Versatile Nature of Oxygen Vacancies in Bismuth Vanadate Bulk and (001) Surface

Bismuth vanadate (BiVO₄) has emerged as one of the most promising photoanode materials for solar fuel production. Oxygen vacancies play a pivotal role in the photoelectrochemical efficiency, yet their electronic nature and contribution to  n-type conductivity are still under debate. Using first-principles calculations, we show that oxygen vacancies in BiVO₄ have two distinguishable geometric configurations characterized by either undercoordinated, reduced V^IVO₃ and Bi^IIO₇ subunits or a V^IV-O-V^IV/V bridge (split vacancy), quenching the oxygen vacancy site. While both configurations have similar energies in the bulk, the (001) subsurface acts like an energetic sink that stabilizes the split oxygen vacancy by ∼1 eV. The barrierless creation of a bridging V₂O₇ unit allows for partial electron delocalization throughout the near-surface region, consistent with recent experimental observations indicating that BiVO₄(001) is an electron-rich surface.