Stable, carrier separation tailorable conjugated microporous polymers as a platform for highly efficient photocatalytic H2 evolution

The molecular design of highly photo-functional polymers with high charge separation efficiency and wide spectral absorption are long term quest for photocatalysis. Herein, we design and develop a series of nitrogen containing conjugated microporous polymers (N-CMPs) with tailored donor-acceptor units for enhancing charge separation and light harvesting for visible light photocatalytic H2 production. By alternating the substitution position (o-, m-, or p-) and the number of electron donor (carbazole, diphenylamine) and acceptor (cyano) units on the 3D-core structure, a series of N-CMPs with adjustable donor-acceptor (D-A) charge separation efficiencies and tuneable band gaps in the range of 1.64-2.29 eV were obtained, enabling the precise control of the photocatalytic activity at the molecular level. The optimized N-CMP (4-CzPN) exhibits a higher visible light H2 production rate at 2103.2 mol/hg and the apparent quantum yield (AQY) at 420 nm reaches 6.4%. Furthermore, the 4-CzPN photocatalyst maintains excellent durability and recycling performance under 25 h continued light irradiation. The outstanding photocatalytic performance of the optimized N-CMPs with n-A structure is attributed to the enhanced polarity and conjugated degree of their core structure, which promotes charge separation and light absorption.