Surface oxygen vacancies in gold based catalysts for CO oxidation

Experimental catalytic activity measurements, diffuse reflectance infrared Fourier spectroscopy, and density functional theory calculations are used to investigate the role and dynamics of surface oxygen vacancies in CO oxidation with O₂ catalyzed by Au nanoparticles supported on a Y-doped TiO₂ catalyst. Catalytic activity measurements show that the CO conversion is improved in a second cycle of reaction if the reactive flow is composed by CO and O₂ (and inert) while if water is present in the flow, the catalyst shows a similar behaviour in two successive cycles. DRIFTS-MS studies indicate the occurrence of two simultaneous phenomena during the first cycle in dry conditions: the surface is dehydroxylated and a band at 2194 cm⁻¹ increases (proportionally to the number of surface oxygen vacancies). Theoretical calculations were conducted in order to explain these observations. On one hand, the calculations show that there is a competition between gold nanoparticles and OH to occupy the surface oxygen vacancies and that the adsorption energy of gold on these sites increases as the surface is being dehydroxylated. On the other hand, these results evidence that a strong electronic transfer from the surface to the O₂ molecule is produced after its adsorption on the Au/TiO₂ perimeter interface (activation step), leaving the gold particle in a high oxidation state. This explains the appearance of a band at a wavenumber unusually high for the CO adsorbed on oxidized gold particles (2194 cm⁻¹) when O₂ is present in the reactive flow. These simultaneous phenomena indicate that a gold redispersion on the surface occurs under reactive flow in dry conditions generating small gold particles which are very active at low temperature. This fact is notably favoured by the presence of surface oxygen vacancies that improve the surface dynamics. The obtained results suggest that the reaction mechanism proceeds through the formation of a peroxo-like complex formed after the electronic transfer from the surface to the gas molecule.