Mechanism of First Proton-Coupled Electron Transfer of Water Oxidation at the ${\rm BiVO}_4$ -Water Interface.

ABSTRACT: The oxygen evolution reaction (OER) at the BiVO4${\rm BiVO}_4$ -water interface is considered to be the bottleneck of the overall water splitting at this aqueous interface. To provide insight into the mechanism of this reaction, the focus is set on the first proton-coupled electron transfer (PCET). The free-energy surface of this first step is obtained by combining on-the-fly probability-enhanced sampling and machine learning potentials at the hybrid functional level of accuracy. Our study reveals that proton transfer precedes electron transfer and determines the reaction barrier, consistent with kinetic-isotope-effect experiments. The calculated reaction barrier amounts to 0.66±0.09$0.66\pm 0.09$ eV. The proton moves from the adsorbed water molecule to a surface O atom through a direct tr

SUBMITTER: Zhuang YB 

PROVIDER: S-EPMC12322655 | biostudies-literature | 2025 Aug

REPOSITORIES: biostudies-literature