Vacancy defect engineered BiVO₄ with low-index surfaces for photocatalytic application: a first principles study

BiVO₄ has been widely investigated as a photocatalyst material for water splitting due to its outstanding photocatalytic properties. In order to further improve its photocatalytic efficiency, it is necessary to conduct an in-depth study of improvement strategies, such as defect engineering. By focusing on the (001) and (011) surfaces, we carried out a systematic theoretical research on pristine and defective systems, including Bi, V and O vacancies. Based on density functional theory (DFT), the electronic properties, band alignments and Gibbs free energy of pristine and defective BiVO₄ have been analyzed. The electronic structures of the (001) and (011) surfaces show different band gaps, and O vacancies make the BiVO₄ become an n-type semiconductor, while Bi and V vacancies tend to form a p-type semiconductor. Moreover, the band edge positions indicate that holes are indeed easily accumulated on the (011) surface while electrons tend to accumulate on (001). However, the (011) surface with Bi and V vacancies does not have enough oxidation potential to oxidize water. The reaction free energy shows that O and Bi vacancies could lower the overpotential to some extent.