Atomistic Structural Engineering of Conjugated Microporous Polymers Promotes Photocatalytic Biomass Valorization

Abstract Polymer photocatalysts have great promise for solar fuel production due to their flexible structural and functional designability. However, their photocatalytic efficiencies are still unsatisfactory, limited by their intrinsically large exciton binding energy and fast charge recombination. Herein, the atomistic structural engineering of donor–acceptor (D−A) polymer photocatalysts for enhanced charge separation and photocatalytic hydrogen production is proposed. By changing the electron affinity of the acceptor units, the electron delocalization and exciton binding energy of the polymeric networks can be readily tuned, resulting in enhanced charge separation efficiency and photocatalytic activity. The optimal sample shows the highest H₂ production rate of 3207 µmol g⁻¹ h⁻¹ in the presence of ascorbic acid as the sacrificial agent. Moreover, the photocatalytic H₂ production can be coupled with almost stoichiometrical conversion of 5‐hydroxymethyl furfural to 2,5‐diformylfuran.