Solvation Environments in Porous Ionic Liquids Determine Selectivity in CO₂ Conversion to Cyclic Carbonates

Porous ionic liquids, which are suspensions of nanoporous particles in ionic liquids that maintain permanent porosity, are effective and selective media for the conversion of styrene oxide into styrene carbonate, absorbing CO₂ [Zhou et al. Chem. Commun. 2021, 57, 7922-7925]. Here we elucidate the mechanism of selectivity using polarizable molecular dynamics simulations, which provide a detailed view on the structure of the porous ionic liquid and on the local solvation environments of the reacting species. The porous ionic liquids studied are composed of tetradecyltrihexylphosphonium chloride, or [P₆₆₆₁₄]Cl, and the ZIF-8 zinc-methylimidazolate metal-organic framework (MOF). The CL&Pol polarizable force field was extended to represent epoxide and cyclic carbonate functional groups, allowing the ionic liquid, the reactants, and the MOF to be all represented by fully flexible, polarizable force fields, providing a detailed description of interactions. The presence of reactant and product molecules leads to changes in the structure of the ionic liquid, revealed by domain analysis. The structure of local solvation environments, namely, the arrangement of charged moieties and CO₂ around the epoxide ring of the reactant molecules, clearly indicate ring-opening the reaction mechanism. The MOF acts as a reservoir of CO₂ through its free volume. The solute molecules are found in the accessible outer cavities of the MOF, which promotes reaction of the epoxide with CO₂ excluding other epoxide molecules, thereby preventing the formation of oligomers, which explains the selectivity toward conversion to cyclic carbonates.