Construction of zwitterionic porous organic frameworks with multiple active sites for highly efficient CO2 adsorption and synergistic conversion

Robust ZPOFs with multiple active sites are facilely constructed and show remarkable CO 2 adsorption and conversion performance under mild/green conditions. • Novel ZPOFs with multiple active sites are prepared via ionothermal polymerization. • The ZPOFs show exciting dual-functions for CO 2 adsorption and conversion. • The ZPOF-mediated CO 2 coupling reaction can proceed under mild/green conditions. • The present ZPOF is easily separated and shows good stability and reusability. • The optimum catalyst exhibits excellent broad substrate scope. Porous organic frameworks fabricated by well-defined monomeric compounds with different active sites have been regarded as the promising nano-materials for improving the efficiency of CO 2 capture and utilization. In this study, novel zwitterionic porous organic frameworks (ZPOFs) alternately connected by benzimidazole, triazine and imidazolium modules were prepared facilely via ZnCl 2 -catalyzed bi-component polymerization. The influences of different monomer concentration and polymerization temperature on structural properties of the ZPOFs were discussed in detail. It indicates that the ZPOFs present attractive structure characteristics of high specific surface area and hierarchical pore structure, and have abundant hydrogen bond donors, Lewis bases and nucleophilic groups, respectively. The ZPOFs as-obtained were applied to CO 2 adsorption and conversion into cyclic carbonate by coupling with epoxide. The experiment results showed that the ZPOFs could afford the highest CO 2 adsorption capacity of 2505 μmol/g at 273 K and 1.0 bar CO 2 pressure. The effects of ZPOFs structures and reactions conditions on the catalytic performance were investigated. Under the optimized conditions of 70 o C, 2.0 MPa CO 2 for 2.0 h, and cooperating with tetrabutylammonium iodide (TBAI) cocatalyst, the ZPOF-450-30 could efficiently and selectively catalyze the CO 2 /epoxides cycloaddition reaction to yield corresponding cyclic carbonates. Moreover, the ZPOF-450-30 catalyst could be simply separated with durable high stability and activity. Finally, we compared the catalytic behaviors with reported similar heterogeneous catalysts and proposed a feasible ZPOFs-catalyzed mechanism.