Transition from Sequential to Concerted Proton-Coupled Electron Transfer of Water Oxidation on Semiconductor Photoanodes.

Accelerating proton transfer has been demonstrated as key to boosting water oxidation on semiconductor photoanodes. Herein, we study proton-coupled electron transfer (PCET) of water oxidation on five typical photoanodes [i.e., α-FeO, BiVO, TiO, plasmonic Au/TiO, and nickel-iron oxyhydroxide (NiFeOOH)-modified silicon (Si)] by combining the rate law analysis of HO molecules with the H/D kinetic isotope effect (KIE) and operando spectroscopic studies. An unexpected and universal half-order kinetics is observed for the rate law analysis of HO, referring to a sequential proton-electron transfer pathway, which is the rate-limiting factor that causes the sluggish water oxidation performance. Surface modification of the NiFeOOH electrocatalyst is observed to break this limitation and exhibits a normal first-order kinetics accompanied by much enhanced H/D KIE values, facilitating the turnover frequency of water oxidation by 1 order of magnitude. It is the first time that NiFeOOH is found to be a PCET modulator. The rate law analysis illustrates an effective strategy for modulating PCET kinetics of water oxidation on semiconductor surfaces.