Synergistic Bifunctionality in Zn (II)‐Porphyrin‐Based Imidazolium Functionalized Porous Organic Polymers for Efficient Catalysis of CO₂‐Epoxide Cycloaddition

The development of bifunctional catalytic materials bearing Lewis acid and base activity sites toward the cycloaddition of CO 2 and epoxides to value‐added cyclic carbonate under cocatalyst‐free conditions is needed in particular. In this work, an imidazolium functionalized Zn (II)‐porphyrin ZnTAEImP was first designed and synthesized. Subsequently, a series of porous organic polymers, named POP‐ZnTAEImP/DVB(1: m ) ( m = 30, 50, 70), were prepared through the free‐radical copolymerization of ZnTAEImP with divinylbenzene (DVB). The obtained POP‐ZnTAEImP/DVB(1: m ) exhibited a high specific surface area and good thermal stability. As bifunctional heterogeneous catalysts, POP‐ZnTAEImP/DVB(1: m ) showed excellent catalytic activities in CO 2 cycloaddition with epichlorohydrin under the condition of solvent‐free. In particular, the POP‐ZnTAEImP/DVB(1:50) demonstrated the highest catalytic activity (TON = 2880) and was applicable to a variety of epoxides. Furthermore, only a slight decrease in catalytic activity was observed after five cycles. Activation energy ( E a ) for this reaction was determined to be 52.4 kJ/mol. This work provides a valuable strategy for designing efficient binary heterogeneous catalysts for the high‐efficiency fixation of CO 2 .