Heterogeneous conversion of CO₂ into cyclic carbonates at ambient pressure catalyzed by ionothermal-derived meso-macroporous hierarchical poly(ionic liquid)s

Meso-macroporous hierarchical poly(ionic liquid)s (MPILs) with extremely high ionic site densities and tunable pore structures were ionothermally synthesized through the free radical self-polymerization of our newly designed rigid bis-vinylimidazolium salt monomer. The synthesis avoided the use of any templates, gave a high yield (>99%) and allowed recycling of the IL solvent; thus it is facile, atom-efficient, environmentally friendly and sustainable. The synthesized MPILs possessed distinctive features of polycation matrices, abundant halogen anions, and large surface areas. They not only presented enhanced CO₂ capture, but led to breakthroughs in the heterogeneous catalytic conversion of CO₂ into cyclic carbonates: (1) unprecedented high activity at atmospheric pressure and low temperature; (2) good substrate compatibility, even being active towards the extremely inert aliphatic long carbon-chain alkyl epoxides. This result renders the first occasion of a metal-solvent-additive free recyclable heterogeneous cycloaddition of CO₂ at such mild conditions.