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 μmol_CO g_cat ^-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.