期刊
JOURNAL OF THE IRANIAN CHEMICAL SOCIETY
卷 10, 期 4, 页码 733-744出版社
SPRINGER
DOI: 10.1007/s13738-012-0207-z
关键词
Ionic liquid; Desulfurization; Density functional theory; Electronic properties; NBO analyses; Topological properties
资金
- Natural Science Foundation of China [21176259]
- Awarded foundation for excellent young and middle-aged scientist of Shandong Province, China [BS2010NJ024]
- Natural Science Foundation of Shandong Province, China [ZR2011BQ004]
To deepen the understanding the interactions of thiophenic compounds in ionic liquids, we have performed a systemic study on the electronic structures, and topological properties of interactions between N-ethyl-N-ethylimidazolium diethyl phosphate ([EEIM][DEP]) ionic liquid and 3-methylthiophene (3-MT), benzothiophene (BT), or dibenzothiophene (DBT) using density functional theory. From NBO atomic charges and electrostatic potential analyses, most of the positive charge is located on C2-H2 in the [EEIM] cation, and the negative charge is focused on oxygen atoms in [DEP] anion, implying oxygen atoms in [DEP] should easily attack C2-H2 in [EEIM]. The electrostatic interaction between anion and cation may be dominant for the formation of the [EEIM]-[DEP] ion pair. The large stabilizing effect is due to the strong orbital interactions between the antibonding orbital of proton donor sigma*(C2-H2) in [EEIM] cation and the lone pairs of proton acceptor LP(O) in [DEP] anion. A common feature of [EEIM][DEP], [EEIM][DEP]-3-MT/BT/DBT complexes is the presence of hydrogen bonds between [EEIM] cation and [DEP] anion. This work has also given the interacting mechanism of 3-MT, BT, and DBT adsorption on [EEIM][DEP] ionic liquid. Both [EEIM] cation and [DEP] anion are shown to play important roles in interactions between 3-MT, BT, DBT and [EEIM][DEP], which has been corroborated by NBO and AIM analyses. The pi center dot center dot center dot pi, pi center dot center dot center dot C-H and hydrogen bonding interactions occur between [EEIM][DEP] and 3-MT, BT, DBT. The strength of sulfur involved interactions between 3-MT, BT, DBT and [EEIM][DEP] follows the order of 3-MT > BT > DBT. The order of interaction energies between [EEIM][DEP] and 3-MT, BT, DBT is 3-MT < BT < DBT, in agreement with the order of extractive selectivity from fuel oils (DBT > BT > 3-MT) in terms of sulfur partition coefficients.
作者
我是这篇论文的作者
点击您的名字以认领此论文并将其添加到您的个人资料中。
推荐
暂无数据