Enhanced CO2 capture in binary mixtures of 1-alkyl-3-methylimidazolium tricyanomethanide ionic liquids with water

The absorption of carbon dioxide and water in the 1-butyl-3-methylimidazoliun tricyanomethanide ([C4C1im][TCM]) and 1-octyl-3-methylimidazolium tricyanomethanide ([C8C1im][TCM]) ionic liquids (ILs) was systematically investigated for the first time as a function of the H2O content by means of a gravimetric system together with in-situ Raman spectroscopy, excess molar volume (VE) and viscosity deviation measurements. Although CO2 absorption was marginally affected by water at low H2O molar fractions for both ILs, increase of the H2O content resulted in a marked enhancement of both the CO2 solubility (ca. fourfold) and diffusivity (ca. tenfold) in the binary [CnC1im][TCM]/H2O systems, in contrast to the weak and/or detrimental influence of water in most physically and chemically CO2 absorbing ILs. In-situ Raman spectroscopy on the IL/CO2 systems verified that CO2 is physically absorbed in the dry ILs with no significant effect on their structural organization. A pronounced variation of distinct tricyanomethanide Raman modes was though disclosed in the [CnC1im][TCM]/H2O mixtures, attesting to the gradual disruption of the anion-cation coupling by the hydrogen bonded water molecules to the [TCM] anions, in accordance with the positive excess molar volumes and negative viscosity deviations for the binary systems. Most importantly, CO2 absorption in the ILs/H2O mixtures at high water concentrations revealed that the [TCM] Raman modes tend to restore their original state for the heavily hydrated ILs, in qualitative agreement with the intriguing non-monotonous transients of CO2 absorption kinetics unveiled by the gravimetric measurements for the hybrid solvents. A molecular exchange mechanism between CO2 in the gas phase and H2O in the liquid phase was thereby proposed to explain the enhanced CO2 absorption in the hybrid [CnC1im][TCM]//H2O solvents based on the subtle competition between the TCM-H2O and TCM-CO2 interactions, which renders these ILs very promising for CO2 separation applications