New Theoretical Strategy for the Correlation of Oxygen Evolution Performance and Metal Catalysts Adsorption at BiVO₄ Surfaces

The oxygen evolution reaction (OER) is the limiting process in photoelectrochemical water splitting. Bismuth vanadate (BiVO₄) is a very promising photoanode material for this but suffers experimentally from poor catalytic performance for OER. Here, we theoretically explored, by means of density functional theory calculations, supporting single metal atoms (i.e., Ag, Au, Pd, and Pt) as an effective strategy to enhance the catalytic activity of BiVO₄. The OER performance of different surfaces was evaluated with the intermediate adsorption energies from a thermodynamic viewpoint. The electronic structure study was employed in details to comprehend the adsorption-changing mechanism. Based on the results, several linear relationships were derived among the adsorption energies of reaction intermediates in this work, and a volcano plot was presented to unravel the theoretical activities over different BiVO₄ surfaces. It was found that the metal center dominated the interaction with the intermediates and the substrate played an instrumental role in achieving a qualified energy-level matching requirement for bonding. A new method for calculating the d-band center of singe-metal atoms was proposed to describe the correlation of intermediate adsorption strengths and electronic structure quantificationally. Moreover, this work could provide some in-depth understanding of the excellent performance of single-atom catalysts and open some new perspectives for catalysts design.