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Preparation, characterization of new Co(II) and Cu(II) phthalocyanines and their catalytic performances in aerobic oxidation of substituted phenols

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Abstract

Substituted phenol pollutants are produced as by products of many industrial processes. Aerobic oxidations for their degradation in the context of effluent treatment or environmental remediation often lack selectivity. In this work Co(II) and Cu(II) phthalocyanines-catalyzed approach is described that converts substituted phenols into less harmfull products. New cobalt(II) and copper(II) phthalocyanine complexes are used as catalyst for degradation of substituted phenols with different oxidants. The oxidation process exhibits remarkable selectivity and conversion owing to the fact that Co(II) and Cu(II) phthalocyanines work with high performance.

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References

  1. Juretica, D., Kusica, H., Dionysioub, D.D., Loncaric Bozica, A.: Environmental aspects of photooxidative treatment of phenolic compounds. J. Hazard. Mater. 262, 377–386 (2013)

    Article  Google Scholar 

  2. Rappoport, Z.: The Chemistry of Phenols. Part 2. Wiley, West Sussex (2003)

    Book  Google Scholar 

  3. Pera-Titus, M., Garcia-Molina, V., Banos, M.A., Gimenez, J., Esplugas, S.: Degradation of chlorophenols by means of advanced oxidation processes: a generalreview. Appl. Catal. B 47, 219–256 (2004)

    Article  CAS  Google Scholar 

  4. EPA, July 2002, http://www.scorecard.org

  5. EC Decision 2455/2001/EC of the European Parliament and of the Council of November 20, 2001 establishing the list of priority substances in the field ofwater policy and amending Directive 2000/60/EC.(L 331 of 15-12-2001)

  6. World Health Organization, Guidelines for Drinking Water Quality. Vol.II: Health Criteria and Supporting Information, World Health Organization, Geneva, Switzerland, (1984)

  7. Shannon, R.D., Boardman, G.D., Dietrich, A.M., Bevan, D.R.: Mitochondrial response to chlorophenols as a short-term toxicity assay. Environ. Toxicol. Chem. 10, 57–66 (1991)

    Article  CAS  Google Scholar 

  8. Bıyıklıoglu, Z., Saka, E.T., Gökce, S., Kantekin, H.: Synthsis, characterization andinvestigation of homogeneous oxidation activities of peripherallytetra-substituted Co(II) and Fe(II) phthalocyanines: oxidation of cyclohexene. J. Mol. Catal. A 378, 156–163 (2013)

    Article  Google Scholar 

  9. Han, Z., Hana, X., Zhao, X., Yua, J., Xu, H.: Iron phthalocyanine supported on amidoximated PAN fiber aseffective catalyst for controllable hydrogen peroxide activation inoxidizing organic dyes. J. Hazard. Mater. 320, 27–35 (2016)

    Article  CAS  Google Scholar 

  10. Pirkanniemi, K., Sillanpaa, M., Sorokin, A.: Degradative hydrogen peroxide oxidation of chelates catalysed by metallophthalocyanines. Sci. Total Environ. 307, 11–18 (2003)

    Article  CAS  Google Scholar 

  11. Shen, C.S., Wen, Y.Z., Kang, X.D., Liu, W.P.: H2O2-induced surface modification: a facile, effective and environmentally friendly pretreatment of chitosan for dyes removal. Chem. Eng. J. 166, 474–482 (2011)

    Article  CAS  Google Scholar 

  12. Shena, C., Wena, Y., Shenb, Z., Wuc, J., Liua, W.: Facile, green encapsulation of cobalt tetrasulfophthalocyanine monomers in mesoporous silicas for the degradative hydrogen peroxide oxidation of azo dyes. J. Hazard. Mater. 193, 209–215 (2011)

    Article  Google Scholar 

  13. Sorokin, A.B.: µ-Nitrido diiron phthalocyanine and porphyrin complexes: unusual structures with interesting catalytic properties. Adv. Inorg. Chem. 70, 107–165 (2017)

    Article  Google Scholar 

  14. Özer, M., Yılmaz, F., Erer, H., Kani, İ, Bekaroğlu, Ö: Synthesis, characterization and catalytic activity of novel Co(II) and Pd(II)-perfluoroalkylphthalocyanine in fluorous biphasic system; benzyl alcohol oxidation. Appl. Organomet. Chem. 23, 55–61 (2009)

    Article  Google Scholar 

  15. Makinde, Z.O., Louzada, M., Mashazi, P., Nyokong, T., Khene, S.: Electrocatalytic behaviour of surface confined pentanethio cobalt(II) binuclear phthalocyanines towards the oxidation of 4-chlorophenol. Appl. Surf. Sci. 425, 702–712 (2017)

    Article  CAS  Google Scholar 

  16. Saka, E.T., Caglar, Y.: New Co(II) and Cu(II) phthalocyanine catalysts reinforced by long alkyl chains for the degradation of organic pollutants. Catal. Lett. 147, 1471–1477 (2017)

    Article  CAS  Google Scholar 

  17. Sorokin, A.B.: Phthalocyanine metal complexes in catalysis. Chem. Rev. 113, 8152–8192 (2013)

    Article  CAS  Google Scholar 

  18. L’Hera, M., Göktug, Ö, Durmuş, M., Ahsen, V.: A water soluble zinc phthalocyanine: physicochemical, electrochemical studies and electropolymerization. Electrochim. Acta 213, 655–662 (2016)

    Article  Google Scholar 

  19. Bıyıklıoğlu, Z., Durmuş, M., Kantekin, H.: Tetra-2-[2-(dimethylamino)ethoxy]ethoxy substituted zinc phthalocyanines and their quaternized analoques: Synthesis, characterization, photophysical and photochemical properties. J. Photochem. Photobiol. A 222, 87–96 (2011)

    Article  Google Scholar 

  20. Bıyıklıoğlu, Z., Çakır, V., Çakır, D., Kantekin, H.: Crown ether-substituted water soluble phthalocyanines and their aggregation, electrochemical studies. J. Organomet. Chem. 749, 18–25 (2014)

    Article  Google Scholar 

  21. Bıyıklıoğlu, Z., Kantekin, H., Acar, I.: The synthesis and characterization of new organosoluble long chain-substituted metal-free and metallophthalocyanines by microwave irradiation. Inorg. Chem. Commun. 11, 1448–1451 (2008)

    Article  Google Scholar 

  22. Acar, İ, Kantekin, H., Bıyıklıoğlu, Z.: The synthesis, using microwave irradiation and characterization of novel, metal-free and metallophthalocyanines. J. Organomet. Chem. 695, 151–155 (2010)

    Article  CAS  Google Scholar 

  23. Bıyıklıoğlu, Z., Güner, E.T., Topçu, S., Kantekin, H.: Synthesis, characterization and electrochemistry of a new organosoluble metal-free and metallophthalocyanines. Polyhedron 27, 1707–1713 (2008)

    Article  Google Scholar 

  24. Gök, H.Z., Kantekin, H., Gök, Y., Herman, G.: The synthesis and characterization of novel metal-free and metallophthalocyanines bearing four 27-membered dioxadiazapentathia macrocycles. Dyes Pigm. 74, 699–705 (2007)

    Article  Google Scholar 

  25. Sorokin, A.B.: Phthalocyanine metal complexes in catalysis. Chem. Rev. 113, 8152 – 8191 (2013)

    Article  CAS  Google Scholar 

  26. Isci, Ü, Dumoulin, F., Sorokin, A.B., Ahsen, V.: N-bridged dimers of tetrapyrroles complexed by transition metals: syntheses, characterization methods, and uses as oxidation catalysts. Turk. J. Chem. 38, 923–949 (2014)

    Article  Google Scholar 

  27. Cimen, Y., Türk, H.: Oxidation of 2,3,6-trimethylphenol with potassium peroxymonosulfate catalyzed by iron and cobalt phthalocyanine tetrasulfonates in a methanol-water mixture. Appl. Catal. A 340, 52–58 (2008)

    Article  CAS  Google Scholar 

  28. Günay, T., Cimen, Y.: Degradation of 2,4,6-trichlorophenol with peroxymonosulfate catalyzed by soluble and supported iron porphyrins. Environ. Pollut. 231, 1013–1020 (2017)

    Article  Google Scholar 

  29. Kamıloglu, A.A., Acar, I., Bıyıklıoglu, Z., Saka, E.T.: Peripherally tetra-{2-(2,3,5,6-tetrafluorophenoxy)ethoxy} substituted cobalt(II), iron(II) metallophthalocyanines: synthesis and their electrochemical, catalytic activity studies. J. Organomet. Chem. 828, 59–67 (2017)

    Article  Google Scholar 

  30. Cakir, V., Cakir, D., Göksel, M., Durmus, M., Bıyıklıoglu, Z., Kantekin, H.: Synthesis, photochemical, bovine serum albumin and DNA binding properties of tetrasubstituted zinc phthalocyanines and their water soluble derivatives. J. Photochem. Photobiol. A 299, 138–151 (2015)

    Article  CAS  Google Scholar 

  31. Demirbas, U., Akcay, H.T., Koca, A., Kantekin, H.: Synthesis, characterization and investigation of electrochemical and spectroelectrochemical properties of peripherally tetra 4-phenylthiazole-2-thiol substituted metal-free, zinc(II), copper(II) and cobalt(II) phthalocyanines. J. Mol. Struct. 1141, 643–649 (2017)

    Article  CAS  Google Scholar 

  32. Dube, E., Nwaji, N., Oluwole, D.O., Mack, J., Nyokong, T.: Investigation of photophysicochemical properties of zinc phthalocyanines conjugated to metallic nanoparticles. J. Photochem. Photobiol. A 349, 148–161 (2017)

    Article  CAS  Google Scholar 

  33. Acar, I., Bayrak, R., Saka, E.T., Bıyıklıoglu, Z., Kantekin, H.: Novel metal-free, metallophthalocyanines and their quaternized derivatives: synthesis, spectroscopic characterization and catalytic activity of cobalt phthalocyanine in 4-nitrophenol oxidation. Polyhedron 50, 345–353 (2013)

    Article  CAS  Google Scholar 

  34. Saka, E.T., Bıyıklıoğlu, Z., Kantekin, H., Kani, İ: Synthesis, characterization and catalytic activity of peripherally tetra-substituted Co(II) phthalocyanines for cyclohexene oxidation. Appl. Organomet. Chem. 27, 59–67 (2013)

    Article  CAS  Google Scholar 

  35. Kopkallı, Y.T., Türk, H.: Catalysis of autoxidation of 2,6-di-tert-butylphenol in water by metallophthalocyanine tetrasulfonates bound to polyelectrolyte supports. Turk. J. Chem. 20, 54–61 (1996)

    Google Scholar 

  36. Colomba, C., Kudrik, E.V., Afanasiev, P., Sorokin, A.B., Catalysis Today, 235, 14 (2014)

  37. Kothari, V.M., Tazuma, J.J.: Selective autoxidation of some phenols using salcomines and metal phthalocyanines. J. Catal. 41, 180–189 (1976)

    Article  CAS  Google Scholar 

  38. Meunier, B., Sorokin, A.B.: Oxidation of pollutants catalyzed by metallophthalocyanines. Acc. Chem. Res. 30, 470–476 (1997)

    Article  CAS  Google Scholar 

  39. Hadasch, A., Sorokin, A.B., Rabion, A., Meunier, B.: Sequential addition of H2O2, pH and solvent effects as key factors in the oxidation of 2,4,6-trichlorophenol catalyzed by iron tetrasulfophthalocyanine. New J. Chem. 22, 45–51 (1998)

    Article  CAS  Google Scholar 

  40. Sanchez, M., Chap, N., Cazaux, J., Meunier, B.: Metallophthalocyanines linked to organic copolymers as efficient oxidative supported catalysts. Eur. J. Inorg. Chem. 7, 1775–1783 (2001)

    Article  Google Scholar 

  41. Agboola, B., Ozoemena, K.I., Nyokong, T.: Hydrogen peroxide oxidation of 2-chlorophenol and 2,4,5-trichlorophenol catalyzed by monomeric and aggregated cobalt tetrasulfophthalocyanine. J. Mol. Catal. A 227, 209–216 (2005)

    Article  CAS  Google Scholar 

  42. Ichinohe, T., Miyasaka, H., Isoda, A., Kimura, M., Hanabusa, K., Shirai, H.: Functional metallomacrocycles and their polymers, Part 37. Oxidative decomposition of 2,4,6-trichlorophenol by polymer-bound phthalocyanines. React. Funct. Polym. 43, 63–70 (2000)

    Article  CAS  Google Scholar 

  43. Pergrale, C., Sorokin, A.B.: CR Acad Sci Ser IIc: Chim 2000 pp:803–810

  44. Saka, E.T., Sarkı, G., Kantekin, H.: Facile synthesis of highly active Co(II) and Fe(II) phthalocyanine catalysts for aerobic oxidation of phenolic compounds. J. Coord. Chem. 68, 1132–1141 (2015)

    Article  CAS  Google Scholar 

  45. Di Paola, A., Augugliaro, V., Palmisano, L., Pantaleo, G., Savinov, E.: Heterogeneous photocatalytic degradation of nitrophenols. J. Photochem. Photobiol. A 155, 207–214 (2003)

    Article  Google Scholar 

  46. Türk, H., Cimen, Y.: Oxidation of 2,6-di-tert-butylphenol with tert-butylhydroperoxide catalyzed by cobalt(II) phthalocyanine tetrasulfonate in a methanol–water mixture and formation of an unusual product 4,4′-dihydroxy-3,3′,5,5′-tetra-tert-butylbiphenyl. J. Mol. Catal. A 234, 19–24 (2005)

    Article  Google Scholar 

  47. Kharasch, M.S., Joshi, B.S.: Base-catalyzed oxidations of hindered phenols. J. Org. Chem. 22, 1439 (1957)

    Article  CAS  Google Scholar 

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Acknowledgements

This study was supported by the Research Fund of Karadeniz Technical University, (Project No: 5302), Trabzon-Turkey.

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  1. Department of Chemistry, Faculty of Sciences, Karadeniz Technical University, 61080, Trabzon, Turkey

    Ece Tugba Saka

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Correspondence to Ece Tugba Saka.

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Saka, E.T. Preparation, characterization of new Co(II) and Cu(II) phthalocyanines and their catalytic performances in aerobic oxidation of substituted phenols. J Incl Phenom Macrocycl Chem 91, 61–69 (2018). https://doi.org/10.1007/s10847-018-0800-6

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