Lewis Acid‐Base Bifunctional Ionic Covalent Organic Frameworks for CO ₂ Chemical Fixation

Abstract Ionic covalent organic frameworks (iCOFs) exhibit unique advantages as heterogeneous catalysts due to their permanent porosity, programmable charge transport, and tunable host‐guest interactions. Here, the fabrication of cationic iCOFs via direct solvothermal assembly and integrate zinc ions (Zn(II))‐imine centers are reported to construct bifunctional heterogeneous catalysts. The resultant catalyst, Zn@PD‐iCOF, achieves remarkable yields (up to 99%) of cyclic carbonates in carbon dioxide (CO 2 )‐epoxides cycloaddition reactions under mild conditions (at 80 °C, 0.1 MPa CO 2 ) without the need for co‐catalysts and solvents, superior to most previously reported ionic catalysts. This exceptional performance stems from hierarchically ordered pores structure, fully exposed dual active sites (ion pair and Lewis acid site), and their synergistic electronic coupling. Moreover, the catalyst retains >90% activity over twelve consecutive cycles, demonstrating exceptional stability. This study establishes a blueprint for designing task‐specific COFs catalysts for efficient CO 2 chemical fixation.