Oxidation of 2,4,6-Trichlorophenol Catalyzed by Tetraphenylporphyrin Tetrasulfonate with Different Metal Ions in the Presecence ofDifferent Oxidants

Yıl 2017, Cilt: 17 Sayı: 2, 449 - 459, 31.08.2017

Yasemin Çimen Tuğçe Günay

Öz

In this study, the oxidation of 2,4,6-trichlorophenol (TCP) catalyzed by iron-tetraphenylporphyrin tetrasulfonate ([FeTSPP]) in the presence of tert-butyl hydroperoxide (But OOH) or hydrogen peroxide (H2O2) was investigated. The reactions were carried out in %10-15 of water in methanol solutions by volume at room temperature and the effects of the concentration of substrate, catalyst and oxidant on the outcome of the reactions were investigated. The product compositions of the reaction mixtures were identified using GC-MS and amounts of the products were calculated using GC chromatograms. When the catalyst:substrate:oxidant mole ratios were kept in 1:500:300 in the catalysis by [FeTSPP], the highest turnover number (TON) and turnover frequency (TOF) values of 512 were obtained with H2O2.In addition, the catalytic activities of cobalt-, nickel-, paladium- and copper-tetraphenylporphyrin tetrasulfonates were investigigated for oxidation of TCP and it was determined that these structures did not show any activity. In order to improve recyclability of the catalyst, [FeTSPP] was bound to Amberlite IRA-900 resin. When the [FeTSPP]-IRA was used as a catalyst, it was determined that conversion of TCP decreased and optimum time increased for oxidation and also its recycling numbers did not increased.

Anahtar Kelimeler

Oxidation, Metalloporphyrin tetrasulfonate, Catalyst, 2,4,6, trichlorophenol

2,4,6-Triklorofenolün Çeşitli Oksidantlarla Farklı Metal İyonlarını İçeren Tetrafenilporfirin Tetrasülfonat Katalizörlüğünde Oksidasyonu

Öz

Bu çalışmada demir-tetrafenilporfirin tetrasülfonat ([FeTSPP]) katalizörlüğündetert-bütil hidroperoksit (ButOOH) veya hidrojen peroksit (H2O2) varlığında 2,4,6-triklorofenolün (TCP) oksidasyonu araştırılmıştır. Reaksiyonlar hacimce %10-15 su içeren metanol çözeltilerinde oda sıcaklığında yürütülmüş ve oksidasyonlar üzerine substrat, katalizör ve oksidant derişimlerinin etkileri incelenmiştir. Reaksiyon karışımlarının ürün bileşimleri GC-MS, nicel analizleri ise GC kullanılarak yapılmıştır. [FeTSPP] katalizörlüğünde TCP nin H2O2ile oksidasyonunda en yüksek katalitik döngü sayısı (Turnover number, TON) ve katalitik döngü frekansı (Turnover frequency, TOF) 512,0 olarak katalizör:substrat:oksidant mol oranı 1:500:300 olan reaksiyon içinelde edilmiştir. Ayrıca kobalt-, nikel-, paladyum- ve bakır-tetrafenilporfirin tetrasülfonatın TCP oksidasyonu için katalitik aktiviteleri incelenmiş ve bu yapıların katalitik aktivite göstermediği belirlenmiştir. Tekrar kullanılabilirliğini iyileştirmek amacıyla [FeTSPP],Amberlite IRA-900 reçinesine bağlanmış, ancak [FeTSPP]-IRA heterojen katalizörü ile yürütülen deneylerde TCP dönüşümünün azaldığı, optimum oksidasyon süresinin arttığı ve çevrim sayısının arttırılamadığı belirlenmiştir.

Anahtar Kelimeler

Oksidasyon; Metalo-tetrafenilporfirin tetrasülfonat; Katalizör; 2, 4, 6-triklorofenol

Kaynakça

• Adler, A.D., Longo, F.R., Finarelli, J.D., Goldmacher, J., Assour, J. and Korsakoff, L., 1967. A simplified synthesis for meso-tetraphenylporphine. Journal of Organic Chemistry, 32(2), 476-476.
• Agboola, B., Ozoemena, K.I. Nyokong, T., 2005. Hydrogen peroxide oxidation of 2-chlorophenol and 2,4,5-trichlorophenol catalyzed by monomeric and aggregated cobalt tetrasulfophthalocyanine. Journal of Molecular Catalysis A: Chemical, 227, 209–216
• Alexander, M., 1981. Biodegradation of chemicals of environmental concern. Science, 211(4478), 132-138.
• Chaliha, S. and Bhattacharyya, K.S., 2008. Catalytic wet oxidation of 2-chlorophenol, 2,4-dichlorophenol and 2,4,6-trichlorophenol in water with Mn(II)-MCM41. Chemical Engineering Journal, 139, 575-588.
• Chaliha, S. and Bhattacharyya, K.G., 2008. Wet oxidative method for removal of 2,4,6-trichlorophenol in water using Fe(III), Co(II), Ni(II) supported MCM41 catalysts. Journal of Hazardous Materials,150, 728–736.
• Christoforidis, K.C., Louloudi, M., Milaeva, E.R., Sanakis, Y. and Deligiannakis, Y., 2007. EPR study of a novel [Fe–porphyrin] catalyst. Molecular Physics, 105(15- 16), 2185-2194.
• Christoforidis, K.C., Louloudi, M., Milaeva, E.R. and Deligiannakis, Y., 2010a.Mechanism of catalytic decomposition of pentachlorophenol by a highly recyclable heterogeneous SiO2–[Fe-porphyrin] catalyst. Journal of Catalysis, 270(1), 153-162.
• Christoforidis, K.C., Louloudi, M. and Deligiannakis, Y., (2010b).Complete dechlorination of pentachlorophenol by a heterogeneous SiO2–Fe–porphyrin catalyst. Applied Catalysis B: Environmental, 95(3), 297-302.
• Christoforidis, K.C., Serestatidou, E., Louloudi, M., Konstantinou, I.K., Milaeva, E.R. and Deligiannakis, Y., 2011. Mechanism of catalytic degradation of 2,4,6- trichlorophenol by a Fe-porphyrin catalyst.Applied Catalysis B: Environmental, 101(3-4), 417-424.
• Díaz-Díaz, G., Celis-García, M., Blanco-López, M.C., Lobo- Castañón, M.J., Miranda-Ordieres, A.J. and Tuñón- Blanco, P., 2010. Heterogeneous catalytic 2,4,6- trichlorophenol degradation at hemin–acrylic copolymer.Applied Catalysis B: Environmental, 96(1- 2), 51-56.
• Dolphin, D.; Traylor, T.G.; Xie, L.Y., 1997. Polyhaloporphyrins: Unusual Ligands for Metals and Metal-Catalyzed Oxidations. Acc. Chem. Res.30, 251–259. Fleischer, E.B., Palmer, J.M., Srivastava, T.S. and Chatterjee, A., 1971. Thermodyamic and kinetic properties of an iron-porphyrin system. Journal of the American Chemical Society, 93 (13), 3162-3167.
• Franzen, S., Sasan, K., Sturgeon, B.E., Lyon, B.J., Battenburg, B.J., Gracz, H., Dumariah, R. and Ghiladi, R., 2012. Nonphotochemical base-catalyzed hydroxylation of 2,6-dichloroquinone by H2O2 occurs by a radical mechanism. The Journal of Physical Chemistry B, 116(5), 1666-1676.
• Fukushima, M., Sawada, A., Kawasaki, M., Ichikawa, H., Morimoto, K., Tatsumi, K. and Aoyama, M., 2003. Influence of humic substances on the removal of pentachlorophenol by a biomimetic catalytic system with a water-soluble ıron(III)−porphyrin complex. Environmental Science & Technology, 37(5), 1031- 1036.
• Fukushima, M. and Tatsumi, K., 2006. Complex formation of water-soluble iron(III)-porphyrin with humic acids and their effects on the catalytic oxidation of pentachlorophenol.Journal of Molecular Catalysis A: Chemical, 245(1–2), 178-184.
• Fukushima, M. and Shigematsu, S., 2008. Introduction of 5,10,15,20-tetrakis(4-hydroxyphenyl)-porphine iron(III) into humic acid via formaldehyde polycondensation. Journal of Molecular Catalysis A: Chemical, 293(1), 103-109.
• Görner, H. and von Sonntag, C., 2008. Photoprocesses of chloro-substituted p-benzoquinones. The Journal of Physical Chemistry A, 112(41), 10257-10263.
• Hadasch, A., Sorokin, A., Rabion A. and Meunier. B., 1998. Sequential addition of H pH and solvent eþ ects as key factors in 2O2 , the oxidation of 2,4,6-trichlorophenol catalyzed by iron tetrasulfophthalocyanine. New Journal of Chemistry, 45-51.
• Hemmert, C., Renz, M. and Meunier, B., 1999. Oxidative degradation of chlorinated phenols catalyzed by a non-heme iron(III) complex. Journal of Molecular Catalysis A: Chemical, 137(1), 205-212.
• Labat, G., Seris, J.L. and Meunier, B., 1990. Oxidative degradation of aromatic pollutants by chemical models of ligninase based on porphyrin complexes. Angewandte Chemie International Edition in English, 29(12), 1471-1473.
• Lente, G. and Espenson, J.H., 2004a. A kinetic study of the early steps in the oxidation of chlorophenols by hydrogen peroxide catalyzed by a water-soluble iron(III) porphyrin. New Journal of Chemistry, 28(7), 847-852.
• Lente, G. and Espenson, J.H., 2004b. Photoreduction of 2,6-dichloroquinone in aqueous solution: Use of a diode array spectrophotometer concurrently to drive and detect a photochemical reaction. Journal of Photochemistry and Photobiology A: Chemistry, 163 (1–2), 249-258.
• Malinski, T. in: Kadish, K.M., Smith, K.M., Guilard, R. (Eds.), 2000. Porphyrin Handbook Applications: Past, Present and Future, vol. 6, Academic Press, New York, p 231, Chapter 44.
• McKeown, N. B., 1998. Phthalocyanine Materials; Synthesis, Structure and Function. Cambridge University Press: Cambridge.
• Nakagaki, S., Ferreira, G.K.B., Ucoski,G.M. and Castro, K.A.D. de F., 2013. Chemical reactions catalyzed by metalloporphyrin-based metal-organic frameworks. Molecules,18, 7279-7308.
• Pera-Titus, M.,Garcia-Molina, V.,Banos, M.A.,Gimenez, J. andEsplugas, S., 2004. Degradation of chlorophenols by means of advanced oxidation processes: a general review.Applied Catalysis. B: Environmental,47, 219-256.
• Sanchez, M., Hadasch, A., Fell, R.T. and Meunier, B., 2001. Key role of the phosphate buffer in the H2O2 oxidation of aromatic pollutants catalyzed by ıron tetrasulfophthalocyanine.Journal of Catalysis, 202(1), 177-186.
• Sorokin, A., Meunier, B. and Séris, J.L., 1995. Efficient oxidative dechlorination and aromatic ring cleavage of chlorinated phenols catalyzed by iron sulfophthalocyanine. Science268 (5214), 1163-1166.
• Sorokin, A., De Suzzoni-Dezard, S., Poullain, D., Noël, J.P. and Meunier, B., 1996. CO2as the ultimate degradation product in the H2O2 oxidation of 2,4,6- trichlorophenol catalyzed by iron tetrasulfophthalocyanine. Journal of the American Chemical Society, 118(31), 7410-7411.
• Sorokin, A. and Meunier, B., 1996. Oxidative degradation of polychlorinated phenols catalyzed by metallosulfophthalocyanines. Chemistry–A European Journal, 2(10), 1308-1317.