Improved carbon dioxide absorption in double-charged ionic liquids.

Four divalent ionic liquids based on imidazolium cations with alkyl or ether functionalized side-chains were synthesised and characterized: 3,3'-(tetraethyleneglycol-1,11-diyl)bis(1-methyl-1H-imidazolium)bromide, [tetraEG(mim)2][Br]2, 3,3'-(tetraethyleneglycol-1,11-diyl)bis(1-methyl-1H-imidazolium)acetate, [tetraEG(mim)2][OAc]2, 1-butyl-3-methylimidazolium malonate, [C4mim]2[Mal], and 3-butyl-1-methylimidazolium glutarate, [C4mim]2[Glut]. Their densities vary between 1.1 and 1.5 g cm-3 and their viscosities between 0.2 and 4 Pa s at 353 K. We found that the molar volumes are not additive, especially in the case of the divalent ionic liquids based on the double-charged imidazolium cations, meaning that they cannot be predicted using common group contribution methods. The reason for this behaviour could be explained by the structure of the cations, which is dominated by intramolecular hydrogen bonding. The carboxylate-based divalent ionic liquids absorb reversibly large quantities of carbon dioxide following a chemical mechanism described before. An improved 1 : 1 stoichiometry is achieved both in a double-charged imidazolium acetate ionic liquid and in imidazolium carboxylate salts with double charged anions. This behaviour places these ionic liquids amongst the best performing for carbon dioxide absorption.

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.

Using hydrogenated and perfluorinated gases to probe the interactions and structure of fluorinated ionic liquids.

After studying the properties of a mixture of hydrogenated and fluorinated ionic liquids we have measured the solubility of perfluoromethane, perfluoroethane and perfluoropropane in 1-alkyl-3-methylimidazolium based ionic liquids with hydrogenated or fluorinated alkyl side-chains: 1-octyl-3-methylimidazolium bis[trifluoromethylsulfonyl]amide ([C8C1Im][NTf2]), 1-octyl-3-methylimidazolium bis[pentafluoroethylsulfonyl]amide ([C8C1Im][BETI]), 1-(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)-3-methylimidazolium bis[trifluoromethylsulfonyl]amide ([C8H4F13C1Im][NTf2]), and 1-(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)-3-methylimidazolium bis[pentafluoroethylsulfonyl]amide ([C8H4F13C1Im][BETI]). The ionic liquids expand on mixing and mix endothermally with a relatively high enthalpy of mixing (ΔmixH for [C8C1Im]x[C8H4F13C1Im](1-x)[NTf2] of ca. 0.85 kJ mol-1 for x = 0.5) when compared with other ionic mixtures. The solubility of the perfluorinated gases is larger in the fluorinated ionic liquids when compared with that of their hydrogenated counterparts and follows the order [C8H4F13C1Im][BETI] > [C8H4F13C1Im][NTf2] > [C8C1Im][BETI] > [C8C1Im][NTf2], a behaviour explained by a slightly more favourable enthalpy of solvation. The fluorinated ionic liquids nevertheless do not dissolve larger quantities of perfluorinated gases than their hydrogenated equivalents, as observed by comparing the results herein for perfluoroethane to those measured previously for ethane in the same ionic liquids. By using molecular simulations to study the microscopic structure of the solutions, we could show that the gases, hydrogenated and fluorinated, are always preferentially solvated in the apolar domains of the ionic liquids, and the hydrogenated hydrocarbon gases are always more soluble, independent of the fluorination of the ionic liquid.

Molecular dynamics simulations of polyethers and a quaternary ammonium ionic liquid as CO2 absorbers.

The properties of mixtures of butyltrimethylammonium bis(trifluoromethylsulfonyl)imide, [N4111][NTf2], with poly(ethyleneglycol) dimethyl ether, PEO, were described as a function of PEO chain size by molecular dynamics simulations. Both PEO chain size and mixture composition revealed to play a significant role in determining the structure and the dynamics of the fluids. The remarkably higher viscosity observed for mixtures composed by 0.25 mole fraction of PEO was attributed to the increase in the gauche population of OCCO dihedral of the polyether of longer chains. The negative solvation enthalpy (ΔsolH < 0) and entropy (ΔsolS < 0) revealed a favorable CO2 absorption by the neat and mixture systems. The CO2 absorption was higher in neat PEO, particularly considering longer chains. The gas solubility in the mixtures presented intermediate values in comparison to the neat PEO and neat ionic liquid. The CO2 solutions had their structures discussed in the light of the calculated radial and spatial distribution functions.

Dynamic Ion Gels from the Complex Coacervation of Oppositely Charged Poly(ionic liquid)s.

A cationic poly(ionic liquid) (PIL) with pendent butyl imidazolium cations and free bis(trifluoromethylsulfonyl)imide (TFSI) anions and an anionic PIL with pendent TFSI anions and free 1-butyl-3-methylimidazolium cations are synthesized by postpolymerization chemical modification and reversible addition-fragmentation chain-transfer radical copolymerization, respectively. Upon mixing solutions of these two PILs in acetone with stoichiometric amounts of ion pairs, ionic exchanges induce coacervation and, after solvent evaporation, lead to the formation of a dynamic ion gel (DIG) and the concomitant release of free [1-methyl-3-butyl imidazolium]TFSI ionic liquid (IL). A comparison of thermal (Tg), ion conducting (σDC), and viscoelastic (elastic moduli (G')) properties for DIGs and their parent polyelectrolytes, as well as extracted and IL-doped DIGs, demonstrates the formation of ionic cross-links and the ability to easily produce polymer electrolytes with enhanced ionic conductivity (σDC up to 4.5 × 10-5 S cm-1 at 30 °C) and higher elastic moduli (G' up to 4 kPa at 25 °C and 1 rad s-1), making them highly desirable in many electrochemical applications, including supercapacitors, soft robotics, electrochromic devices, sensors, and solar cells.