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Encapsulation of Co phthalocyanine in alumina-pillared clays and their characterization

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Clays and Clay Minerals

Abstract

Alumina-pillared montmorillonite clays (Al-PILC), prepared under ultrasonic (US) agitation and normal stirring (S) methods, have been used as a host material to encapsulate Co phthalocyanine (CoPc) complex. The amount of Co varies from 0.27 to 1.48 wt.% in the samples, depending on the input concentration of Co. Powder X-ray diffraction and other characterization techniques reveal that the structure of Al-PILC remains intact after the incorporation of the complex into the pores through a pyridine solution of the complex by ultrasonic agitation. A substantial decrease in the BET surface area and total pore volume of Al-PILC points to the occupation of the CoPc moieties within the porous structure of the pillared clay. This is further supported by the observation of a band at 1489 cm−1 in the Fourier transform infrared (FTIR) spectra of the encapsulated samples. The FTIR and diffuse reflectance ultraviolet-visible (DRUV-Vis) spectral results indicate that the encapsulated CoPc complex in the clay matrix undergoes distortion in order to accommodate itself within the pores of the Al-PILC. The encapsulated samples prepared by ultrasonification show better dispersion of the complex than the samples prepared under normal stirring conditions. Compared to the ‘neat’ complex, the encapsulated samples (CoPc in Al-PILC) exhibit greater turnover in the test reaction of the oxidation of benzyl alcohol to benzaldehyde with tertbutyl hydroperoxide as the oxidant at 373 K. The method of preparation and consequent site isolation of CoPc in Al-PILC influence the catalytic activity.

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References

  • Armengol, E., Corma, A., Fortiés, V., García, H. and Prince, J. (1999) Cu2+-phthalocyanine and Co2+-perfluorophthalocyanine incorporated inside Y faujasite and mesoporous MCM-41 as heterogeneous catalysts for the oxidation of cyclohexane. Applied Catalysis A: General, 181, 305–312.

    Article  Google Scholar 

  • Balkus Jr., K.J. and Gabrielov, A.G. (1995) Zeolite encapsulated metal complexes. Journal of Inclusion Phenomena and Molecular Recognition in Chemistry, 21, 159–184.

    Google Scholar 

  • Bernstein, P.A. and Lever, A.B.P. (1992) Protonation of cobalt tetrapentoxyphthalocyanine as a function of oxidation state. Inorganica Chimica Acta, 198–200, 543–555.

    Article  Google Scholar 

  • Coudurier, G. and Lefebvre, F. (1994) Catalyst Characterization. Physical Techniques for Solid Materials. Plenum Press, New York, pp. 11–44.

    Google Scholar 

  • De Vos, D.E., Thibault-Starzyk, F., Knops-Gerrits, P.P., Parton, R.F. and Jacobs, P.A. (1994) A critical overview of the catalytic potential of zeolite supported metal complexes. Macromolecular Symposia, 80, 157–184.

    Article  Google Scholar 

  • Ferreira, R., Silva, M., Freire, C., Castro, B. and Figueiredo, J.L. (2000) Encapsulation of copper (II) complexes with pentadentate N3O2 Schiff base ligands derived from acetylacetone in NaX zeolite. Microporous Mesoporous Material, 38, 391–401.

    Article  Google Scholar 

  • Ferreira, R., Freire, C., Castro, B., Carvalho, A., Pires, J. and Carvalho, M.B. (2002) Encapsulation of copper (II) complexes with pentadentate N3O2 Schiff base ligands in a pillared layered clay. European Journal of Inorganic Chemistry, 11, 3032–3038.

    Article  Google Scholar 

  • Figueras, F. (1988) Pillared clays as catalysts. Catalysis Review Science and Engineering 30, 457–499.

    Article  Google Scholar 

  • Herron, N. (1986) A cobalt oxygen carrier in zeolite Y. A molecular ‘ship in a bottle’. Inorganic Chemistry, 25, 4714–4717.

    Article  Google Scholar 

  • Jacob, C.R., Varkey, S.P. and Ratnasamy, P. (1998) Zeolite-encapsulated copper (X2-salen) complexes. Applied Catalysis A: General, 168, 353–364.

    Article  Google Scholar 

  • Janczak, J. and Kubiak, R. (2003) Stereochemistry and properties of the M (II)-N(py) coordination bond in the low-spin dipyridinated iron (II) and cobalt (II) phthalocyanines. Inorganica Chimica Acta, 342, 64–76.

    Article  Google Scholar 

  • Katdare, S.P., Ramaswamy, Veda and Ramaswamy, A.V. (1997) Intercalation of Al oligomers into Ca2+-montmor-illonite using ultrasonics. Journal of Material Chemistry, 7, 2197–2199.

    Article  Google Scholar 

  • Katdare, S.P., Ramaswamy, Veda and Ramaswamy, A.V. (1999) Ultrasonication: a competitive method of intercalation for the preparation of alumina pillared montmorillonite catalyst. Catalysis Today, 49, 313–320.

    Article  Google Scholar 

  • Kobayashi, T., Kurokawa, F., Uyeda, N. and Suito, E. (1970) The metal-ligand vibrations in the infrared spectra of various metal phthalocyanines. Spectrochimica Acta, 20, 1305–1311.

    Article  Google Scholar 

  • Parton, R, De Vos, D. and Jacobs, P.A. (1992) Pp. 555–578 in: Microporous Solids: Synthesis, Structure and Reactivity. Proceedings of the NATO Advanced Study Institute on Zeolite (E.G. Derouane, F. Lemos, C. Naccache and F.R. Riberio, editors). Kluwer, Dordrecht, The Netherlands.

    Google Scholar 

  • Pinnavaia, T.J., Tzou, M.S., Landau, S.D. and Raythatha, R.H. (1984) On the pillaring and delamination of smectite clay catalysts by polyoxy cations of aluminium. Journal of Molecular Catalysis, 27, 195–212.

    Article  Google Scholar 

  • Raja, R. and Ratnasamy, P. (1996) Selective oxidation with copper complexes incorporated in molecular sieves. Studies in Surface Science and Catalysis, 101, 181–190.

    Article  Google Scholar 

  • Ramaswamy, Veda, Sivarama Krishnan, M. and Ramaswamy, A.V. (2002) Immobilization and characterization of copper chlorophthalocyanine on alumina-pillared montmorillonite. Journal of Molecular Catalysis A: Chemical, 181, 81–89.

    Article  Google Scholar 

  • Rollmann, L.D. and Iwamoto, R.T. (1968) Electrochemistry, electron paramagnetic resonance and visible spectra of cobalt, nickel, copper and metal-free phthalocyanines in dimethyl sulfoxide. Journal of the American Chemical Society, 90, 1455–1463.

    Article  Google Scholar 

  • Sing, K.S.W. (1970) Surface Area Determination (D.H. Everett and B.H. Ottewill, editors). Butterworths, London, p. 25.

  • Stymne, B., Sauvage, F.X. and Wettermark, G. (1980) A spectroscopic study of complexation of phthalocyanines with pyridine. Spectrochimica Acta, 36A, 397–402.

    Article  Google Scholar 

  • Zhan, H., Wang, M. and Chen, W. (2002) In situ synthesis of metallophthalocyanines in inorganic matrix. Materials Letters, 55, 97–103.

    Article  Google Scholar 

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  1. Catalysis Division, National Chemical Laboratory, Pune, 411 008, India

    Neelam Jagtap & Veda Ramaswamy

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  1. Neelam Jagtap
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  2. Veda Ramaswamy
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Correspondence to Veda Ramaswamy.

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Jagtap, N., Ramaswamy, V. Encapsulation of Co phthalocyanine in alumina-pillared clays and their characterization. Clays Clay Miner. 54, 54–61 (2006). https://doi.org/10.1346/CCMN.2006.0540107

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  • DOI: https://doi.org/10.1346/CCMN.2006.0540107

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