Hostname: page-component-78c5997874-fbnjt Total loading time: 0 Render date: 2024-11-05T13:52:12.812Z Has data issue: false hasContentIssue false
  • English
  • Français

Changes in Structure, Morphology, Porosity, and Surface Activity of Mesoporous Halloysite Nanotubes Under Heating

Published online by Cambridge University Press:  01 January 2024

Peng Yuan ,
Daoyong Tan ,
Faïza Annabi-Bergaya ,
Wenchang Yan ,
Mingde Fan ,
Dong Liu  and
Hongping He
Peng Yuan*
Affiliation:
CAS Key Laboratory of Mineralogy and Metallogeny, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou 510640, China
Daoyong Tan
Affiliation:
CAS Key Laboratory of Mineralogy and Metallogeny, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou 510640, China Graduate School of the Chinese Academy of Science, Beijing 100049, China
Faïza Annabi-Bergaya
Affiliation:
Centre de Recherche sur la Matière Divisée, CNRS-Université d’Orléans, 1b, Rue de La Férollerie, Orléans Cedex 2, France
Wenchang Yan
Affiliation:
CAS Key Laboratory of Mineralogy and Metallogeny, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou 510640, China Graduate School of the Chinese Academy of Science, Beijing 100049, China
Mingde Fan
Affiliation:
College of Environment and Resources, Inner Mongolia University, Hohhot 010021, China
Dong Liu
Affiliation:
CAS Key Laboratory of Mineralogy and Metallogeny, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou 510640, China
Hongping He
Affiliation:
CAS Key Laboratory of Mineralogy and Metallogeny, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou 510640, China
*
*E-mail address of corresponding author: [email protected]
Rights & Permissions [Opens in a new window]

Abstract

Core share and HTML view are not available for this content. However, as you have access to this content, a full PDF is available via the ‘Save PDF’ action button.

The objective of the present study was to investigate changes in the structural, textural, and surface properties of tubular halloysite under heating, which are significant in the applications of halloysite as functional materials but have received scant attention in comparison with kaolinite. Samples of a purified halloysite were heated at various temperatures up to 1400°C, and then characterized by X-ray diffraction, electron microscopy, Fourier-transform infrared spectroscopy, thermal analysis, and nitrogen adsorption. The thermal decomposition of halloysite involved three major steps. During dehydroxylation at 500–900°C, the silica and alumina originally in the tetrahedral and octahedral sheets, respectively, were increasingly separated, resulting in a loss of long-range order. Nanosized (5–40 nm) γ-Al2O3 was formed in the second step at 1000–1100°C. The third step was the formation of a mullite-like phase from 1200 to 1400°C and cristobalite at 1400°C. The rough tubular morphology and the mesoporosity of halloysite remained largely intact as long as the heating temperature was <900°C. Calcination at 1000°C led to distortion of the tubular nanoparticles. Calcination at higher temperatures caused further distortion and then destruction of the tubular structure. The formation of hydroxyl groups on the outer surfaces of the tubes during the disconnection and disordering of the original tetrahedral and octahedral sheets was revealed for the first time. These hydroxyl groups were active for grafting modification by an organosilane (γ-aminopropyltriethoxysilane), pointing to some very promising potential uses of halloysite for ceramic materials or as fillers for novel clay-polymer nanocomposites.

Keywords

GroupMetahalloysiteOrganosilane ModificationThermal TransformationTubular HalloysiteStructural and Textural Properties
Type
Article
Information
Clays and Clay Minerals , Volume 60 , Issue 6 , December 2012 , pp. 561 - 573
Copyright
Copyright © Clay Minerals Society 2012

References

Antill, S.J., 2003 Halloysite: A low-cost alternative nanotube Australian Journal of Chemistry 56 723–723.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
Bergaya, F. Dion, P. Alcover, J.-F. Clinard, C. and Tchoubar, D., 1996 TEM study of kaolinite thermal decomposition by controlled-rate thermal analysis Journal of Materials Science 31 5069–5075.CrossRefGoogle Scholar
Brindley, G.W. Lemaitre, J., Newman, A.C.D., 1987 Thermal, oxidation and reduction reactions of clay minerals Chemistry of Clays and Clay Minerals Harlow, Essex, UK Longman Scientific & Technical 319–364.Google Scholar
Brindley, G.W. and Nakahira, M., 1959 The kaolinite-mullite reaction series: I. A survey of outstanding problems Journal of the American Ceramic Society 42 311–314.CrossRefGoogle Scholar
Brown, I.W.M. MacKenzie, K.J.D. Bowden, M.E. and Meinhold, R.H., 1985 Outstanding problems in the kaolinite- mullite reaction sequence investigated by 29Si and 27Al solid-state nuclear magnetic resonance: II. High-temperature transformations of metakaolinite Journal of the American Ceramic Society 68 298–301.CrossRefGoogle Scholar
Bunker, B.C. Kirkpatrick, R.J. Brow, R.K. Turner, G.L. and Nelson, C., 1991 Local structure of alkaline-earth boroaluminate crystals and glasses: II. 11B and 27Al MAS NMR spectroscopy of alkaline-earth boroaluminate glasses Journal of the American Ceramic Society 74 1430–1438.CrossRefGoogle Scholar
Dion, P. Alcover, J.-F. Bergaya, F. Ortega, A. Llewellyn, P.L. and Rouquerol, F., 1998 Kinetic study by controlled-transformation rate thermal analysis of the dehydroxylation of kaolinite Clay Minerals 33 269–276.CrossRefGoogle Scholar
Djemai, A. Balan, E. Morin, G. Hernandez, G. Labbe, J.C. and Muller, J.P., 2001 Behavior of paramagnetic iron during the thermal transformations of kaolinite Journal of the American Ceramic Society 84 1017–1024.CrossRefGoogle Scholar
Drago, R.S., 1992 Physical Methods for Chemists 2nd edition Mexico Saunders College Publishing.Google Scholar
Farmer, V.C., 1998 Differing effects of particle size and shape in the infrared and Raman spectra of kaolinite Clay Minerals 33 601–604.CrossRefGoogle Scholar
Frost, R.L. and Johansson, U., 1998 Combination bands in the infrared spectroscopy of kaolins - a DRIFT spectroscopic study Clays and Clay Minerals 46 466–477.CrossRefGoogle Scholar
Frost, R.L. and Vassallo, A.M., 1996 The dehydroxylation of the kaolinite clay minerals using infrared emission spectroscopy Clays and Clay Minerals 44 635–651.CrossRefGoogle Scholar
Groen, J.C. Peffer, L.A.A. and Pérez-Ramírez, J., 2003 Pore size determination in modified micro- and mesoporous materials. Pitfalls and limitations in gas adsorption data analysis Microporous and Mesoporous Materials 60 1–17.CrossRefGoogle Scholar
Gregg, S.J. and Sing, K.S.W., 1982 Adsorption, Surface Area and Porosity 2nd edition London Academic Press.Google Scholar
He, H.P. Guo, J.G. Zhu, J.X. Yuan, P. and Hu, C., 2004 Si-29 and Al-27 MAS NMR spectra of mullites from different kaolinites Spectrochimica Acta Part A — Molecular and Biomolecular Spectroscopy 60 1061–1064.CrossRefGoogle Scholar
Hughes, A.D. and King, M.R., 2010 Use of naturally occurring halloysite nanotubes for enhanced capture of flowing cells Langmuir 26 12155–12164.CrossRefGoogle ScholarPubMed
Joussein, E. Petit, S. Churchman, J. Theng, B. Righi, D. and Delvaux, B., 2005 Halloysite clay minerals — a review Clay Minerals 40 383–426.CrossRefGoogle Scholar
Joussein, E. Petit, S. Fialips, C.-I. Vieillard, P. and Righi, D., 2006 Differences in the dehydration-rehydration behavior of halloysites: New evidence and interpretations Clays and Clay Minerals 54 473–484.CrossRefGoogle Scholar
Kohyama, N. Fukushima, K. and Fukami, A., 1978 Observation of the hydrated form of tubular halloysite by an electron microscope equipped with an environmental cell Clays and Clay Minerals 26 25–40.CrossRefGoogle Scholar
Koretsky, C.M. Sverjensky, D.A. Salisbury, J.W. and D’Aria, D.M., 1997 Detection of surface hydroxyl species on quartz, γ-alumina, and feldspars using diffuse reflectance infrared spectroscopy Geochimica et Cosmochimica Acta 61 2193–2210.CrossRefGoogle Scholar
Kristóf, J. Frost, R.L. Horváth, E. Kocsis, L. and Inczéy, J., 1998 Thermoanalytical investigations on intercalated kaolinites Journal of Thermal Analysis and Calorimetry 53 467–475.CrossRefGoogle Scholar
Lee, S. Kim, Y.J. and Moon, H.-S., 1999 Phase transformation sequence from kaolinite to mullite investigated by an energy-filtering transmission electron microscope Journal of the American Ceramic Society 82 2841–2848.CrossRefGoogle Scholar
Levis, S.R. and Deasy, P.B., 2002 Characterisation of halloysite for use as a microtubular drug delivery system International Journal of Pharmaceutics 243 125–134.CrossRefGoogle ScholarPubMed
Li, C.P. Liu, J.G. Qu, X.Z. Guo, B.C. and Yang, Z.Z., 2008 Polymer-modified halloysite composite nanotubes Journal of Applied Polymer Science 110 3638–3646.CrossRefGoogle Scholar
Liu, D. Yuan, P. Tan, D.Y. Liu, H.M. Fan, M.D. Yuan, A.H. Zhu, J.X. and He, H.P., 2010 Effects of inherent/enhanced solid acidity and morphology of diatomite templates on the synthesis and porosity of hierarchically porous carbon Langmuir 26 18624–18627.CrossRefGoogle ScholarPubMed
Lvov, Y.M. Shchukin, D.G. Mohwald, H. and Price, R.R., 2008 Halloysite clay nanotubes for controlled release of protective agents ACS Nano 2 814–820.CrossRefGoogle ScholarPubMed
MacKenzie, K.J.D. Brown, I.W.M. Meinhold, R.H. and Bowden, M.E., 1985 Outstanding problems in the kaolinite-mullite reaction sequence investigated by 29Si and 27Al solid-state nuclear magnetic-resonance: I. Metakaolinite Journal of the American Ceramic Society 68 293–297.CrossRefGoogle Scholar
Madejová, J. and Komadel, P., 2001 Baseline studies of the Clay Minerals Society source clays: Infrared methods Clays and Clay Minerals 49 410–432.CrossRefGoogle Scholar
Massiot, D. Dion, P. Alcover, J.F. and Bergaya, F., 1995 27Al and 29Si MAS NMR study of kaolinite thermal decomposition by controlled rate thermal analysis Journal of the American Ceramic Society 78 2940–2944.CrossRefGoogle Scholar
Morrow, B.A. and McFarlan, A.J., 1992 Surface vibrational modes of silanol groups on silica Journal of Physical Chemistry 96 1395–1400.CrossRefGoogle Scholar
Morterra, C. and Magnacca, G., 1996 A case study: Surface chemistry and surface structure of catalytic aluminas, as studied by vibrational spectroscopy of adsorbed species Catalysis Today 27 497–532.CrossRefGoogle Scholar
Okada, K. Otsuka, N. and Ossaka, J., 1986 Characterization of spinel phase formed in the kaolin-mullite thermal sequence Journal of the American Ceramic Society 69 C–251-C-253.CrossRefGoogle Scholar
Percival, H.J. Duncan, J.F. and Foster, P.K., 1974 Interpretation of the kaolinite-mullite reaction sequence from infrared absorption spectra Journal of the American Ceramic Society 57 57–61.CrossRefGoogle Scholar
Rocha, J. and Klinowski, J., 1990 29Si and 27Al magic-angle-spinning NMR studies of the thermal transformation of kaolinite Physics and Chemistry of Minerals 17 179–186.CrossRefGoogle Scholar
Sato, R.K. Mcmillan, P.F. Dennison, P. and Dupree, R., 1991 High-resolution Al-27 and Si-29 MAS NMR investigation of SiO2-Al2O3 glasses Journal of Physical Chemistry 95 4483–4489.CrossRefGoogle Scholar
Shchukin, D.G. Sukhorukov, G.B. Price, R.R. and Lvov, Y.M., 2005 Halloysite nanotubes as biomimetic nanoreactors Small 1 510–513.CrossRefGoogle ScholarPubMed
Shoval, S. Champagnon, B. and Panczer, G., 1997 The quartz-cristobalite transformation in heated chert rock composed of micro and crypto-quartz by micro-Raman and FT-IR spectroscopy methods Journal of Thermal Analysis 50 203–213.CrossRefGoogle Scholar
Shoval, S. Boudeulle, M. Yariv, S. Lapides, I. and Panczer, G., 2001 Micro-Raman and FT-IR spectroscopy study of the thermal transformations of St. Claire dickite Optical Materials 16 319–327.CrossRefGoogle Scholar
Sing, K.S.W. and Williams, R.T., 2004 Review: The use of molecular probes for the characterization of nanoporous adsorbents Particle & Particle Systems Characterization 21 71–79.CrossRefGoogle Scholar
Singh, B., 1996 Why does halloysite roll? — A new model Clays and Clay Minerals 44 191–196.CrossRefGoogle Scholar
Smith, M.E. Neal, G. Trigg, M.B. and Drennan, J., 1993 Structural characterization of the thermal transformation of halloysite by solid-state NMR Applied Magnetic Resonance 4 157–170.CrossRefGoogle Scholar
Sonuparlak, B. Sarikaya, M. and Aksay, I.A., 1987 Spinel phase formation during the 980°C exothermic reaction in the kaolinite-to-mullite reaction series Journal of the American Ceramic Society 70 837–842.CrossRefGoogle Scholar
Tonle, I.K. Diaco, T. Ngameni, E. and Detellier, C., 2007 Nanohybrid kaolinite-based materials obtained from the interlayer grafting of 3-aminopropyltriethoxysilane and their potential use as electrochemical sensors Chemistry of Materials 19 6629–6636.CrossRefGoogle Scholar
Vassallo, A.M. Coleclarke, P.A. Pang, L.S.K. and Palmisano, A.J., 1992 Infrared-emission spectroscopy of coal minerals and their thermal transformations Applied Spectroscopy 46 73–78.CrossRefGoogle Scholar
Voll, D. Lengauer, C. Beran, A. and Schneider, H., 2001 Infrared band assignment and structural refinement of Al-Si, Al-Ge, and Ga-Ge mullites European Journal of Mineralogy 13 591–604.CrossRefGoogle Scholar
Voll, D. Angerer, P. Beran, A. and Schneider, H., 2002 A new assignment of IR vibrational modes in mullite Vibrational Spectroscopy 30 237–243.CrossRefGoogle Scholar
Yuan, P. Wu, D.Q. He, H.P. and Lin, Z.Y., 2004 The hydroxyl species and acid sites on diatomite surface: A combined IR and Raman study Applied Surface Science 227 30–39.CrossRefGoogle Scholar
Yuan, P. Southon, P.D. Liu, Z. Green, M.E.R. Hook, J.M. Antill, S.J. and Kepert, C.J., 2008 Functionalization of halloysite clay nanotubes by grafting with γ-aminopropyl-triethoxysilane Journal of Physical Chemistry C 112 15742–15751.CrossRefGoogle Scholar
Yuan, P. Southon, P.D. Liu, Z. and Kepert, C.J., 2012 Organosilane functionalization of halloysite nanotubes for enhanced loading and controlled release Nanotechnology 23 375705.CrossRefGoogle Scholar
Zhuravlev, L.T., 1993 Surface characterization of amorphous silica — a review of work from the former USSR Colloids and Surfaces A — Physicochemical and Engineering Aspects 74 71–90.Google Scholar