Carbon Dioxide Conversion Upgraded by Host‐guest Cooperation between Nitrogen‐Rich Covalent Organic Framework and Imidazolium‐Based Ionic Polymer

The chemical conversion of CO2 into value‐added chemicals is one promising approach for CO2 utilization. It is crucial to explore highly efficient catalysts containing task‐specific components for CO2 fixation. Here, a host‐guest catalytic system was developed by integrating nitrogen‐rich covalent organic framework (TT‐COF) and imidazolium‐based ionic polymer (ImIP), which serve as hydrogen‐bonding donor and nucleophilic agent, respectively, for cooperatively facilitating the activation of the epoxides and subsequent CO2 cycloaddition. The catalytic activity of the host‐guest system was remarkably superior to those of ImIP, TT‐COF, and their physical mixture. Furthermore, selective adsorption for CO2 over N2 rendered this catalytic system effective for the cycloaddition reaction of the simulated flue gas. The protocols for the unification of two catalytically active components provide new opportunities for the development of composite systems in multiple applications. Host–gust composites are developed through integrating nitrogen‐rich covalent organic framework and imidazolium‐based ionic polymer to serve as hydrogen‐bonding donor and nucleophilic agent, respectively, for the activation and ring opening of epoxides. Excellent catalytic activity and recyclability are achieved in the cycloaddition reaction of CO2 with epoxides.