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

H2O2 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. Cu3‐BT‐COF, Cu3‐pT‐COF and TFP‐BT‐COF) with regulated redox molecular junctions have been prepared to study H2O2 photosynthesis coupled with furfuryl alcohol (FFA) photo‐oxidation to furoic acid (FA). The FA generation efficiency of Cu3‐BT‐COF was found to be 575 mM g−1 (conversion ≈100 % and selectivity >99 %) and the H2O2 production rate can reach up to 187 000 μM g−1, which is much higher than Cu3‐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 H2O2 production and FFA photo‐oxidation to increase the efficiency. This is the first report about COFs for H2O2 photosynthesis coupled with biomass valorization, which might facilitate the exploration of porous‐crystalline catalysts in this field. [ABSTRACT FROM AUTHOR]