Molecular engineering of donor–acceptor-type conjugated microporous polymers for dual effective photocatalytic production of hydrogen and hydrogen peroxide

Conjugated microporous polymers (CMPs) have garnered increasing attention as emerging polymeric photocatalysts for solar-driven hydrogen (H₂) and hydrogen peroxide (H₂O₂) production, owing to their high surface areas, extended π-conjugation, and tunable architectures. In pursuit of this goal, we undertook the rational design and synthesis of two donor-acceptor CMPs, PyPh-DBZS and ANTh-DBZS, <i>via</i> Suzuki coupling polymerization. These CMPs integrate electron-rich pyrene (PyPh) or tetrathienoanthracene (ANTh) donor units with the electron-deficient benzothiophene <i>S</i>,<i>S</i>-dioxide (DBZS) acceptor moiety, enabling efficient dual photocatalytic generation of H₂ and H₂O₂. Notably, both polymers exhibit excellent thermal stability with <i>T</i>₁₀ values exceeding 590 °C and high char yields at 800 °C. PyPh-DBZS CMP exhibited an exceptional H₂ evolution rate (HER) of 133 241 μmol g^-1 h^-1. At the same time, ANTh-DBZS CMP achieved superior H₂O₂ production (24.51 mM g^-1), demonstrating structure-dependent charge separation under visible light irradiation. These results offer critical design principles for the rational emergence of new-generation CMPs photocatalysts, paving the way toward efficient and sustainable H₂ and H₂O₂ production.