Imidazole-based organic polymer frameworks as metal- and halogen-free heterogeneous platforms for efficient CO2 cycloaddition

Abstract

Developing effective metal- and halogen-free heterogeneous catalysts for the CO2 cycloaddition remains a challenge. In this study, novel imidazole-based hyper-crosslinked polymers (HCP-BZ, HCP-BP and HCP-TBZ) with abundant N sites were constructed via a one-pot polymerization, and employed as heterogeneous catalysts for the CO2 cycloaddition reaction. The special skeletal pore structure with abundant hierarchical pore structures and uniformly distributed active sites were demonstrated by various characterization technologies. The optimal HCP-TBZ(16:1) exhibits a good CO2 selective adsorption performance with a CO2 adsorption capacity of 2.23 mmol/g and CO2/N2 adsorption selectivity of 41 at 273 K and 0.1 MPa. Additionally, the resulting catalyst HCP-TBZ(16:1) achieves an excellent catalytic performance with 96 % yield and 99 % selectivity without metal, halogen, cocatalyst and solvent additions (120 °C, 1.0 MPa CO2, 5 h). Moreover, the HCP-TBZ(16:1) also exhibits a satisfactory catalytic activity under the mild conditions (70 °C, 1.0 MPa CO2), and can effectively catalyze the cyclic carbonate preparation from the dilute CO2 (15 %CO2/85 %N2). The comparable catalytic activity and the determined structural stability, reusability and universality make the prepared imidazole-based HCPs a potential heterogeneous catalyst candidate for the CO2 cycloaddition. This study will provide some guidance for developing metal-free and halogen-free CO2 adsorption and conversion platforms.