Hostname: page-component-669899f699-tzmfd Total loading time: 0 Render date: 2025-04-24T12:59:13.378Z Has data issue: false hasContentIssue false
  • English
  • Français

The Surface Chemistry of Imogolite

Published online by Cambridge University Press:  28 February 2024

Jon Petter Gustafsson
Jon Petter Gustafsson*
Affiliation:
KTH (Royal Institute of Technology), Department of Civil and Environmental Engineering, SE-100 44 Stockholm, Sweden
*
E-mail of corresponding author: gustafip@aom.kth.se
Get access Rights & Permissions [Opens in a new window]

Abstract

Imogolite is a tubular aluminosilicate which is common in Andosols and Spodosols. The high pH at point-of-zero charge at the outer parts of the tube and the anomalously high chloride adsorption of imogolite suggested that there may be structural charge associated with this mineral. The structural charge may arise because of changes in bond valence imposed by the incorporation of orthosilicate anions in a gibbsite-type sheet. By using a Basic Stem Model approach, it is shown that the surface charge properties of imogolite are explained if the mean Al-O bond valence of the outer -Al2OH groups is higher than the inner -Al2OHSiO3 groups. Hence, a weak positive charge is developed on the outer tube walls whereas a negative charge develops in the tubular pores. The best model fits were obtained where either one or two units of structural charge per unit cell of tube were assumed. The model may also explain why imogolite tubes are normally aggregated in large bundles in close hexagonal packing, because bound counterions may hold the tubes together. However, to arrive at good model descriptions, the deprotonation of -Al2OH groups must occur at a higher pH than that expected when assuming that all surface oxygens form two hydrogen bridges with H2O. A more precise structure of imogolite is required to test fully this hypothesis.

Keywords

AdsorptionBasic Stem ModelBond ValenceChlorideImogolitePoint-of-Zero ChargeSurface Charge
Type
Research Article
Information
Clays and Clay Minerals , Volume 49 , Issue 1 , February 2001 , pp. 73 - 80
Copyright
Copyright © 2001, The Clay Minerals Society

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.)

Article purchase

Temporarily unavailable

References

Ackerman, W.C. Smith, D.M. Huling, J.C. Kim, Y.-W. Bailey, J.K. and Brinker, C.J., (1993) Gas/vapor adsorption in imogolite: A microporous tubular aluminosilicate Langmuir 9 1051–1057 10.1021/la00028a029.Google Scholar
Ackerman, W.C. Hua, D.W. Kim, Y.W. Huling, J.C. and Smith, D.M., (1994) Adsorption studies of pure and modified imogolite as a potential pore size standard Studies in Surface Science and Catalysis 87 735–744 10.1016/S0167-2991(08)63136-5.Google Scholar
Allison, J.D. Brown, D.S. and Novo-Gradac, K.J., (1991) MINTEQA2/PRODEFA2. A Geochemical Assessment Model for Environmental Systems USA EPA/600/3-91/021 U.S. Environmental Protection Agency, Athens, Georgia 30613.Google Scholar
Behrens, S.H. and Borkovec, M., (1999) Electrostatic interaction of colloidal surfaces with variable charge Journal of Physical Chemistry B 103 2918–2928 10.1021/jp984099w.Google Scholar
Brown, I.D. and Altermatt, D., (1985) Bond-valence parameters obtained from a systematic analysis of the inorganic crystal structure database Acta Crystallographica B41 244–247 10.1107/S0108768185002063.Google Scholar
Brunauer, S. Emmett, P.H. and Teller, E., (1938) Adsorption of gases in multimolecular layers Journal of the American Chemical Society 60 309–319 10.1021/ja01269a023.Google Scholar
Clark, C.J. and McBride, M.B., (1984) Cation and anion retention by natural and synthetic allophane and imogolite Clays and Clay Minerals 32 291–299 10.1346/CCMN.1984.0320407.Google Scholar
Cradwick, P.D.G. Farmer, V.C. Russell, J.D. Masson, C.R. Wada, K. and Yoshinaga, N., (1972) Imogolite, a hydrated silicate of tubular nature Nature Physical Science 240 187–199 10.1038/physci240187a0.Google Scholar
Denaix, L. Lamy, I. and Bottero, J.Y., (1999) Structure and affinity towards Cd2+, Cu2+, Pb2+ of synthetic colloidal amorphous aluminosilicates and their precursors Colloids Surfaces A158 315–325 10.1016/S0927-7757(99)00096-5.Google Scholar
Dzombak, D.A. and Morel, F.M.M., (1990) Surface Complexation Modeling. Hydrous Ferric Oxide New York Wiley and Sons.Google Scholar
Egashira, K. and Aomine, S., (1974) Effects of drying and heating on the surface area of allophane and imogolite Clay Science 4 2331–2342.Google Scholar
Farmer, V.C. Adams, M.J. Fraser, A.R. and Palmieri, F., (1983) Synthetic imogolite: Properties, synthesis, and possible applications Clay Minerals 18 459–472 10.1180/claymin.1983.018.4.11.Google Scholar
Goodman, B.A. Russell, J.D. Montez, B. Oldfield, E. and Kirkpatrick, P.J., (1985) Structural studies of imogolite and allophanes by aluminium-27 and silicon-29 nuclear magnetic resonance spectroscopy Phyics and Chemistry of Minerals 12 342–346 10.1007/BF00654344.Google Scholar
Gustafsson, J.P. Bhattacharya, P. and Karltun, E., (1999) Mineralogy of poorly crystalline aluminium phases in B horizons of Podzols in southern Sweden Applied Geochemistry 14 707–718 10.1016/S0883-2927(99)00002-5.Google Scholar
Harsh, J.B. Traina, S.J. Boyle, J. and Yang, Y., (1992) Adsorption of cations on imogolite and their effect on surface charge characteristics Clays and Clay Minerals 40 700–706 10.1346/CCMN.1992.0400609.Google Scholar
Hiemstra, T. De Wit, J.C.M. and Van Riemsdijk, W.H., (1989) Multisite proton adsorption modeling at the solid/solution interface of (hydr)oxides: A new approach. II. Application to various important (hydr)oxides Journal of Colloid and Interface Science 133 105–117 10.1016/0021-9797(89)90285-3.Google Scholar
Hiemstra, T. Venema, P. and Van Riemsdijk, W.H., (1996) Intrinsic proton affinity of reactive surface groups of metal (hydr)oxides: The bond valence principle Journal of Colloid and Interface Science 184 680–692 10.1006/jcis.1996.0666.Google Scholar
Hiemstra, T. Yong, H. and Van Riemsdijk, W.H., (1999) Interfacial charging phenomena of aluminium (hydr)oxides Langmuir 15 5942–5955 10.1021/la9903604.Google Scholar
Hoshino, H. Urakawa, H. Donkai, N. and Kajiwara, K., (1996) Simulation of mesophase formation of rodlike molecule, imogolite Polymer Bulletin 36 257–264 10.1007/BF00294915.Google Scholar
Ildefonse, P. Kirkpatrick, M.J. Montez, B. Calas, G. Flank, A.M. and Lagarde, P., (1994) 27Al MAS NMR and aluminium X-ray adsorption near-edge structure study of imogolite and allophanes Clays and Clay Minerals 42 276–284 10.1346/CCMN.1994.0420306.Google Scholar
Ohshima, H., (1998) Surface charge density/surface potential relationship for a cylindrical particle in an electrolyte solution Journal of Colloid and Interface Science 200 291–297 10.1006/jcis.1998.5433.Google Scholar
Pohl, P.I. Faulon, J.-L. and Smith, D.M., (1996) Pore structure of imogolite computer models Langmuir 12 4463–4468 10.1021/la9600715.Google Scholar
Rietra, R.P.J.J. Hiemstra, T. and Van Riemsdijk, W.H., (1999) Sulfate adsorption on goethite Journal of Colloid and Interface Science 218 511–521 10.1006/jcis.1999.6408.Google Scholar
Su, C. and Harsh, J.B., (1993) The electrophoretic mobility of imogolite and allophane in the presence of inorganic anions and citrate Clays and Clay Minerals 41 461–471 10.1346/CCMN.1993.0410407.Google Scholar
Su, C. Harsh, J.B. and Bertsch, P.M., (1992) Sodium and chloride sorption by imogolite and allophanes Clays and Clay Minerals 40 280–286 10.1346/CCMN.1992.0400305.Google Scholar
Theng, B.K.G. Russell, M. Churchman, G.J. and Parfitt, R.L., (1982) Surface properties of allophane, halloysite, and imogolite Clays and Clay Minerals 30 143–149 10.1346/CCMN.1982.0300209.Google Scholar
Venema, P. Hiemstra, T. and Van Riemsdijk, W.H., (1996) Comparison of different site binding models for cation sorption: Description of pH dependency, salt dependency, and cation-proton exchange Journal of Colloid and Interface Science 181 45–59 10.1006/jcis.1996.0355.Google Scholar
Venema, P. Hiemstra, T. Weidler, P.G. and Van Riemsdijk, W.H., (1998) Intrinsic proton affinity of reactive surface groups of metal (hydr)oxides: Application to iron (hydr)oxides Journal of Colloid and Interface Science 198 282–295 10.1006/jcis.1997.5245.Google Scholar
Wada, K., Dixon, J.B. and Weed, S.D., (1989) Allophane and imogolite Minerals in Soil Environments 2nd edition USA SSSA Book Series no. 1, Soil Science Society of America, Madison, Wisconsin 1051–1087.Google Scholar
Yoshinaga, N. and Aomine, A., (1962) Imogolite in some Ando soils Soil Science and Plant Nutrition 8 22–29 10.1080/00380768.1962.10430993.Google Scholar