ChemSusChem, 2017, 10, 1160-1165.

Porousionic polymers as a robust and efficient platform   for capture and chemical fixation ofatmospheric CO₂.

Direct use of atmospheric CO2 as a C1 source to synthesizehigh‐value chemicals through environmentally benign processes is of greatinterest, yet challenging. Porous heterogeneous catalysts that are capable ofsimultaneously capturing and converting CO2 arepromising candidates for such applications. Herein, a family of organic ionicpolymers with nanoporousstructure, large surface area, strong affinity for CO2, and very high density ofcatalytic active sites (halide ions) was synthesized through the free‐radicalpolymerization of vinylfunctionalizedquaternary phosphoniumsalts. The resultant porous ionic polymers (PIPs) exhibit excellent activitiesin the cycloaddition of epoxides with atmospheric CO2, outperforming the correspondingsoluble phosphonium saltanalogues and ranking among the highest of known metal‐free catalytic systems.The high CO2 uptakecapacity of the PIPs facilitates the enrichment of CO2 molecules around thecatalytic centers, thereby benefiting its conversion. We have demonstrated forthe first time that atmospheric CO2 canbe directly converted to cyclic carbonates at room temperature using aheterogeneous catalytic system under metal‐solvent free conditions. Moreover,the catalysts proved to be robust and fully recyclable, demonstrating promisingpotential for practical utilization for the chemical fixation of CO2. Our work thereby paves a way tothe advance of PIPs as a new type of platform for capture and conversion of CO2.