Effective N‐formylation of Amines with CO2 in Anaerobic Fermentation Gas Catalyzed by Triply Synergistic Effect of Ionic Porous Organic Polymer

Abstract The anaerobic fermentation gas (AFG) with CO 2 removed is a sustainable energy resource, and converting CO 2 in AFG to value‐added chemicals can kill two birds with one stone. Herein, an ionic porous organic polymer (IPOP‐3) catalyst, with triply synergistic effect of its hydroxide anions, nitrogen activation sites and porous structure, is synthesized. IPOP‐3 exhibits an excellent ability to enrich and convert 50 vol.% CO 2 by the reactions with various amines into corresponding formamides. The catalyst is also successfully applied to the N ‐formylation of CO 2 in AFG, and can be easily recovered and reused. The plausible mechanism for the catalytic N ‐formylation is proposed. The hydroxide anion in IPOP‐3 activates the Si−H bond of phenyl silane which reacts with the captured CO 2 to form formate anion to facilitate the subsequent conversion into formamide. Our work provides a new idea for the purification of AFG and the resource utilization of CO 2 .