Nearly Barrierless Four-Hole Water Oxidation Catalysis on Semiconductor Photoanodes with High Density of Accumulated Surface Holes

The sluggish water oxidation reaction (WOR) is considered the kinetic bottleneck of artificial photosynthesis due to the complicated four-electron and four-proton transfer process. Herein, we find that the WOR can be kinetically nearly barrierless on four representative photoanodes (i.e., α-Fe₂O₃, TiO₂, WO₃, and BiVO₄) under concentrated light irradiation, wherein the rate-limiting O-O bond formation step is driven by accumulated surface photogenerated holes that exhibit a superior fourth-order kinetics. The activation energy is about 0.03 eV for the fourth-order kinetic pathway, which is quantitatively estimated by combining the Population model and Butler-Volmer model with the Eyring-like equation and is further confirmed by density functional theory calculations. The WOR rate under this condition shows more than 1 order of magnitude enhancement compared with that of first-, second-, or third-order kinetics. Focusing on α-Fe₂O₃, the accumulated high-density surface holes form adjacent Fe^V═O intermediates that effectively activate surface-adsorbed H₂O molecules via the hydrogen-bonding effect, as revealed by operando Raman measurements and ab initio molecular dynamics simulations. This work discloses a systematic understanding of the internal relations between activation energy and reaction orders of surface holes for future WOR study.