摘要
Bi/Sb dual-doping forms synergistic site pairs in ZnIn 2 S 4 , switching O 2 to Yeager-type adsorption. • Yeager-type enables direct 2e - ORR, suppresses •O 2 - , and boosts H 2 O 2 selectivity. • Bi/Sb-ZIS achieves 2612.6 μmol·g⁻¹·h⁻¹ H 2 O 2 and 91.8% TC degradation for integrated purification. Photocatalytic oxygen reduction provides a sustainable route for green hydrogen peroxide (H 2 O 2 ) synthesis, yet its efficiency is often hindered by slow multi‑step electron transfer and competing side reactions. Here, we engineer the surface microenvironment of ZnIn 2 S 4 through Bi/Sb dual doping, creating spatially and electronically complementary “Bi–Sb synergistic site pairs”. These dual sites collectively steer O 2 into a Yeager adsorption configuration and promote direct one‑step 2e - reduction, shifting the dominacnt ORR mechanism from the conventional, radical-prone two-step route to a highly efficient and selective direct pathway. The optimized catalyst achieves a high H 2 O 2 production rate of 2612.6 μmol·g −1 ·h −1 in simulated antibiotic wastewater while simultaneously degrading 91.8% of tetracycline. Mechanistic studies reveal that this pathway switching originates from the synergistic electron transfer at the dual sites, which not only stabilizes the Yeager‑type adsorption conformation but also largely suppresses the formation of •O 2 - intermediates. This work provides an effective bifunctional photocatalyst for integrated “Pollutant Solutions purification–chemical synthesis” systems and establishes a general design principle for controlling multi‑electron reaction pathways through the rational construction of synergistic active sites. Download: Download high-res image (191KB) Download: Download full-size image Bi/Sb-ZIS promotes Yeager-type O 2 adsorption and direct 2e - ORR, delivering exceptional H 2 O 2 yield and pollutant degradation in a dual-functional photocatalytic system.
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