title: Is There Any Preferential Interaction of Ions of Ionic Liquids with DMSO and H2O? A Comparative Study from MD Simulation.
abstract: Recently, some binary ionic liquid (IL)/cosolvent systems have shown better performance than the pure ILs in fields such as CO2 absorption, catalysis, cellulose dissolution, and electrochemistry. However, interactions of ILs with cosolvents are still not well understood at the molecular level. In this work, H2O and DMSO were chosen as the representative protic and aprotic solvents to study the effect of cosolvent nature on solvation of a series of ILs by molecular dynamics simulations and quantum chemistry calculations. The concept of preferential interaction of ions was proposed to describe the interaction of cosolvent with cation and anion of the ILs. By comparing the interaction energies between IL and different cosolvents, it was found that there were significantly preferential interactions of anions of the ILs with water, but the same was not true for the interactions of cations/anions of the ILs with DMSO. Then, a detailed analysis and comparison of the interactions in IL/cosolvent systems, hydrogen bonds between cations and anions of the ILs, and the structure of the first coordination shells of the cations and the anions were performed to reveal the existing state of ions at different molar ratios of the cosolvent to a given IL. Furthermore, a systematic knowledge for the solvation of ions of the ILs in DMSO was given to understand cellulose dissolution in IL/cosolvent systems. The conclusions drawn from this study may provide new insight into the ionic solvation of ILs in cosolvents, and motivate further studies in the related applications.
authors.affiliation: †Collaborative Innovation Center of Henan Province for Green Manufacturing of Fine Chemicals, School of Chemistry and Chemical Engineering, Key Laboratory of Green Chemical Media and Reactions, Ministry of Education, Henan Normal University, Xinxiang, Henan 453007, P. R. China.
authors.forename: Yuling
authors.initials: Y
authors.lastname: Zhao
authors.affiliation: †Collaborative Innovation Center of Henan Province for Green Manufacturing of Fine Chemicals, School of Chemistry and Chemical Engineering, Key Laboratory of Green Chemical Media and Reactions, Ministry of Education, Henan Normal University, Xinxiang, Henan 453007, P. R. China.
authors.forename: Jianji
authors.initials: J
authors.lastname: Wang
authors.affiliation: †Collaborative Innovation Center of Henan Province for Green Manufacturing of Fine Chemicals, School of Chemistry and Chemical Engineering, Key Laboratory of Green Chemical Media and Reactions, Ministry of Education, Henan Normal University, Xinxiang, Henan 453007, P. R. China.
authors.forename: Huiyong
authors.initials: H
authors.lastname: Wang
authors.affiliation: †Collaborative Innovation Center of Henan Province for Green Manufacturing of Fine Chemicals, School of Chemistry and Chemical Engineering, Key Laboratory of Green Chemical Media and Reactions, Ministry of Education, Henan Normal University, Xinxiang, Henan 453007, P. R. China.
authors.forename: Zhiyong
authors.initials: Z
authors.lastname: Li
authors.affiliation: ‡Beijing Key Laboratory of Ionic Liquids Clean Process, State Key Laboratory of Multiphase Complex System, Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190, P. R. China.
authors.forename: Xiaomin
authors.initials: X
authors.lastname: Liu
authors.affiliation: ‡Beijing Key Laboratory of Ionic Liquids Clean Process, State Key Laboratory of Multiphase Complex System, Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190, P. R. China.
authors.forename: Suojiang
authors.initials: S
authors.lastname: Zhang