Reversing electron transfer in a covalent triazine framework for efficient photocatalytic hydrogen evolution

Covalent triazine-based frameworks (CTFs) have emerged as some of the most important materials for photocatalytic water splitting. However, development of CTF-based photocatalytic systems with non-platinum cocatalysts for highly efficient hydrogen evolution still remains a challenge. Herein, we demonstrated, for the first time, a one-step phosphidation strategy for simultaneously achieving phosphorus atom bonding with the benzene rings of CTFs and the anchoring of well-defined dicobalt phosphide (Co₂P) nanocrystals (∼7 nm). The hydrogen evolution activities of CTFs were significantly enhanced under simulated solar-light (7.6 mmol h^-1 g^-1), more than 20 times higher than that of the CTF/Co₂P composite. Both comparative experiments and in situ X-ray photoelectron spectroscopy reveal that the strong interfacial P-C bonding and the anchoring of the Co₂P cocatalyst reverse the charge transfer direction from triazine to benzene rings, promote charge separation, and accelerate hydrogen evolution. Thus, the rational anchoring of transition-metal phosphides on conjugated polymers should be a promising approach for developing highly efficient photocatalysts for hydrogen evolution.