Benzotrifuran‐Based Covalent Organic Frameworks for Artificial Photosynthesis of H2O2 from H2O, O2, and Sunlight

Abstract Hydrogen peroxide (H 2 O 2 ) is an important green chemical and a potential energy carrier. Artificial photosynthesis of H 2 O 2 from only H 2 O and O 2 under sunlight is a fascinating and sustainable tactic. However, deficient proton sources come from the kinetically sluggish H 2 O oxidation process (∼s) seriously impede half‐reaction of O 2 reduction (µs∼ms), leading to inferior photocatalytic efficiency. Herein, we prepare a benzotrifuran‐based covalent organic framework featuring electron donor–acceptor character with hydrazone linkage. Spatially separated donor–acceptor π‐stacking columns offer rich O 2 reduction and H 2 O oxidation active sites, also serve as channels for photoinduced charge separation and transport. Importantly, the 1D pore containing abundant heteroatoms facilitates H 2 O delivery to oxidation sites and reduces reaction energy barrier, thus improving the kinetic of H 2 O oxidation. Accordingly, this porous framework achieves efficient H 2 O 2 photocatalysis with an average mass rate of up to 9800 µmol g −1 h −1 from H 2 O and O 2 in the absence of any sacrificial reagent under simulated sunlight by balancing O 2 reduction and H 2 O oxidation reactions.