Unveiling the integrated function of metallo‐/ionic‐covalent organic polymers for boosting atmospheric CO2 conversion

Abstract Multifunctional metallo‐/ionic‐covalent organic polymers (TCTB@Zn‐iCOPs) were constructed through one‐pot multicomponent reaction in a deep eutectic solvent at room temperature. The structures of various TCTB@Zn‐iCOPs were characterized, demonstrating their successful integration of multiple sites and excellent structural stability. Then TCTB@Zn‐iCOPs were employed to transform atmospheric CO2 into cyclic carbonates. The results showed that satisfactory product yields were obtained under mild and additive‐free conditions, with a high TOF value of 101 h−1; furthermore, the optimized TCTB@Zn‐iCOP2 exhibited excellent versatility in catalyzing the cycloaddition reactions between various substituted epoxides and CO2, and its activity did not significantly decrease after being reused for five times. Compared with previously reported nonmetallic iCOPs, the TCTB@Zn‐iCOP2 shows significantly improved activity and stability. Finally, DFT calculations were conducted along with a comparison of energy barriers for possible reaction paths, gaining an in‐depth understanding of the synergistic catalytic mechanism involving multiple sites.