Modulating Yeager Adsorption Configuration of O₂ Through Cd Doping in Zn₃In₂S₆ for Photosynthesis of H₂O₂

Abstract The photocatalytic oxygen reduction reaction (ORR) is a key pathway for producing hydrogen peroxide (H₂O₂). While most previous studies have focused on the two‐step 2e⁻ ORR process, the one‐step two‐electron ORR route offers thermodynamic and kinetic advantages that can significantly enhance 2e⁻ ORR activity and selectivity. In this study, a photocatalyst design is reported by incorporating cadmium into vacancy‐rich Zn₃In₂S₆ (Cd‐S_V/ZIS). This catalyst enables H₂O₂ production via a one‐step 2e⁻ ORR process without the use of sacrificial agents, achieving a high H₂O₂ yield of 39.42 µmol g⁻¹ min⁻¹ under UV–vis light irradiation, outperforming most reported ZIS‐based photocatalysts. Theoretical simulations and experimental results demonstrate that Cd doping improves the carrier kinetics of the catalyst, broadens its light absorption range, and promotes the Yeager adsorption configuration of O₂, leading to highly active and selective H₂O₂ generation. This study provides insights into the design of efficient ZIS‐based photocatalysts for H₂O₂ production.