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

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. © 2024 Wiley-VCH GmbH.