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Organisationseinheit der BAM
In any given matrix control over the final particle size distribution requires a constitutive understanding of the mechanisms and kinetics of the particle evolution. In this contribution we report on the formation mechanism of silver nanoparticles embedded in a soda-lime silicate glass matrix. For the silver ion-exchanged glass it is shown that at temperatures below 410 °C only molecular clusters (diameter <1 nm) are forming which are most likely silver dimers. These clusters grow to nanoparticles (diameter >1 nm) by annealing above this threshold temperature of 410 °C. It is evidenced that the growth and thus the final silver nanoparticle size are determined by matrix-assisted reduction mechanisms. As a consequence, particle growth proceeds after the initial formation of stable clusters by addition of silver monomers which diffuse from the glass matrix. This is in contrast to the widely accepted concept of particle growth in metal–glass systems, in which it is assumed that the nanoparticle formation is predominantly governed by Ostwald ripening processes.
A unique direct electrodeposition technique involving very high current densities, high voltages and high electrolyte concentrations is applied for highly selective mass synthesis of stable, isolable, surfactant-free, single-crystalline Bi hexagons on a Cu wire at room temperature. A formation mechanism of the hexagons is proposed. The morphology, phase purity, and crystallinity of the material are well characterized by FESEM, AFM, TEM, SAED, EDX, XRD, and Raman spectroscopy. The thermal stability of the material under intense electron beam and intense laser light irradiation is studied. The chemical stability of elemental Bi in nitric acid shows different dissolution rates for different morphologies. This effect enables a second way for the selective fabrication of Bi hexagons. Bi hexagons can be oxidized exclusively to α-Bi2O3 hexagons. The Bi hexagons are found to be promising for thermoelectric applications. They are also catalytically active, inducing the reduction of 4-nitrophenol to 4-aminophenol. This electrodeposition methodology has also been demonstrated to be applicable for synthesis of bismuth-based bimetallic hybrid composites for advanced applications.
Hydrogen economy is a central aspect of future energy supply, as hydrogen can be used as energy storage and fuel. In order tomake water electrolysis efficient, the limiting oxygen evolution reaction (OER) needs to be optimized. Therefore, C-based composite materials containing earth-abundant Fe and Mn were synthesized, characterized and tested in the OER. For pyrolysis temperatures above 700°C N-rich multi-walled carbon nanotubes (MWCNT) are obtained. Inside the tubes Fe3C particles are formed, Fe and Mn oxides are incorporated in the carbon matrix and metal spinel nanoparticles cover the outer surface. The best catalyst prepared at 800°C achieves a low overpotential of 389 mV (at 10 mA/cm2) and high stability (22.6 h). From electrochemical measurements and characterization it can be concluded that the high activity is mainly provided by MWCNT, Fe3C and the metal oxides in the conductive carbon matrix. The metal spinel nanoparticles in
contrast protect the MWCNT from oxidation and thereby contribute to the high stability.