Pauling‐Type Adsorption of O 2 Induced by Heteroatom Doped ZnIn 2 S 4 for Boosted Solar‐Driven H 2 O 2 Production

Breaking the trade‐off between activity and selectivity has perennially been a formidable endeavor in the field of hydrogen peroxide (H 2 O 2 ) photosynthesis, especially the side‐on configuration of oxygen (O 2 ) on the catalyst surface will cause the cleavage of O−O bonds, which drastically hinders the H 2 O 2 production performance. Herein, we present an atomically heteroatom P doped ZnIn 2 S 4 catalyst with tunable oxygen adsorption configuration to accelerate the ORR kinetics essential for solar‐driven H 2 O 2 production. Indeed, the spectroscopy characterizations (such as EXAFS and in situ FTIR) and DFT calculations reveal that heteroatom P doped ZnIn 2 S 4 at substitutional and interstitial sites, which not only optimizes the coordination environment of Zn active sites, but also facilitates electron transfer to the Zn sites and improves charge density, avoiding the breakage of O−O bonds and reducing the energy barriers to H 2 O 2 production. As a result, the oxygen adsorption configuration is regulated from side‐on (Yeager‐type) to end‐on (Pauling‐type), resulting in the accelerated ORR kinetics from 874.94 to 2107.66 μmol g −1 h −1 . This finding offers a new avenue toward strategic tailoring oxygen adsorption configuration by the rational design of doped photocatalyst.