Effect of Linking Pattern of Dibenzothiophene-<i>S</i>,<i>S</i>-dioxide-Containing Conjugated Microporous Polymers on the Photocatalytic Performance

Abstract

Conjugated microporous polymers (CMPs) exhibit great potential for photocatalytic hydrogen generation due to their tunable electronic structure. The rational molecular design is a key point for developing an efficient CMP photocatalyst. Herein, we developed two CMPs photocatalysts via the copolymerization from pyrene and dibenzothiophene-S,S-dioxide building blocks. The effect of the linking pattern of the building block of dibenzothiophene-S,S-dioxide on the photocatalytic hydrogen evolution was explored. The polymer of PyDOBT-1 with 3,7-linking pattern shows a superior photocatalytic performance to PyDOBT-2 with 2,8-linking pattern because the 3,7-linking pattern enhances the conjugation chain length and improves the coplanarity of the polymeric backbone, which facilitate the charges migration along the polymer chain. As a result, the bare PyDOBT-1 shows an impressive visible light activity with a hydrogen evolution rate (HER) of 5697 μmol h–1 g–1. Notably, an outstanding HER of 12986 μmol h–1 g–1 was also obtained by the Pt-modified PyDOBT-1 under the full-arc spectrum (λ > 300 nm), which lies toward the upper end compared to that of the reported organic photocatalysts.