Construction of highly active WO3/TpPa-1-COF S-scheme heterojunction toward photocatalytic H2 generation

• WO 3 /TpPa-1-COF is synthesized through an in-situ growth approach. • Internal electric field drives the charge carrier diffusion in S-scheme mode. • WO 3 /TpPa-1-COF has strong redox abilities and high charge separation efficiency. • WO 3 /TpPa-1-COF display superior photocatalytic H 2 generation performance. The rapid charge recombination and low surface reaction kinetics are the two major constraints to the photocatalytic performance of covalent organic frameworks (COFs). To accelerate the charge separation behavior, TpPa-1-COF is decorated with WO 3 via an in-situ growth approach, and the resultant WO 3 /TpPa-1-COF composites show significantly improved photocatalytic performance. Especially, when the WO 3 loading arrives at 3 wt%, 3%WO 3 /TpPa-1-COF exhibits the maximum photocatalytic H 2 evolution rate of 19.89 mmol g −1 h −1 , which is approximately 4.8 times higher than that of pure TpPa-1-COF. The apparent quantum efficiency (AQE) of 3%WO 3 /TpPa-1-COF at 420 nm is detected to be 12.4%. X-ray photoelectron spectroscopy (XPS) characterization confirms the formation of internal electric field between WO 3 and TpPa-1-CF, which can drive the photogenerated charge carrier diffusion in S-scheme mode. As a result, WO 3 /TpPa-1-COF composite possesses high charge separation efficiency and strong redox ability, which is further supported by the photoelectrochemical results, thus benefiting the photocatalysis process. This work provides a rational strategy to modify COFs in photocatalytic water splitting.