Molecular engineering of novel D−A1−A2 conjugated microporous polymers by efficient electron donor for highly enhanced photocatalytic hydrogen generation

Among the various advanced photocatalytic materials, the organic conjugated microporous polymer (CMP) photocatalysts have garnered significant interest due to their exceptional efficiency in photogenerated electron transfer and their structural versatility. In this study, we developed two novel donor-acceptor 1 -acceptor 2 CMP systems through varying the electron donor unit. Pyrene (P) and triphenylamine (T) were acted as donor units (D), respectively, meanwhile dibenzothiophene-S,S-dioxide (BTDO, A 1 ) and 3,4-ethylenedioxythiophene (EDOT, A 2 ) as their acceptors to construct two D−A 1 −A 2 type CMP photocatalysts, P-BTDO-EDOT and T-BTDO-EDOT. Their photocatalytic performances were compared and studied through photocatalytic hydrogen production. The findings show that P-BTDO-EDOT possesses higher photocatalytic hydrogen production activity (87.21 mmol g −1  h −1 ) than T-BTDO-EDOT (66.25 mmol g −1  h −1 ) under visible light, attributing to its stable conjugated architecture, larger specific surface area, exceptional optoelectronic capability, wider light absorption, donor unit pyrene with strong electron-donating and efficient charge separation ability. This work not only highlights the potential for designing innovative CMP molecular structures with D−A 1 −A 2 system, but also opens up a new pathway for developing high-efficiency photocatalysts.