P and Cu Dual Sites on Graphitic Carbon Nitride for Photocatalytic CO₂Reduction to Hydrocarbon Fuels with High C₂H₆Evolution

The light‐driven CO 2 reduction to multi‐carbon products is especially meaningful, while the low efficiency of multi‐electron transfer and sluggish C−C coupling greatly hinder its development. Herein, we report a photocatalyst comprising of P and Cu dual sites anchored on graphitic carbon nitride (P/Cu SAs@CN), which achieves a high C 2 H 6 evolution rate of 616.6 μmol g −1 h −1 in reducing CO 2 to hydrocarbons. The detailed spectroscopic characterizations identify the formation of charge‐enriched Cu sites, where the isolated P atoms serve as hole capture sites during photocatalysis. Theoretical simulations combined with in situ FTIR measurement reveal a kinetically feasible process for the formation of C−C coupling intermediate (*OC−COH) and confirm the favorable production of C 2 H 6 on the P/Cu SAs@CN photocatalyst. This work offers new insights into the photocatalyst design with atomic precision toward highly efficient photocatalytic CO 2 conversion to high value‐added carbon products.