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Cation Exchange and Pillaring of Smectites by Aqueous Fe Nitrate Solutions

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Clays and Clay Minerals

Abstract

A comparative study of the behavior of four types of smectite is reported: two with a low Fe content, SHCa-1 (hectorite from San Bernadino, California), SWy-1 (montmorillonite from Wyoming) and two nontronites NG-1 (from Hohen Hagen, Germany) and SWa-1 (Grant County, Washington). Cation exchange was performed with a freshly prepared 1 M Fe nitrate aqueous solution. Intercalation with the same solution partially neutralized with an anhydrous carbonate solution, giving a molar ratio of OH−/Fe = 2 was also studied. The modified clays were characterized by X-ray diffraction, N2 adsorption-desorption, Mossbauer spectroscopy, thermogravimetric analysis, atomic absorption spectroscopy, X-ray fluorescence and inductively coupled plasma analysis.

In the cation exchange process, the goethite impurities grew with the Fe-rich clays but not with the Fe-poor clays. This exchange was also found to have no effect on the thermal stability and structure of the clay minerals with low Fe content, whereas it had a slight effect on the structure of the Fe-rich clays and on their thermal stability. The extent of the intercalation, however, appears to depend on the expandability of the clay layers to accommodate the Fe(III) polycations, and increases from the nontronites to montmorillonite and to hectorite. This intercalation treatment has only a slight effect on both the structure and the thermal stability of hectorite and montmorillonite. In contrast, the nontronites undergo a dramatic change in both their structure and thermal stability. The formation of Fe oxyhydroxide and oxide phases in both procedures becomes very important when the initial structural Fe content of the clay minerals is high, increasing from SHCa-1, SWy-1, SWa-1 to NG-1. The contribution of the structural Fe of the clays to the formation of the Fe oxyhydroxide is not negligible, because of partial leaching of Fe from the octahedral sheet of Fe-rich clays due to the low pH of the solutions.

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References

  • Bakas, T., Moukarika, A., Papaefthymiou, V. and Lavados, A. (1994) Redox treatment of an Fe/Al pillared Montmorillonite: A Mössbauer Study. Clays and Clay Minerals, 42, 634–642.

    Article  Google Scholar 

  • Brindley, G.W. and Yamanaka, S. (1979) A study of hydroxychromium montmorillonite and the form of the hydroxychromium polymers. American Mineralogist, 64, 830–835.

    Google Scholar 

  • Celis, R., Cornejo, J. and Hermosin, M.C. (1996) Surface fractal dimensions of synthetic clay-hydrous iron oxide associations from nitrogen adsorption isotherms and mercury porosimetry. Clay Minerals, 31, 355–363.

    Article  Google Scholar 

  • Cervini-Silva, J., Wu, J., Stucki, J.W. and Larson, R.A. (2000) Adsorption kinetics of pentachloroethane in iron-bearing smectites. Clays and Clay Minerals, 48, 132–138.

    Article  Google Scholar 

  • Chen, J.P., Hausladen, C.M. and Yang, R.T. (1995) Delaminated Fe2O3-pillared clay: Its preparation, characterization and activities for selective catalytic reduction of NO by NH3. Journal of Catalysis, 151, 135–146.

    Article  Google Scholar 

  • Cornélis, A. and Laszlo, P. (1993) Molding clays into efficient catalysts. SYNLETT, 155–161.

    Google Scholar 

  • Doff, D.H., Gangas, J.N., Allan, M.E.J. and Coey, D.M.J. (1988) Preparation and characterization of iron oxide pillared montmorillonite. Clay Minerals, 23, 367–377.

    Article  Google Scholar 

  • Dramé, H. (1998) Physical-chemical modifications of clay minerals: Characterization and environmental prospects as catalyst and adsorbent. PhD thesis, University of Ottawa, Canada, 343 pp.

    Google Scholar 

  • Ferreiro, E.A., Helmy, K.A. and De Bussetti G.S. (1995) Interaction of Fe-oxyhydroxide colloidal particles with montmorillonite. Clay Minerals, 30, 195–200.

    Article  Google Scholar 

  • Gangas, N.H., Simpoulos, A., Kostikas, A., Yassoflou, N.J. and Filippakis, S. (1973) Mössbauer studies of small particles of iron oxides in soil. Clays and Clay Minerals, 21, 151–160.

    Article  Google Scholar 

  • Gangas, N.H., Wonterghem, V.J., Morup, S. and Koch, J.W.C. (1985) Magnetic bridging in nontronite by intercalated iron. Journal of Physics C: Solid State Physics, 18, L1011–L1015.

    Article  Google Scholar 

  • Giles, C.H., McEwan, T.H., Nakhwa, S.N. and Smith, D.J. (1960) Studies in adsorption Part II. A system of classification of solution adsorption isotherms. Journal of the Chemical Society, 3973.

    Google Scholar 

  • Goodman, B.A. and Lewis, D.G. (1981) Mössbauer spectra of aluminous goethite(α-FeOOH). Journal of Soil Science, 32, 351–363.

    Article  Google Scholar 

  • Goodman, B.A., Russell, J.D., Fraser, A.R. and Woodhams, F.W.D. (1976) A Mössbauer and I.R. Spectroscopy study of the structure of nontronite. Clays and Clay Minerals, 24, 53–59.

    Article  Google Scholar 

  • Gopalakrishnan, J. (1995) Chimie douce approaches to the synthesis of metastable oxide materials. Chemistry of Materials, 7, 1226–1275.

    Article  Google Scholar 

  • Goss, C.J. (1987) The kinetics and reaction mechanism of goethite to hematite transformation. Mineralogical Magazine, 51, 437–451.

    Article  Google Scholar 

  • Gregg, S.J. and Sing, W.S.K. (1982) Adsorption, Surface Area and Porosity. Academic Press, New York.

    Google Scholar 

  • Hargraves, P., Rancourt, D.G. and Lalonde, A.E. (1990) Single-crystal Mössbauer study of phlogopite mica. Canadian Journal of Physics, 60, 128–144.

    Article  Google Scholar 

  • Horvath, G. and Kawazoe, K. (1983) Method of the calculation of effective pore size distribution in molecular sieve carbon. Journal of Chemical Engineering Japan, 16, 471–475.

    Article  Google Scholar 

  • Jefferson, D.A., Tricker, J.M. and Winterbottom, A.P. (1975) Electron-microscopic and Mössbauer spectroscopic studies of iron-stained kaolinite minerals. Clays and Clay Minerals, 23, 355–360.

    Article  Google Scholar 

  • Jimenez-Lopez, A., Maza-Rodriguez, J., Olivera-Pastor, P., Maireles-Torres, P. and Rodriguez-Castellon, E. (1993) Pillared clays prepared from the reaction of chromium acetate with montmorillonite. Clays and Clay Minerals, 41, 328–334.

    Article  Google Scholar 

  • Komadel, P., Schmidt, D., Madejová, J. and Číčel, B. (1990) Alteration of smectites by treatments with hydrochloric acid and sodium carbonate solutions. Applied Clay Science, 5, 113–122.

    Article  Google Scholar 

  • Lagaly, G. and Beneke, K. (1991) Intercalation and exchange reactions of clay minerals and non-clay layer compounds. Colloid & Polymer Science, 269, 1198–1211.

    Article  Google Scholar 

  • Lear, R.P., Komadel, P. and Stucki, J.W. (1988) Mössbauer spectroscopy identification of iron oxides in nontronite from Hohen Hagen, Federal Republic of Germany. Clays and Clay Minerals, 36, 376–378.

    Article  Google Scholar 

  • Lenoble, V., Bouras, O., Deluchat, V., Serpaud, B. and Bollinger, J.C. (2002) Arsenic adsorption onto pillared clays and iron oxides. Journal of Colloid and Interface Science, 255, 52–58.

    Article  Google Scholar 

  • Maes, N. and Vansant, E.F. (1995) Study of Fe2O3-pillared clays synthesized using the trinuclear Fe (Ill)-aceto complex as pillaring precursor. Microporous Materials, 4, 43–51.

    Article  Google Scholar 

  • McBride, M.B. (1994) Environmental Chemistry of Soils. Oxford University Press, Oxford, UK, 406 pp.

    Google Scholar 

  • Murad, E. (1987) Mössbauer spectra of nontronites: Structural implications and characterization of associated iron oxides. Zeitschrift für Pflanzenernahrung Bodenkunde, 150, 279–285

    Article  Google Scholar 

  • Murad, E. (1988) Properties and behavior of iron oxides as determined by Mössbauer spectroscopy: Pp. 309–350 in: Iron in Soils and Clay Minerals (J.W. Stucki, B.A. Goodman and U. Schwertmann, editors). D. Reidel, Dordrecht, The Netherlands.

    Chapter  Google Scholar 

  • Murad, E. and Johnston, H.J. (1987) Iron oxide and oxhyhydroxides. In: Mössbauer Spectroscopy Applied to Inorganic Chemistry, Vol. 2 (G.J. Long, editor). Plenum Publishing Corporation, New York.

  • Murphy, P.J., Posner, M.A. and Quick, J.P. (1975) Chemistry of Iron in Soils. Ferric hydrolysis products. Australian Journal of Soil Research, 13, 189–201.

    Article  Google Scholar 

  • Mishra, T., Parida, K.M. and Rao, S.B. (1996) A comparative study of textural and acidic properties of Fe(III) pillared montmorillonite and pillared acid activated montmorillonite. Journal of Colloid and Interface Science, 183, 176–183.

    Article  Google Scholar 

  • Nait-Ajjou, A., Dramé, H., Detellier, C. and Alper, H. (1997) Cation-exchanged montmorillonite catalyzed hydration of styrene derivatives. Journal of Molecular Catalysis A: Chemical, 126, 55–60.

    Article  Google Scholar 

  • Occelli, M.L., Stencel, J.M. and Suib, S.L. (1991) Spectroscopic characterization of some iron containing pillared clays. Journal of Molecular Catalysis, 64, 221–236.

    Article  Google Scholar 

  • Oliveira, L.C.A., Rios, R.V.R.A., Fabris, J.D., Sapag, K., Garg, V.K. and Lago, R.M. (2003) Clay-iron oxide magnetic composites for the adsorption of contaminants in water. Applied Clay Science, 22, 169–177.

    Article  Google Scholar 

  • Pinnavaia, T.J. (1983) Intercalated clay catalysts. Science, 220, 365–371.

    Article  Google Scholar 

  • Rightor, E.G., Ming-Shin Izou, M.S. and Pinnavaia, T.J (1991) Iron oxide pillared clay with large gallery height: synthesis and properties as a Fischer-Tropsch catalyst. Journal of Catalysis, 130, 29–40.

    Article  Google Scholar 

  • Ruan, H.D. and Gilkes, R.J. (1995) Acid dissolution of synthetic aluminous goethite before and after transformation to hematite by heating. Clay Minerals, 30, 55–65.

    Article  Google Scholar 

  • Simpoulos, A., Kostikas, A., Sigalas, I., Gangas, N.H. and Moukariko, A. (1975) Mössbauer study of transformations induced in clay by firing clays. Clays and Clay Minerals, 23, 393–399.

    Article  Google Scholar 

  • Silver, J., Sweeney, M. and Morrison, L.E.G. (1980) A Mössbauer spectroscopy study of some clay minerals of the Eastern Caribbean West Indies. Part I: Spectra from 80 to 300 K. Thermochimica Acta, 35, 153–167.

    Article  Google Scholar 

  • Spiro, T.G., Allerton, E.S., Renner, J., Terzis, A., Bils, R. and Saltman, P. (1966) The hydrolytic polymerization of iron (III). Journal of the American Chemical Society, 88, 2721.

    Article  Google Scholar 

  • Steinfink, H. and Govea, L. (1994) Synthesis and magnetic properties of iron pillared montmorillonites. Pp. 347–357 in: New Trends in Magnetism, Magnetic Materials, and their Applications (J.L. Moran-Lopez and J.M. Sanchez, editors). Plenum Press, New York.

    Google Scholar 

  • Takada, T., Kiyama, M., Bando, Y., Nakamura, T., Shiga, T., Yamamoto, N., Endoh, Y. and Takaki, H. (1964) Mössbauer study of α, β and γ-FeOOH. Journal of the Physics Society of Japan, 19, 1744.

    Article  Google Scholar 

  • Van Olphen, H. (1977) An Introduction to Clay and Colloid Chemistry. John Wiley & Sons, New York.

    Google Scholar 

  • Van Olphen, H. and Fripiat, J.J., editors (1979) Data Handbook for Clay Materials and other Non-Metallic Minerals. Pergamon Press, New York

    Google Scholar 

  • Velde, B. (1992) Introduction to Clay Minerals. Chapman & Hall, London.

    Book  Google Scholar 

  • Villemure, G. (1987) Photochemical Applications of the Intercalation of Organic Cations in Clay Minerals. PhD thesis, University of Ottawa, Canada, pp. 63–65.

    Google Scholar 

  • Yamanaka, S. and Hattori, M. (1988) Iron oxide pillared clay. Catalysis Today, 2, 261–270.

    Article  Google Scholar 

  • Yutaka, M. (1993) Catalysis by metal ions intercalated in layer lattice silicates. Advances in Catalysis, 39, 203–327.

    Google Scholar 

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  1. Institute for Research in Construction, Building Envelop and Structure, National Research Council of Canada, 1200 Montreal Road, Ottawa, Canada, K1A 0R6

    Harouna Dramé

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Dramé, H. Cation Exchange and Pillaring of Smectites by Aqueous Fe Nitrate Solutions. Clays Clay Miner. 53, 335–347 (2005). https://doi.org/10.1346/CCMN.2005.0530402

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  • DOI: https://doi.org/10.1346/CCMN.2005.0530402

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