title: Enhanced gas absorption in the ionic liquid 1-n-hexyl-3-methylimidazolium bis(trifluoromethylsulfonyl)amide ([hmim][Tf2N]) confined in silica slit pores: a molecular simulation study.
abstract: Two-dimensional NPxyT and isostress-osmotic (N2PxyTf1) Monte Carlo simulations were used to compute the density and gas absorption properties of the ionic liquid (IL) 1-n-hexyl-3-methylimidazolium bis(trifluoromethylsulfonyl)amide ([hmim][Tf2N]) confined in silica slit pores (25-45 Å). Self-diffusivity values for both gas and IL were calculated from NVE molecular dynamics simulations using both smooth and atomistic potential models for silica. The simulations showed that the molar volume of [hmim][Tf2N] confined in 25-45-Å silica slit pores is 12-31% larger than that of the bulk IL at 313-573 K and 1 bar. The amounts of CO2, H2, and N2 absorbed in the confined IL are 1.1-3 times larger than those in the bulk IL because of the larger molar volume of the confined IL compared to the bulk IL. The CO2, N2, and H2 molecules are generally absorbed close to the silica wall where the IL density is very low. This arrangement causes the self-diffusivities of these gases in the confined IL to be 2-8 times larger than those in the bulk IL at 298-573 K. The solubilities of water in the confined and bulk ILs are similar, which is likely due to strong water interactions with [hmim][Tf2N] through hydrogen bonding, so that the molar volume of the confined IL plays a less important role in determining the H2O solubility. Water molecules are largely absorbed in the IL-rich region rather than close to the silica wall. The self-diffusivities of water correlate with those of the confined IL. The confined IL exhibits self-diffusivities larger than those of the bulk IL at lower temperatures, but smaller than those of the bulk IL at higher temperatures. The findings from our simulations are consistent with available experimental data for similar confined IL systems.
authors.affiliation: US Department of Energy, National Energy Technology Laboratory, Pittsburgh, Pennsylvania 15236, United States. shiw@netl.doe.gov
authors.forename: Wei
authors.initials: W
authors.lastname: Shi
authors.forename: David R
authors.initials: DR
authors.lastname: Luebke
mesh_terms: D000327:Adsorption; D002245:Carbon Dioxide / Q000737:chemistry*; D007093:Imidazoles / Q000737:chemistry*; D052578:Ionic Liquids / Q000737:chemistry*; D008958:Models, Molecular; D056004:Molecular Dynamics Simulation; D009010:Monte Carlo Method; D012822:Silicon Dioxide / Q000737:chemistry*; D013438:Sulfhydryl Compounds / Q000737:chemistry*; D013499:Surface Properties
chemical_list: C584873:1-n-hexyl-3-methylimidazolium bis(trifluoromethylsulfonyl)amide; D007093:Imidazoles; D052578:Ionic Liquids; D013438:Sulfhydryl Compounds; D002245:Carbon Dioxide; D012822:Silicon Dioxide