Triazine-Based Conjugated Microporous Polymers With Different Linkage Units for Visible Light-Driven Hydrogen...

Conjugated microporous polymers (CMPs), as a kind of two-dimensional material, have attracted extensive attention due to their advantages in visible light-driven photocatalytic splitting of water for hydrogen evolution. However, improving the microstructure and electronic structure of the material to enhance their photocatalytic performance for hydrogen evolution remains a challenge. We designed and reported two analogous CMPs including CMP-1 and CMP-2 that contain triazine and dibenzothiophene-S,S-dioxide units, which were prepared by Pd-catalyzed Suzuki-Miyaura coupling reaction. The main difference of two CMPs is that the triazine units are connected to benzene unit (CMP-1) or thiophene unit (CMP-2). Both of the CMPs exhibit excellent light capture capability, and compared with CMP-2, CMP-1 has faster separation rates and lower recombination rates for the charge carriers (electron/hole), and then, a higher hydrogen evolution rate was obtained from water decomposition reaction. We find the H₂ production rate of CMP-1 can be up to 9,698.53 μmol g^-1h ^-1, which is about twice of that of CMP-2. This work suggests that molecular design is a potent method to optimize the photocatalytic performance toward hydrogen evolution of the CMPs.