Integrating Covalent Organic Framework with Transition Metal Phosphide for Noble‐Metal‐Free Visible‐Light‐Driven Photocatalytic H2 Evolution

2D covalent organic frameworks (COFs) are considered as one kind of the most promising crystalline porous materials for solar-driven hydrogen production. However, adding noble metal co-catalysts into the COFs-based photocatalytic system is always indispensable. Herein, through a simple solvothermal synthesis method, TpPa-1-COF, a typical 2D COF, which displays a wide light absorption region, is rationally combined with transition metal phosphides (TMPs) to fabricate three TMPs/TpPa-1-COF hybrid materials, named Ni12 P5 (Ni2 P or CoP)/TpPa-1-COF. The incorporated TMPs can be served as electron collectors for accelerating the transfer of charges on TpPa-1-COF, thus the composites are demonstrated to be efficient photocatalysts for promoting water splitting. Benefitting from the richer surface reactive sites and lower H* formation energy barrier, the Ni12 P5 can most effectively improve the photocatalytic performance of the TpPa-1-COF, and the H2 evolution rate can reach up to 31.6 µmol h-1 , approximately 19 times greater than pristine TpPa-1-COF (1.65 µmol h-1 ), and is comparable to the Pt/TpPa-1-COF (38.8 µmol h-1 ). This work is the first example of combining COFs with TMPs to construct efficient photocatalysts, which may offer new insight for constructing noble-metal-free COF-based photocatalysts.