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 CO 2 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‐iCOP 2 exhibited excellent versatility in catalyzing the cycloaddition reactions between various substituted epoxides and CO 2 , and its activity did not significantly decrease after being reused for five times. Compared with previously reported nonmetallic iCOPs, the TCTB@Zn‐iCOP 2 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.