Rational design of novel D–A₁–A₂ conjugated microporous polymers for boosting spatial charge separation with enhanced photocatalytic hydrogen evolution

Conjugated microporous polymers (CMPs) featuring donor–acceptor (D–A) structures have garnered significant attention for their potential in hydrogen production, primarily due to their excellent charge transfer efficiency and large specific surface area. However, the uncontrollable composition in D–A structure severely limits the improvement of photocatalytic activity. In this study, employing pyrene as the donor, dibenzothiophene-S-S-dioxide (BTDO, A₁) and 1-methyl-1,2,4-triazole (TAME, A₂) as acceptors, the innovative tri-component CMP photocatalysts featuring a donor–acceptor₁–acceptor₂ (D–A₁–A₂) configuration were developed and created. By regulating the ratio of D and A, as well as BTDO and TAME in the polymer backbone, the optimized copolymer Py-BTDO-TAME-2 exhibits superior hydrogen production activity (27.53 mmol g⁻¹h⁻¹) in the absence of Pt co-catalyst under visible light, owing to the broad light absorption, high specific surface area and enhanced charge separation capability. The findings of this study indicate that utilizing a D–A₁–A₂ structural design method can greatly improve the photocatalytic performance of CMP photocatalysts.