Carbon Dioxide in a Supported Ionic Liquid Membrane: Structural and Rotational Dynamics Measured with 2D IR and Pump–Probe Experiments

Supported ionic liquid membranes (SILMs) are porous membranes impregnated with ionic liquids (ILs) and used as advanced carbon capture materials. Here, two-dimensional infrared (2D IR) and IR polarization selective pump-probe (PSPP) spectroscopies were used to investigate CO₂ reorientation and spectral diffusion dynamics in SILMs. The SILM contained 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonly)imide in the poly(ether sulfone) membrane with average pore size of ∼350 nm. Two ensembles of CO₂ were observed in the SILM, one in the IL phase in the membrane pores and the other in the supporting membrane polymer. CO₂ in the polymer displayed a red-shifted IR absorption spectrum and a shorter vibrational lifetime of the asymmetric stretch mode compared to the IL phase. Despite the relatively large pore sizes, the complete orientational randomization of CO₂ and structural fluctuations of the IL (spectral diffusion) in the pores are slower than in the bulk IL by ∼2-fold. The implication is that the IL structural change induced by the polymer interface can propagate out from the interface more than a hundred nanometers, influencing the dynamics. The dynamics in the polymer are even slower. This study demonstrates that there are significant differences in the dynamics of ILs in SILMs on a molecular level compared to the bulk IL, and the study of dynamics in SILMs can provide important information for the design of SILMs for CO₂ capture.