掺硼金刚石电极电催化氧化酚类有机物的取代基效应

引用本文: 何亚鹏, 陈荣玲, 王超男, 李红东, 黄卫民, 林海波. 掺硼金刚石电极电催化氧化酚类有机物的取代基效应[J]. 物理化学学报, 2017, 33(11): 2253-2260. doi: 10.3866/PKU.WHXB201705292 shu

Citation: HE Ya-Peng, CHEN Rong-Ling, WANG Chao-Nan, LI Hong-Dong, HUANG Wei-Min, LIN Hai-Bo. Electrochemical Oxidation of Substituted Phenols on a Boron Doped Diamond Electrode[J]. Acta Physico-Chimica Sinica, 2017, 33(11): 2253-2260. doi: 10.3866/PKU.WHXB201705292 shu

掺硼金刚石电极电催化氧化酚类有机物的取代基效应

1.
吉林大学化学学院, 长春 130012;
2.
吉林大学超硬材料国家重点实验室, 长春 130012
基金项目:
国家自然科学基金（21273097，21573093），广东省引进创新创业团队计划项目（2013C092），吉林省重大科技攻关招标项目（20130204003GX）和国家重点研发计划（2016YFC1102802）资助

摘要: 本文主要以当前水环境中存在酚类有机污染物为研究对象，探讨酚类有机污染物在掺硼金刚石（BDD）电极上的取代基效应，具体研究具有不同位置及种类官能团的取代酚类有机污染物在BDD电极上的电催化氧化过程，通过化学需氧量和浓度变化考察有机污染物在电催化降解过程中的降解趋势，深入分析电极种类、官能团位置与种类与电催化氧化活性之间的联系的同时，研究阳极材料电催化氧化有机污染物的机理及动力学。结果表明，有机物在电极表面的电催化过程以电产生羟基自由基为媒介，对苯二酚在不同电极上的电催化活性与电极析氧电位及表面产生羟基自由基量有着重要的联系，BDD电极拥有最强的电催化氧化活性；不同取代基团的对位取代酚在BDD电极上的电化学降解实验显示电催化反应速率受取代官能团自身的电子效应制约，有机物矿化过程中羟基自由基首先进攻苯环的对位发生取代反应，同时取代基脱离苯环过程成为整个取代酚类电化学降解过程的决速步骤，且有机物的电催化反应速率与取代基特征Hammett常数σ呈近似线性关系。

关键词:

English

Electrochemical Oxidation of Substituted Phenols on a Boron Doped Diamond Electrode

1.
College of Chemistry, Jilin University, Changchun 130012, P. R. China;
2.
State Key Laboratory of Superhard Materials, Jilin University, Changchun 130012, P. R. China
Received Date: 11 April 2017
Revised Date: 22 May 2017
Fund Project:
The project was supported by the National Natural Science Foundation of China (21273097, 21573093), Funding for Innovative Research and Development Project of Guangdong Province (2013C092), the Science Foundation of Jilin Province of China (No. 20130204003GX) and National Key Research and Development Program (2016YFC1102802).

Abstract: In this work, the effect of different phenolic substituents on the electrochemical oxidation of phenols on a boron doped diamond (BDD) electrode was investigated. The specific relationship between the position and type of substituent and the electrochemical oxidation activity on the BDD electrode was systematically studied by employing Chemical Oxygen Demand and concentration variation. Electrochemical mineralization of hydroquinone was conducted on electrodes with different oxygen evolution potentials. It was found that there exists an important relationship between the electrochemical activity and the ability to generate hydroxyl radicals. A high activity was achieved on the BDD electrode owing to its higher electro-generation ability for hydroxyl radicals. The mineralization of substituted phenols is indirectly conducted by the hydroxyl radicals and the divorce of the substituent group is the rate determining step for the mineralization process. Meanwhile, the electrochemical mineralization rate towards substituted phenol contaminants is limited by the electronic effects of the substituents. The mineralization rate increases with increasing electron donating ability of the substituent. A linear relationship is found to exist between the reaction rate and the Hammett constant during degradation of substituted phenols.

Key words:

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1.
沈阳化工大学材料科学与工程学院沈阳 110142

掺硼金刚石电极电催化氧化酚类有机物的取代基效应

English

Electrochemical Oxidation of Substituted Phenols on a Boron Doped Diamond Electrode

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通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

掺硼金刚石电极电催化氧化酚类有机物的取代基效应

English

Electrochemical Oxidation of Substituted Phenols on a Boron Doped Diamond Electrode

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南： 你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

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