It is highly desired to explore closely contacted polymer semiconductor/g-C3N4 heterojunction photocatalysts with promoted photogenerated-carrier separation and extended visible-light response for efficient visible-light-driven H2 production. Here, we first synthesized the nitro-terminated oligothiophene (OTh) by the controlled copolymerization of thiophene and 2-nitrothiophene monomers, then constructed the nitro-terminated oligothiophene/crystallinity-improved g-C3N4 (OTh/g-C3N4) heterojunctions by a grinding-induced combination strategy. The ratio-optimized 20OTh5/g-C3N4 shows highly efficient H2 production activity up to 3.63 mmol h-1 g-1 under visible-light irradiation, with ∼25.9-time enhancement compared to that of g-C3N4. As verified by time-resolved photoluminescence spectra, surface photovoltage spectra, and the fluorescence spectra related to •OH amounts, the improved photocatalytic activity is due to the promoted photogenerated-carrier transfer and separation in the heterojunctions and the expanded visible-light response. It is also confirmed that the controlled OTh chain length, improved g-C3N4 crystallinity, and tight interface contact dependent on the hydrogen bonds and N···S interactions between OTh and g-C3N4 are reasonable for enhanced photogenerated-carrier separation with the electron transfer from OTh to g-C3N4. This work illustrates a feasible strategy to construct efficient polymer semiconductor/g-C3N4 heterojunction photocatalysts for solar-light-driven H2 production.
Keywords: H2 production; charge transfer and separation; crystallinity-improved g-C3N4; nitro-terminated oligothiophene modification; visible-light catalysis.