title: Metal-organic framework supported ionic liquid membranes for CO2 capture: anion effects.
abstract: IRMOF-1 supported ionic liquid (IL) membranes are investigated for CO(2) capture by atomistic simulation. The ILs consist of identical cation 1-n-butyl-3-methylimidazolium [BMIM](+), but four different anions, namely hexafluorophosphate [PF(6)](-), tetrafluoroborate [BF(4)](-), bis(trifluoromethylsulfonyl)imide [Tf(2)N](-), and thiocyanate [SCN](-). As compared with the cation, the anion has a stronger interaction with IRMOF-1 and a more ordered structure in IRMOF-1. The small anions [PF(6)](-), [BF(4)](-), and [SCN](-) prefer to locate near to the metal-cluster, particularly the quasi-spherical [PF(6)](-) and [BF(4)](-). In contrast, the bulky and chain-like [BMIM](+) and [Tf(2)N](-) reside near the phenyl ring. Among the four anions, [Tf(2)N](-) has the weakest interaction with IRMOF-1 and thus the strongest interaction with [BMIM](+). With increasing the weight ratio of IL to IRMOF-1 (W(IL/IRMOF-1)), the selectivity of CO(2)/N(2) at infinite dilution is enhanced. At a given W(IL/IRMOF-1), the selectivity increases as [Tf(2)N](-) < [PF(6)](-) < [BF(4)](-) < [SCN](-). This hierarchy is predicted by the COSMO-RS method, and largely follows the order of binding energy between CO(2) and anion estimated by ab initio calculation. In the [BMIM][SCN]/IRMOF-1 membrane with W(IL/IRMOF-1) = 1, [SCN](-) is identified to be the most favorable site for CO(2) adsorption. [BMIM][SCN]/IRMOF-1 outperforms polymer membranes and polymer-supported ILs in CO(2) permeability, and its performance surpasses Robeson's upper bound. This simulation study reveals that the anion has strong effects on the microscopic properties of ILs and suggests that MOF-supported ILs are potentially intriguing for CO(2) capture.
authors.affiliation: Department of Chemical and Biomolecular Engineering, National University of Singapore, 117576, Singapore.
authors.forename: Krishna M
authors.initials: KM
authors.lastname: Gupta
authors.forename: Yifei
authors.initials: Y
authors.lastname: Chen
authors.forename: Zhongqiao
authors.initials: Z
authors.lastname: Hu
authors.forename: Jianwen
authors.initials: J
authors.lastname: Jiang
mesh_terms: D000838:Anions / Q000737:chemistry; D002245:Carbon Dioxide / Q000737:chemistry*; D052578:Ionic Liquids / Q000737:chemistry*; D008567:Membranes, Artificial; D008958:Models, Molecular; D056004:Molecular Dynamics Simulation; D009584:Nitrogen / Q000737:chemistry; D009942:Organometallic Compounds / Q000737:chemistry*
chemical_list: D000838:Anions; D052578:Ionic Liquids; D008567:Membranes, Artificial; D009942:Organometallic Compounds; C512711:zinc benzenedicarboxylate; D002245:Carbon Dioxide; D009584:Nitrogen