Synthesis of a Pyridine–Zinc‐Based Porous Organic Polymer for the Co‐catalyst‐Free Cycloaddition of Epoxides

The synthesis of solid catalysts for the co‐catalyst‐free cycloaddition of CO 2 has attracted much attention. Herein, we report a hierarchical porous organic polymer, Py‐Zn@MA, that is able to catalyze the cycloaddition reaction of epoxides and CO 2 without using any additives or co‐catalyst to afford turnover frequency (TOF) values as high as 250 and 97 h −1 at 130 °C by using pure and diluted CO 2 (simulating flue gas), respectively. These results are superior to those obtained from previously reported heterogeneous co‐catalyst‐free systems. The high activity of Py‐Zn@MA is mainly attributed to its bifunctional nature with ZnBr 2 and pyridine activating the epoxide in a cooperative way. Notably, Py‐Zn@MA can be easily prepared on a large scale without using any catalyst and the chemicals are cost effective. Moreover, Py‐Zn@MA shows good substrate universality for the cycloaddition reactions of epoxides. Our designed porous organic polymer Py‐Zn@MA material has the potential to serve as an efficient catalyst for the direct conversion of flue gas with epoxides into value‐added cyclic carbonates.