Phosphate ester functionalized fluorene-benzothiadiazole alternating copolymer/hydroxylated g-C3N4 heterojunctions for efficient hydrogen evolution under visible-light irradiation

It is highly desirable to explore functionalized polymer semiconductor/g-C3N4 heterojunction photocatalysts with the tight interfacial connection for promoting the photogenerated electron-hole pair separation, improving the hydrophilicity, extending the visible light response and achieving the efficient visible light-driven H2 evolution. Herein, we synthesized novel poly[9,9-bis(3-ethyl phosphate propyl)fluorene-alt-benzothiadiazole] (PPFBT) with a phosphate ester on every repeating unit by the Suzuki polymerization and then fabricated PPFBT/hydroxylated g-C3N4 (PPFBT/CN-OH) heterojunctions via a surface hydroxyl-induced assembly process. The ratio-optimized 5PPFBT/CN-OH shows the hydrogen evolution activity of 2662.4 μmol·g-1·h-1, an 11.1-time enhancement compared to CN-OH. The improved photocatalytic activity is mainly attributed to the enhanced electron-hole pair separation due to the tight interfacial connection by hydrogen bond (P=O…H-O) and N…S interactions between PPFBT and CN-OH. It is verified that abundant phosphate ester groups of PPFBT improve the hydrophilicity and form coordination bonds with platinum (P=O:Pt) as a cocatalyst to facilitate water splitting for H2 evolution. It is also confirmed that the enhanced electron-hole pair separation is mainly dependent on the excited high-energy level electron transfer from CN-OH to PPFBT. This work provides a rational molecular design strategy for constructing efficient functionalized polymer semiconductor/g-C3N4 heterojunctions for sunlight-driven H2 evolution.