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电化学(中英文) ›› 2017, Vol. 23 ›› Issue (6): 718-723.  doi: 10.13208/j.electrochem.160827

• 研究论文 • 上一篇    下一篇

Ce3+/Ce4+电对在混酸(硫酸和甲磺酸)中的电化学行为

李照华*,徐蛟龙, 吴 婷   

  1. 灵宝金源朝辉铜业有限公司 技术研发部,河南 灵宝 472500
  • 收稿日期:2016-08-27 修回日期:2017-01-05 出版日期:2017-12-28 发布日期:2017-01-10
  • 通讯作者: 李照华 E-mail:lzh0814@163.com
  • 基金资助:

    三门峡市科技攻关计划项目(No. 2016010108)资助

Electrochemical Behaviors of Ce3+/Ce4+ Couple in a Mixed-Acid Medium of CH3SO3H and H2SO4

LI Zhao-hua*, XU Jiao-long,WU Ting   

  1. Research and Development Department, Lingbao JinYuan ZhaoHui Copper Co., Ltd, Lingbao 472500, Henan, China
  • Received:2016-08-27 Revised:2017-01-05 Published:2017-12-28 Online:2017-01-10
  • Contact: LI Zhao-hua E-mail:lzh0814@163.com

摘要:

采用循环伏安、线性扫描、交流阻抗等技术研究了Ce3+/Ce4+电对在混酸(硫酸与甲磺酸)中的电化学行为,并对该体系在间接有机电合成中的应用进行了探索.结果表明:当硫酸和甲磺酸(MSA)浓度分别为0.8和1.0 mol·L-1时,Ce3+/Ce4+电对具有最佳的电化学活性;在上述配比的混酸介质中,铈盐的溶解度得到了大幅提高,同时电解氧化铈(III)离子的电流效率较高(92.1%),与纯硫酸体系中的电流效率接近(92.8%),明显高于纯甲磺酸体系(78.5%);该混酸介质中Ce4+在氧化茴香醚生成茴香醛这一过程中也表现出很好的氧化能力.

关键词: 混酸, 电流效率, 溶解度, 电流效率

Abstract:

In order to determine the optimum molar ratio between methanesulfonic acid (MSA) and sulfuric acid, linear sweep voltammetry (LSV), cyclic voltammetry (CV), and electrochemical impedance spectroscopy (EIS) were used to investigate the electrochemical behaviors of cerium (III)/cerium (IV) (Ce3+/Ce4+couple on a Pt electrode in a mixed acid solution. Various concentrations of sulfuric acid were considered in the experiments, while the concentration of MSA was fixed at 1.0 mol·L-1. It was found that the optimum concentration of sulfuric acid was 0.8 mol·L-1 since the current response was the highest in the control groups and Ce3+ was easier to be oxidized to Ce4+. In the mixed acid solution, the solubility of cerium (III) increased to 0.95 mol·L-1 from 0.25 mol·L-1 in 1.3 mol·L-1 sulfuric acid solution. Electrolytic experiment and liquid-phase oxidation had been taken to explore the application of the mixed acid medium. The results revealed that Ce3+ exhibited the excellent electrochemical activity and Ce4+demonstrated a stronger oxidation capacity in the mixed acid solution.

Key words: mixed acid, current efficiency, solubility, current efficiency

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