Energy Sciences

We present a combined computational and experimental study of the adsorption of water on the Mo-doped BiVO₄(010) surface, revealing how excess electrons influence the dissociation of water and lead to hydroxyl-induced alterations of the surface electronic structure. By comparing ambient pressure resonant photoemission spectroscopy (AP-ResPES) measurements with the results of first-principles calculations, we show that the dissociation of water on the stoichiometric Mo-doped BiVO₄(010) surface stabilizes the formation of a small electron polaron on the VO₄ tetrahedral site and leads to an enhanced concentration of localized electronic charge at the surface. Our calculations demonstrate that the dissociated water accounts for the enhanced V⁴⁺ signal observed in ambient pressure X-ray photoelectron spectroscopy and the enhanced signal of a small electron polaron inter-band state observed in AP-ResPES measurements. For ternary oxide surfaces, which may contain oxygen vacancies in addition to other electron-donating dopants, our study reveals the importance of defects in altering the surface reactivity toward water and the concomitant water-induced modifications to the electronic structure.