Artificial photosynthesis of hydrogen peroxide (HO) from oxygen and water is a promising approach for converting low-density solar energy into versatile chemical energy. However, the generation of HO through a single-channel oxygen reduction reaction (ORR) is prevalent, while the water oxidation reaction (WOR) is frequently neglected. Herein, we constructed Z-scheme ZnInS/UiO66-NH (ZIS/UNH) heterojunctions, integrating the ORR and WOR dual pathways for photocatalytic HO generation without noble cocatalysts and sacrificial agents. The optimized ZIS/UNH exhibits the highest HO yield of 0.85 mmol g h, which is 2.2 and 14 times those of ZIS and UNH, respectively. The formation of the Z-scheme heterojunction efficiently promotes the separation and transfer of photogenerated carriers while retaining holes with high oxidizing ability and electrons with strong reducing ability. The free radical quenching and DMPO-ESR radical trapping experiments demonstrate that the ZIS/UNH heterojunctions produce HO in a dual-channel mode different from the single-channel ZIS. The pathways for HO generated by ZIS/UNH consist of a two-step single-electron ORR with ·O as an intermediate product and a direct one-step WOR.
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