Controlling Near-Surface Ni Composition in Octahedral PtNi(Mo) Nanoparticles by Mo Doping for a Highly Active Oxygen Reduction Reaction Catalyst.

We report and study the translation of exceptionally high catalytic oxygen electroreduction activities of molybdenum-doped octahedrally shaped PtNi(Mo) nanoparticles from conventional thin-film rotating disk electrode screenings (3.43 ± 0.35 A mgPt-1 at 0.9 VRHE) to membrane electrode assembly (MEA)-based single fuel cell tests with sustained Pt mass activities of 0.45 A mgPt-1 at 0.9 Vcell, one of the highest ever reported performances for advanced shaped Pt alloys in real devices. Scanning transmission electron microscopy with energy dispersive X-ray analysis (STEM-EDX) reveals that Mo preferentially occupies the Pt-rich edges and vertices of the element-anisotropic octahedral PtNi particles. Furthermore, by combining in situ wide-angle X-ray spectroscopy, X-ray fluorescence, and STEM-EDX elemental mapping with electrochemical measurements, we finally succeeded to realize high Ni retention in activated PtNiMo nanoparticles even after prolonged potential-cycling stability tests. Stability losses at the anodic potential limits were mainly attributed to the loss of the octahedral particle shape. Extending the anodic potential limits of the tests to the Pt oxidation region induced detectable Ni losses and structural changes. Our study shows on an atomic level how Mo adatoms on the surface impact the Ni surface composition, which, in turn, gives rise to the exceptionally high experimental catalytic ORR reactivity and calls for strategies on how to preserve this particular surface composition to arrive at performance stabilities comparable with state-of-the-art spherical dealloyed Pt core-shell catalysts.

X-ray powder diffraction to analyse bimetallic core-shell nanoparticles (gold and palladium; 7-8 nm).

A comparative X-ray powder diffraction study on poly(N-vinyl pyrrolidone) (PVP)-stabilized palladium and gold nanoparticles and bimetallic Pd-Au nanoparticles (both types of core-shell nanostructures) was performed. The average diameter of Au and Pd nanoparticles was 5 to 6 nm. The two types of core-shell particles had a core diameter of 5 to 6 nm and an overall diameter of 7 to 8 nm, i.e. a shell thickness of 1 to 2 nm. X-ray powder diffraction on a laboratory instrument was able to distinguish between a physical mixture of gold and palladium nanoparticles and bimetallic core-shell nanoparticles. It was also possible to separate the core from the shell in both kinds of bimetallic core-shell nanoparticles due to the different domain size and because it was known which metal was in the core and which was in the shell. The spherical particles were synthesized by reduction with glucose in aqueous media. After purification by multiple centrifugation steps, the particles were characterized with respect to their structural, colloid-chemical, and spectroscopic properties, i.e. particle size, morphology, and internal elemental distribution. Dynamic light scattering (DLS), differential centrifugal sedimentation (DCS), atomic absorption spectroscopy (AAS), ultraviolet-visible spectroscopy (UV-vis), high-angle annular dark field imaging (HAADF), and energy-dispersed X-ray spectroscopy (EDX) were applied for particle characterization.

Strain and electric-field control of magnetism in supercrystalline iron oxide nanoparticle-BaTiO3 composites.

The manipulation of the magnetism of self-assembled iron oxide nanoparticle (NP) monolayers on top of BaTiO3 (BTO) single crystals is reported. We observe strain induced magnetoelectric coupling (MEC) as shown by measurements of both the magnetization and magneto-electric AC susceptibility (MEACS). The magnetization, coercivity, remanent magnetization and MEACS signal as a function of temperature show abrupt jumps at the BTO phase transition temperatures. Hereby the jump values are opposite for in-plane and out-of-plane measurements. Grazing incidence small angle X-ray scattering (GISAXS) and scanning electron microscopy (SEM) confirm a hexagonal close-packed supercrystalline order of the NP monolayers. Cross-sectional scanning transmission electron microscopy (STEM) experiments provide information about the layer structure of the sample. This work opens up viable possibilities for fabricating energy-efficient electronic devices by self-assembly techniques.

Conjugation of thiol-terminated molecules to ultrasmall 2 nm-gold nanoparticles leads to remarkably complex 1H-NMR spectra.

Gold nanoparticles, functionalized by aliphatic and aromatic mercapto-functionalized carboxylic acids and by two small peptides (CG and CGGRGD), respectively, were synthesized by the reduction of HAuCl4 with NaBH4 in the presence of the above ligands. After purification by centrifugation or filtration and redispersion, the dispersed nanoparticles were analysed by differential centrifugal sedimentation (DCS), high-resolution transmission electron microscopy (HRTEM), and a variety of NMR spectroscopic techniques: 1H-NMR, 1H,1H-COSY and 1H-DOSY. The hydrodynamic diameter of the particles was between 1.8 and 4.4 nm, as determined by DOSY, in good agreement with the DCS and HRTEM results. Diffusion ordered spectroscopy (DOSY) turned out to be a valuable and non-destructive tool to determine the hydrodynamic diameter of dispersed nanoparticles and to control the purity of the final particles. The coordination of the organic molecules to the gold nanoparticles resulted in distinct and complex changes in the 1H-NMR spectra. These were only partially explainable but clearly caused by the vicinity of the molecules to the gold nanoparticle.

Nanostructure of wet-chemically prepared, polymer-stabilized silver-gold nanoalloys (6 nm) over the entire composition range.

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.

In situ fabrication of ultrathin porous alumina and its application for nanopatterning Au nanocrystals on the surface of ion-sensitive field-effect transistors.

In situ fabrication in a single step of thin films of alumina exhibiting a thickness of less than 100 nm and nanopores with a highly regular diameter distribution in order to pattern nanostructures over field-effect devices is a critical issue and has not previously been demonstrated. Here we report the fabrication in situ of 50 nm thick ultrathin nanoporous alumina membranes with a regular pore size directly over metal-free gate ion-sensitive field-effect transistors. Depositing thin films of aluminum by an electron beam at a relatively low rate of deposition on top of chips containing the transistors and using a conventional single-step anodization process permits the production of a well-adhering nanoporous ultrathin layer of alumina on the surface of the devices. The anodization process does not substantially affect the electrical properties of the transistors. The small thickness and pore size of ultrathin alumina membranes allow them to be sequentially employed as masks for patterning Au nanocrystals grown by an electroless approach directly on the top of the transistors. The patterning process using a wet chemical approach enables the size of the patterned crystals to be controlled not only by the dimensions of the pores of alumina, but also by the concentration of the reactants employed. Surface modification of these nanocrystals with alkanethiol molecules demonstrates that the electrostatic charge of the functional groups of the molecules can modulate the electrical characteristics of the transistors. These results represent substantial progress towards the development of novel nanostructured arrays on top of field-effect devices that can be applied for chemical sensing or non-volatile memories.

Al13Fe4 as a low-cost alternative for palladium in heterogeneous hydrogenation.

Replacing noble metals in heterogeneous catalysts by low-cost substitutes has driven scientific and industrial research for more than 100 years. Cheap and ubiquitous iron is especially desirable, because it does not bear potential health risks like, for example, nickel. To purify the ethylene feed for the production of polyethylene, the semi-hydrogenation of acetylene is applied (80 × 10(6) tons per annum; refs 1-3). The presence of small and separated transition-metal atom ensembles (so-called site-isolation), and the suppression of hydride formation are beneficial for the catalytic performance. Iron catalysts necessitate at least 50 bar and 100 °C for the hydrogenation of unsaturated C-C bonds, showing only limited selectivity towards semi-hydrogenation. Recent innovation in catalytic semi-hydrogenation is based on computational screening of substitutional alloys to identify promising metal combinations using scaling functions and the experimental realization of the site-isolation concept employing structurally well-ordered and in situ stable intermetallic compounds of Ga with Pd (refs 15-19). The stability enables a knowledge-based development by assigning the observed catalytic properties to the crystal and electronic structures of the intermetallic compounds. Following this approach, we identified the low-cost and environmentally benign intermetallic compound Al(13)Fe(4) as an active and selective semi-hydrogenation catalyst. This knowledge-based development might prove applicable to a wide range of heterogeneously catalysed reactions.

Geometric origin of magnetic frustration in the µ-Al4Mn giant-unit-cell complex intermetallic.

The structurally ordered µ-Al(4)Mn complex intermetallic phase with 563 atoms in the giant unit cell shows the typical broken-ergodicity phenomena of a magnetically frustrated spin system. The low-field zero-field-cooled and field-cooled magnetic susceptibilities show splitting below the spin freezing temperature T(f) = 2.7 K. The ac susceptibility exhibits a frequency-dependent cusp, associated with a frequency-dependent freezing temperature T(f)(ν). The decay of the thermoremnant magnetization is logarithmically slow in time and shows a dependence on the aging time t(w) and the cooling field H(fc) typical of an ultraslow out-of-equilibrium dynamics of a nonergodic spin system that approaches thermal equilibrium, but can never reach it on the experimentally accessible time scale. The above features classify the µ-Al(4)Mn complex intermettalic among spin glasses. The origin of frustration of magnetic interactions was found to be geometrical due to the distribution of a significant fraction of Mn spins on triangles with antiferromagnetic coupling. The µ-Al(4)Mn phase is a geometrically frustrated spin glass.

Plastic-deformation mechanism in complex solids.

In simple crystalline materials, plastic deformation mostly takes place by the movement of dislocations. Although the underlying mechanisms in these materials are well explored, in complex metallic alloys--crystalline solids containing up to thousands of atoms per unit cell--the defects and deformation mechanisms remain essentially unknown. Owing to the large lattice parameters of these materials, extended dislocation concepts are required. We investigated a typical complex metallic alloy with 156 atoms per unit cell using atomic-resolution aberration-corrected transmission electron microscopy. We found a highly complex deformation mechanism, based on the movement of a dislocation core mediating strain and separate escort defects. On deformation, the escort defects move along with the dislocation core and locally transform the material structure for the latter. This mechanism implies the coordinated movement of hundreds of atoms per elementary glide step, and nevertheless can be described by simple rearrangement of basic structural subunits.

[The influence of clofibrate on elevated serum lactate levels in diabetic patients treated with biguanides (author's transl)]. / Der Einfluss von Clofibrat auf erhöhte Serumlaktatspiegel bei mit Biguaniden behandelten Diabetikern.

The increments in serum lactate and ketone bodies induced by biguanides in 11 diabetics were decreased by a combined treatment with clofibrate and phenformin. Lactate concentration was nearly the same on a placebo or on the combined drug treatment. While-body weight reduction in subjects was without influence on the clofibrate-induced lowering of lactate it inhibited a decrease of ketone bodies. The effect of clofibrate on lactate was directly correlated to its serum triglyceride lowering effect. The decrease in lactate points to an improved lactate utilization. A combined clofibrate-biguanide treatment is only indicated in selected patients, predominantly in diabetics with endogenous hypertriglyceridemia, however, contraindications of both drugs have to be observed.