Spirobifluorene-Based D-A Type Conjugated Polymer Photocatalysts for Water Splitting

Exploring synthetic pathways for efficient photocatalysts has always been a major goal in catalysis. The performance of organic photocatalysts is affected by a variety of complex factors, and how to understand the structure–effect relationship is the key to designing efficient photocatalysts. This work explored the feasibility of constructing large-specific-surface-area conjugated microporous polymers (CMPs) based on stereoscopic units like spirobifluorene and achieving efficient photocatalytic activity by modulating the donor–acceptor (D-A) ratio with dibenzothiophene sulfone. Crosslinked pore structures were successfully constructed, and the specific surface area increased with the ratio of spirobifluorene. When the molar ratio of D-A was 1:20, polymer Spso-3 showed the highest photocatalytic hydrogen production activity, at 22.4 mmol h–1 g–1. The findings indicate that constructing D-A type CMPs should be a promising approach to improving the performance of photocatalytic water separation. The appropriate push–pull effect of the D-A structure promotes the photo-induced separation of electron–hole pairs, and the porous structure built on steric units offers ample space for catalytic reactions. This work could provide case references for structural design and the structure–effect relationship of efficient polymer photocatalysts.