biostudies-literaturePan JNational Natural Science Foundation of China540-545https://www.ebi.ac.uk/biostudies/studies/S-EPMC8978636biostudies-literatureUnknown12(1)The activity of the hydrogen evolution reaction (HER) during photoelectrochemical (PEC) water-splitting is limited when using BiVO₄ with an exposed [110] facet because the conduction band minimum is below the H⁺/H₂O potential. Here, we enhance the photocatalytic hydrogen production activity through introducing an oxygen vacancy. Our first-principles calculations show that the oxygen vacancy can tune the band edge positions of the [110] facet, originating from an induced internal electric field related to geometry distortion and charge rearrangement. Furthermore, the induced electric field favors photogenerated electron-hole separation and the enhancement of atomic activity. More importantly, oxygen-vacancy-induced electronic states can increase the probability of photogenerated electron transitions, thus improving optical absorption. This study indicates that oxygen-defect engineering is an effective method for improving the photocatalytic activity when using PEC technology.RSC advancesEnhancing the photocatalytic hydrogen production activity of BiVO₄ [110] facets using oxygen vacancies.PMC8978636117743022190301412074332Zhang WPan JHu JMa XfalseEnhancing the photocatalytic hydrogen production activity of BiVO₄ [110] facets using oxygen vacancies.The activity of the hydrogen evolution reaction (HER) during photoelectrochemical (PEC) water-splitting is limited when using BiVO₄ with an exposed [110] facet because the conduction band minimum is below the H⁺/H₂O potential. Here, we enhance the photocatalytic hydrogen production activity through introducing an oxygen vacancy. Our first-principles calculations show that the oxygen vacancy can tune the band edge positions of the [110] facet, originating from an induced internal electric field related to geometry distortion and charge rearrangement. Furthermore, the induced electric field favors photogenerated electron-hole separation and the enhancement of atomic activity. More importantly, oxygen-vacancy-induced electronic states can increase the probability of photogenerated electron transitions, thus improving optical absorption. This study indicates that oxygen-defect engineering is an effective method for improving the photocatalytic activity when using PEC technology.2021-01-01T00:00:00Z2021 Dec2025-04-19T13:00:38.618Z2025-04-19T13:00:38.618ZS-EPMC89786363542448510.1039/d1ra07121a