title: Theoretical investigation of the interaction between aromatic sulfur compounds and [BMIM](+)[FeCl4](-) ionic liquid in desulfurization: A novel charge transfer mechanism.
abstract: In this work, interaction nature between a group of aromatic sulfur compounds and [BMIM](+)[FeCl4](-) have been investigated by density functional theory (DFT). A coordination structure is found to be critical to the mechanism of extractive desulfurization. Interaction energy and extractive selectivity follow the order: thiophene (TH)<dibenzothiophene (DBT)≈benzothiophene (BT). Alkylation of TH or BT (e.g. 3-methylthiophene, and 3-methylbenzothiophene) leads to a stronger interaction with ionic liquid, but steric hindrance effects of some alkylic derivatives (e.g. 2,7-dimethylbenzothiophene) lead to a weaker interaction with ionic liquid. The mechanism of extractive desulfurization is attributed to the charge transfer effect. During extractive desulfurization, electrons on aromatic sulfur compounds transfer into the Lewis part of ionic liquid, namely, [FeCl4](-). Furthermore, it is better to consider the Lewis acidity of Fe-containing ionic liquid by the whole unit (such as [FeCl4](-) and aromatic sulfur compounds (X)) rather than only Fe or S atom.
authors.affiliation: School of Chemistry and Chemical Engineering, Jiangsu University, Zhenjiang 212013, PR China.
authors.forename: Hongping
authors.initials: H
authors.lastname: Li
authors.affiliation: School of Chemistry and Chemical Engineering, Jiangsu University, Zhenjiang 212013, PR China. Electronic address: zhuws@ujs.edu.cn.
authors.forename: Wenshuai
authors.initials: W
authors.lastname: Zhu
authors.affiliation: Key Laboratory of Tropical Medicinal Plant Chemistry of Ministry of Education, College of Chemistry and Chemical Engineering, Hainan Normal University, Haikou 571158, Hainan, PR China.
authors.forename: Yonghui
authors.initials: Y
authors.lastname: Chang
authors.affiliation: School of Chemistry and Chemical Engineering, Jiangsu University, Zhenjiang 212013, PR China.
authors.forename: Wei
authors.initials: W
authors.lastname: Jiang
authors.affiliation: School of Chemistry and Chemical Engineering, Jiangsu University, Zhenjiang 212013, PR China; Institute for Energy Research, Jiangsu University, Zhenjiang 212013, PR China.
authors.forename: Ming
authors.initials: M
authors.lastname: Zhang
authors.affiliation: School of Chemistry and Chemical Engineering, Jiangsu University, Zhenjiang 212013, PR China.
authors.forename: Sheng
authors.initials: S
authors.lastname: Yin
authors.affiliation: School of Chemistry and Chemical Engineering, Jiangsu University, Zhenjiang 212013, PR China.
authors.forename: Jiexiang
authors.initials: J
authors.lastname: Xia
authors.affiliation: Institute for Energy Research, Jiangsu University, Zhenjiang 212013, PR China. Electronic address: lihm@ujs.edu.cn.
authors.forename: Huaming
authors.initials: H
authors.lastname: Li
mesh_terms: D004583:Electrons; D052578:Ionic Liquids / Q000737:chemistry*; D007477:Ions / Q000737:chemistry*; D007501:Iron / Q000737:chemistry*; D013457:Sulfur Compounds / Q000737:chemistry*; D013876:Thiophenes / Q000737:chemistry
chemical_list: D052578:Ionic Liquids; D007477:Ions; D013457:Sulfur Compounds; D013876:Thiophenes; C088015:benzothiophene; C017311:ferrate ion; D007501:Iron; C016366:dibenzothiophene
keywords: Benzothiophene; Density functional theory; Dibenzothiophene; Extractive desulfurization; Fe-containing ionic liquids; Thiophene