Enhancing Photocatalytic CO 2 RR by Modulating the Active Sites of COF‐Based Catalysts

Abstract The catalytic conversion of CO 2 into valuable chemicals using metalized covalent organic frameworks (COFs) as catalysts is a promising method for reducing atmospheric CO 2 levels. Herein, a aldehyde‐amine COF (TAPT‐Tp) at room temperature and pressure and their metallized results is synthesized, Ni‐TAPT‐Tp and Ti‐TAPT‐Tp. The photocatalytic results indicate that the CO 2 to CO reduction rate is 6182.5 µmol g −1 h −1 for Ni‐TAPT‐Tp, but only 1615.4 µmol g −1 h −1 for Ti‐TAPT‐Tp. Density functional theory (DFT) simulations further demonstrate that for intermediates * CO 2 , * COOH, and * CO, the energy of Ni‐TAPT‐Tp is consistently lower than that of Ti‐TAPT‐Tp, indicating that Ni‐TAPT‐Tp exhibits superior photocatalytic performance for CO 2 RR. This work provides a reference for optimizing the coordination structure of M‐COFs to obtain highly active and selective CO 2 RR.