The molecular behavior of pyridinium/imidazolium based ionic liquids and toluene binary systems

Abstract

Imidazolium and pyridinium-based ionic liquids (ILs) have attracted increasing attention in the extraction of aromatic VOCs. However, fundamental studies on the mechanism of capturing aromatic VOCs have been less reported. In this work, the interactions between two ILs, 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (EMIMTFSI) and N-butylpyridinium bis(trifluoromethylsulfonyl)imide (BpyTFSI), and toluene (C₆H₅CH₃), were investigated by using attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR), excess infrared spectroscopy, hydrogen nuclear magnetic resonance (¹H NMR) spectroscopy and quantum chemical calculations. Some conclusions were obtained as follows: (1) H atoms on EMIMTFSI/BpyTFSI were located above or below the benzene ring and were mainly formed as C2–H⋯π bonds and C2,6–H⋯π bonds with C₆H₅CH₃, respectively. C–H⋯π bonds played a significant role in capturing aromatic compounds. (2) Upon adding C₆H₅CH₃, the two IL-C₆H₅CH₃ system's interaction strength was as follows: EMIMTFSI-C₆H₅CH₃ > BpyTFSI-C₆H₅CH₃. (3) Since C₆H₅CH₃ was unable to disrupt the interactions between cations and anions of ion pairs in the two studied IL-C₆H₅CH₃ systems, only ion cluster-C₆H₅CH₃ and ion pair-C₆H₅CH₃ complexes were observed. This work may provide theoretical insights into the separation mechanism for capturing VOCs.