XPS characterization of Au/TiO sub(2) catalysts: Binding energy assessment and irradiation effects

X-ray photoelectron spectroscopy (XPS) was employed to study the surface composition and electronic structure of Au/TiO sub(2) catalysts in comparison with TiO sub(2) (anatase) and to reveal time-dependent X-ray irradiation damage of the samples. The occurrence of Au nano-sized particles on a TiO sub(2) support was found to result in a slight shift of Ti 2p core-level spectrum and in changes of the valence band and X-ray induced Auger spectra, compared to TiO sub(2)-only. It was shown that for different means of energy referencing the charge-corrected Au 4f sub(7/2) binding energy in Au/TiO sub(2) catalysts was 0.15-0.45 eV lower than that in pure bulk Au. Exposure to X-rays of Au/TiO sub(2) catalysts and pure TiO sub(2) caused a reduction of Ti 4+ oxidation state and desorption of oxygen from the surface. As a result, the surface chemical composition and electronic structure of the samples changed with time. The X-ray irradiation affected charge transfer processes in Au/TiO sub(2) so that the pattern of X-ray induced damage in the Au-based catalyst turned out to be quite different from that in TiO sub(2), with some characteristics displaying the very opposite features. Decreasing of the Au 4f sub(7/2) binding energy and concurrent increasing of the fraction of Ti super(3+) species observed in the beginning of X-ray irradiation of Au/TiO sub(2) may be taken as direct evidence for charge transfer from oxygen vacancies created by irradiation to Au particles.