Strong Hole Trapping Due to Oxygen Dimers in BiVO4: Effect on the Water Oxidation Reaction

We present a study of hole bipolarons in BiVO4. We show that in the presence of two holes O-O dimers are formed, leading to strong charge trapping. While the formation of bipolarons in bulk BiVO4 requires overcoming a kinetic barrier, we find that these defects should be spontaneously formed at the surface of the material and its interface with water. Through molecular dynamics simulations, we study the effect of bipolarons on the water-splitting reaction and show that their presence may be especially beneficial in alkaline conditions.