Hydrophilicity‐Controlled Conjugated Microporous Polymers for Enhanced Visible‐Light‐Driven Photocatalytic H2 Evolution

Abstract To take advantage of high surface area of network conjugated microporous polymers, four linear or network conjugated polymers L‐PDBT, L‐PDBT‐O, N‐PDBT, and N‐PDBT‐O are designed in terms of water‐compatibility, and it turned out that microporous network N‐PDBT‐O exhibited the highest hydrogen evolution rate (HER) at 366 µmol h −1 under visible light irradiation (λ > 420 nm, one of best reported pristine polymer‐based photocatalysts), which is three times higher than the corresponding linear L‐PDBT‐O. Water contact angle measurements revealed that benzothiophene‐sulfone‐based conjugated polymers display better water compatibility and adsorption, and the synergic effect of better hydrophilic surface and higher surface area of N‐PDBT‐O might eventually lead to more exposed active sites in comparison to linear L‐PDBT‐O in the H 2 evolution suspension system. The hydrophilicity‐controlled strategy could be applied to design of other network conjugated microporous polymer photocatalysts in an attempt to improve the activity.