Relative Local Electron Density Tuning in Metal‐Covalent Organic Frameworks for Boosting CO2 Photoreduction

The high local electron density and efficient charge carrier separation are two important factors to affect photocatalytic activity, especially for the CO2 photoreduction reaction. However, the systematic studies on the structure‐functional relationship regarding the above two factors based on precisely structure model are rarely reported. Herein, as a proof‐of‐concept, we developed a new strategy on the evaluation of local electron density by controlling the relative electron‐deficient (ED) and electron‐rich (ER) intensity of monomer at a molecular level based on three rational‐designed vinylene‐linked sp2 carbon‐covalent organic frameworks (COFs). As expected, the as‐prepared vinylene‐linked sp2 carbon‐conjugated metal‐covalent organic framework (MCOFs) (VL‐MCOF‐1) with molecular junction exhibited excellent activities for CO2‐to‐HCOOH conversion (283.41 μmol g−1 h−1) and high selectivity of 97.1 %, much higher than the VL‐MCOF‐2 and g‐C34N6‐COF, which is due to the synergistic effect of the multi‐electronic metal clusters (Cu3(PyCA)3) (PyCA=pyrazolate‐4‐carboxaldehyde) as strong ER roles and cyanopyridine units as ED roles and active sites, as well as the boosted photo‐induced charge separation efficiency of vinyl connection and increased light utilization ability. These results not only provide a strategy for regulating the electron‐density distribution of photocatalysts at the molecular level but also offers profound insights for metal clusters‐based COFs to effective CO2 conversion.