Unique PCoN Surface Bonding States Constructed on g‐C 3 N 4 Nanosheets for Drastically Enhanced Photocatalytic Activity of H 2 Evolution

Developing high‐efficiency and low‐cost photocatalysts by avoiding expensive noble metals, yet remarkably improving H 2 evolution performance, is a great challenge. Noble‐metal‐free catalysts containing Co(Fe)NC moieties have been widely reported in recent years for electrochemical oxygen reduction reaction and have also gained noticeable interest for organic transformation. However, to date, no prior studies are available in the literature about the activity of N‐coordinated metal centers for photocatalytic H 2 evolution. Herein, a new photocatalyst containing g‐C 3 N 4 decorated with CoP nanodots constructed from low‐cost precursors is reported. It is for the first time revealed that the unique P(δ − )Co(δ + )N(δ − ) surface bonding states lead to much superior H 2 evolution activity (96.2 µmol h −1 ) compared to noble metal (Pt)‐decorated g‐C 3 N 4 photocatalyst (32.3 µmol h −1 ). The quantum efficiency of 12.4% at 420 nm is also much higher than the record values (≈2%) of other transition metal cocatalysts‐loaded g‐C 3 N 4 . It is believed that this work marks an important step toward developing high‐performance and low‐cost photocatalytic materials for H 2 evolution.