Skip to main content
Log in

Self-Organized Inorganic-Organic Hybrids Induced by Silylating Agents with Phyllosilicate-Like Structure and the Influence of the Adsorption of Cations

  • Published:
Clays and Clay Minerals

Abstract

Two analogous inorganic-organic hybrids with a phyllosilicate-like structure SILMgl and SILMg2, containing 3-aminopropyl- and N-propylethylenediaminetrimethoxysilane were synthesized through a sol-gel process. These hybrids adsorbed divalent cations of cobalt, nickel, copper, and zinc from aqueous solution to give the effectiveness of adsorption capacities in the sequence Cu2+ > Zn2+ > Ni2+ > Co2+. SILMgl has a higher capacity of adsorption than SILMg2. Elemental analysis, X-ray diffractometry, thermal analysis, infrared and nuclear magnetic resonance spectroscopies, and energy dispersive system microscopy characterized all hybrids. The proposed adsorption mechanism involves dissolution of the precursor matrix, formation of a phyllosilicate around the adsorbed ion, and a complexation of the cation by the amino-pendant groups in the interlayer. These new phyllosilicates are more crystalline than the original hybrids. The adsorption of Co2+ increases the interlayer distance to maximum values of 1.81 and 2.24 Å for SILMg1 and SILMg2, respectively. Thermal analysis data showed a decrease of thermal stability with cation adsorption. Si-O-Si groups were detected by infrared spectroscopy in all hybrids and a band at 1384 cm1 was assigned to the nitrate counter anion, which indicates the participation of this ion in the sphere of coordination of the interlayer complexes. The photomicrographs obtained by scanning electron microscopy showed the organized distribution of the sheet structure for these synthesized phyllosilicates.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Subscribe and save

Springer+ Basic
$34.99 /Month
  • Get 10 units per month
  • Download Article/Chapter or eBook
  • 1 Unit = 1 Article or 1 Chapter
  • Cancel anytime
Subscribe now

Buy Now

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Similar content being viewed by others

References

  • Bem-Naim, A. (1987) Solvation Thermodynamics. Plenium Press, New York, 246 pp.

    Book  Google Scholar 

  • Blinker, C.J. and Scherer, G.W. (1990) Sol-Gel Science-The Physics and Chemistry of Sol-Gel Processing. Academic Press, New York, 908 pp.

    Google Scholar 

  • Burkett, S.L., Press, A., and Mann, S. (1997) Synthesis, characterization and reactivity of layered inorganic-organic nanocomposites based on 2:1 trioctahedral phyllosilicates. Chemical Materials, 9, 1071–1073.

    Article  Google Scholar 

  • Carrado, K.A. and Langqiu, X. (1999) Materials with controlled mesoporosity derived from synthetic polyvinylpyrrolidone-clay composites. Microporous and Mesoporous Materials, 27, 87–94.

    Article  Google Scholar 

  • Cestari, A.R. and Airoldi, C. (1997) Chemisorption on thiolsilicas: Divalent cations as a function of pH and primary amines on thiol-mercury adsorbed. Journal of Colloid and Interface Science, 195, 338–342.

    Article  Google Scholar 

  • Decarreau, A. (1985) Partitioning of divalent elements between octahedral sheets of trioctahedral smectites and water. Geochimica et Cosmochimica Acta, 49, 1537–1544.

    Article  Google Scholar 

  • Decarreau, A., Grauby, O., and Petit, S. (1992) The actual distribution of octahedral cations in 2:1 clay minerals: Results from clay synthesis. Applied Clay Science, 7, 147167.

    Article  Google Scholar 

  • De Vynck, I. (1980) Synthese de phyllosilicates de cobalt, de nickel, de cuivre et de zinc. Silicates Industriels, 3, 51–66.

    Google Scholar 

  • Farias, R.F. and Airoldi, C. (2000) Effect of addition of divalent transition metal chlorides on the structure and thermal stability of lamellar silica synthesized by neutral amine route. Journal of Solid State Chemistry, 149, 113–119.

    Article  Google Scholar 

  • Farmer, V.C. (1964) The infrared spectra of layer silicates. Spectrochimica Acta, 20, 1149–1173.

    Article  Google Scholar 

  • Fonseca, M.G., Silva, C.R., and Airoldi, C. (1999) Aminated phyllosilicates synthesized via a sol-gel process. Langmuir, 15, 5048–5055.

    Article  Google Scholar 

  • Fukushima, Y. and Tami, M. (1995) An organic/inorganic hybrid layered polymer: Methacrylate-magnesium(nickel) phyllosilicate. Chemical Communications, 241–242.

    Google Scholar 

  • Fukushima, Y. and Tami, M. (1996) Synthesis of 2:1 type 3- (methacrylate)propyl magnesium(nickel) phyllosilicate. Bulletin of the Chemical Society of Japan, 69, 3667–3671.

    Article  Google Scholar 

  • Hong, Y-S. and Kim, S-J. (1997) A layered phyllosilicate compound containing l, 12-diaz-3, 4:9, 10-dibenzo-5, 8-diox- acyclopentadecane. Bulletin of the Korean Chemical Society, 18, 236–239.

    Google Scholar 

  • Kadkhodayan, A., Chi-Li, L., and Pinnavaia, T.J. (1988) Chemical modification of the gallery surfaces in layered silicate clays (LSC’s) for catalytic applications in nucleophilic displacement reactions. In Chemically Modified Surfaces in Science and Industry, D.E. Leyden and W.T. Collins, eds., Gordon and Breach Science, London, 221–238.

    Google Scholar 

  • Krestov, G.A. (1991) Thermodynamics of Solvation: Solution and Dissolution; Ions and Solvents; Structure and Energetics. Ellis Horwood, London, 284 pp.

    Google Scholar 

  • Komarneni, S., Kozai, N., and Roy, R. (1998) Novel function for anionic clays: Selective transition metal cation uptake by diadochy. Journal of Material Chemistry, 6, 1329–1331.

    Article  Google Scholar 

  • Lishko, T.P., Glushchenko, L.V., Kholin, Y.V., Zaitev, Z.N., Bugaevskii, A., and Donskaya, N.D. (1991) Complexation on silica gels chemically modified by amines of various denticity. Russian Journal of Physical Chemistry, 65, 1584–1588.

    Google Scholar 

  • Mizutani, T., Fukushima, Y., Okada, A., and Kamigaito, O. (1990) Synthesis of nickel and magnesium phyllosilicates with 1:1 and 2:1 layer structures. Bulletin of the Chemical Society of Japan, 63, 2094–2098.

    Article  Google Scholar 

  • Mosser, C., Mestdagh, M., Decarreau, A., and Herbilion, A.J. (1990) Spectroscopic (ESR, EXAFS) evidence of Cu for (Al-Mg) substitution in octahedral sheets of smectites. Clay Minerals, 25, 271–281.

    Article  Google Scholar 

  • Nakamoto, K. (1986) Infrared Spectra of Inorganic and Coordination Compounds. John Wiley and Sons, New York, 484 pp.

    Google Scholar 

  • Newman, A.C.D. and Brown, G. (1980) The chemical constitution of clays. In Crystal Structures of Clay Minerals and Their X-ray Identification, G.W. Brindley and G. Brown, eds., Mineralogical Society, London, 1–128.

    Google Scholar 

  • Pavia, D.L., Lampman, G.M., and Kriz, G.S. (1996) Introduction to Spectroscopy: A Guide for Students of Organic Chemistry. Saunders College Publishing, Orlando, 511 pp.

    Google Scholar 

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

    Article  Google Scholar 

  • Rayner, J.H. and Brown, G. (1973) The crystal structure of talc. Clays and Clay Minerals, 21, 103–144.

    Article  Google Scholar 

  • Silva, C.R. and Airoldi, C. (1997) Acid and base catalysts in the hybrid silica sol-gel process. Journal of Colloid and Interface Science, 195, 381–387.

    Article  Google Scholar 

  • Silverstein, R.M., Bassler, G.C., and Morrel, T.C. (1991) Spectrometric Identification of Organic Compounds. John Wiley and Sons, London, 387 pp.

    Google Scholar 

  • Ukrainczyk, L., Bellman, R.A., and Anderson, A.B. (1997) Template synthesis and characterization of layered Al- and Mg-silsesquioxanes. Journal Physical Chemistry B, 101, 531–539.

    Article  Google Scholar 

  • Velde, B. (1992) Introduction to Clay Minerals. Chapman and Hall, London, 198 pp.

    Book  Google Scholar 

  • Wesolowski, M. (1984) Thermal decomposition of talc: A review. Thermochimica Acta, 78, 395–421.

    Article  Google Scholar 

  • Whilton, N.T., Burkett, S.L., and Mann, S. (1998) Hybrid lamellar nanocomposites based on organically functionalized magnesium phyllosilicate clays with interlayer reactivity. Journal of Material Chemistry, 8, 1927.

    Article  Google Scholar 

  • Wilkins, R.W.T. and Ito, J. (1967) Infrared spectra of some synthetic talcs. American Mineralogist, 52, 1649–1661.

    Google Scholar 

  • Yang, J.J., El-Nahhal, I.M., I-Ssuer, C., and Maciel, G.E. (1997) Synthesis and solid-state NMR structural characterization of polysiloxane-immobilized amine ligands and their metal complexes. Journal of Non-Crystalline Solids, 209, 19–39.

    Article  Google Scholar 

  • Xiang, Y. and Villemure, G. (1996) Electrodes modified with synthetic clay minerals: Electrochemistry of cobalt smectites. Clays and Clay Minerals, 44, 515–521.

    Article  Google Scholar 

  • Xiao, J. and Villemure, G. (1998) Preparation, characterization and electrochemistry of synthetic copper clays. Clays and Clay Minerals, 48, 195–203.

    Article  Google Scholar 

Download references

Author information

Authors and Affiliations

Authors

Corresponding author

Correspondence to Claudio Airoldi.

Rights and permissions

Reprints and permissions

About this article

Cite this article

Da Fonseca, M.G., Barone, J.S. & Airoldi, C. Self-Organized Inorganic-Organic Hybrids Induced by Silylating Agents with Phyllosilicate-Like Structure and the Influence of the Adsorption of Cations. Clays Clay Miner. 48, 638–647 (2000). https://doi.org/10.1346/CCMN.2000.0480605

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1346/CCMN.2000.0480605

Key Words

Navigation