We addressed the interaction of oxygen with silver by synchrotron based near ambient pressure X-ray photoelectron spectroscopy at temperatures relevant for industrial oxidation reactions performed with silver catalysts. For silver single crystals, polycrystalline foils and powders in equilibrium with gas phase O 2 , we observed the dynamics of the formation of five different atomic oxygen species with relative abundances depending on the temperature and time. Correlation of their formation kinetics with spectroscopic features and thermal stability indicates that these are distinct species with different electronic structures, which might relate to the different roles of silver in oxidation reactions.
Model catalysts-Ag on highly oriented pyrolytic graphite (Ag/HOPG)-have been studied using scanning tunneling microscopy (STM), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS) and X-ray induced Auger electron spectroscopy (XAES). Two types of catalysts were compared: Ag nanoparticles supported on sputtered and non-sputtered HOPG, and the influence of graphite surface defects on the stabilization of Ag nano-sized particles was discussed. A procedure for the preparation of stable (up to 250 1C under a submillibar oxygen/ ethylene pressure) silver nanoparticles is suggested. The disappearance of Ag particles in STM images after a sample treatment in the ambient conditions is explained in terms of silver penetration into graphite and the loss of conductivity due to adsorption of contaminants.
The preparation of model silver catalysts supported on highly oriented pyrolytic graphite is described, and the effect of the Ag particle size on the catalytic ethylene oxidation into ethylene oxide, studied by in situ XPS and mass spectrometry, is considered. For a mean particle diameter of 8 nm, the adsorbed oxygen species characterized by an O 1s binding energy of 530.8 ± 0.2 eV (electrophilic oxygen) forms on the silver surface exposed to the ethylene–oxygen reaction mixture. Larger silver particles with a mean diameter of 40 nm additionally contain the adsorbed oxygen species characterized by an O 1s binding energy of 529.2 ±0.2 eV (nucleophilic oxygen). The presence of both oxygen species on the surface of the larger particles ensures the formation of ethylene oxide, while the sample with the smaller silver particles is inactive in the epoxidation reaction. The O 1s signal at 530.8 eV is partly due to oxygen dissolved in the subsurface layers of silver
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