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‐SV/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.