Hostname: page-component-78c5997874-lj6df Total loading time: 0 Render date: 2024-11-05T14:45:01.850Z Has data issue: false hasContentIssue false
  • English
  • Français

The acidity of trivalent cation-exchanged montmorillonite. Temperature-Programmed desorption and infrared studies of pyridine and n-butylamine

Published online by Cambridge University Press:  09 July 2018

C. Breen ,
A. T. Deane  and
J. J. Flynn
C. Breen
Affiliation:
School of Chemical Sciences, National Institute for Higher Education, Glasnevin, Dublin 9, Eire
A. T. Deane
Affiliation:
School of Chemical Sciences, National Institute for Higher Education, Glasnevin, Dublin 9, Eire
J. J. Flynn
Affiliation:
School of Chemical Sciences, National Institute for Higher Education, Glasnevin, Dublin 9, Eire
Get access Rights & Permissions [Opens in a new window]

Abstract

Temperature-programmed desorption (TPD) and IR spectroscopy were used to characterize the number and strength of acid sites in Al3+-, Cr3+- and Fe3+-exchanged montmorillonite. The bases pyridine and n-butylamine occupied three different sites in the interlamellar space: (i) physisorbed base, (ii) base bound to Lewis acid sites, and (iii) protonated base. TPD profiles for pyridine were characterized by maxima at 40°, 150° and 340°C, whilst those for n-butylamine occurred at 30°, 200° and 410°C. The Al3+- and Cr3+-exchanged forms were stable up to pretreatment temperatures of 300°C, but the Fe3+-form required > 3 day exposure to base vapour to re-establish the high-temperature desorption peak. Variable-temperature IR studies showed that the number of Brönsted-bound pyridine molecules increased with increased outgassing temperature.

Type
Research Article
Information
Clay Minerals , Volume 22 , Issue 2 , June 1987 , pp. 169 - 178
Copyright
Copyright © The Mineralogical Society of Great Britain and Ireland 1987

Access options

Get access to the full version of this content by using one of the access options below. (Log in options will check for institutional or personal access. Content may require purchase if you do not have access.)

References

Adams, J.M., Reid, P.I. & Walters, M. J. (1977) The cation exchange capacity of clays. School Sci. Rev. 59, 722– 724.Google Scholar
Adams, J.M., Clement, D.E. & Graham, S.H. (1981) Low temperature reaction of alcohols to form t-butyl ethers using clay catalysts. J. Chem. Res. 254-255.Google Scholar
Adams, J.M. & Breen, C. (1982) The temperature stability of the ⩾19·4 Å intercalates of the Na+- montmorillonite: pyridine/water system and the rate of their conversion to the 14·8 A intercalate. J. Colloid Interface Sci. 89, 272–289.Google Scholar
Adams, J.M., Bylina, A. & Graham, S.H. (1982a) Conversion of 1-hexene to di-2-hexylether using a Cu2+- smectite catalyst. J. Catal. 75, 190–195.Google Scholar
Adams, J.M., Clement, D.E. & Graham, S.H. (1982b) Synthesis of methyl t-butyl ether from methanol and isobutene using a clay catalyst. Clays Clay Miner. 30, 129–134.CrossRefGoogle Scholar
Atkins, M.P., Smith, D.J.H. & Westlake, D.J. (1983) Montmorillonite catalysts for ethylene hydration. Clay Miner. 18, 423–429.CrossRefGoogle Scholar
Ballantine, J.A., Davies, M.E., Purnell, J.H., Rayanakorn, M. & Thomas, J.M. (1981a) Chemical conversion using sheet silcates: Novel intermolecular dehydrations of alcohols to form ethers and polymers. J.C.S. Chem. Comm. 427-428.Google Scholar
Ballantine, J.A., Davies, M., Purnell, J.H., Rayanakorn, M., Thomas, J.M. & Williams, K.J. (1981b) Chemical conversion using sheet silicates: Facile ester synthesis by direct addition of acids to alkenes. J.C.S. Chem. Comm. 8-9.CrossRefGoogle Scholar
Ballantine, J.A., Purnell, J.H., Rayanakorn, M., Williams, K.J. & Thomas, J.M. (1985) Organic reactions catalysed by sheet silicates: intermolecular elimination of ammonia from primary amines. J. Mol. Catal. 30, 373–388.Google Scholar
Bennet, H. & Reed, R.A. (1971) Chemical Methods of Silicate Analysis. Academic Press, London, pp. 71–79.Google Scholar
Burgess, J. (1978) Metal Ions in Solution. John Wiley and Sons, London, pp. 259–265.Google Scholar
Gregory, R., Smith, D.J.H. & Westlake, D.J. (1983) The production of ethyl acetate and acetic acid using clay catalysts. Clay Miner. 18, 431–435.Google Scholar
Lercher, J.A., Ritter, G. & Winek, H. (1985) Acid-base properties of silica-alumina mixed oxides derived from NaX zeolites. J. Colloid Interface Sci. 106, 215–221.CrossRefGoogle Scholar
Morishige, K., Kittaka, S., Katsuragi, S. & Morimoto, T. (1982) Thermal desorption and infra red studies of ammonia, amines and pyridines chemisorbed on chromic oxide. J. Chem. Soc., Faraday Trans. 1 78, 2947– 2957.Google Scholar
Morishige, K., Kittaka, S. & Takao, S. (1984) Thermal desorption and infra red studies of methylamines adsorbed on dehydrated alkaline-earth-metal X zeolites. J. Chem. Soc., Faraday Trans. 1 80, 993–1003.Google Scholar
Mortland, M.M. (1968) Protonation of compounds on clay mineral surfaces: 9th lnt. Congr. Soil Sci. 1, 691– 699.Google Scholar
Mortland, M.M. & Raman, K.V. (1968) Surface acidity of smectites in relation to hydration, exchangeable cation and structure. Clays Clay Miner. 16, 393–398.Google Scholar
Noller, H. & Ritter, G. (1984) Temperature-programmed desorption of methanol, ethanol, propan-l-ol and propan-2-ol on silica-magnesia mixed oxides. J. Chem. Soc., Faraday Trans. 1 80, 275–283.Google Scholar
Occelli, M.L. & Lester, J.E. (1984) Nature of active sites and coking reactions in a a pillared clay mineral. Ind. Eng. Chem. Res. and Dev. 24, 27–32.Google Scholar
Plee, D., Borg, F., Gatineau, L. & Fripiat, J.J. (1985) High resolution solid state 27Al and 29Si nuclear magnetic resonance study of pillared clays. J. Am. Chem. Soc. 107, 2362–2369.Google Scholar
Ritter, A., Noller, H. & Lercher, J.A. (1982) Acetonitrile on silica-magnesia mixed oxides. Temperature-programmed desorption and infra-red study. J. Chem. Soc., Faraday Trans. 1 78, 2239–2249.Google Scholar
Russell, J.D. (1965) Infra-red study of the reactions of ammonia with montmorillonite and saponite. Trans. Farad. Soc. 61, 2284–2294.Google Scholar
Tanabe, K. (1970) Solid Acids and Bases - Their Catalytic Properties. Academic Press, New York.Google Scholar
Tennakoon, D.T.B., Schogl, R., Rayment, T., Klinowski, J., Jones, W. & Thomas, J.M. (1983) The characterization of clay-organic systems. Clay Miner. 18, 357–371.Google Scholar
Tennakoon, D.T.B., Jones, W. & Thomas, J . M . (1986) Structural aspects of metal-oxide pillared sheet silicates. An investigation by magic angle spinning nuclear magnetic resonance, fourier transform infra-red spectroscopy and powder x-ray diffraction. J. Chem. Soc., Faraday Trans. 1 82, 3081–3095.Google Scholar
Thomas, J.M. (1982) Sheet silicate intercalates: New agents for unusual chemical conversions. Pp 56–97 in: Intercalation Chemistry (Whittingham, M. S. and Jacobson, A. J., editors). Academic Press, New York.Google Scholar
van Olphen, H. & Deeds, C.T. (1961) Stepwise hydration of clay-organic complexes. Nature 194, 176–177.CrossRefGoogle Scholar
Ward, J.W. (1968) Spectroscopic study of the surface of zeolite Y: The adsorption of pyridine. J. Colloid Interface Sci. 28, 269–277.Google Scholar