Institute for Chemical- and Bioengineering, Department of Chemistry and Applied Biosciences, ETH Zurich, HCI, CH-8093 Zurich, Switzerland.
J Phys Chem B. 2010 Feb 18;114(6):2111-7. doi: 10.1021/jp911403s.
Two commonly used ionic liquids (ILs), 1-butyl-3-methylimidazolium tetrafluoroborate ([bmim][BF(4)]) and 1-butyl-3-methylimidazolium hexafluorophosphate ([bmim][PF(6)]), as well as binary and ternary mixtures of them with water and/or supercritical CO(2) (scCO(2)) were investigated by means of infrared spectroscopy at high pressure. The experiments were performed using attenuated total reflection (ATR) infrared spectroscopy on dry and wet ILs at 40 degrees C and pressures up to 150 bar of scCO(2). The studies indicate that the content of water does not change significantly the solubility of CO(2) in the ionic liquids tested. Furthermore, the presence of water does not change significantly the interaction between the IL anion and CO(2), which explains why the presence of water in IL does not modify the solubility of CO(2) in the system, even in the case of an initial molar ratio of approximately 50/50 of water in [bmim][BF(4)]. We show that despite the limited solubility of water in supercritical CO(2) an ionic liquid can be efficiently dried using scCO(2) extraction even in the case of a hydrophilic ionic liquid (e.g., [bmim][BF(4)]). During the scCO(2) extraction, the concentration of water was followed in situ using attenuated total reflection (ATR) infrared spectroscopy. After extraction, no residual water could be detected by this technique, which corresponds approximately to a water concentration of below 320 ppm.
两种常用的离子液体(ILs),1-丁基-3-甲基咪唑四氟硼酸盐([bmim][BF(4)])和 1-丁基-3-甲基咪唑六氟磷酸盐([bmim][PF(6)]),以及它们与水和/或超临界 CO(2)(scCO(2))的二元和三元混合物,通过高压红外光谱进行了研究。实验在 40°C 和高达 150 巴的 scCO(2)压力下,使用衰减全反射(ATR)红外光谱对干燥和湿 ILs 进行了。研究表明,水的含量不会显著改变所测试的 ILs 中 CO(2)的溶解度。此外,水的存在不会显著改变 IL 阴离子与 CO(2)之间的相互作用,这解释了为什么水中存在于 IL 中不会改变 CO(2)在体系中的溶解度,即使在水与 [bmim][BF(4)]摩尔比约为 50/50 的初始条件下也是如此。我们表明,尽管水在超临界 CO(2)中的溶解度有限,但即使是亲水性 IL(例如 [bmim][BF(4)]),也可以使用 scCO(2)萃取有效地干燥。在 scCO(2)萃取过程中,使用衰减全反射(ATR)红外光谱原位跟踪水的浓度。萃取后,该技术无法检测到残留的水,这对应于大约低于 320 ppm 的水浓度。