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 H₂O 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-C₃N₄ under the same conditions. In situ Fourier-transform (FT)IR analysis indicated that CT-COF could adsorb and activate the CO₂ and H₂O 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.