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铜电极上硝基苯化合物的电化学还原特性及pH对还原的影响

[Electrochemical reduction characteristics of nitro-benzene compounds at the copper electrode and the influence of pH on reduction].

作者信息

Xu Wen-ying, Fan Jin-hong, Gao Ting-yao

机构信息

The National Engineering Research Center for Urban Pollution Control, Tongji University, Shanghai 200092, China.

出版信息

Huan Jing Ke Xue. 2005 Mar;26(2):102-7.

Abstract

The electrochemical reduction characteristics of nitro-benzene compounds were investigated using cyclic voltammetry technique. The reductive reactivity of the nitro-benzene compounds at the copper electrode was evaluated, the reduction mechanisms of the nitrobenzene compounds at the copper electrode and the influences of pH on them were also discussed in this paper. The experimental results show that nitro-benzene compounds is capable of reducing directly at the copper electrode, and the reduction peaks were at - 0.58V and - 1.32V or so (vs. SCE). Both acidity and basicity favor reduction of nitro-group at the copper electrode: the elimination reaction is easy to occur in the alkaline medium with the formation of nitroso-group; in the acid medium the probability of the reaction between the obtained electrons nitro group and hydrogen ions raises, which causes magnification of the current through the solution; in addition, the growth of hydrogen atoms in number favors the occurring of the addition and substitution reactions at the electrode. pH strongly influenced the electrochemical reduction characteristics of the nitrobenzene compounds at the copper electrode, and it mainly depends on the properties of the substituents on the benzene ring, their configurations and numbers, and their location versus nitro group on the benzene ring. The results provide a theoretical and experimental basis for investigating the reduction mechanisms by the catalyzed iron inner electrolysis process.

摘要

采用循环伏安法研究了硝基苯化合物的电化学还原特性。评估了硝基苯化合物在铜电极上的还原反应活性,探讨了硝基苯化合物在铜电极上的还原机理以及pH值对其的影响。实验结果表明,硝基苯化合物能够在铜电极上直接还原,还原峰约在-0.58V和-1.32V(相对于饱和甘汞电极)。酸性和碱性条件均有利于硝基在铜电极上的还原:在碱性介质中,消除反应容易发生并生成亚硝基;在酸性介质中,硝基获得的电子与氢离子反应的概率增加,导致通过溶液的电流增大;此外,氢原子数量的增加有利于电极上加成和取代反应的发生。pH值强烈影响硝基苯化合物在铜电极上的电化学还原特性,这主要取决于苯环上取代基的性质、其构型和数量以及它们相对于苯环上硝基的位置。该结果为研究催化铁内电解法的还原机理提供了理论和实验依据。

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