2-甲基萘醌在二甲基亚砜和乙腈中的电化学氧化还原机理研究

doi:10.7503/cjcu20180132

高等学校化学学报 ›› 2018, Vol. 39 ›› Issue (9): 2025.doi: 10.7503/cjcu20180132

2-甲基萘醌在二甲基亚砜和乙腈中的电化学氧化还原机理研究

朱云, 李丹, 金葆康()

安徽大学化学化工学院, 合肥 230601

收稿日期:2018-02-12 出版日期:2018-09-07 发布日期:2018-05-07
作者简介:
联系人简介: 金葆康, 男, 博士, 教授, 博士生导师, 主要从事电分析化学和光谱电化学研究. E-mail: bkjinhf@aliyun.com
基金资助:
国家自然科学基金(批准号: 21175001, 21375001)资助.

Study on Redox Mechanism of 2-Methyl-naphthoquinonein Dimethyl Sulfoxide and Acetonitrile^†

ZHU Yun, LI Dan, JIN Baokang^*()

School of Chemistry & Chemical Engineering, Anhui University, Hefei 230601, China

Received:2018-02-12 Online:2018-09-07 Published:2018-05-07
Contact: JIN Baokang E-mail:bkjinhf@aliyun.com
Supported by:
† Supported by the National Natural Science Foundation of China(Nos.21175001, 21375001).

摘要/Abstract

摘要：

采用电化学技术和现场红外光谱技术研究了2-甲基萘醌(MQ)在二甲亚砜(DMSO)和乙腈溶剂中的电化学性质. 当在0~-1.8 V电势范围进行循环伏安扫描时, MQ在不同溶剂中表现出不同的电化学行为. 结合红外光谱循环伏吸收图(CVA)、导数循环伏吸图(DCVA)及变温电化学实验, 推断MQ在DMSO中第一步被还原为阴离子自由基MQ^·-, 第二步被还原为二价阴离子MQ^2-, 该过程为连续的两步单电子转移过程; 在乙腈溶剂中, MQ在发生电化学反应的同时发生二聚: 第一步还原产物阴离子自由基与二价阴离子发生化学反应, 且二聚体在后继的电化学过程中被还原.

关键词: 2-甲基萘醌, 现场红外光谱电化学, 循环伏吸法, 导数循环伏吸法, 变温电化学

Abstract:

The electrochemical characteristics of 2-methyl-naphthoquinone(MQ) was investigated in dimethyl sulfoxide(DMSO) and acetonitrile by cyclic voltammetry(CV) and in-situ Fourier transform infrared(FTIR) spectroelectrochemistry. The electrochemical performance of MQ is distinct in different solvent when the scan range was from 0 V to -1.8 V. The results of cyclic voltabsorptometry(CVA), derivative cyclic voltabsorptometry(DCVA) and high-temperature CV indicated MQ is reduced to anionic radical MQ^·- firstly in DMSO, and then converted to dianion MQ^2- , which was two-step one-electron transfering process. Nevertheless, MQ in acetonitrile dimerization took place accompanied by electrochemical reduction, in which anionic radical MQ^·- and dianion MQ^2- formed the dimer and further ruduced at more negative potential.

Key words: 2-Methyl-naphthoquinone, in-situ IR spectroelectrochemistry, Cyclic voltabsorptometry, Derivative cyclic voltabsorptometry, Variable-temperature electrochemistry

中图分类号:

O646

TrendMD:

朱云, 李丹, 金葆康. 2-甲基萘醌在二甲基亚砜和乙腈中的电化学氧化还原机理研究. 高等学校化学学报, 2018, 39(9): 2025.

ZHU Yun,LI Dan,JIN Baokang. Study on Redox Mechanism of 2-Methyl-naphthoquinonein Dimethyl Sulfoxide and Acetonitrile^†. Chem. J. Chinese Universities, 2018, 39(9): 2025.

图/表 6

Fig.1 Cyclic voltammogram(A) and the corresponding 3D spectra(B) in DMSO containing 10 mmol/L MQ and 0.2 mol/L Bu4NClO4 as the supporting electrolyte The potential scan rate was 10 mV/s. The IR spectrum recorded at -0.2 V was used as the reference spectrum.

Fig.2 CVA(A) and DCVA(B) curves for peaks at 1664, 1503 and 1202 cm-1To make the DCVA data readily comparable to CV, the DCVA data of 1664 cm-1 were multiplied by -1, and 1503 cm-1 in the second reduction and the first oxidation were multiplied by -1.

Fig.3 Cyclic voltammogram(A) and the corresponding 3D spectra(B) in acetonitrile containing 5 mmol/L MQ and 0.2 mol/L Bu4NClO4 as the supporting electrolyteThe potential scan rate was 10 mV/s. The scan range was 0—-1.6 V. The IR spectrum recorded at 0 V was used as the reference spectrum.

Fig.4 Corresponding CVA(A) and DCVA(B) of Fig.3(B)

Fig.5 Consecutive CV(A), the corresponding 3D spectra(B), CVA(C) and DCVA(D) in acetonitrile containing 5 mmol/L MQ and 0.2 mol/L Bu4NClO4 as the supporting electrolyteThe potential scan rate was 10 mV/s. The scan range was 0— -1.6 V. The IR spectrum recorded at 0 V was used as the reference spectrum. Arrow: increased number of scans.

Fig.6 Cyclic voltammogram at various temperatures in acetonitrile containing 10 mmol/L MQ and 0.2 mol/L Bu4NClO4 as the supporting electrolyteThe potential scan rate was 10 mV/s. The scan range was 0— -1.6 V.

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2-甲基萘醌在二甲基亚砜和乙腈中的电化学氧化还原机理研究

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2-甲基萘醌在二甲基亚砜和乙腈中的电化学氧化还原机理研究

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Study on Redox Mechanism of 2-Methyl-naphthoquinonein Dimethyl Sulfoxide and Acetonitrile^†