Oxygen species on the silver surface oxidized by MW-discharge

A polycrystalline silver surface has been studied by synchrotron radiation photoelectron spectroscopy after deep oxidation by microwave discharge in an O2 atmosphere. Oxidized structures with high oxygen content, AgOx with x > 1, have been found on the silver surface after oxidation at 300-400 K. The line shapes observed in the O1s spectra were decomposed into five components and indicated that complex oxidized species were formed. An analysis of the oxidized structures with binding energies, Еb(O1s), greater than 530 eV pointed to the presence of both Ag-O and O-O bonds. We have carried out a detailed experimental study of the valence band spectra in a wide spectral range (up to 35 eV), which has allowed us to register the multicomponent structure of spectra below Ag4d band. These features were assigned to the formation of Ag-O and O-O bonds composed of molecular (associative) oxygen species. DFT model calculations showed that saturation of the defect oxidized silver surface with oxygen leads to the formation of associative oxygen species, such as superoxides, with electrophilic properties and covalent bonding. The high stability of oxygen-rich silver structures, AgOx, can be explained by the formation of small silver particles during the intensive MW oxidation, which can stabilize such oxygen species.