Catalytic non-redox carbon dioxide fixation in cyclic carbonates

by Saravanan Subramanian, Julius Oppenheim, Doyun Kim, Thien S Nguyen, Wahyu MH Silo, Byoungkook Kim, William A Goddard III, Cafer T Yavuz
Chem Year: 2019 DOI:


If cycloaddition of CO2 to epoxides is to become a viable non-redox CO2 fixation path, it is crucial that researchers develop an active, stable, selective, metal-free, reusable, and cost-effective catalyst. To this end, we report here a new catalyst that is based on imidazolinium functionality and is synthesized from an unprecedented, one-pot reaction of the widely available monomers terephthalaldehyde and ammonium chloride. We show that this covalent organic polymer (COP)-222 exhibits quantitative conversion and selectivity for a range of substrates under ambient conditions and without the need for co-catalysts, metals, solvent, or pressure. COP-222 is recyclable and has been demonstrated to retain complete retention of activity for over 15 cycles. Moreover, it is scalable to at least a kilogram scale. We determined the reaction mechanism by using quantum mechanics (density functional theory), showing that it involves nucleophilic-attack-driven epoxide ring opening (ND-ERO). This contrasts with the commonly assumed mechanism involving the concerted addition of chemisorbed CO2.


Co2 utilization cyclic carbonate heterogeneous catalysis non-redox carbon fixation imidazolinium chloride porous polymer density functional theory