Iodine-Induced Redirection of Active Sources in Cu-Based Catalysts during Efficient and Stable Water Oxidation

Enhancing the mechanistic regulation of the oxygen evolution reaction (OER) is crucial for developing efficient and stable electrocatalysts. However, the dynamic variation of surface structure during the electrocatalytic process limits the accurate identification of the active source and underlying reaction mechanism. Herein, we report an iodine-doping strategy to direct the reconstruction of active species in CuS catalysts toward an unconventional oxygen vacancy oxidation mechanism, thereby overcoming the activity and stability limitations. Mechanistic analysis indicates that the electronic manipulation, weak coordination of Cu-S bonds, and lattice distortion induced by iodine-doping facilitate the thermodynamically favorable Cu²⁺ to Cu³⁺ oxidation during OER. The decisively formed oxygen vacancies are emphasized as a genuine active source to promote hydroxyl adsorption, with hypervalent Cu species acting as auxiliary sites to accelerate deprotonation by strengthening Cu-O covalent. Consequently, the optimal iodine-doped CuS exhibits a reduced overpotential of 189 mV at 10 mA cm^-2 and superb stability prolonging to 1250 h. When used as a bifunctional electrode in a membrane electrode assembly electrolyzer, it also exhibits a low voltage of 1.65 V at 1 A cm^-2, with electrolysis durability of 480 h and a low hydrogen cost of US$1.70/kg H₂, outperforming the 2026 targets set by the U.S. Department of Energy.