The advanced oxidation of 2,4-dinitrophenol (DNP), 2,5-DNP, and 3,4-DNP in aqueous solution has been investigated using a multi-gas, dielectric barrier discharge. Dielectric barrier discharge was operated in the aqueous solution and gas boundary. The degradation was measured by high performance liquid chromatography (HPLC). The acceleration of the advanced-oxidation has been investigated by the combination of the anion exchange polymer membrane. The result indicated that the degradation pathways involve a rapid detachment of the nitro group and a slow opening of the aromatic-ring. The hydroxyl radical and the excited hydroxyl anion are responsible for the primary attack of the DNP with the production of dihydroxy-nitrobenzenes. The attack of hydroxyl radical occurs at the benzene ring carbon activated by the presence of a phenolic OH group and a nitro group. The result suggested that the reaction is dominated by a pseudo-first order kinetic reaction. The degradation process is interpreted using Molecular Orbital Theory.
References
[1]
Locke, B.R., Sato, M., Sunka, P., Hoffmann, M.R. and Chang, J.-S. (2006) Electrohydraulic Discharge and Nonthermal Plasma for Water Treatment. Industrial and Engineering Chemistry Research, 45, 882-905. https://doi.org/10.1021/ie050981u
[2]
Gao, J.Z., Pu, L.M., Yang, W., Yu, J. and Li, Y. (2004) Oxidative Degradation of Nitrophenols in Aqueous Solution Induced by Plasma with Submersed Glow Discharge Electrolysis. Plasma Process and Polymers, 1, 171-176.
https://doi.org/10.1002/ppap.200400012
[3]
Servais, P., Billen, G. and Hascoet, M.C. (1987) Determination of the Biodegradable Fraction of Dissolved Organic Matter in Waters. Water Research, 21, 445-450.
[4]
Qu, R.-J., Feng, M.-G., Wang, X.-G. Huang, Q.-G., Lu, J.-H., Wang, L.-S. and Wang, Z.-Y. (2015) Rapid Removal of Tetrabromobisphenol A by Ozonation in Water: Oxidation Products, Reaction Pathways and Toxicity Assessment. PLoS ONE, 10, 1-17.
[5]
Wang, X.-Y., Zhou, M.H. and Jin, X.L. (2012) Application of Glow Discharge Plasma for Wastewater Treatment. Electrochimica Acta, 83, 501-512.
https://doi.org/10.1016/j.electacta.2012.06.131
[6]
Gong, J.Y., Wang, J., Xie, W.J. and Cai, W.-M. (2008) Enhanced Degradation of Aqueous Methyl Orange by Contact Glow Discharge Electrolysis Using Fe2+ as Catalyst. Journal of Applied Electrochemistry, 38, 1749-1755.
https://doi.org/10.1007/s10800-008-9626-z
[7]
Tang, Q.-O., Jiang, W.J., Zhang, Y., Wei, W.Y. and Lim, T.M. (2009) Degradation of Azo Dye Acid Red 88 by Gas Phase Dielectric Barrier Discharges. Plasma Chemistry and Plasma Processing, 29, 291-305. https://doi.org/10.1007/s11090-009-9181-3
[8]
Huang, F.-M., Chen, L., Wang, H.-L., Feng, T.-Z. and Yan, Z.-C. (2012) Degradation of methyl Orange by Atmospheric DBD Plasma: Analysis of the Degradation Effects and Degradation Path. Journal of Electrostatistics, 70, 43-47.
https://doi.org/10.1016/j.elstat.2011.10.001
[9]
Huang, F.M., Chan, L., Wang, H.L. and Yan, Z.C. (2010) Analysis of the Degradation Mechanism of Methylene Blue by Atmospheric Pressure Dielectric Barrier Discharge Plasma. Chemical Engineering Journal, 162, 250-256.
https://doi.org/10.1016/j.cej.2010.05.041
[10]
Xue, J., Chen, L. and Wang, H.-L. (2008) Degradation Mechanism of Alizarin Red in Hybrid Gas-Liquid Phase Dielectric Barrier Discharge Plasmas: Experimental and Theoretical Examination. Chemical Engineering Journal, 138, 120-127.
https://doi.org/10.1016/j.cej.2007.05.055
[11]
Lukes, P. and Locke, B.R. (2005) Degradation of Substituted Phenols in a Hybrid Gas-Liquid Electrical Discharge Reactor. Industrial and Engineering Chemistry Research, 44, 2921-2930. https://doi.org/10.1021/ie0491342
[12]
Katayama-Hirayama, K., Toda, N., Tauchi, A., Fujioka, A., Akitsu, T., Kaneko, H. and Hirayama K. (2014) Degradation of Dibromophenols by UV Irradiation. Journal of Environmental Sciences, 26, 184 188,
[13]
Kojima, S., Katayama-Hirayama, K. and Akitsu, T. (2016) Degradation of Aqueous 2,6-Dibromophenol Solution by In-Liquid Barrier Microplasma. World Journal of Engineering and Technology, 4, 423-432. https://doi.org/10.4236/wjet.2016.43042
[14]
Ji, Y.-F., Li, J.-H., Lu, J.-H., Shi, Y.-Y., Zhou, L., Yang, Y., Yang, P.-Z., Wang, L., Ferronato, C. and Chovelon, J.M. (2018) Rethinking Sulfate Redical-Based Oxidation of Nitrophenols: Formation of Toxic Poly-Nitrophenols, Nitrated Bisphenols and Diphenyl Ethers. Journal of Hazardous Materials, 361, 152-161.
https://doi.org/10.1016/j.jhazmat.2018.08.083
[15]
Kang, S.-F., Wang, T.-H. and Lin, Y.-H. (2008) Decolorization and Degradation of 2,4-Dinitrophenol by Fenton’s Reagent. Journal of Environmental Science and Health, Part A, 34, 935-950. https://doi.org/10.1080/10934529909376874
[16]
Fukui, K., Yonezawa, T. and Shingu, H. (1952) A Molecular Orbital Theory of Reactivity in Aromatic Hydrocarbons. The Journal of Chemical Physics, 20, 722-725.
[17]
Fleming, I. (1978) Frontier Orbitals and Organic Chemical Reactions. Wiley, London, 24-109.
[18]
BiomedicalCAChe 6.0 Users Guide, 2003, Fujitsu.
[19]
Somekawa, K. (2013) Molecular Orbital Calculation of Organic Molecules and the Application. Kyushu University Press, Fukuoka.
