Synergistically interactive P–Co–N bonding states in cobalt phosphide-decorated covalent organic frameworks for enhanced photocatalytic hydrogen evolution

Non-noble materials with high efficiency and stability are essential for renewable energy applications. Herein, cobalt phosphide nanoparticles-decorated covalent organic frameworks (CTF-CoP) are synthesized via an in situ self-assembly method combined with the calcination process. In such a configuration, an intimate interaction between CoP and CTF matrix is gained through the Co-N chemical bonds, which not only significantly enhance the recyclability of CoP nanoparticles but also significantly improve the charge separation efficiency. Besides, the synergistically interactive P^δ--Co^δ+-N^δ- states induced by the polarization effect of N-anchoring sites benefit for the adsorption and dissociation of water molecules in CTF-CoP. Consequently, CTF-CoP exhibits a higher photocatalytic hydrogen evolution rate (261.7 μmol g^-1 h^-1) and better durability as compared with the physically fixed CTF/CoP composite (64.8 μmol g^-1 h^-1) and even the noble metal-based CTF-Pt (191.3 μmol g^-1 h^-1). This work provides an avenue to construct highly stable non-noble photocatalyst for energy conversion and also emphasizes the potential of CTFs in constructing efficient heterojunctions.