Benzotrifuran-Based Covalent Organic Frameworks for Artificial Photosynthesis of HO from HO, O, and Sunlight.

Hydrogen peroxide (HO) is an important green chemical and a potential energy carrier. Artificial photosynthesis of HO from only HO and O under sunlight is a fascinating and sustainable tactic. However, deficient proton sources come from the kinetically sluggish HO oxidation process (∼s) seriously impede half-reaction of O 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 reduction and HO oxidation active sites, also serve as channels for photoinduced charge separation and transport. Importantly, the 1D pore containing abundant heteroatoms facilitates HO delivery to oxidation sites and reduces reaction energy barrier, thus improving the kinetic of HO oxidation. Accordingly, this porous framework achieves efficient HO photocatalysis with an average mass rate of up to 9800 µmol g h from HO and O in the absence of any sacrificial reagent under simulated sunlight by balancing O reduction and HO oxidation reactions.