间溴苯甲酸在Pt电极上的电氧化反应

引用本文: 叶咏薇, 王希, 郑万芳, 李美超, 马淳安. 间溴苯甲酸在Pt电极上的电氧化反应[J]. 物理化学学报, 2013, 29(03): 553-558. doi: 10.3866/PKU.WHXB201301101 shu

Citation: YE Yong-Wei, WANG Xi, ZHENG Wan-Fang, LI Mei-Chao, MA Chun-An. Electrooxidation Reaction of 3-Bromobenzoic Acid on Pt Electrode[J]. Acta Physico-Chimica Sinica, 2013, 29(03): 553-558. doi: 10.3866/PKU.WHXB201301101 shu

间溴苯甲酸在Pt电极上的电氧化反应

基金项目:
国家重点基础研究发展计划(973)项目(2012CB722604) (973)项目(2012CB722604)

国家自然科学基金(21206147)资助 (21206147)

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:

English

Electrooxidation Reaction of 3-Bromobenzoic Acid on Pt Electrode

1.
Research Center of Analysis and Measurement, College of Chemical Engineering and Materials Science, Zhejiang University of Technology, Hangzhou 310032, P. R. China
Received Date: 30 October 2012
Available Online: 25 February 2013
Fund Project:
国家重点基础研究发展计划(973)项目(2012CB722604)

国家自然科学基金(21206147)资助

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 od 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 intermediate product was debrominated to form phenol. When the potential shifted to more positive values, phenol was electrooxided to produce dihydroxybenzene and benzoquinone. Maleic acid and fumaric acid were also detected as the reaction products of the ring-opening reaction.

Key words:

3-Bromobenzoic acid
/ In situ Fourier transform infrared spectroscopy
/ Electrooxidation
/ Decarboxylation reaction
/ Debromination reaction

1. [1]
  
  (1) Scialdone, O.; Guarisco, C.; Galia, A.; Lo, C. C.; Bunce, N. J.;Konstantinov, A. D. J. Electroanal. Chem. 2010, 641, 14.doi: 10.1016/j.jelechem.2010.01.018
  (1) Scialdone, O.; Guarisco, C.; Galia, A.; Lo, C. C.; Bunce, N. J.;Konstantinov, A. D. J. Electroanal. Chem. 2010, 641, 14.doi: 10.1016/j.jelechem.2010.01.018
2. [2]
  (2) Ma, C. A.; Li, M. C.; Liu, Y. N.; Xu, Y. H. Electrochim. Acta2010, 55, 3171. doi: 10.1016/j.electacta.2009.12.086(2) Ma, C. A.; Li, M. C.; Liu, Y. N.; Xu, Y. H. Electrochim. Acta2010, 55, 3171. doi: 10.1016/j.electacta.2009.12.086
3. [3]
  (3) Konstantinov, A.; Bejan, D.; Bunce, N.; Chittim, B.; McCrindle,R.; Potter, D.; Tashiro, C. J. Chemosphere 2008, 72, 1159.doi: 10.1016/j.chemosphere.2008.03.046(3) Konstantinov, A.; Bejan, D.; Bunce, N.; Chittim, B.; McCrindle,R.; Potter, D.; Tashiro, C. J. Chemosphere 2008, 72, 1159.doi: 10.1016/j.chemosphere.2008.03.046
4. [4]
  (4) Pera-Titus, M.; García-Molina, V.; Baños, M. A.; Giménez, J.;Esplugas, S. Appl. Catal. B: Environ. 2004, 47 (4), 219. doi: 10.1016/j.apcatb.2003.09.010(4) Pera-Titus, M.; García-Molina, V.; Baños, M. A.; Giménez, J.;Esplugas, S. Appl. Catal. B: Environ. 2004, 47 (4), 219. doi: 10.1016/j.apcatb.2003.09.010
5. [5]
  (5) Chen, G.;Wang, Z. Y.; Xia, D. G. Electrochem. Commun. 2004,6, 268. doi: 10.1016/j.elecom.2003.12.011(5) Chen, G.;Wang, Z. Y.; Xia, D. G. Electrochem. Commun. 2004,6, 268. doi: 10.1016/j.elecom.2003.12.011
6. [6]
  (6) Benedict, R. T.; Stapleton, H. M.; Letcher, R. J.; Mitchelmore,C. I. Chemosphere 2007, 69 (6), 987. doi: 10.1016/j.chemosphere.2007.05.010(6) Benedict, R. T.; Stapleton, H. M.; Letcher, R. J.; Mitchelmore,C. I. Chemosphere 2007, 69 (6), 987. doi: 10.1016/j.chemosphere.2007.05.010
7. [7]
  (7) Zhu, Y. H.; Xu, Y. H.; Ma, H.; Zhao, F. M.; Ma, C. A. ActaPhys. -Chim. Sin. 2009, 25 (6), 1190. [朱英红, 徐颖华,马昊, 赵峰鸣, 马淳安. 物理化学学报, 2009, 25 (6), 1190.]doi: 10.3866/PKU.WHXB20090625(7) Zhu, Y. H.; Xu, Y. H.; Ma, H.; Zhao, F. M.; Ma, C. A. ActaPhys. -Chim. Sin. 2009, 25 (6), 1190. [朱英红, 徐颖华,马昊, 赵峰鸣, 马淳安. 物理化学学报, 2009, 25 (6), 1190.]doi: 10.3866/PKU.WHXB20090625
8. [8]
  (8) Zheng, L.; Zhu, C. Z.; Xu, Y.; Lu, X.; Hou, H. Q. Resarch ofEnvironmental Sciences 2004, 17 (6), 54. [郑璐, 朱承驻,徐莺, 卢霄, 侯惠奇. 环境科学研究, 2004, 17 (6), 54.](8) Zheng, L.; Zhu, C. Z.; Xu, Y.; Lu, X.; Hou, H. Q. Resarch ofEnvironmental Sciences 2004, 17 (6), 54. [郑璐, 朱承驻,徐莺, 卢霄, 侯惠奇. 环境科学研究, 2004, 17 (6), 54.]
9. [9]
  (9) Wang, Y. L.; Cai, N. C.; Huo, Y. D.; Chen, H. Acta Phys. -Chim.Sin. 2001, 17 (7), 609. [王玉玲, 蔡乃才, 霍耀东, 陈浩. 物理化学学报, 2001, 17 (7), 609.] doi: 10.3866/PKU.WHXB20010707(9) Wang, Y. L.; Cai, N. C.; Huo, Y. D.; Chen, H. Acta Phys. -Chim.Sin. 2001, 17 (7), 609. [王玉玲, 蔡乃才, 霍耀东, 陈浩. 物理化学学报, 2001, 17 (7), 609.] doi: 10.3866/PKU.WHXB20010707
10. [10]
  (10) Fang, L.; Huang, J.; Yu, G.;Wang, L. N. Chemosphere 2008, 71,258. doi: 10.1016/j.chemosphere.2007.09.041(10) Fang, L.; Huang, J.; Yu, G.;Wang, L. N. Chemosphere 2008, 71,258. doi: 10.1016/j.chemosphere.2007.09.041
11. [11]
  (11) Sun, S. G.; ng, H. Petrochemical Technology 2001, 30, 806.[孙世刚, 贡辉. 石油化工, 2001, 30, 806.](11) Sun, S. G.; ng, H. Petrochemical Technology 2001, 30, 806.[孙世刚, 贡辉. 石油化工, 2001, 30, 806.]
12. [12]
  (12) Zhang, X. X.; Zhang, Y. X.; Jiang, J. Z. J. Mol. Struct. 2004,673, 103.(12) Zhang, X. X.; Zhang, Y. X.; Jiang, J. Z. J. Mol. Struct. 2004,673, 103.
13. [13]
  (13) Miki, A.; Ye, S.; Senzaki, T.; Osawa, M. J. Electroanal. Chem.2004, 563, 23. doi: 10.1016/j.jelechem.2003.09.014(13) Miki, A.; Ye, S.; Senzaki, T.; Osawa, M. J. Electroanal. Chem.2004, 563, 23. doi: 10.1016/j.jelechem.2003.09.014
14. [14]
  (14) Trettenhahn, G.; Köberl, A. Electrochim. Acta 2007, 52, 2716.doi: 10.1016/j.electacta.2006.09.028(14) Trettenhahn, G.; Köberl, A. Electrochim. Acta 2007, 52, 2716.doi: 10.1016/j.electacta.2006.09.028
15. [15]
  (15) Su, K. M.; Pan, T. Y.; Zhang, Y. L. Spectrum Analysis Method;East China University of Science and Technology Press:Shanghai, 2002; pp 106-107. [苏克曼, 潘铁英, 张玉兰. 波谱解析法. 上海: 华东理工大学出版社, 2002: 106-107.](15) Su, K. M.; Pan, T. Y.; Zhang, Y. L. Spectrum Analysis Method;East China University of Science and Technology Press:Shanghai, 2002; pp 106-107. [苏克曼, 潘铁英, 张玉兰. 波谱解析法. 上海: 华东理工大学出版社, 2002: 106-107.]
16. [16]
  (16) Li, M. C.; Bao, D. D.; Ma, C. A. Electrochim. Acta 2011, 56,4100. doi: 10.1016/j.electacta.2011.01.115(16) Li, M. C.; Bao, D. D.; Ma, C. A. Electrochim. Acta 2011, 56,4100. doi: 10.1016/j.electacta.2011.01.115
17. [17]
  (17) Sundaraganesan, N.; Meganathan, C.; Karthikeyan, B.Spectrochim. Acta A 2008, 70, 430. doi: 10.1016/j.saa.2007.12.022(17) Sundaraganesan, N.; Meganathan, C.; Karthikeyan, B.Spectrochim. Acta A 2008, 70, 430. doi: 10.1016/j.saa.2007.12.022
18. [18]
  (18) Chetty, R.; Christensen, P. A.; lding, B. T.; Scott, K. Appl.Catal. A: Gen. 2004, 271, 185. doi: 10.1016/j.apcata.2004.02.059(18) Chetty, R.; Christensen, P. A.; lding, B. T.; Scott, K. Appl.Catal. A: Gen. 2004, 271, 185. doi: 10.1016/j.apcata.2004.02.059
19. [19]
  (19) Zhou, M. H.;Wu, Z. C.;Wang, D. H. Chem. J. Chin. Univ.2003, 24 (9), 1637. [周明华, 吴祖成, 汪大翚. 高等学校化学学报, 2003, 24 (9), 1637.](19) Zhou, M. H.;Wu, Z. C.;Wang, D. H. Chem. J. Chin. Univ.2003, 24 (9), 1637. [周明华, 吴祖成, 汪大翚. 高等学校化学学报, 2003, 24 (9), 1637.]
20. [20]
  (20) Wang, H.;Wang, J. L. Electrochim. Acta 2008, 53, 6402. doi: 10.1016/j.electacta.2008.04.080(20) Wang, H.;Wang, J. L. Electrochim. Acta 2008, 53, 6402. doi: 10.1016/j.electacta.2008.04.080
21. [21]
  (21) Li, M. C.; Bao, D. D.; Ma, C. A. Chem. J. Chin. Univ. 2011, 32 (1), 129. [李美超, 鲍丹丹, 马淳安. 高等学校化学学报,2011, 32 (1), 129.](21) Li, M. C.; Bao, D. D.; Ma, C. A. Chem. J. Chin. Univ. 2011, 32 (1), 129. [李美超, 鲍丹丹, 马淳安. 高等学校化学学报,2011, 32 (1), 129.]
22. [22]
  (22) Swaminathan, J.; Ramalingam, M.; Saleem, H.; Sethuraman, V.;Ameen, M. T. N. Spectrochim. Acta A 2009, 74, 1247. doi: 10.1016/j.saa.2009.09.054(22) Swaminathan, J.; Ramalingam, M.; Saleem, H.; Sethuraman, V.;Ameen, M. T. N. Spectrochim. Acta A 2009, 74, 1247. doi: 10.1016/j.saa.2009.09.054
23. [23]
  (23) Johnson, S. K.; Houk, L. L.; Feng, J.; Houk, R. S.; Johnson, D.C. Enviro. Sci. Technol. 1999, 33, 2638. doi: 10.1021/es981045r(23) Johnson, S. K.; Houk, L. L.; Feng, J.; Houk, R. S.; Johnson, D.C. Enviro. Sci. Technol. 1999, 33, 2638. doi: 10.1021/es981045r
24. [24]
  (24) Jin, G. P.; Lin, X. Q.; Ding, Y. F. J. Solid State Electrochem.2006, 10, 987. doi: 10.1007/s10008-005-0068-9(24) Jin, G. P.; Lin, X. Q.; Ding, Y. F. J. Solid State Electrochem.2006, 10, 987. doi: 10.1007/s10008-005-0068-9
25. [25]
  (25) Tong, S. P.; Ma, C. A.; Fei, H. Acta Phys. -Chim. Sin. 2007, 23 (3), 424. [童少平, 马淳安, 费会. 物理化学学报, 2007, 23 (3), 424.] doi: 10.3866/PKU.WHXB20070327
  (25) Tong, S. P.; Ma, C. A.; Fei, H. Acta Phys. -Chim. Sin. 2007, 23 (3), 424. [童少平, 马淳安, 费会. 物理化学学报, 2007, 23 (3), 424.] doi: 10.3866/PKU.WHXB20070327

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1.
沈阳化工大学材料科学与工程学院沈阳 110142

间溴苯甲酸在Pt电极上的电氧化反应

English

Electrooxidation Reaction of 3-Bromobenzoic Acid on Pt Electrode

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通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

间溴苯甲酸在Pt电极上的电氧化反应

English

Electrooxidation Reaction of 3-Bromobenzoic Acid on Pt 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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