P-Mediated Cu-N Sites in Carbon Nitride Realizing CO Photoreduction to C H with Selectivity Modulation.

Photocatalytic CO reduction to high value-added C products (e.g., C H ) is of considerable interest but challenging. The C H product selectivity strongly hinges on the intermediate energy levels in the CO reduction pathway. Herein, Cu-N sites anchored phosphorus-modulated carbon nitride (CuACs/PCN) is designed as a photocatalyst to tailor the intermediate energy levels in the the C H formation reaction pathway for realizing its high production with tunable selectivity. Theoretical calculations combined with experimental data demonstrate that the formation of the C-C coupling intermediates can be realized on Cu-N sites and the surrounding doped P facilitates the production of C H . Thus, CuACs/PCN exhibits a high C H selectivity of 53.2% with a yielding rate of 30.51 µmol g . The findings reveal the significant role of the coordination environment and surrounding microenvironment of Cu single atoms in C H formation and offer an effective approach for highly selective CO photoreduction to produce C H .