Surface Hydroxylation during Water Splitting Promotes the Photoactivity of BiVO(010) Surface by Suppressing Polaron-Mediated Charge Recombination.

Polaron-based electron transport restricts the photoelectrochemical (PEC) water splitting efficiency of BiVO. However, the location and dynamics of polarons are significantly dependent on the surface hydroxylation. By performing ab initio nonadiabatic molecular dynamics simulations, we demonstrated that hydroxylation of BiVO(010) surface greatly alleviates the detrimental effect of oxygen-vacancy-induced electron polaron (EP). Surface hydroxylation stabilizes the EP at the surface to facilitate water splitting, makes the polaron a shallow localized state, and reduces the intensity of high-frequency V-O bond stretching vibrations. By decreasing the nonadiabatic coupling and decoherence time, the charge carrier lifetimes are extended by 1-3 orders of magnitude depending on the hydroxylation coverage. Our study not only reveals that the surface hydroxylation mitigated detrimental impacts of polarons in metal oxides but also provided valuable insights into the benign effect of intermediate species on the photocatalytic reactivity.