Clarifying the Roles of Oxygen Vacancy in W-Doped BiVO₄ for Solar Water Splitting

Most oxide semiconductor photoanode materials for water splitting are synthesized in ambient environment. Oxygen vacancy exists in these samples making them intrinsically n-type at the as-synthesized state. Oxygen vacancy has been widely reported for enhancing the performance of a photoanode by improving the electron conductivity. Besides the effect on the bulk materials properties, oxygen vacancy also plays an important role in the interfacial charge transfer to electrolyte, on which much less attention has been paid in the past. Herein, we found that although air-annealed W-doped BiVO4 has a higher electron density, lower surface charge transfer resistance, and a slightly better light absorption than the O2-annealed sample, the latter displays a higher photocurrent density. Experimentally we found that the enhanced performance comes from a better charge separation efficiency, despite that the presence of oxygen vacancy does lead to a better charge transfer efficiency. Theoretical calculation finds that there is a localized state formed inside the bandgap in W-doped BiVO4 with oxygen vacancy, which serves as recombination center to reduce its charge separation efficiency. Oxygen vacancy on the V site activates two different kinds of V into reactive sites for improved surface catalysis. Oxygen vacancy also facilitates the adsorption of the OHads, Oads, and OOHads involved in a water splitting process, which benefits the surface catalytic process. It is predicted from this study that better performance can be achieved by introducing oxygen vacancy on the surface of a doped BiVO4 and simultaneously avoiding oxygen vacancy in the bulk. The current study provides an important understanding of the roles played by oxygen vacancy in doped photoanode materials.