Ab Initio Molecular Dynamics Simulation the Electron and Hole Polarons at the Interface between Water and the Surfaces of BiVO₄

Understanding the distribution of electrons and holes at the interface between a semiconductor and water is crucial for comprehending charge carrier separation in semiconductor-based photocatalytic water splitting. Nevertheless, this process is inadequately understood. In this study, we employed ab initio molecular dynamics (MD) to investigate the electron and hole polarons at the interface of water and BiVO4 (BVO) on both the (001) and (101) facets at room temperature. Our observations revealed that on both the (001) and (101) facets, electron polarons tend to localize on V sites in the second layer beneath the interface. In contrast, hole polarons on the (001) facet are predominantly localized on an oxygen atom within the bulk region, distant from the interface. On the (101) facet, the hole polaron remains localized at the interface. This distinct distribution of electron and hole polarons likely contributes to the charge separation between the (001) and (101) facets of BVO. These findings offer valuable insights into comprehending charge carrier distribution at the interfaces of other semiconductors and water, facilitating the design of high-efficiency charge separation semiconductor photocatalysts.