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Deintercalation of Hydrazine-Intercalated Low-Defect Kaolinite

Published online by Cambridge University Press:  28 February 2024

Ray L. Frost ,
J. Theo Kloprogge ,
Janos Kristof  and
Erzsebet Horvath
Ray L. Frost*
Affiliation:
Centre for Instrumental and Developmental Chemistry, Queensland University of Technology, 2 George Street, GPO Box 2434, Brisbane, Q 4001, Australia
J. Theo Kloprogge
Affiliation:
Centre for Instrumental and Developmental Chemistry, Queensland University of Technology, 2 George Street, GPO Box 2434, Brisbane, Q 4001, Australia
Janos Kristof
Affiliation:
Department of Analytical Chemistry, University of Veszprem, H 8201 Veszprem, PO Box 158, Hungary
Erzsebet Horvath
Affiliation:
Research Group for Analytical Chemistry, Hungarian Academy of Sciences, H 8201 Veszprem, PO Box 158, Hungary
*
E-mail of corresponding author: r.frost@qut.edu.au
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Abstract

The deintercalation of a low-defect kaolinite intercalated with hydrazine was studied by X-ray diffraction, diffuse reflectance infrared spectroscopy (DRIFT), and Raman microscopy over 30 d. X-ray diffraction showed that the kaolinite was fully intercalated. More than 120 h were required for the hydrazine-intercalate to decompose. The Raman spectra of the hydrazine intercalate showed only a single band at 3620 cm−1, which was attributed to the innerhydroxyl group. Upon deintercalation, additional Raman bands were observed at 3626 and 3613 cm−1. These bands decreased in intensity with further deintercalation. As deintercalation proceeded, the bands assigned to the inner-surface hydroxyl groups at 3695, 3682, 3670, and 3650 cm−1 occurred and increased in intensity. DRIFT spectra showed two bands at 3620 and 3626 cm−1 for the fully intercalated kaolinite only. Upon deintercalation, an additional band assigned to intercalated water was observed at 3599 cm−1 and increased in intensity at the expense of the 3626-cm−1 band. Bands attributed to the innersurface hydroxyl groups increased in intensity with deintercalation. Both the Raman and DRIFT spectra showed complexity in the NH-stretching region with two sets of NH-symmetric and antisymmetric stretching bands. Deintercalation was followed by the loss of intensity of these bands. Significant changes were also observed in the hydroxyl deformation and water-bending modes as a result of deintercalation. A model of hydrazine intercalation of kaolinite based on the insertion of a hydrazine-water unit is proposed. The hydrated end of the hydrazine molecule hydrogen bonds with the innersurface hydroxyl groups resulting in the formation of a band at 3626 cm−1 in the DRIFT spectra.

Keywords

HydrazineHydrogen BondingHydroxyl GroupsIntercalation of KaolinitePowder X-ray DiffractionRaman Microscopy
Type
Research Article
Information
Clays and Clay Minerals , Volume 47 , Issue 6 , December 1999 , pp. 732 - 741
Copyright
Copyright © 1999, The Clay Minerals Society

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References

Barrios, J. Plançon, A. Cruz, M.I. and Tchoubar, C., 1977 Qualitative and quantitative study of stacking faults in a hydrazine treated kaolinite—relationship with the infrared spectra Clays and Clay Minerals 25 422–429 10.1346/CCMN.1977.0250608.CrossRefGoogle Scholar
Costanzo, P.M. and Giese, R.F., 1986 Ordered halloysite: Dimethyl sulfoxide intercalate Clays and Clay Minerals 34 105–107 10.1346/CCMN.1986.0340115.CrossRefGoogle Scholar
Costanzo, P.M. and Giese, R.F., 1990 Ordered and disordered organic intercalates of 8.4 A synthetically hydrated kaolinite Clays and Clay Minerals 38 160–170 10.1346/CCMN.1990.0380207.CrossRefGoogle Scholar
Costanzo, P.M. Giese, R.F. and Clemency, C.V., 1984 Synthesis of a 10 A hydrated kaolinite Clays and Clay Minerals 32 29–35 10.1346/CCMN.1984.0320104.CrossRefGoogle Scholar
Cruz, M. Laycock, A. White, J.L. and Heller, L., 1969 Perturbation of the OH groups in intercalated kaolinite donor-accepted complexes Proceedings of the International Clay Conference, 1969, Tokyo, Volume 1 Jerusalem Israel University Press 775–789.Google Scholar
Cruz, M. Jacobs, H. and Fripiat, J.J., 1973 The nature of interlayer bonding in kaolin minerals Proceedings of the International Clay Conference, 1972 35–46.Google Scholar
Durig, J.R. Bush, S.E. and Mercer, E.E., 1966 Vibrational spectrum of hydrazine-d4 and a Raman study of hydrogen bonding in hydrazine Journal of Chemical Physics 44 4238–4247 10.1063/1.1726612.CrossRefGoogle Scholar
Frost, R.L., 1998 Hydroxyl deformation in kaolins Clays and Clay Minerals 46 280–289 10.1346/CCMN.1998.0460307.CrossRefGoogle Scholar
Frost, R.L. Tran, T.T. and Kristof, J., 1997 Intercalation of an ordered kaolinite — a Raman microscopy study Clay Minerals 32 587–596 10.1180/claymin.1997.032.4.09.CrossRefGoogle Scholar
Frost, R.L. Kristof, J. Paroz, G.N. Tran, T.H. and Kloprogge, J.T., 1998 The role of water in the intercalation of kaolinite with potassium acetate Journal of Colloid and Interface Science 204 227–236 10.1006/jcis.1998.5604.CrossRefGoogle ScholarPubMed
Johnston, C.T. and Stone, D.A., 1990 Influence of hydrazine on the vibrational modes of kaolinite Clays and Clay Minerals 38 121–128 10.1346/CCMN.1990.0380202.CrossRefGoogle Scholar
Ledoux, R.L. and White, J.L., 1966 Infrared studies of hydrogen bonding interaction between kaolinite surfaces and intercalated potassium acetate, hydrazine, formamide and urea Journal of Colloid Interface Science 21 127–152 10.1016/0095-8522(66)90029-8.CrossRefGoogle Scholar
Olejnik, S. Posner, A.M. and Quirk, J.P., 1970 The intercalation of polar organic compounds into kaolinite Clay Minerals 8 421–434 10.1180/claymin.1970.008.4.05.CrossRefGoogle Scholar
Tunney, J. and Detellier, C., 1994 Preparation and characterisation of an 8.4 A hydrate of kaolinite Clays and Clay Minerals 42 473–476 10.1346/CCMN.1994.0420414.CrossRefGoogle Scholar
Wada, K., 1961 Lattice expansion of kaolin minerals by treatment with potassium acetate American Mineralogist 46 78–91.Google Scholar
Weiss, A. Thielepape, W. Ritter, W. Schafer, H. and Goring, G., 1963 Zur Kenntnis von Hydrazin-Kaolinit Anorganische Allgemeine Chemie 320 183–204 10.1002/zaac.19633200122.CrossRefGoogle Scholar
Weiss, A. Thielepape, W. Orth, H., Heller, L. and Weiss, A., 1966 Neue Kaolin-it-Einlagerungsverbindungen Proceedings of the International Clay Conference Jerusalem, I Jerusalem Israel University Press 277–293.Google Scholar