Rational Design of Covalent Organic Framework Catalysts for Photocatalytic Carbon Dioxide Fixation

The photo‐thermal synergistic conversion of CO2, which harnesses complementary photochemical and thermochemical processes to enhance catalytic efficiency, is gaining increasing attention. Notably, photo‐mediated CO2 cycloaddition exhibits significant promise for practical applications. Catalysts based on metallosalen structures have garnered considerable attention for their role in the formation of cyclic carbonates through CO2 cycloaddition, owing to their favorable CO2 and epoxide activation capabilities. In this study, we establish a computational database comprising 300 Salen(Zn)‐COFs and screen for optimal photothermal catalysts for CO2 cycloaddition. Three parameters determine catalyst selection: π‐conjugation extent, CO2 adsorption energy values, and epoxide binding energy values. This approach identifies three pyrene‐functionalized COF candidates—Py‐EDA‐COF, Py‐DAC‐COF, and Py‐OPD‐COF—as superior catalytic materials. These three COFs demonstrate outstanding performance in photo‐driven CO2 cycloaddition with various epoxides, particularly phenyl glycidyl ether. Furthermore, we demonstrate that the substituents on the diamine backbone of the salen moiety significantly modulate catalytic activity. Among them, the Py‐OPD‐COF, which features a benzene unit that enhances π conjugation and exhibits strong electron‐donating properties, achieves the highest conversion rate (84%) and a turnover frequency (TOF) of 115.2 h−1, surpassing all previously reported catalysts. This research establishes a viable strategy for the developing of highly efficient catalysts for photo‐driven CO2 conversion.