Skip to main content
SpringerLink
Log in

Crystal Growth of Layered Silicate Grafted with Organic Groups on Monodisperse Spherical Silica Particles

  • Published:
Clays and Clay Minerals

Abstract

Control of the structure and morphology of clay crystals presents a challenge in the synthesis of materials for adsorption and catalysis. In the present study, direct crystallization of a phyllosilicate grafted with organosilyl (methylsilyl and phenylsilyl) groups on the surface of monodisperse spherical silica particles (2.6 μm) is reported. Methyl- and phenyltriethoxysilanes were allowed to react hydrothermally in a Teflon-lined autoclave with silica, MgCl2, and LiF in the presence of urea for 2 or 4 days. X-ray diffraction patterns revealed that the fine platy particles formed were a trioctahedral hectorite-like layered silicate. Greater temperature (150°C) was required to achieve homogeneous coverage of the original spherical silica particles with the hectorite-like particles. The diameter of the initial silica grains increased slightly to 3.0 μm after the hydrothermal reactions, while the original spherical shape and size distribution were maintained. Solid-state 29Si nuclear magnetic resonance analyses confirmed that the presence of resonances attributed to the RSi(OMg)(OSi)2 and RSi(OMg)(OH)(OSi) (R = methyl or phenyl) environments of the silicon proved the formation of covalent bonds between phyllosilicate sheets and the organic moieties. The crystallinity of the layered silicates increased when the reactions ran for a longer time (4 days).

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

Access this article

Log in via an institution

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

Instant access to the full article PDF.

Institutional subscriptions

Similar content being viewed by others

References

  • Bailey, S.W., editor (1988) Hydrous Phyllosilicates (exclusive of Micas). Reviews in Mineralogy, vol.19. Mineralogical Society of America, Washington D.C.

    Google Scholar 

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

    Article  Google Scholar 

  • Carrado, K.A., Xu, L., Gregory, D.M., Song, K., Seifert, S., and Botto, R.E. (2000) Crystallization of a layered silicate clay as monitored by small-angle X-ray scattering and NMR. Chemistry of Materials, 12, 3052–3059.

    Article  Google Scholar 

  • Carrado, K.A., Xu, L., Csencsits, R., and Muntean, J.V. (2001) Use of organo- and alkoxysilanes in the synthesis of grafted and pristine clays. Chemistry of Materials, 13, 3766–3773.

    Article  Google Scholar 

  • Carrado, K.A., Csencsits, R., Thiyagarajan, P., Seifert, S., Macha, S.M., and Harwood, J.S. (2002) Crystallization and textural porosity of synthetic clay minerals. Journal of Materials Chemistry, 12, 3228–3237.

    Article  Google Scholar 

  • Chen, H., Zhang, F., Fu, S., and Duan X. (2006) Orientationcontrolled monolayer assembly of zeolite crystals on glass and mica by covalent linkage of surface-bound epoxide and amine groups. Advanced Materials, 18, 3089–3093.

    Article  Google Scholar 

  • Chhowalla, M., Shin, H.S., Eda, G., Li, L. J., Loh, K.P., and Zhang, H. (2013) The chemistry of two-dimensional layered transition metal dichalcogenide nanosheets. Nature Chemistry, 5, 263–275.

    Article  Google Scholar 

  • Cool, P. and Vansant, E. F. (2004) Pillared clay and porous clay heterostructures. Pp. 261–311 in: Handbook of Layered Materials (S.M. Auerbach, K.A. Carrado, and P.K. Dutta, editors). CRC Press, Boca Raton, Florida, USA.

    Google Scholar 

  • da 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 

  • da Fonseca, M.G., Barone, J.S., and Airoldi, C. (2000a) Selforganized inorganic-organic hybrids induced by silylating agents with phyllosilicate-like structure and the influence of the adsorption of cations. Clays and Clay Minerals, 48, 638–647.

    Article  Google Scholar 

  • da Fonseca, M.G., Silva, C.R., Barone, J.S., and Airoldi, C. (2000b) Layered hybrid nickel phyllosilicates and reactivity of the gallery space. Journal of Materials Chemistry, 10, 789–795.

    Article  Google Scholar 

  • Fujii, K. and Hayashi, S. (2005) Hydrothermal syntheses and characterization of alkylammonium phyllosilicates containing CSiO3 and SiO4 units. Applied Clay Science, 29, 235–248.

    Article  Google Scholar 

  • Fujii, K., Hayashi, S., and Kodama, H. (2003) Synthesis of an alkylammonium/ magnesium phyllosilicate hybrid nanocomposite consisting of a smectite-like layer and organosiloxane layers. Chemistry of Materials, 15, 1189–1197.

    Article  Google Scholar 

  • Fukushima, Y. and Tani, M. (1995) An organic/inorganic hybrid layered polymer: methacrylate-magnesium (nickel) phyllosilicate. Journal of Chemical Society; Chemical Communications, 2, 241–242.

    Article  Google Scholar 

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

    Article  Google Scholar 

  • Giles, C.H., Smith, D., and Huitson, A. (1974) A general treatment and classification of the solute adsorption isotherm. Journal of Colloid and Interface Science, 47, 755–765.

    Article  Google Scholar 

  • Jaber, M. and Miehe-Brendle, J. (2008) Synthesis, characterization and applications of 2:1 phyllosilicates and organophyllosilicates: Contribution of fluoride to study the octahedral sheet. Microporous and Mesoporous Materials, 107, 121–127.

    Article  Google Scholar 

  • Jaber, M., Miehe-Brendle, J., Roux, M., Dentzer, J., Dred, R.L., and Guth, J.L. (2002) A new Al, Mg-organoclay. New Journal of Chemistry, 26, 1597–1600.

    Article  Google Scholar 

  • Jaber, M., Miehe-Brendle, J., Delmotte, L., and Dred, R.L. (2005) Formation of organoclays by a one-step synthesis. Solid State Sciences, 7, 610–615.

    Article  Google Scholar 

  • Katagiri, K., Goto, Y., Nozawa, M., and Koumoto, K. (2009) Preparation of layered double hydroxide coating films via the aqueous solution process using binary oxide gel films as precursor. Journal of the Ceramic Society of Japan, 117, 356–358.

    Article  Google Scholar 

  • Kloprogge, J.T. (1998) Synthesis of smectites and porous pillared clay catalysts: A review. Journal of Porous Materials, 5, 5–41.

    Article  Google Scholar 

  • Langmuir, I. (1918) The adsorption of gases on plane surface of glass, mica and platinum. Journal of the American Chemical Society, 40, 1361–1403.

    Article  Google Scholar 

  • Liu, S., Ye, H., Zhou, Y., and Zhao, J. (2006) Hydrolytic cocondensation of phenyltriethoxysilane with γ-aminopropyltriethoxysilane in the presence of sodium dodecyl sulfate. Polymer Journal, 38, 220–225.

    Article  Google Scholar 

  • Ogawa, M. and Kuroda, K. (1995) Photofunctions of intercalation compounds. Chemical Reviews, 9, 399–438.

    Article  Google Scholar 

  • Ogawa, M., Okutomo, S., and Kuroda, K. (1998) Control of interlayer microstructures of a layered silicate by surface modification with organochlorosilanes. Journal of the American of Chemical Society, 120, 7361–7362.

    Article  Google Scholar 

  • Okada, T. (2018) Direct crystallization of layered silicates on the surface of amorphous silica. The Chemical Record, DOI: https://doi.org/10.1002/tcr.201700071.

    Google Scholar 

  • Okada, T. and Ogawa, M. (2017) Inorganic-organic interactions. Pp. 163–186 in: Inorganic Nanosheets and Nanosheet-Based Materials (T. Nakato, J. Kawamata, and S. Takagi, editors). Springer, Berlin.

    Chapter  Google Scholar 

  • Okada, T., Ide, Y., and Ogawa, M. (2012a) Organic-inorganic hybrids based on ultrathin oxide layers - designed nanostructures for molecular recognition. Chemistry - An Asian Journal, 7, 1980–1992.

    Article  Google Scholar 

  • Okada, T., Yoshido, S., Miura, H., Yamakami, T., Sakai, T., and Mishima, S. (2012b) Swellable microsphere of a layered silicate produced by using monodispersed silica particles. The Journal of Physical Chemistry C, 116, 21864–21869.

    Article  Google Scholar 

  • Okada, T., Seki, Y., and Ogawa, M. (2014) Designed nanostructures of clay for controlled adsorption of organic compounds. Journal of Nanoscience and Nanotechnology, 14, 2121–2134.

    Article  Google Scholar 

  • Okada, T., Oguchi, J., Yamamoto, K., Shiono, T., Fujita, M., and Iiyama, T. (2015a) Organoclays in water cause expansion that facilitates caffeine adsorption. Langmuir, 31, 180–187.

    Article  Google Scholar 

  • Okada, T., Suzuki, A., Yoshido, S., and Minamisawa, H.M. (2015b) Crystal architectures of a layered silicate on monodisperse spherical silica particles cause the topochemical expansion of the core-shell particles. Microporous and Mesoporous Materials, 215, 168–174.

    Article  Google Scholar 

  • Okada, T., Sueyoshi, M., and Minamisawa, H. M. (2015c) In situ crystallization of Al-containing silicate nanosheets on monodisperse amorphous silica microspheres. Langmuir, 31, 13842–13849.

    Article  Google Scholar 

  • Okada, T., Shimizu, K., and Yamakami, T. (2016a) An inorganic anionic polymer filter disc: Direct crystallization of a layered silicate nanosheet on a glass fiber filter. RSC Advances, 6, 26130–26136.

    Article  Google Scholar 

  • Okada, T., Kobari, H., and Haeiwa, T. (2016b) Effects of fluoride and urea on the crystal growth of a hectorite-like layered silicate on a silica surface. Applied Clay Science, 132-133, 320–325.

    Article  Google Scholar 

  • Okada, T., Kumasaki, A., Shimizu, K., Yamagishi, A., and Sato, H. (2016c) Application of hectorite-coated silica gel particles as a packing material for chromatographic resolution. Journal of Chromatographic Science, 54, 1238–1243.

    Article  Google Scholar 

  • Okada, T., Yoshida, T., and Iiyama, T. (2017) Kinetics of interlayer expansion of a layered silicate driven by caffeine intercalation in the water phase using transmission X-ray diffraction. The Journal of Physical Chemistry B, 121, 6919–6925.

    Article  Google Scholar 

  • Pérez-Carvajal, J., Aranda, P., Berenguer-Murcia, A., Cazorla-Amorós, D., Coronas, J., and Ruiz-Hitzky, E. (2013) Nanoarchitectures based on layered titanosilicates supported on glass fibers: Application to hydrogen storage. Langmuir, 29, 7449–7455.

    Article  Google Scholar 

  • Pinnavaia, T.J., Tzou, M.S., Landau, S.D., and Raythatha, R. H. (1984) On the pillaring and delamination of smectite clay catalysts by polyoxo cations of aluminum. Journal of Molecular Catalysis, 27, 195–212.

    Article  Google Scholar 

  • Rogez, G., Massobrio, C., Rabu, P., and Drillon, M. (2011) Layered hydroxide hybrid nanostructures: A route to multifunctionality. Chemical Society Reviews, 40, 1031–1058.

    Article  Google Scholar 

  • Ruiz-Hitzky, E. and Rojo, J.M. (1980) Intracrystalline grafting on layer silicic acids. Nature, 287, 28–30.

    Article  Google Scholar 

  • Ruiz-Hitzky, E., Rojo, J.M., and Lagaly, G. (1985) Mechanism of the grafting of organosilanes on mineral surfaces. Colloid and Polymer Science, 263, 1025–1030.

    Article  Google Scholar 

  • Sugahara, Y., Okada, S., Sato, S., Kuroda, K., and Kato, C. (1994) 29Si-NMR study of hydrolysis and initial polycondensation processes of organoalkoxysilanes. I I. Methyltriethoxysilane. Journal of Non-Crystalline Solids, 167, 21–28.

    Article  Google Scholar 

  • Thiesen, P., Beneke, K., and Lagaly, G. (2000) Alkylammonium derivatives of layered alkali silicates and micro- and mesoporous materials: I. Lithium sodium silicate (silinaite). Journal of Materials Chemistry, 10, 1177–1184.

    Article  Google Scholar 

  • Thiesen, P., Beneke, K., and Lagaly, G. (2002) Silylation of a crystalline silicic acid: an MAS NMR and porosity study. Journal of Materials Chemistry, 12, 3010–3015.

    Article  Google Scholar 

  • Webster, C.E., Drago, R.S., and Zerner, M.C. (1998) Molecular dimensions for adsorptives. Journal of the American Chemical Society, 120, 5509–5516.

    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 Materials Chemistry, 8, 1927–1932.

    Article  Google Scholar 

  • Yamaguchi, N., Nakamura, T., Tadanaga, K., Matsuda, A., Minami, T., and Tatsumisago, M. (2006) Direct formation of Zn-Al layered double hydroxide films with high transparency on glass substrate by the sol-gel process with hot water treatment. Crystal Growth & Design, 6, 1726–1729.

    Article  Google Scholar 

  • Zhang, F., Zhao, L., Chen, H., Xu, S., Evans, D.G., and Duan, X. (2008) Corrosion resistance of superhydrophobic layered double hydroxide films on aluminum. Angewandte Chemie International Edition, 47, 2466–2469.

    Article  Google Scholar 

  • Zhang, T., Zhou, Y., He, M., Zhu, Y., Bu, X., and Wang, Y. (2013) Biomimetic fabrication of hierarchically structured LDHs/ZnO composites for the separation of bovine serum albumin. Chemical Engineering Journal, 219, 278–285.

    Article  Google Scholar 

  • Zhang, T., Zhou, Y., Bu, X., Xue, J., Hu, J., Wang, Y., and Zhang, M. (2014) Bio-inspired fabrication of hierarchically porous Mg-Al composites for enhanced BSA adsorption properties. Microporous and Mesoporous Materials, 188, 37–45.

    Article  Google Scholar 

Download references

Author information

Authors and Affiliations

  1. Department of Chemistry and Materials Engineering, Shinshu University, Nagano, 380-8553, Japan

    Masahiro Yamauchi & Tomohiko Okada

Authors
  1. Masahiro Yamauchi
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Tomohiko Okada
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Tomohiko Okada.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Yamauchi, M., Okada, T. Crystal Growth of Layered Silicate Grafted with Organic Groups on Monodisperse Spherical Silica Particles. Clays Clay Miner. 66, 104–113 (2018). https://doi.org/10.1346/CCMN.2018.064097

Download citation

  • Received:

  • Revised:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1346/CCMN.2018.064097

Key Words

Search

Navigation