Regulation of Redox Molecular Junctions in Covalent Organic Frameworks for H2O2 Photosynthesis Coupled with Biomass Valorization

Abstract H 2 O 2 photosynthesis coupled with biomass valorization can not only maximize the energy utilization but also realize the production of value‐added products. Here, a series of COFs (i.e. Cu 3 ‐BT‐COF, Cu 3 ‐pT‐COF and TFP‐BT‐COF) with regulated redox molecular junctions have been prepared to study H 2 O 2 photosynthesis coupled with furfuryl alcohol (FFA) photo‐oxidation to furoic acid (FA). The FA generation efficiency of Cu 3 ‐BT‐COF was found to be 575 mM g −1 (conversion ≈100 % and selectivity >99 %) and the H 2 O 2 production rate can reach up to 187 000 μM g −1 , which is much higher than Cu 3 ‐pT‐COF, TFP‐BT‐COF and its monomers. As shown by theoretical calculations, the covalent coupling of the Cu cluster and the thiazole group can promote charge transfer, substrate activation and FFA dehydrogenation, thus boosting both the kinetics of H 2 O 2 production and FFA photo‐oxidation to increase the efficiency. This is the first report about COFs for H 2 O 2 photosynthesis coupled with biomass valorization, which might facilitate the exploration of porous‐crystalline catalysts in this field.