Oxygen vacancies at oxide surfaces: ab initio density functional theory studies on vanadium pentoxide

Abstract.

The local electronic structure at the V₂O₅ (010) surface is studied by ab initio density functional theory (DFT) methods using gradient-corrected functionals (RPBE) where embedded clusters as large as V₂₀O₆₂H₂₄, representing one or two crystal layers of the substrate, are used as models. Results of local binding and charging of differently coordinated surface-oxygen sites as well as densities of states allow a characterization of the detailed electronic structure of the surface. Electronic and geometric details of surface-oxygen vacancies as well as hydrogen adsorption are studied by appropriate clusters. A comparison of the data, concerning vacancy energies, charging, geometric relaxation, and diffusion, shows sizeable variations between different oxygen sites and can give further insight into possible mechanisms of surface relaxation and reconstruction. Hydrogen is found to stabilize at all surface-oxygen sites forming surface-OH and H₂O species. As a result, the binding of surface oxygen with its vanadium neighbors is weakened. Therefore, the presence of hydrogen at the oxide surface facilitates oxygen removal and can contribute to the enhanced yield of oxygenated products near vanadia-based surfaces.