A Metal‐Free Donor–Acceptor Covalent Organic Framework Photocatalyst for Visible‐Light‐Driven Reduction of CO2 with H2O

Visible-light-driven CO₂ reduction to valuable chemicals without sacrificial agents and cocatalysts remains challenging, especially for metal-free photocatalytic systems. Herein, a novel donor-acceptor (D-A) covalent organic framework (CT-COF) was constructed by the Schiff-base reaction of carbazole-triazine based D-A monomers and possessed a suitable energy band structure, strong visible-light-harvesting, and abundant nitrogen sites. CT-COF as a metal-free photocatalyst could reduce CO₂ with gaseous H₂ O to CO as the main carbonaceous product with approximately stoichiometric O₂ evolution under visible-light irradiation and without cocatalyst. The CO evolution rate (102.7 μmol g^-1 h^-1 ) was 68.5 times that of g-C₃ N₄ under the same conditions. In situ Fourier-transform (FT)IR analysis indicated that CT-COF could adsorb and activate the CO₂ and H₂ O molecules and that COOH* species may be a key intermediate. DFT calculations suggested that nitrogen atoms in the triazine rings may be photocatalytically active sites.