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Acta Phys. Chim. Sin.  2013, Vol. 29 Issue (05): 973-980    DOI: 10.3866/PKU.WHXB201302283
ELECTROCHEMISTRY AND NEW ENERGY     
Dechlorination of Benzenyltrichloride in CH3CN Solvent at a Silver Cathode
XU Ying-Hua, MA Hong-Xing, CAI Qian-Qian, ZHU Ying-Hong, MA Chun-An
State Key Laboratory Breeding Base of Green Chemistry-Synthesis Technology, College of Chemical Engineering and Materials, Zhejiang University of Technology, Hangzhou 310032, Zhejiang Province, P. R. China
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Abstract  

The reductive dechlorination mechanism of benzenyltrichloride at an Ag cathode was investigated using cyclic voltammetry (CV) and potentiostatic electrolysis, in CH3CN solvent containing 0.1 mol·L- tetrabutylammonium perchlorate (TBAP). The adsorption of Cl- generated during dechlorination was detected using wide anode region CV, based on its anodic reaction with Ag. The CV results indicated that: (1) Ag exhibited better electrocatalytic activity than Hg for the dechlorination; (2) the first reduction peak, which was divided from the reduction peak of benzenyltrichloride at -1.19 V (vs Ag/Ag+) when the scan rate was ≤50 mV·s-1, is an adsorption controlled process and its electron transfer occurred in a concerted way, and the electron transfer coefficient is approximately 0.25; (3) the potential region where departing Cladsorbed on Ag ranged from -0.75 to -1.75 V (vs Ag/Ag+ ). The electrolysis results indicated that dechlorination product selectivity was strongly dependent on the Ag electrode potential.



Key wordsAg electrode      Reductive dechlorination      Dechlorination mechanism      Wide anode region CV      Adsorption of Cl-     
Received: 11 January 2013      Published: 28 February 2013
MSC2000:  O646  
Fund:  

The project was supported by the National Natural Science Foundation of China (21106133) and National Key Basic Research Program of China (973) (2012CB722604).

Cite this article:

XU Ying-Hua, MA Hong-Xing, CAI Qian-Qian, ZHU Ying-Hong, MA Chun-An. Dechlorination of Benzenyltrichloride in CH3CN Solvent at a Silver Cathode. Acta Phys. Chim. Sin., 2013, 29(05): 973-980.

URL:

http://www.whxb.pku.edu.cn/Jwk_wk/wlhx/10.3866/PKU.WHXB201302283     OR     http://www.whxb.pku.edu.cn/Jwk_wk/wlhx/Y2013/V29/I05/973

(1) Ma, C. A. An Introduction to Organic Electrochemical Synthesis,1st ed.; Science Press: Beijing, 2002; pp 211-213. [马淳安.有机电化学合成导论. 第一版. 北京: 科学出版社, 2002:211-213.]
(2) Huang, B. B. Electrocatalytic Properties of Transition MetalsTowards Reduction of Chlorinated Volatile Organic Compounds (Cl-VOCs). Ph. D. Dissertation, South China University ofTechnoloay, Guangzhou, 2012. [黄彬彬. 过渡金属电极对挥发性有机氯化物的电催化还原研究[D]. 广州: 华南理工大学,2012.]
(3) Isse, A. A.; Sandonà, G.; Durante, C.; Gennaro, A. ElectrochimicaActa 2009, 54 (12), 3235. doi: 10.1016/j.electacta.2008.12.034
(4) Fedurco, M.; Coppex, L.; Augustynski, J. J. Phys. Chem. B2002, 106 (10), 2625. doi: 10.1021/jp013299w
(5) Huang, Y. F.;Wu, D. Y.;Wang, A.; Ren, B.; Rondinini, S. B.;Tian, Z. Q.; Amatore, C. J. Am. Chem. Soc. 2010, 132 (28),17199.
(6) Isse, A. A.; Mussini, P. R.; Gennaro, A. J. Phys. Chem. C 2009,113 (33), 14983. doi: 10.1021/jp904797m
(7) Andrieux, C. P.; Gorande, A. L.; Saveant, J. M. J. Am. Chem.Soc. 1992, 114 (17), 6893.
(8) Rondinini, S. B.; Mussini, P. R.; Crippa, F.; Sello, G.Electrochem. Commun. 2000, 2 (7), 491. doi: 10.1016/S1388-2481(00)00065-5
(9) Rondinini, S. B.; Mussini, P. R.; Muttini, P.; Sello, G.Electrochim. Acta 2001, 46 (20-21), 3245. doi: 10.1016/S0013-4686(01)00616-8
(10) Ardizzone, S.; Cappelletti, G.; Doubova, L. M.; Mussini, P. R.;Passeri, S. M.; Rondinini, S. B. Electrochim. Acta 2003, 48 (25-26), 3789. doi: 10.1016/S0013-4686(03)00512-7
(11) Isse, A. A.; Giusti, A. D.; Gennaro, A.; Falciola, L.; Mussini, P.R. Electrochim. Acta 2006, 51 (23), 4956. doi: 10.1016/j.electacta.2006.01.039
(12) Ardizzone, S.; Cappelletti, G.; Mussini, P. R.; Rondinini, S. B.;Doubova, L. M. J. Electroanal. Chem. 2002, 532 (1-2), 285.doi: 10.1016/S0022-0728(02)00950-6
(13) Mussini, P. R.; Ardizzone, S.; Cappelletti, G.; Longhi, M.;Rondinini, S. B.; Doubova, L. M. J. Electroanal. Chem. 2003,552 (30), 213.
(14) Isse, A. A.; Falciola, L.; Mussini, P. R.; Gennaro, A. Chem.Commun. 2006, No. 3, 344.
(15) Isse, A. A.; Berzi, G.; Falciola, L.; Rossi, M.; Mussini, P. R.;Gennaro, A. J. Appl. Electrochem. 2009, 39 (11), 2217.doi: 10.1007/s10800-008-9768-z
(16) Saez, V.; Esclapez, M. D.; Bonete, P.; Gonzalez-Garcia, J.;Perez, J. M. Electrochim. Acta 2008, 53 (7), 3210. doi: 10.1016/j.electacta.2007.11.023
(17) Wang, A.; Huang,Y. F.; Sur, U. K.;Wu, D.Y.; Ren, B.; Rondinini,S. B.; Amatore, C.; Tian, Z. Q. J. Am. Chem. Soc. 2010, 132 (28), 9534. doi: 10.1021/ja1024639
(18) Li, M. C.; You, N. N.; Ma, C. A. Acta Chim. Sin. 2011, 69, 2766.[李美超, 尤楠楠, 马淳安. 化学学报, 2011, 69, 2766]
(19) Huang, B. B.; Lsse, A. A.; Durante, C.;Wei, C. H.; Gennaro, A.Electrochim. Acta 2012, 70 (30), 50.
(20) Rondinini, S. B.; Vertova, A. Electroreduction of HalogenatedOrganic Compounds. In Electrochemistry for the Environment;Comninellis, C., Chen, G., Eds.; Springer: New York, 2010; pp279-306.
(21) Xu, Y. H.; Zhang, H.; Chu, C. P.; Ma, C. A. J. Electroanal.Chem. 2012, 664, 39. doi: 10.1016/j.jelechem.2011.10.010
(22) Xu, Y. H.; Zhu, Y. H.; Zhao, F. M.; Ma, C. A. Appl. Catal. A2007, 324, 83. doi: 10.1016/j.apcata.2007.02.049
(23) Ma, C. A.; Ma, H.; Xu, Y. H.; Chu, Y. Q.; Zhao, F. M.;Electrochem. Commun. 2009, 11 (11), 2133. doi: 10.1016/j.elecom.2009.09.013
(24) Gisselbrecht, J. P.; Lund, H. Acta Chemica Scandinavica B1985, 39, 773.
(25) Zhu, Y. H.; Xu, Y. H.; Mao, H.; Zhao, F. M.; Ma, C. A. ActaPhys. -Chim. Sin. 2009, 25, 6. [朱英红, 徐颖华, 马昊, 赵峰鸣, 马淳安. 物理化学学报, 2009, 25, 6.] doi: 10.3866/PKU.WHXB20090102
(26) Poizot, P.; Dantras, L. L.; Simonet, J. Electrochem. Commun.2008, 10 (6), 864. doi: 10.1016/j.elecom.2008.03.016

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[2] Tian Zhong-Qun; Li Wu-Hu; Gao Jin-Song; Mao Bing-Wei. Evidence for Different Responsing Rates of Different sers Bands of Surface Species on Change of Electrode Potentials[J]. Acta Phys. Chim. Sin., 1993, 9(06): 721-723.