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The Effect of Structural Order on Nanotubes Derived From Kaolin-Group Minerals

Published online by Cambridge University Press:  01 January 2024

Jakub Matusik ,
Adam Gaweł ,
Elżbieta Bielańska ,
Władysław Osuch  and
Krzysztof Bahranowski
Jakub Matusik*
Affiliation:
AGH University of Science and Technology, Faculty of Geology, Geophysics and Environmental Protection, al. Mickiewicza 30, 30-059 Krakow, Poland
Adam Gaweł
Affiliation:
AGH University of Science and Technology, Faculty of Geology, Geophysics and Environmental Protection, al. Mickiewicza 30, 30-059 Krakow, Poland
Elżbieta Bielańska
Affiliation:
Institute of Catalysis and Surface Chemistry, Polish Academy of Sciences, ul. Niezapominajek 8, 30-239 Krakow, Poland
Władysław Osuch
Affiliation:
AGH University of Science and Technology, Faculty of Metal Engineering and Industrial Computer Science, al. Mickiewicza 30, 30-059 Krakow, Poland
Krzysztof Bahranowski
Affiliation:
AGH University of Science and Technology, Faculty of Geology, Geophysics and Environmental Protection, al. Mickiewicza 30, 30-059 Krakow, Poland
*
* E-mail address of corresponding author: [email protected]
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Abstract

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Kaolin-group clay minerals can be modified to form nanotubular and mesoporous structures with interesting catalytic properties, but knowledge of the best methods for preparing these structures is still incomplete. The objective of this study was to investigate intercalation/deintercalation as a method for the delamination and rolling of kaolinite layers in relation to structural order. To prepare nanotubular material, kaolinites of different crystallinities and halloysite (all from Polish deposits) were chosen. The experimental procedure consisted of four stages: (1) preparation of a dimethyl sulfoxide precursor intercalate; (2) interlayer grafting with 1,3-butanediol; (3) hexylamine intercalation; and (4) deintercalation of amine-intercalated minerals using toluene as the solvent. Structural perturbations and changes in the morphology of the minerals were examined by X-ray diffraction, Fourier transform infrared spectroscopy, differential scanning calorimetry, and transmission electron microscopy (TEM). The number of rolled kaolinite layers depended heavily on the efficiency of the intercalation steps. An increase in the structural disorder and extensive delamination of the minerals subjected to chemical treatment were recorded. Kaolinite particles which exhibited tubular morphology or showed rolling effects were observed using TEM. The nanotubes formed were ∼30 nm in diameter, with their length depending on the particle sizes of the minerals.

Keywords

HalloysiteIntercalationKaoliniteNanotubesRollingStructural Order
Type
Research Article
Information
Clays and Clay Minerals , Volume 57 , Issue 4 , August 2009 , pp. 452 - 464
Copyright
Copyright © The Clay Minerals Society 2009

References

Aparicio, P. Galán, E. and Ferrell, R.E., 2006 A new kaolinite order index based on XRD profile fitting Clay Minerals 41 811–817 10.1180/0009855064140220.CrossRefGoogle Scholar
Bahranowski, K. Serwicka, E.M. Stoch, L. and Strycharski, P., 1993 On the possibility of removal of non-structural iron from kaolinite-group minerals Clay Minerals 28 379–391 10.1180/claymin.1993.028.3.04.CrossRefGoogle Scholar
Bates, T.F. Hildebrand, F.A. and Swineford, A., 1950 Morphology and structure of endellite and halloysite American Mineralogist 35 463–484.Google Scholar
Brigatti, M.F. Galán, E. Theng, B.K.G. and Lagaly, G., 2006 Structures and mineralogy of clay minerals Handbook of Clay Science. Developments in Clay Science 1 19–87 10.1016/S1572-4352(05)01002-0.CrossRefGoogle Scholar
Churchman, G.J. Whitton, J.S. Claridge, G.G.C. and Theng, B.K.G., 1984 Intercalation method using formamide for differentiating halloysite from kaolinite Clays and Clay Minerals 32 241–248 10.1346/CCMN.1984.0320401.CrossRefGoogle Scholar
Costanzo, P.M. Giese, RF Jr. and Lipsicas, M., 1984 Static and dynamic structure of water in hydrated kaolinites. I. The static structure Clays and Clay Minerals 32 419–428 10.1346/CCMN.1984.0320511.CrossRefGoogle Scholar
Deng, Y. White, G.N. and Dixon, J.B., 2002 Effect of structural stress on the intercalation rate of kaolinite Journal of Colloid and Interface Science 250 379–393 10.1006/jcis.2001.8208.CrossRefGoogle ScholarPubMed
Dong, W. Li, W. Yu, K. Krishna, K. Song, L. Wang, X. Wang, Z. Coppens, M.O. and Feng, S., 2003 Synthesis of silica nanotubes from kaolin clay Chemical Communications 11 1302–1303 10.1039/b300335c.CrossRefGoogle Scholar
Elbokl, T.A. and Detellier, C., 2006 Aluminosilicate nano-hybrid materials. Intercalation of polystyrene in kaolinite Journal of Physics and Chemistry of Solids 67 950–955 10.1016/j.jpcs.2006.01.008.CrossRefGoogle Scholar
Farmer, V.C. and Farmer, V.C., 1974 The layer silicates The Infrared Spectra of Minerals London Mineralogical Society 331–363 10.1180/mono-4.15.CrossRefGoogle Scholar
Farmer, V.C. and Russell, J.D., 1967 Infrared absorption spectrometry in clay studies Clays and Clay Minerals 15 121–142 10.1346/CCMN.1967.0150112.CrossRefGoogle Scholar
Gardolinski, J.E.F.C. and Lagaly, G., 2005 Grafted organic derivatives of kaolinite: I. Synthesis, chemical and rheological characterization Clay Minerals 40 537–546 10.1180/0009855054040190.CrossRefGoogle Scholar
Gardolinski, J.E.F.C. and Lagaly, G., 2005 Grafted organic derivatives of kaolinite: II. Intercalation of primary n-alkylamines and delamination Clay Minerals 40 547–556 10.1180/0009855054040191.CrossRefGoogle Scholar
Hayashi, S., 1997 NMR study of dynamics and evolution of guest molecules in kaolinite/dimethylsulfoxide intercalation compound Clays and Clay Minerals 45 724–732 10.1346/CCMN.1997.0450511.CrossRefGoogle Scholar
Hinckley, D.N., 1962 Variability in ‘Crystallinity’ values among the kaolin deposits of the coastal plain of Georgia and South Carolina Clays and Clay Minerals 11 229–235 10.1346/CCMN.1962.0110122.CrossRefGoogle Scholar
Hope, E.W. and Kittrick, J.A., 1964 Surface tension and the morphology of halloysite American Mineralogist 49 859–866.Google Scholar
Inagaki, S. Fukushima, Y. and Kuroda, K., 1993 Synthesis of highly ordered mesoporous materials from a layered polysilicate Journal of the Chemical Society, Chemical Communications 8 680 10.1039/c39930000680.CrossRefGoogle Scholar
Joussein, E. Petit, S. Churchman, J. Theng, B. Righi, D. and Delvaux, B., 2005 Halloysite clay minerals — areview Clay Minerals 40 383–426 10.1180/0009855054040180.CrossRefGoogle Scholar
Klapyta, Z. Fujita, T. and Iyi, N., 2001 Adsorption of dodecyl- and octadecyltrimethylammonium ions on a smectite and synthetic micas Applied Clay Science 19 5–10 10.1016/S0169-1317(01)00059-X.CrossRefGoogle Scholar
Kogure, T. and Inoue, A., 2005 Determination of defect structures in kaolin minerals by high-resolution transmission electron microscopy (HRTEM) American Mineralogist 90 85–89 10.2138/am.2005.1603.CrossRefGoogle Scholar
Komori, Y. Sugahara, Y. and Kuroda, K., 1999 Intercalation of alkylamines and water into kaolinite with methanol kaolinite as intermediate Applied Clay Science 15 241–252 10.1016/S0169-1317(99)00014-9.CrossRefGoogle Scholar
Lin, H.P. and Mou, C.Y., 1996 ‘Tubules-Within-a-Tubule’ Hierarchical Order of Mesoporous Molecular Sieves in MCM-41 Science 273 765 10.1126/science.273.5276.765.CrossRefGoogle ScholarPubMed
Liu, M. Guo, B. Du, M. Lei, Y. and Jia, D., 2008 Natural inorganic nanotubes reinforced epoxy resin nanocomposites Journal of Polymer Research 15 205–212 10.1007/s10965-007-9160-4.CrossRefGoogle Scholar
Machado, G.S. Freitas Castro, K.A.D. Wypych, F. and Nakagaki, S., 2008 Immobilization of metalloporphyrins into nanotubes of natural halloysite toward selective catalysts for oxidation reactions Journal of Molecular Catalysis A: Chemical 283 99–107 10.1016/j.molcata.2007.12.009.CrossRefGoogle Scholar
Madhusoodana, C.D. Kameshima, Y. Nakajima, A. Okada, K. Kogure, T. and MacKenzie, K.J.D., 2006 Synthesis of high surface Al-containing mesoporous silica from calcined and acid leached kaolinites as the precursors Journal of Colloid and Interface Science 297 724–731 10.1016/j.jcis.2005.10.051.CrossRefGoogle Scholar
Murakami, J. Itagaki, T. and Kuroda, K., 2004 Synthesis of kaolinite-organic nanohybrids with butanediols Solid State Ionics 172 279–282 10.1016/j.ssi.2004.02.048.CrossRefGoogle Scholar
Murray, H.H., 2000 Traditional and new applications for kaolin, smectite and palygorskite: a general overview Applied Clay Science 17 207–221 10.1016/S0169-1317(00)00016-8.CrossRefGoogle Scholar
Nakagaki, S. and Wypych, F., 2007 Nanofibrous and nanotubular supports for the immobilization of metalloporphyrins as oxidation catalysts Journal of Colloid and Interface Science 315 142–157 10.1016/j.jcis.2007.06.032.CrossRefGoogle ScholarPubMed
Nakagaki, S. Machado, G.S. Halma, M. Santos Marangon, A.A. Freitas Castro, K.A.D. Mattoso, N. and Wypych, F., 2006 Immobilization of iron porphyrins in tubular kaolinite obtained by an intercalation/delamination procedure Journal of Catalysis 242 110–117 10.1016/j.jcat.2006.06.003.CrossRefGoogle Scholar
Olejnik, J. Aylmore, L.A.G. Posner, A.M. and Quirk, J.P., 1968 Infrared spectra of kaolin mineral-dimethyl sulfoxide complexes Journal of Physical Chemistry 72 241–249 10.1021/j100847a045.CrossRefGoogle Scholar
Patterson, A.L., 1939 The Scherrer formula for X-ray particle size determination Physical Review 56 978–982 10.1103/PhysRev.56.978.CrossRefGoogle Scholar
Plancon, A. and Zacharie, C., 1990 An expert system for the structural characterization of kaolinites Clay Minerals 25 249–260 10.1180/claymin.1990.025.3.01.CrossRefGoogle Scholar
Plancon, A. Giese, R.F. and Snyder, R., 1988 The Hinckley index for kaolinites Clay Minerals 23 249–260 10.1180/claymin.1988.023.3.02.CrossRefGoogle Scholar
Plançon, A. Giese, R.F. Snyder, R. Drits, V.A. and Bookin, A.S., 1989 Stacking faults in the kaolin-group-minerals: Defect structures of kaolinite Clays and Clay Minerals 37 203–210 10.1346/CCMN.1989.0370302.CrossRefGoogle Scholar
Poyato-Ferrera, J., Becker, H.O., and Weiss, A. (1977) Phase changes in kaolinite-amine-complexes. Proceedings of the International Clay Conference, Oslo, 148–150.Google Scholar
Robertson, I.D.M. and Eggleton, R.A., 1991 Weathering of granitic muscovite to kaolinite and halloysite and of plagioclase-derived kaolinite to halloysite Clays and Clay Minerals 39 113–126 10.1346/CCMN.1991.0390201.CrossRefGoogle Scholar
Serwicka, E.M. and Bahranowski, K., 2004 Environmental catalysis by tailored materials derived from layered minerals Catalysis Today 90 85–92 10.1016/j.cattod.2004.04.012.CrossRefGoogle Scholar
Singh, B., 1996 Why does halloysite roll? — A new model Clays and Clay Minerals 44 191–196 10.1346/CCMN.1996.0440204.CrossRefGoogle Scholar
Singh, B. and Mackinnon, I.D.R., 1996 Experimental transformation of kaolinite to halloysite Clays and Clay Minerals 44 825–834 10.1346/CCMN.1996.0440614.CrossRefGoogle Scholar
Stoch, L., 1974 Mineraly Ilaste (‘Clay Minerals’) Warsaw Geological Publishers.Google Scholar
Thompson, J.G. and Cuff, C., 1985 Crystal structure of kaolinite: dimethylsulfoxide intercalate Clays and Clay Minerals 33 490–500 10.1346/CCMN.1985.0330603.CrossRefGoogle Scholar
Tunney, J.J. and Detellier, C., 1993 Interlamellar covalent grafting of organic units on kaolinite Chemistry of Materials 5 747–748 10.1021/cm00030a002.CrossRefGoogle Scholar
Tunney, J.J. and Detellier, C., 1997 Interlamellar amino functionalization of kaolinite Canadian Journal of Chemistry 75 1766–1772 10.1139/v97-610.CrossRefGoogle Scholar
Weiss, A. and Russow, J., 1963 Uber das Einrollen von Kaolinitkristallen zu halloysitahnlichen rohren und einen unterschied zwischen halloysit und rohrchenformigem kaolinit Proceedings of the International Clay Conference, Stockholm 2 69–79.Google Scholar
Wiewióra, A. and Brindley, G.W., 1969 Potassium acetate intercalation in kaolinite and its removal: Effect of material characteristics Proceedings of the International Clay Conference, Tokyo 1 723–733.Google Scholar
Zhang, X. and Xu, Z., 2007 The effect of microwave on preparation of kaolinite/dimethylsulfoxide composite during intercalation process Materials Letters 61 1478–1482 10.1016/j.matlet.2006.07.057.CrossRefGoogle Scholar
Zimowska, M. Michalik-Zym, A. Połtowicz, J. Bazarnik, M. Bahranowski, K. and Serwicka, E.M., 2007 Catalytic oxidation of cyclohexane over metalloporphyrin supported on mesoporous molecular sieves of FSM-16 type — steric effects induced by nanospace constraints Catalysis Today 124 55–60 10.1016/j.cattod.2007.03.048.CrossRefGoogle Scholar