Oxidation‐Reduction Molecular Junction Covalent Organic Frameworks for Full Reaction Photosynthesis of H2O2

Abstract The full reaction photosynthesis of H 2 O 2 that can combine water‐oxidation and oxygen‐reduction without sacrificial agents is highly demanded to maximize the light‐utilization and overcome the complex reaction‐process of anthraquinone‐oxidation. Here, a kind of oxidation‐reduction molecular junction covalent‐organic‐framework (TTF‐BT‐COF) has been synthesized through the covalent‐coupling of tetrathiafulvalene (photo‐oxidation site) and benzothiazole (photo‐reduction site), which presents visible‐light‐adsorption region, effective electron‐hole separation‐efficiency and photo‐redox sites that enables full reaction generation of H 2 O 2 . Specifically, a record‐high yield (TTF‐BT‐COF, ≈276 000 μM h −1 g −1 ) for H 2 O 2 photosynthesis without sacrificial agents has been achieved among porous crystalline photocatalysts. This is the first work that can design oxidation‐reduction molecular junction COFs for full reaction photosynthesis of H 2 O 2 , which might extend the scope of COFs in H 2 O 2 production.