Constructing dual charge-transfer tunnels within highly charge-confined COFs for efficient photosynthesis of hydrogen...

Insufficient charge separation and sluggish two-electron water-oxidation reaction are two critical factors restricting the photosynthesis performance of metal-free covalent organic frameworks (COFs) for hydrogen peroxide (H₂O₂) generation from naturally abundant water and air. Herein, we develop a facile strategy to simultaneously boost the charge-separation efficiency and water-oxidation capability through constructing short and rapid charge-transfer tunnels within highly charge-confined COFs via replacing the phenyl with pyrimidine. Compared with a single charge-transfer tunnel within a lowly charge-confined COF-5-(4-aminophenyl)pyrimidin-2-amine (APM) with pyrimidine, dual charge-transfer tunnels are constructed within a highly charge-confined COF-5,5'-bipyrimidine-2,2'-diamine (BPM) with bipyrimidine due to the ground-state charge transfer between para-carbon and meta-nitrogen, which significantly accelerates the intermolecular charge-transfer process and prevents charge recombination. This strategy also decreases the energy barrier of rate-determining water oxidation in H₂O₂ photosynthesis and thus promotes the effective generation of the key *OH intermediates, facilitating the generation of H₂O₂ at a production rate of 5521 μmol g^-1 h^-1 from water, oxygen and light without sacrificial reagents or additional energy consumption by COF-BPM. Furthermore, COF-BPM can also efficiently produce H₂O₂ under broad pH conditions, in widely available real water, on a floatable foam sheet, in a continuous-flow reactor and in a scaled-up reactor by using natural solar light for water decontamination.