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Preparation and Characterization of Montmorillonites Pillared by Cationic Silicon Species

Abstract

The hydrolysis of 2-(2-trichlorosilylethyl)pyridine (TCSEP) or 3-aminopropyltrimethoxysilane (APTMS) yields a complex mixture of oligomers, the composition of which is a function of time. 29Si NMR measurements show that the same oligosilsesquioxanes can be obtained from both compounds after prolonged hydrolysis. Ion exchange by montmorillonite with the pillaring solution obtained from TCSEP results in partial intercalation, with a noticeable fraction of the clay exchange sites occupied by protons not by the Si cationic species. Calcination of this pillared clay results in a mixture of phases showing 1.86 or 1.56 nm basal spacings. Pillaring of the same montmorillonite by the solution obtained by partial hydrolysis of APTMS results in a homogeneous solid with a basal spacing of 2 nm, which reduces to 1.65 nm upon calcination above 773 K. The microporous volume (pores < 1 nm) of these Si-clays, determined after calcination at 773 K, 0.15 ml/g for the PILC obtained from TCSEP, and 0.186 ml/g for the PILC obtained from APTMS is comparable to that measured for Al or Zr pillared clays. A better thermal stability is observed for the clay pillared by APTMS, which retains a large microporosity (0.167 ml/g) up to 973 K in air. These Si-pillared clays show a small number of weakly acidic sites and some strongly acidic sites retaining ammonia up to 723 K, which are most likely localized on the clay layers.

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References

  • Burch, R. (1988) Pillared clays: Catalysis Today 2, 185–366.

    Article  Google Scholar 

  • Choudary, B. M., Valli, V. L. K., and Durga Prasad, A. (1990a) A new vanadium-pillared montmorillonite catalyst for the regioselective epoxidation of allylic alcohols: J. Chem. Soc. Chem. Commun., 721–722.

    Google Scholar 

  • Choudary, B. M., Valli, V. L. K., and Durga Prasad, A. (1990b) An improved asymmetric epoxidation of allyl alcohols using titanium-pillared montmorillonite as a heterogeneous catalyst: J. Chem. Soc. Chem. Commun., 1186–1187.

    Google Scholar 

  • Endo, T., Mortland, M. M., and Pinnavaia, T. J. (1980) Intercalation of silica in smectite: Clays & Clay Minerals 28, 105–110.

    Article  Google Scholar 

  • Farfan Torres, E. M., Grange, P., and Delmon, B. (1988) Preparacion y caracterizacion de montmorillonitas intercaladas con silicio: Adas XI Simp. Ibero Amer. Catalisis, Guanajuato (Mexico) 1988, F. Cossio, O. Bermudez, G. del Angel, and R. Gomez, eds., IMP-SIC, 271–277.

    Google Scholar 

  • Fetter, G., Tichit, D., Massiani, P., Dutartre, R., and Figueras, F. (1990) Preparation and characterization of montmorillonite pillared by cationic silicon species: in Proceedings 12th Ibero-American Symp. Catalysis, Rio de Janeiro (Brasil), 1990: Instituto Brasileiro Petroleo Ed, 448–457.

    Google Scholar 

  • Figueras, F. (1988) Pillared clays as catalysts: Catal. Rev. Sci-Eng. 30, 457–499.

    Article  Google Scholar 

  • Figueras, F., Klapyta, Z., Massiani, P., Mountassir, Z., Tichit, D., Fajula, F., Gueguen, C., Bosquet, J., and Auroux, A. (1990) Use of competitive ion exchange for intercalation of montmorillonite with hydroxy-aluminium species: Clays & Clay Minerals 38, 257–264.

    Article  Google Scholar 

  • Figueras, F., Mattrod Bashi, A., Fetter, G., Thrierr, A., and Zanchetta, J. V. (1989) Preparation and thermal properties of Zr-intercalated clays: J. Catal. 119, 91–96.

    Article  Google Scholar 

  • Guan, J., Min Enze, and Yu. Z. (1986) A class of pillared interlayered clay molecular sieve with regularly interstratified mineral structure: Eur. Pat. 0 197 012, 31 pp.

    Google Scholar 

  • Johnson, I. J., Werpy, T. A., and Pinnavaia, T. J. (1988) Tubular silicate-layered silicate intercalation compounds: A new family of pillared clays: J. Amer. Chem. Soc. 110, 8545–8547.

    Article  Google Scholar 

  • Kintzinger, J. P. and Marsmann, H. (1981) Oxygen-17 and Silicon-29 in NMR, Basic Principles and Progress, Vol. 17, P. Diehl, E. Fluck, and R. Klosfeld, eds., Springer Verlag, Berlin, 235 pp.

  • Lewis, R. M., Ott, K. C., and Van Santen, R. A. (1985) Silica-clay complexes: US Pat. 4,510,257, 14 pp.

    Google Scholar 

  • Lippmaa, E., Mägi, M., Samoson, A., Engelhardt, G., and Grimmer, A. R. (1980) Structural studies of silicates by solid-state high resolution 29Si NMR: J. Amer. Chem. Soc. 102, 4889–4893.

    Article  Google Scholar 

  • Matsuda, T., Matsukata, M., Kikuchi, E., and Morita, Y. (1986) Reaction of 1,2,4-trimethylbenzene and methanol on montmorillonite catalysts pillared by aluminium hy-droxyl complexes: Appl. Catal. 21, 297–306.

    Article  Google Scholar 

  • Moini, A. and Pinnavaia, T. J. (1988) A new strategy for the synthesis of pillared clays with super galleries: Direct intercalation of metal oxide sols (DIMOS): Solid Slate Ionics 26, 119–123.

    Article  Google Scholar 

  • Occelli, M. L., Innes, R. A., Hwu, F. S. S.( and Hightower, J. W. (1985) Sorption and catalysis on sodium-mont-morillonite interlayered with aluminum oxide clusters: Appl. Catal. 14, 69–82.

    Article  Google Scholar 

  • Pinnavaia, T. J. (1992) Approaches to the synthesis of supergallery pillared clays: in Expanded Clays and Other Microporous Solids, M. L. Occelli and H. E. Robson, eds., Van Nostrand Reinhold, New York, 1–12.

    Google Scholar 

  • Pinnavaia, T. J., Mortland, M. M., and Endo, T. (1983) Silica-clay complexes: U.S. Pat. 4,367,163, 9 pp.

    Google Scholar 

  • Pinnavaia, T. J., Tzou, M.S., and Landau, S.D. (1988) New chromia pillared clay catalysts: J. Amer. Chem. Soc. 107, 4783–4785.

    Article  Google Scholar 

  • Plee, D., Gatineau, L., and Fripiat, J. J. (1987) Pillaring processes of smectites with and without tetrahedral substitution: Clays & Clay Minerals 35, 81–88.

    Article  Google Scholar 

  • Sprung, R., Davis, M. E., Kauffman, J. S., and Dybowski, C. (1990) Pillaring of magadiite with silicate species: Ind. Eng. Chem. Res. 29, 213–220.

    Article  Google Scholar 

  • Tichit, D., Fajula, F., Figueras, F., Ducourant, B., Mascherpa, G., Gueguen, C., and Bosquet, J. (1988) Sintering of montmorillonites pillared by hydroxy-aluminium species: Clays & Clay Minerals 36, 369–375.

    Article  Google Scholar 

  • Vaughan, D. E. W., Lussier, R. J., and Magee, J. S. (1979) Pillared interlayered clay materials useful as catalysts and sorbents: U.S. Pat. 4,176,090, 14 pp.

    Google Scholar 

  • Vaughan, D. E. W., Lussier, R. J., and Magee, J. S. (1981) Stabilized pillared clays: U.S. Pat. 4,248,739, 4 pp.

    Google Scholar 

  • Voronkov, A. G. and Laurentyev, V. I. (1982) Polyhedral oligosilsesquioxanes and their homo derivatives: in Topics in Current Chemistry, Vol. 102, Springer Verlag, Berlin, 199–236.

    Article  Google Scholar 

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Fetter, G., Tichit, D., Massiani, P. et al. Preparation and Characterization of Montmorillonites Pillared by Cationic Silicon Species. Clays Clay Miner. 42, 161–169 (1994). https://doi.org/10.1346/CCMN.1994.0420206

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  • DOI: https://doi.org/10.1346/CCMN.1994.0420206

Key Words

  • Cationic silicon complexes
  • Intercalation
  • Microporosity
  • Montmorillonite
  • Oligosilsesquioxanes
  • Pillared clays
  • Thermal stability