All-organic covalent organic frameworks/perylene diimide urea polymer S-scheme photocatalyst for boosted H2 generation

Conjugated covalent organic frameworks (COFs) hold great promise in photocatalytic hydrogen evolution owing to their high crystallinity, large surface area, and distinct structure. However, COFs exhibit poor charge separation. Therefore, investigating highly effective COF-based photocatalysts is crucial. For the first time, conjugated COF/perylene diimide urea polymer (PUP) all-organic heterostructure with S-scheme interfacial charge-transfer channels was successfully developed manufactured via situ coupling of two-dimensional triazine-based imine-linked COF (denoted as TATF-COF) PUP. The optimal hydrogen-evolution rate 94.5 mmol h−1 g−1 for TATF-COF/PUP 3.5 times that pure TATF-COF comparable or even higher than previously reported photocatalysts, resulting an apparent quantum efficiency up 19.7% at 420 nm. improved directional transfer driven by tuned built-in electric field enhanced oxidation reduction reaction rates photogenerated carriers contribute synergistically boosted H2 evolution. Experiments theoretical studies reveal plausible spatial charge-separation mechanisms under visible-light irradiation. This study provides advanced methods constructing high-efficiency modulation band structures.