Probing the Reorganization of Ionic Liquids' Structure Induced by CO₂ Sorption

The sorption of CO₂ is often used to modify the macroscopic properties of liquids and solids. In the particular case of ionic liquids, different from molecular liquids, the sorption of CO₂ may not induce volume expansions due to the strong Coulombic interactions between the ions of the fluid. However, a considerable viscosity decrease has been systematically observed. In order to understand the mechanisms of properties modifications in ionic fluids, herein we used Raman spectroscopy to probe the effect of CO₂ on the structure of ionic liquids. It is shown that CO₂ perturbs the electrostatic interactions between cations and anions, thus inducing a change in the polar domain of ionic liquids. It is observed that ionic liquids having bulkier ions are more prone to be perturbed by CO₂ in comparison to ionic liquids having smaller ions. These results reveal new means of controlling the electrostatic forces between the ions and contributes to the mechanistic understanding of the modification of the macroscopic properties of ionic liquids by CO₂ sorption.