Integrating amino groups within conjugated microporous polymers by versatile thiol–yne coupling for light-driven hydrogen evolution

Conjugated microporous polymers (CMPs) are emerging as promising catalysts for photocatalytic hydrogen evolution, but hydrophobic surface and less active site exposure severely limit their efficiency. Herein, we contribute an effective and versatile strategy to function CMPs with abundant amino groups via radical thiol-yne reaction. As a result, the modified CMPs retain the light absorption ability and morphology, and better water compatibility along with more active sites exposure may accelerate subsequent proton reduction under visible light irradiation (λ > 420 nm). The hydrogen evolution rate (HER) and apparent quantum yields (AQYs) at 420 nm of modified CMPs were increased up to 27.2 times and 47.1 times in comparison to original CMPs. Photocatalytic H2 evolution activity evaluation of BBT-SC2CH3, BBT-SC2N(CH3)2 and SC2NHAc in which amino groups were replaced with methyl, dimethyl amino or N-acetyl group revealed the crucial role of nitrogen, and aliphatic chain length between sulfur and nitrogen also proved important. Therefore, this protocol provides good opportunities for designing advanced CMPs and expands their application as photocatalyts for energy conversion.