Enhancing 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.