Linking the Photoinduced Surface Potential Difference to Interfacial Charge Transfer in Photoelectrocatalytic Water Oxidation

Charge transfer at the semiconductor/solution interface is fundamental to photoelectrocatalytic water splitting. Although insights into charge transfer in the electrocatalytic process can be gained from the phenomenological Butler-Volmer theory, there is limited understanding of interfacial charge transfer in the photoelectrocatalytic process, which involves intricate effects of light, bias, and catalysis. Here, using operando surface potential measurements, we decouple the charge transfer and surface reaction processes and find that the surface reaction enhances the photovoltage via a reaction-related photoinduced charge transfer regime as demonstrated on a SrTiO₃ photoanode. We show that the reaction-related charge transfer induces a change in the surface potential that is linearly correlated to the interfacial charge transfer rate of water oxidation. The linear behavior is independent of the applied bias and light intensity and reveals a general rule for interfacial transfer of photogenerated minority carriers. We anticipate the linear rule to be a phenomenological theory for describing interfacial charge transfer in photoelectrocatalysis.