Studies on Electrochemical Oxidation Reaction of 2,4-Dichlorophenol on Pt Electrode

doi:10.7503/cjcu20130326

Abstract

Abstract:

Cyclic voltammetry(CV) and in situ FTIR spectrometry were employed to study the electrochemical oxidation mechanism of 2,4-dichlorophenol(2,4-DCP) in NaOH solution. Density functional theory(DFT) was used to calculate the Fukui function for 2,4-DCP and gave the information on possible reactive sites of 2,4-DCP during electrochemical oxidation. CV results show that the Pt electrode exhibits a high electrochemical activity for the electrochemical oxidation reaction of 2,4-DCP. On the basis of in situ FTIR data, the electrochemical oxidation reaction of 2,4-DCP is as follows: (1) C—Cl band of 2,4-DCP is broken to form phenol directly; (2) C—Cl band of 2,4-DCP is broken and C—O band is formed with ·OH radicals, and the Fukui function results show that chlorine atom at 4 position is easier to be replaced with the hydrogen or ·OH radicals. Then hydroxylation reaction happens on the C4-position of phenol leading to form hydroquinone which is subsequently electrochemically oxidized to benzoquinone. With the potential increasing, aliphatic carboxylic acids are formed after the ring cleavage; (3) part of 2,4-DCP is electrochemically oxidized to chloromaleic acid directly. At about 1700 mV, CO₂ could be formed during electrochemical oxidation reaction of 2,4-DCP on Pt electrode.

Key words: 2,4-Dichlorophenol, Electrochemical oxidation, In situ FTIR spectrum, Fukui function

CLC Number:

O646.5

TrendMD:

MA Chun-An, WANG Fen, LU Jin-Jin, LI Mei-Chao, ZHENG Wan-Fang. Studies on Electrochemical Oxidation Reaction of 2,4-Dichlorophenol on Pt Electrode[J]. Chem. J. Chinese Universities, 2013, 34(12): 2850.

References

[1] Liu L. F., Chen F., Yang F. L., Chen Y. S., Crittenden J., Chem. Eng. J., 2012, 181/182, 189—195

[2] Zhao X., Xu T. G., Yao W. Q., Zhang C., Zhu Y. F., Appl. Catal. B: Environ., 2007, 72(1/2), 92—97

[3] Folsom B. R., Chapman P. J., Pritchard P. H., Appl. Environ. Microb., 1990, 56(5), 1279—1285

[4] Ureta-Zañartu M. S., Bustos P., Berríos C., Diez M. C., Mora M. L., Gutiérrez C., Electrochim. Acta, 2002, 47(15), 2399—2406

[5] Gherardini L., Michaud P. A., Panizza M., Comninellis C., Vatistas N., J. Electrochem. Soc., 2001, 148(6), D78—D82

[6] Wang Y., Shen Z. Y., Li Y., Niu J. F., Chemosphere, 2010, 79(10), 987—996

[7] Sun S. G., Yang D. F., Tian Z. W., J. Electroanal. Chem., 1990, 289(1/2), 177—187

[8] Li M. C., Bao D. D., Ma C. A., Electrochim. Acta, 2011, 56(11), 4100—4104

[9] Parr R. G., Yang W. T., J. Am. Chem. Soc., 1984, 106(14), 4049—4050

[10] Yang W. T., Mortier W. J., J. Am. Chem. Soc., 1986, 108(19), 5708—5711

[11] Chetty R., Christensen P. A., Golding B. T., Chem. Commun., 2003, 984—985

[12] Pohjakllio M., Sundholm G., Talonen P., J. Electroanal Chem., 1996, 401(1/2), 191—200

[13] Li M. C., Bao D. D., Ma C. A., Chem. J. Chinese Universities, 2011, 32(1), 129—133(李美超, 鲍丹丹, 马淳安. 高等学校化学学报, 2011, 32(1), 129—133)

[14] Lomnicki S., Lichtenberger J., Xu Z. T., Waters M., Kosman J., Amiridis M. D., Appl. Catal. B: Environ., 2003, 46(1), 105—119

[15] Dobson K. D., McQuillan A. J., Spectrochim. Acta A, 2000, 56(3), 557—565

[16] Chetty R., Christensen P. A., Golding B. T., Scott K., Appl. Catal. A: Gen., 2004, 271(1/2), 185—194

[17] Wu W. C., Liao L. F., Lien C. F., Lin J. L., Phys. Chem. Chem. Phys., 2001, 3, 4456—4461

[18] Liao L. F., Wu W. C., Chen C. Y., Lin J. L., J. Phys. Chem. B, 2001, 105(32), 7678—7685

[19] Xie J. X., Chang J. B., Wang X. M., Application of Infrared Spectroscopy in Organic Chemistry and Drug Chemistry, Science Press, Beijing, 2001, 282(谢晶曦, 常俊标, 王绪明. 红外光谱在有机化学和药物化学中的应用, 北京: 科学出版社, 2001, 282)

[20] Aldereman S. L., Farquar G. R., Poliakoff E. D., Dellinger B., Environ. Sci. Technol., 2005, 39(19), 7396—7401

[21] Christensen P. A., Hamnett A., Weeks S. A., J. Electroanal. Chem., 1988, 250(1), 127—142

[22] K?l?ç M., KoçtÜrk G., San N., Çlnar Z., Chemosphere, 2007, 69(9), 1396—1408

[23] Padmanabhan J., Parthasarathi R., Subramanian V., Chattaraj P. K., Chem. Res. Toxicol., 2006, 19(3), 356—364

[24] Lu T., Chen F. W., J. Comput. Chem., 2012, 33(5), 580—592

[25] Wei J. J., Xu X. H., Liu Y., Wang D. H., Water Res., 2006, 40(2), 348—354