间溴苯甲酸在Pt电极上电氧化反应.pdfVIP

物理化学学报(Wuli Huaxue Xuebao) March Acta Phys. -Chim. Sin. 2013, 29 (3), 553-558 553 [Article] doi: 10.3866/PKU.WHXB201301101 间溴苯甲酸在Pt 电极上的电氧化反应 叶咏薇 王 希 郑万芳 李美超* 马淳安 (浙江工业大学化学工程与材料学院, 分析测试中心, 杭州310032) 摘要: 采用循环伏安法和原位傅里叶变换红外(FTIR)光谱法研究了碱性介质中间溴苯甲酸(3-BBA)在Pt 电极 上的电化学氧化反应. 3-BBA 在Pt 电极上有良好的电化学活性. 在较低的氧化电位作用下(1000 mV), 3-BBA 自由基负离子先在Pt 电极上失去一个电子, 生成对应的自由基, 继而发生脱羧反应生成溴苯自由基阳离子和二 氧化碳. 随着电位的正移, 吸附在电极表面的羟基自由基进攻溴苯阳离子, 发生脱溴反应, 生成苯酚. 随着电位 的升高, 苯酚继续氧化生成苯二酚以及苯醌等, 部分苯环还可经开环得到马来酸和富马酸. 关键词: 间溴苯甲酸; 原位傅里叶变换红外光谱法; 电氧化; 脱羧反应; 脱溴反应 中图分类号: O646 Electrooxidation Reaction of 3-Bromobenzoic Acid on Pt Electrode YE Yong-Wei WANG Xi ZHENG Wan-Fang LI Mei-Chao* MA Chun-An (Research Center of Analysis and Measurement, College of Chemical Engineering and Materials Science, Zhejiang University of Technology, Hangzhou 310032, P. R. China) Abstract: Electrochemical oxidation of 3-bromobenzoic acid (3-BBA) on a Pt electrode in alkali solution was studied by cyclic voltammetry and in situ Fourier transform infrared (FTIR) spectroscopy. The Pt electrode exhibited good performance for the electrooxidation of 3-BBA. At low oxidation potential (1000 mV), one electron was removed from the 3-BBA radical anion and the corresponding free radical was generated. A Bbromobenzene free radical cation and carbon dioxide were obtained after decarboxylation. The bromobenzene cation was then attacked by the hydroxyl radical, which was adsorbed on the anode, and the bromobenzene cation intermed