Phosphorus Tailors thed‐Band Center of Copper Atomic Sites for Efficient CO2Photoreduction under Visible‐Light Irradiation

Photoreduction of CO2 into solar fuels has received great interest, but suffers from low catalytic efficiency and poor selectivity. Herein, two single-Cu-atom catalysts with unique Cu configurations in phosphorus-doped carbon nitride (PCN), namely, Cu1 N3 @PCN and Cu1 P3 @PCN were fabricated via selective phosphidation, and tested in visible light-driven CO2 reduction by H2 O without sacrificial agents. Cu1 N3 @PCN was exclusively active for CO production with a rate of 49.8 μmolCO gcat-1 h-1 , outperforming most polymeric carbon nitride (C3 N4 ) based catalysts, while Cu1 P3 @PCN preferably yielded H2 . Experimental and theoretical analysis suggested that doping P in C3 N4 by replacing a corner C atom upshifted the d-band center of Cu in Cu1 N3 @PCN close to the Fermi level, which boosted the adsorption and activation of CO2 on Cu1 N3 , making Cu1 N3 @PCN efficiently convert CO2 to CO. In contrast, Cu1 P3 @PCN with a much lower Cu 3d electron energy exhibited negligible CO2 adsorption, thereby preferring H2 formation via photocatalytic H2 O splitting.