General Kinetic Model for pH Dependence of Proton-Coupled Electron Transfer: Application to an Electrochemical Water Oxidation System

(ITO) surface. The weak pH dependence is found to arise from the intrinsic differences in the rate constants of participating channels and the dependence of their relative contributions on pH. This model predicts that the apparent maximum rate constant will become pH-independent at higher pH, which is confirmed by experimental measurements. Our analysis also suggests that the dominant channels are electron transfer at lower pH and sequential PCET via electron transfer followed by fast proton transfer at higher pH. This work highlights the importance of considering multiple competing channels simultaneously for PCET processes.