Bi─O Bridges Trigger Lattice Strain-Electronic Synergy at Inherent In Sites in ZnIn₂S₄ for Boosting Solar-to-H₂O₂...

Artificial H₂O₂ photosynthesis without sacrificial agents represents a promising yet challenging route for sustainable chemical production, hindered by low solar-to-chemical conversion (SCC) efficiency (natural photosynthesis is only ∼0.1%). Notably, the abundant inherent active sites within base semiconductors remain substantially underutilized. Here, we incorporate Bi into ZnIn₂S₄ (ZIS) lattices through atomic-level Bi─O coordination, activating inherent In sites via synergistic lattice strain and electron rearrangement. Multiscale characterization confirms the formation of BiO₂S₂-ZIS with quantified 1.51% lattice elongation. Integrated theoretical calculations and in situ spectroscopic analyses reveal that Bi─O coordination increases electron density at adjacent In sites, which lowers the p-band center and enhances carrier separation. Meanwhile, lattice strain strengthens Bi─O orbital hybridization and weakens In─O covalency. Thus, these effects cooperatively optimize carrier dynamics. Then, the O₂ adsorption is Pauling-type at In site to Yeager-type adsorption at the In─Bi dual sites. Simultaneously, Bi─O bridges function as proton reservoirs to facilitate *OOH formation and *H₂O₂ synthesis through enhanced Coulombic interactions. The resulting strain-electron synergy achieves an unprecedented H₂O₂ production rate of 6.06 mmol g^-1 h^-1 and 2.32% SCC efficiency, surpassing all reported inorganic semiconductor photocatalysts. This work demonstrates exceptional photocatalytic performance and establishes a highly effective strategy for inherent site activation.