in the activity for CO oxidation. Lower dislocation densities and less stacking faults result in decreased catalytic activity. These contributions to activity could be studied without any superimposed size effect due to the constant gold particle sizes. © 2010 American Chemical Society.

In-situ scanning tunneling microscopy (STM) and X-ray photoelectron spectroscopy (XPS) measurements have been performed to investigate the formation and thermal stability of mono- and bimetallic Au xFe 1-x (x 1, 0.8, 0.5, 0.2, 0) nanoparticles (NPs) supported on TiO 2(110). Nearly hexagonal arrangements of sizeselected Au, Fe, and Au-Fe NPs with well-defined interparticle distances have been achieved by diblockcopolymer encapsulation. Upon stepwise annealing from 300 to 1060 °C, a remarkable thermal stability of the Au-Fe NPs was observed, maintaining their original spatial arrangement on the TiO 2 surface up to 900 °C. A majority phase of a gold-iron alloy (solid solution) was achieved for our Au 0.5Fe 0.5 NPs in the temperature range of 700 °C - 800 °C, and for Au 0.2Fe 0.8 NPs at 800 °C, while a phase mixture of bcc Fe and Au-Fe alloy was observed for the Au 0.8Fe 0.2 system at 800 °C-900 °C. For all samples the segregation of Au atoms toward the NP surface was detected upon high temperature annealing (800 °C) in vacuum. Nearly complete Au desorption was observed by XPS at 900 °C for Au 0.2Fe 0.8 NPs, at 1000 °C for Au 0.5Fe 0.5 NPs, and at 1060 °C for Au 0.8Fe 0.2 NPs. The enhanced thermal stability of Au in the Au 0.8Fe 0.2 NPs is believed to be related to the formation of core(Fe)/shell(Au) structures. Furthermore, contrary to the case of pure Fe or Fe-rich NPs where nearly complete Fe desorption or Fe diffusion into TiO 2 was observed at 1000 °C, an Fe signal was detected at this temperature for the Au-rich samples (Au 0.8Fe 0.2 and Au 0.5Fe 0.5). © 2009 American Chemical Society.

Carbon nanotubes (CNT) supported platinum-ruthenium (Pt-Ru) catalysts were prepared by impregnation-reduction using an ethanolic solution of H 2PtCl6 and RuCl3. The effect of reduction temperatures on particle size, surface area and their relationship to the electrocatalytic activity for methanol oxidation were investigated. Thermogravimetric analysis, scanning electron microscopy, transmission electron microscopy, X-ray diffraction (XRD) as well as X-ray photoelectron spectroscopy (XPS) were used for the catalyst characterization. XRD analysis showed that the PtRu/ CNT catalysts possibly consist of separate Pt and Ru phases. XPS analysis showed that the catalysts contain hydrous ruthenium oxide in addition to Pt and Ru metal and oxide species. The electrocatalytic activities of the catalysts were investigated in half-cell experiments using cyclic voltammetry, CO stripping voltammetry, chronoamperometry, and impedance spectroscopy. The results showed that the catalyst reduced at a temperature of 350°C had the largest electrochemical surface area, lowest charge transfer resistance and the highest electrocatalytic activity for methanol oxidation. The superior catalytic activity is discussed based on the presence of appropriate amount of hydrated Ru oxide. © 2009 American Chemical Society.

Gold nanoparticles with diameters ranging from 3.2 to 9.7 nm were prepared on an ultrathin anodic aluminum film by means of molecular beam deposition. Coverages ranging from 17.9% to 48.5% and the subsequent anodic anodization behavior were studied. Further oxide growth does not completely cover the gold nanoparticles but takes place preferentially under the particles with a surprisingly low kinetic hindrance. The gold nanoparticles are electrically isolated from the substrate as demonstrated by the absence of electrocatalytic reactions on the gold surface. A strong surface charge phenomenon is observed, which increases with increasing gold coverage that yields an increase of the capacity up to the minimum potential required for further oxide formation. © 2009 American Chemical Society.

Nanoparticles can be produced by wet grinding in stirred media mills if agglomeration is prevented by stabilization of the particles. Since the fracture mechanisms at the lower nanoscale are not yet understood, we studied the evolution of the microstructure within tin dioxide particles. Electrostatic stabilization allows the formation of tin dioxide with a mean particle size of 25 nm as measured by dynamic light scattering. High-resolution transmission electron microscopy (HRTEM) images show particles well below 10 nm and mean crystallite sizes of 9 nm were obtained from X-ray diffraction by applying the Rietveld refinement method. Additionally, TEM and HRTEM analyses were conducted to gain detailed insight into the microstructural effects governing the grinding process. Microscopy revealed surprisingly rich phenomena including the formation of shear bands, twinning and stacking faults that directly affect the grinding behavior. Interestingly the ceramic nanoparticles showed not only fracture patterns expected from brittle fracture but also many traces of plastic deformation. For comparison the uniaxial compression of particles up to 30 nm in diameter was simulated using molecular dynamics. The simulated particles shared microstructural details with the real samples, most importantly the shear bands which lead to significant plastic deformation. The internal microstructure produced during multiple particle stressing events in the mill and also observed in the simulations is directly linked to the fracture mechanism and the experimentally observed grinding limit. © 2009 Acta Materialia Inc.

The effect of pretreatment conditions on the oxidation state and activity of micelle-synthesized Pt nanoparticles supported on ZrO2 was studied for methanol decomposition and oxidation reactions. An O2- pretreatment is observed to be effective for producing clean, stable, and active nanoparticles. Pt-oxide species formed during such pretreatments were found to have little influence in methanol decomposition reactions due to their tendency to reduce. However, these same species are stable during methanol oxidation and appear to take part in a Mars-van Krevelen-type of process, in which bound-oxygen (nanoparticle shell) may be replenished with oxygen from the gas phase. © 2009 Springer Science+Business Media, LLC.

This article discusses the performance of ZrO2-supported size-selected Pt nanoparticles for the decomposition of methanol, ethanol, 2-propanol, and 2-butanol. The potential of each alcohol for the production of H2 and other relevant products in the presence of a catalyst is studied in a packed-bed mass flow reactor operating at atmospheric pressure. All the alcohols studied show some decomposition activity below 200 °C which increased with increasing temperature. In all cases, high selectivity towards H2 formation is observed. With the exception of methanol, all alcohol conversion reactions lead to catalyst deactivation at high temperatures (T > 250 °C for 2-propanol and 2-butanol, T > 325 °C for ethanol) due to carbon poisoning. However, long-term catalyst deactivation can be avoided by optimizing reaction conditions such as operating temperature. © 2009 Elsevier B.V. All rights reserved.

Zinc oxide has a variety of applications in catalysis both as support and as active phase for hydrogenation or dehydrogenation reactions. This review provides an overview of the surface chemistry of ZnO nanoparticles concerning the interaction with small molecules such as CO, CO2, H2, H2O, and CH3OH, which are relevant for the catalytic synthesis of methanol and the water gas shift reaction. These interactions were studied by combining surface-sensitive methods such as infrared spectroscopy, temperature-programmed desorption, and adsorption calorimetry. A thorough understanding of the processes occurring on the different exposed facets of the ZnO particles in an atmosphere of reactive gases was achieved based on the comparison with results obtained in ultra-high vacuum with single-crystalline surfaces, i.e. under well-defined conditions, and by using first-principles calculations. © 2009 Elsevier B.V. All rights reserved.

Active carbon was used as substrate for the CVD of iron in a fluidized-bed reactor. Carbon nanotubes were subsequently grown from ethylene to obtain CNT-AC composites. The functionalization of the carbon composite was performed by conventional HNO 3 treatment in liquid phase and by a recently developed treatment method using HNO 3 vapor. The CVD of Pt was carried out with two different precursors, i.e., Pt(acac) 2 and (CH 3) 3Pt(C 5H 5). One-step CVD in a fluidized-bed reactor was compared with two-step CVD in a fixed-bed reactor. X-ray diffraction, scanning and transmission electron microscopy, online mass spectrometry and X-ray photoelectron spectroscopy were employed for the characterization of the samples. It was found that the HNO 3 vapor treatment was not only more effective in oxygen functionalization, but also more reliable for maintaining the structure/morphology of the hierarchical carbon composite. Highly dispersed Pt nanoparticles supported on CNT-AC were achieved by two-step CVD from (CH 3)3Pt(C 5H 5) in a fixed-bed reactor. © The Electrochemical Society.

Nitrogen-doped carbon nanotubes (N-CNT) obtained by plasma treatment were compared to the conventional acid-treated carbon nanotubes (O-CNT) as catalyst support for platinum-ruthenium (PtRu) nanoparticles in the anodic oxidation of methanol in direct methanol fuel cells. PtRu catalysts were prepared by an impregnation-reduction method from chloride precursors with metal loadings of 20 wt.%, and were characterised by scanning electron microscopy, transmission electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy and electrochemical methods. Voltammetry and chronoamperometry studies showed that the performance of PtRu/N-CNT was significantly higher compared to PtRu/O-CNT and also to the commercial E-TEK PtRu/C catalyst, indicating that N-CNT are an interesting support material for fuel cell electrocatalyst. Nitrogen plasma treatment produced pyridinic and pyrrollic species on the CNT surface, which acts as the anchoring sites for the deposition of PtRu particles. A mechanism for the deposition of PtRu on N-CNT is tentatively proposed and discussed. © 2009 Elsevier Ltd. All rights reserved.

TiO2 and Pt nanoparticles were deposited in the channels of siliceous MCM-48 via a sequential incipient wetness-impregnation method employing (NH4)2PtCl4 as platinum source. The resulting composite Pt/TiO2-MCM-48 (1 wt% Pt, ca. 3 wt% Ti) was characterized using XRD, TEM, nitrogen physisorption, hydrogen chemisorption, UV-vis spectroscopy, and XPS; its catalytic activity for CO oxidation was also explored. These data were compared with those of Pt/MCM-48 prepared via an analogous route. The results reveal that the platinum was deposited inside the intact pore system in both cases. It remains inside upon mild reduction but tends to segregate out of the pore system at higher reduction temperatures or during CO oxidation. Both composites were found to be highly active in CO oxidation, with 50% conversion at 460-475 K after activation of the unreduced catalysts in the (net oxidizing) feed. Striking differences in this activation process between Pt/MCM-48 and Pt/TiO2-MCM-48 suggest that the precursor reduction is influenced by an interaction with the TiO2 component in the latter. © 2009 Springer Science+Business Media, LLC.

Synthesis of shape- and size- controlled α-Fe2O3 nanoparticles was performed through a hydrothermal method assisted with amino acids. The products were characterized by transmission electron microscopy and X-ray diffraction. It was found that the type of amino acids has significant impact on the shape and size of the obtained α-Fe2O3 nanoparticles. The use of acidic amino acids typically leads to the formation of α-Fe2O3 nanoparticles with spindle shape. However, rhombohedrally shaped α-Fe2O3 nanoparticles were formed in the case of basic amino acids. When gold colloidal nanoparticles were deposited on the surfaces of α-Fe2O3 nanoparticles, Au/α-Fe2O3 catalysts display substantial differences in catalytic activities in CO oxidation for the differently shaped α-Fe2O3 nanoparticles used as supports. In general, spindle shaped Au/α-Fe2O3 shows higher catalytic activity than catalysts based on rhombohedral iron oxide. Under our catalytic test conditions, for spindle shaped Au/α-Fe2O3 catalyst, large hematite crystals induce higher catalytic activity than smaller ones, whereas for rhombohedral Au/α-Fe2O3 catalysts, medium-sized α-Fe2O3 nanocrystals show high catalytic activity for CO oxidation. © 2009 Elsevier B.V. All rights reserved.

A highly efficient one-step process to generate Cu-Zn colloids was developed, in which the colloidal particles were synthesized from Cu and Zn stearates by reduction with H2 in a continuously operated stirred tank reactor. The resulting spherical, well separated particles have a size of 5-10 nm, consisting of a crystalline Cu0 core (fcc) stabilized by a Zn stearate shell without long-range order. In situ attenuated total reflection FTIR spectroscopy was used to monitor the shift of the C-O stretching vibration of adsorbed CO as a function of temperature and pressure. The absence of the CO rotation-vibration bands of dissolved CO allowed us to obtain FTIR spectra at a CO pressure of 1.0 MPa at 473 K resulting in three shifted CO bands at 2030-2025, 1979-1978, and 1920 cm-1. These bands indicate the presence of reduced coadsorbed Zn species on the metallic Cu surface. Cyclic CO adsorption experiments demonstrated the dynamics of the interaction between the Cu core and the Zn stearate shell. © 2009 the Owner Societies.