1-丁基-3-甲基咪唑硫酸氢盐离子液体与含氮化合物相互作用的理论研究

刘洁; 牟浩文; 李文深

1-丁基-3-甲基咪唑硫酸氢盐离子液体与含氮化合物相互作用的理论研究

辽宁石油化工大学化学化工与环境学部, 辽宁抚顺 113001

详细信息

通讯作者:
LIU Jie, Tel:13842352536, E-mail:lj13898309829@163.com

中图分类号: O645.13
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- 被引次数: 0
出版历程
- 收稿日期: 2018-03-23
- 修回日期: 2018-08-21
- 网络出版日期: 2021-01-23
- 刊出日期: 2018-11-10

Theoretical study on the interaction between 1-butyl-3-methylimidazolium hydrosulphates ionic liquid and nitrogenous compounds

College of Chemistry, Chemical Engineering and Environmental Engineering, Liaoning Shihua University, Fushun 113001, China

摘要

摘要: 采用密度泛函理论方法研究了1-丁基-3-甲基咪唑硫酸氢盐离子液体[Bmim]HSO₄与氮化物喹啉和吲哚分子的相互作用，并进行了NBO和AIM分析。[Bmim]HSO₄离子对最稳定结构表明，[HSO₄]^-阴离子中的氧原子与咪唑环中正电性较大的C14-H20之间有较强的氢键作用。在分子水平上，NBO和AIM分析证实了喹啉和吲哚分子与[Bmim]HSO₄的阴离子之间有较强的相互作用，其中，喹啉分子中的氮原子与阴离子[HSO₄]^-中氢原子之间的作用以及吲哚分子中N-H的氢原子与[HSO₄]^-中氧原子之间的作用是该离子液体能够有效脱除氮化物的主要动力。
- 离子液体 /
- 脱氮 /
- 密度泛函理论 /
- 喹啉 /
- 吲哚
Abstract: The interaction between 1-butyl-3-methylimidazolium hydrosulphates ionic liquid ([Bmim]HSO₄) and nitrogenous compounds (quinoline and indole) were investigated by density functional theory, and analyzed by NBO and AIM methods. The most stable structure of [Bmim]HSO₄ ionic pair displays a strong hydrogen bond interaction between O atom in [HSO₄]^- anion and C14-H20 in imidazolium ring. NBO and AIM analysis at the molecular level proves that there is a strong interaction between quinoline or indole and the anion of [Bmim]HSO₄. The strong interaction between the active hydrogen of [HSO₄]^- and the N atom of quinoline molecule as well as the hydrogen bond formed between the H atom of N-H in indole molecule and the O atom of [HSO₄]^- are the main driving force for denitrogenation performance of [Bmim]HSO₄.
- ionic liquid /
- denitrogenation /
- density functional theory /
- quinoline /
- indole

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图 1 [Bmim]HSO₄、[Bmim]HSO₄与喹啉/吲哚相互作用的稳定构型及相互作用距离(nm)示意图

Figure 1 Scheme of stable structures and some interacting distances for [Bmim]HSO₄ (a), [Bmim]HSO₄-indole (b) and [Bmim]HSO₄-quinoline (c)

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表 1 [Bmim]HSO₄、[Bmim]HSO₄-喹啉、[Bmim]HSO₄-吲哚中的部分给体-受体相互作用

Table 1 Some donor-acceptor interactions in[Bmim]HSO₄, [Bmim]HSO₄-quinoline and [Bmim]HSO₄-indole

Species	Donor	Acceptor	E(2)/(kJ·mol^-1)
[Bmim]HSO₄	LP(O26)	σ* (C6-H24)	11.13
	LP(O26)	σ*(C14-H20)	18.11
	LP(O28)	σ*(C1-H25)	4.24
	LP(O28)	σ*(C14-H20)	41.59
[Bmim]HSO₄^- quinoline	LP(O26)	σ*(C6-H24)	11.93
	LP(O26)	σ*(C14-H20)	25.88
	LP(O28)	σ*(C1-H25)	6.04
	LP(O28)	σ*(C14-H20)	42.08
	LP(O30)	σ*(C45-H47)	9.79
	LP(N42)	σ*(O29-H31)	101.68
[Bmim]HSO₄^- indole	LP(O26)	σ*(C6-H24)	27.35
	LP(O28)	σ*(C14-H20)	64.01
	LP(O28)	σ*(N42-H47)	72.88
	σ(C36-N42)	σ*(C1-H25)	2.02
	π(C43-C45)	σ*(C3-H8)	1.97

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表 2 [Bmim]HSO₄-喹啉/吲哚的电子密度(ρ)和拉普拉斯量▽²ρ

Table 2 The electron density (ρ) and Laplacian of density (▽²ρ) of [Bmim]HSO₄-quinoline/indole

Species	X…Y	d/nm	ρ/(a.u.)	▽²ρ/(a.u.)
[Bmim]HSO₄-quinoline	O28…H25	0.2313	0.01125	0.04861
	O28…H20	0.1979	0.02277	0.11792
	O26…H20	0.2095	0.01833	0.08887
	O26…H24	0.2170	0.01463	0.06681
	O30…H47	0.2272	0.01399	0.05762
	N42…H31	0.1783	0.03176	0.1542
[Bmim]HSO₄-indole	O28…H20	0.1850	0.02813	0.12824
	O26…H24	0.2047	0.01954	0.09441
	O28…H47	0.1818	0.02843	0.13450
	N42…H25	0.2900	0.00484	0.01662
	C45…H8	0.3112	0.00388	0.01253

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