二元离子液体OMImBF4/HMImPF6中硝基苯的电化学还原

doi:10.11949/j.issn.0438-1157.20151486

化工学报 ›› 2016, Vol. 67 ›› Issue (5): 1998-2004.DOI: 10.11949/j.issn.0438-1157.20151486

二元离子液体OMImBF₄/HMImPF₆中硝基苯的电化学还原

毛信表¹, 何峰强¹, 张寅旭¹, 陈松², 刘莹¹, 马淳安¹

1 浙江工业大学化学工程学院, 绿色化学合成技术国家重点实验室培育基地, 浙江杭州 310032;
2 盐城工学院, 江苏盐城 224051

收稿日期:2015-09-23 修回日期:2015-12-24 出版日期:2016-05-05 发布日期:2016-05-05
通讯作者: 马淳安
基金资助:
国家自然科学基金项目(21076192);国家重点基础研究发展计划项目(2012CB722604);浙江省公益性技术应用研究计划功能离子液体中CO₂电催化合成碳酸二甲酯研究项目(2014C31159)。

Electrochemical reduction of nitrobenzene in binary ionic liquid of OMImBF₄/HMImPF₆

MAO Xinbiao¹, HE Fengqiang¹, ZHANG Yinxu¹, CHEN Song², LIU Ying¹, MA Chun'an¹

1 State Key Laboratory Breeding Base of Green Chemistry-Synthesis Technology, College of Chemical Engineering, Zhejiang University of Technology, Hangzhou 310032, Zhejiang, China;
2 Yancheng Institute of Technology, Yancheng 224051, Jiangsu, China

Received:2015-09-23 Revised:2015-12-24 Online:2016-05-05 Published:2016-05-05
Supported by:
supported by the National Natural Science Foundation of China (2020619), the National Basic Research Program of China (2012CB722604) and the Zhejiang Province Public Technology Applied Research Projects (2014C31159).

摘要/Abstract

摘要：

将离子液体OMImBF₄与HMImPF₆二元复合,研究了离子液体复合前后电导率、红外谱峰等的变化,在不同体积比的OMImBF₄/HMImPF₆体系中采用循环伏安法(CV)、计时电流法(CA)和电化学原位红外光谱法(In-situ FTIRS)等方法探究了硝基苯在铂电极上的电化学还原行为。研究结果表明,OMImBF₄/HMImPF₆的电导率随HMImPF₆体积比的增大而减小,红外谱峰较单一离子液体变化明显;硝基苯在体积比为3:1的二元离子液体OMImBF₄/HMImPF₆体系中的还原峰电位及还原峰电流均优于单一离子液体,且主要产物偶氮苯的选择性及硝基苯的转化率都要优于单一离子液体。硝基苯在此二元离子液体体系中的还原过程受扩散控制,扩散系数D为 2.024×10^-7 cm²·s^-1。

关键词: 硝基苯, 离子液体, 二元混合物, 电化学, 原位红外光谱

Abstract:

A mixture of ionic liquids (ILs), OMImBF₄ and HMImPF₆ was prepared, for which its conductivity and infrared spectroscopy (IR) were measured in comparison with those of components. In the binary IL system with varied volume ratios of OMImBF₄/HMImPF₆, techniques of cyclic voltammetry (CV), chronoamperometry (CA), constant-potential electrolysis, in-situ Flourier transform infrared spectroscopy (in-situ FTIRS), GC-MS and GC were employed to investigate electrochemical reduction of nitrobenzene. It showed that, the conductivity of OMImBF₄/HMImPF₆ decreased with the concentration of HMImPF₆ component, and IR bands of [BF₄]^- and [PF₆]^- in the IL mixture obviously changed from each single component. The OMImBF₄/HMImPF₆ IL system with 3:1 of volume ratio exhibited a higher current density and a more positive potential for the reduction of nitrobenzene, and also the selectivity and yield of main product azobenzene than single component ILs. The rate-determining step in the electrochemical reduction of nitrobenzene is diffusion, of which diffusion coefficient is 2.024×10^-7 cm²·s^-1.

Key words: nitrobenzene, ionic liquids, binary mixture, electrochemistry, in-situ Flourier transforms infrared spectroscopy

中图分类号:

毛信表, 何峰强, 张寅旭, 陈松, 刘莹, 马淳安. 二元离子液体OMImBF₄/HMImPF₆中硝基苯的电化学还原[J]. 化工学报, 2016, 67(5): 1998-2004.

MAO Xinbiao, HE Fengqiang, ZHANG Yinxu, CHEN Song, LIU Ying, MA Chun'an. Electrochemical reduction of nitrobenzene in binary ionic liquid of OMImBF₄/HMImPF₆[J]. CIESC Journal, 2016, 67(5): 1998-2004.

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二元离子液体OMImBF₄/HMImPF₆中硝基苯的电化学还原

Electrochemical reduction of nitrobenzene in binary ionic liquid of OMImBF₄/HMImPF₆

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