Hostname: page-component-78c5997874-mlc7c Total loading time: 0 Render date: 2024-11-13T09:28:34.410Z Has data issue: false hasContentIssue false
  • English
  • Français

Influence of Synthesis Conditions on the Formation of a Kaolinitemethanol Complex and Simulation of its Vibrational Spectra

Published online by Cambridge University Press:  01 January 2024

Jakub Matusik ,
Eva Scholtzová ,
Daniel Tunega  and
Elsa H. Rueda
Jakub Matusik*
Affiliation:
Department of Mineralogy, Petrography and Geochemistry, Faculty of Geology, Geophysics and Environmental Protection, AGH University of Science and Technology, al. Mickiewicza 30, 30-059 Krakow, Poland
Eva Scholtzová
Affiliation:
Institute of Inorganic Chemistry, Slovak Academy of Sciences, Dúbravská Cesta 9, SK-845 36 Bratislava, Slovak Republic
Daniel Tunega
Affiliation:
Institute of Inorganic Chemistry, Slovak Academy of Sciences, Dúbravská Cesta 9, SK-845 36 Bratislava, Slovak Republic Institut für Bodenforschung, Universität für Bodenkultur, Peter-Jordan-Strasse 82b, A-1190 Vienna, Austria
Elsa H. Rueda
Affiliation:
Department of Mineralogy, Petrography and Geochemistry, Faculty of Geology, Geophysics and Environmental Protection, AGH University of Science and Technology, al. Mickiewicza 30, 30-059 Krakow, Poland
*
*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.

Kaolinite is often used as a base for the synthesis of new organo-mineral nanomaterials designed for applications in industry and in environmental protection. To make the mineral structure more likely to interact with organic molecules, a kaolinite-methanol complex (KM) can be used. In the present study, different experimental procedures were tested to investigate the formation of the KM. The kaolinitedimethyl sulfoxide intercalation compound (KDS), either wet or dried, was used as a pre-intercalate. The samples obtained were characterized using X-ray diffraction, Fourier-transform infrared spectroscopy, CHNS elemental analysis, 13C CP-magic angle spinning nuclear magnetic resonance (MAS NMR), and 27Al and 29Si MAS NMR techniques. The method of density functional theory with dispersion corrections (DFT-D2) was used to explain the structure and to simulate the vibrational spectra of KM. Theoretical results were compared with experimental data. The most effective formation of the KM (d001 = 11.1 Å — wet; d001 = 8.7 Å — dried) was observed when the dried KDS precursor was used. In such conditions the degree of intercalation reached ~98% after 24 h of reaction time. As indicated by the CHNS elemental analysis, ~1/6 of the inner-surface OH groups were grafted by OCH3 groups. The esterification reaction was less efficient at higher temperatures or when wet KDS was used. In the latter case, the excess of very polar dimethyl sulfoxide molecules prevented intercalation of methanol and further grafting. Detailed analysis of the results of theoretical simulations revealed that the reaction of the KDS with methanol led to the formation of kaolinite with both grafted methoxy groups and intercalated methanol, and water molecules in the interlayer space. The spectra calculated revealed the contribution of individual vibrational modes into the complex bands, i.e. the energy of C-H vibrations was in the order: νasCHmet > νasCHmtx > νsCHmet > νsCHmtx.

Keywords

DFT-D2GraftingIntercalationKaoliniteMethanolVibrational Spectra
Type
Article
Information
Clays and Clay Minerals , Volume 60 , Issue 3 , June 2012 , pp. 227 - 239
Copyright
Copyright © Clay Minerals Society 2012

References

Avila, L.R. de Faria, E.H. Ciuffi, K.J. Nassar, E.J. Calefi, P.S. Vicente, M.A. and Trujillano, R., 2010 New synthesis strategies for effective functionalization of kaolinite and saponite with silylating agents Journal of Colloid and Interface Science 341 186–193.CrossRefGoogle ScholarPubMed
Benco, L. Tunega, D. Hafner, J. and Lischka, H., 2001 Ab initio density functional theory applied to the structure and proton dynamics of clays Chemical Physics Letters 333 479–484.CrossRefGoogle Scholar
Benco, L. Tunega, D. Hafner, J. and Lischka, H., 2001 Orientation of OH groups in kaolinite and dickite. Ab initio molecular dynamics study American Mineralogist 86 1057–1065.CrossRefGoogle Scholar
Benco, L. Tunega, D. Hafner, J. and Lischka, H., 2001 Upper limit of the O-H...O hydrogen bond. Ab initio study of the kaolinite structure Journal of Physical Chemistry B 105 10812–10817.CrossRefGoogle Scholar
Bish, D.L., 1993 Rietveld refinement of the kaolinite structure at 1.5 K Clays and Clay Minerals 41 738–744.CrossRefGoogle Scholar
Blöchl, P.E., 1994 Projector augmented-wave method Physical Review B 50 17953–17979.CrossRefGoogle ScholarPubMed
Bougeard, D. Smirnov, K.S. and Geidel, E., 2000 Vibrational spectra and structure of kaolinite: A computer simulation study Journal of Physical Chemistry B 104 9210–9217.CrossRefGoogle Scholar
Castellano, R.K., 2004 Progress toward understanding the nature and function of C-H...O interactions Current Organic Chemistry 8 845–865.CrossRefGoogle Scholar
de Faria, E.H. Lima, O.J. Ciuffi, K.J. Nassar, E.J. Vicente, M.A. Trujillano, R. and Calefi, P.S., 2009 Hybrid materials prepared by interlayer functionalization of kaolinite with pyridine-carboxylic acids Journal of Colloid and Interface Science 335 210–215.CrossRefGoogle ScholarPubMed
Desiraju, G.R. and Steiner, T., 2006 The Weak Hydrogen Bond: in Structural Chemistry and Biology New York Oxford University Press.Google Scholar
Duer, M.J. Rocha, J. and Klinowski, J., 1992 Solid-state NMR studies of the molecular motion in the kaolinite: DMSO intercalate Journal of the American Chemical Society 114 6867–6874.CrossRefGoogle Scholar
Farmer, V.C. and Russell, J.D., 1967 Infrared absorption spectrometry in clay studies Clays and Clay Minerals 15 121–142.CrossRefGoogle Scholar
Fellah, M.F., 2011 Direct oxidation of methanol to formaldehyde by N2O on [Fe]1+ and [FeO]1+ sites in Fe-ZSM-5 zeolite: A density functional theory study Journal of Catalysis 282 191–200.CrossRefGoogle Scholar
Franco, F. and Ruiz Cruz, M.D., 2004 Factors influencing the intercalation degree (‘reactivity’) of kaolin minerals with potassium acetate, formamide, dimethylsulphoxide and hydrazine Clay Minerals 39 193–205.CrossRefGoogle Scholar
Frost, R.L. Kristof, J. Horváth, E. and Kloprogge, J.T., 2000 Kaolinite hydroxyls in dimethylsulphoxide-intercalated kaolinites at 77 K - a Raman spectroscopic study Clay Minerals 35 443–454.CrossRefGoogle Scholar
Gardolinski, JEFC and Lagaly, G., 2005 Grafted organic derivatives of kaolinite I. Synthesis, chemical and rheological characterization Clay Minerals 40 537–546.CrossRefGoogle Scholar
Grimme, S. Antony, J. Schwabe, T. and Mück-Lichtenfeld, C., 2007 Density functional theory with dispersion corrections for supramolecular structures, aggregates, and complexes of (bio)organic molecules Organic & Biomolecular Chemistry 5 741–758.CrossRefGoogle ScholarPubMed
Hayashi, S., 1997 NMR study of dynamics and evolution of guest molecules in a kaolinite/dimethyl sulfoxide intercalation compound Clays and Clay Minerals 45 724–732.CrossRefGoogle Scholar
Hirsemann, D. Koster, T.K.J. Wack, J. van Wullen, L. Breu, J. and Senker, J.r., 2011 Covalent grafting to m-hydroxycapped surfaces? A kaolinite case study Chemistry of Materials 23 3152–3158.CrossRefGoogle Scholar
Itagaki, T. and Kuroda, K., 2003 Organic modification of the interlayer surface of kaolinite with propanediols by transesterification Journal of Materials Chemistry 13 1064–1068.CrossRefGoogle Scholar
Johnston, C.T. and Stone, D.A., 1990 Influence of hydrazine on the vibrational modes of kaolinite Clays and Clay Minerals 38 121–128.CrossRefGoogle Scholar
Komori, Y. Sugahara, Y. and Kuroda, K., 1999 Intercalation of alkylamines and water into kaolinite with methanol kaolinite as an intermediate Applied Clay Science 15 241–252.CrossRefGoogle Scholar
Komori, Y. Enoto, H. Takenawa, R. Hayashi, S. Sugahara, Y. and Kuroda, K., 2000 Modification of the interlayer surface of kaolinite with methoxy groups Langmuir 16 5506–5508.CrossRefGoogle Scholar
Kresse, G. and Furthmüller, J., 1996 Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set Computational Materials Science 6 15–50.CrossRefGoogle Scholar
Kresse, G. and Furthmüller, J., 1996 Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set Physical Review B 54 11169–11186.CrossRefGoogle ScholarPubMed
Kresse, G. and Joubert, D., 1999 From ultrasoft pseudopotentials to the projector augmented-wave method Physical Review B 59 1758–1775.CrossRefGoogle Scholar
Kuroda, Y. Ito, K. Itabashi, K. and Kuroda, K., 2011 Onestep exfoliation of kaolinites and their transformation into nanoscrolls Langmuir 27 2028–2035.CrossRefGoogle ScholarPubMed
Ledoux, R.L. and White, J.L., 1964 Infrared studies of the hydroxyl groups in intercalated kaolinite complexes Clays and Clay Minerals 13 289–315.CrossRefGoogle Scholar
Letaief, S. and Detellier, C., 2007 Functionalized nanohybrid materials obtained from the interlayer grafting of aminoalcohols on kaolinite Chemical Communications 25 2613–2615.CrossRefGoogle Scholar
Letaief, S. Tonle, I.K. Diaco, T. and Detellier, C., 2008 Nanohybrid materials from interlayer functionalization of kaolinite. Application to the electrochemical preconcentration of cyanide Applied Clay Science 42 95–101.CrossRefGoogle Scholar
Li, Y. Sun, D. Pan, X. and Zhang, B., 2009 Kaolinite intercalation precursors Clays and Clay Minerals 57 779–786.CrossRefGoogle Scholar
Machado, G.S. Groszewicz, P.B. Castro, KADF Wypych, F. and Nakagaki, S., 2012 Catalysts for heterogeneous oxidation reaction based on metalloporphyrins immobilized on kaolinite modified with triethanolamine Journal of Colloid and Interface Science 374 278–286.CrossRefGoogle ScholarPubMed
Matusik, J. Gaweł, A. Bielańska, E. Osuch, W. and Bahranowski, K., 2009 The effect of structural order on nanotubes derived from kaolin-group minerals Clays and Clay Minerals 57 452–464.CrossRefGoogle Scholar
Matusik, J. Wisła-Walsh, E. Gaweł, A. Bielańska, E. and Bahranowski, K., 2011 Surface area and porosity of nanotubes obtained from kaolin minerals of different structural order Clays and Clay Minerals 59 116–135.CrossRefGoogle Scholar
Matusik, J. Stodolak, E. and Bahranowski, K., 2011 Synthesis of polylactide/clay composites using structurally different kaolinites and kaolinite nanotubes Applied Clay Science 51 102–109.CrossRefGoogle Scholar
Matusik, J. Gaweł, A. and Bahranowski, K., 2012 Grafting of methanol in dickite and intercalation of hexylamine Applied Clay Science 56 63–67.CrossRefGoogle Scholar
Michalková, A. and Tunega, D., 2007 Kaolinite: dimethylsulfoxide intercalate - a theoretical study Journal of Physical Chemistry C 111 11259–11266.CrossRefGoogle Scholar
Michalková, A. Tunega, D. and Turi Nagy, L., 2002 Theoretical study of interactions of dickite and kaolinite with small organic molecules Journal of Molecular Structure (Theochem) 581 37–49.CrossRefGoogle Scholar
Moretti, E. Storaro, L. Chessa, G. Talon, A. Callone, E. Mueller, K.J. Enrichi, F. and Lenarda, M., 2012 Stepwise dansyl grafting on the kaolinite interlayer surface Journal of Colloid and Interface Science 375 112–117.CrossRefGoogle ScholarPubMed
Murakami, J., 2004 Synthesis of kaolinite-organic nanohybrids with butanediols Solid State Ionics 172 279–282.CrossRefGoogle Scholar
Neder, R.B. Burghammer, M. Grasl, T.H. Schulz, H. Bram, A. and Fiedler, S., 1999 Refinement of the kaolinite structure from single-crystal synchrotron data Clays and Clay Minerals 47 487–494.CrossRefGoogle Scholar
Olejnik, S. Aylmore, L.A.G. Posner, A.M. and Quirk, J.P., 1968 Infrared spectra of kaolin mineral-dimethyl sulfoxide complexes Journal of Physical Chemistry 72 241–249.CrossRefGoogle Scholar
Perdew, J.P. and Wang, Y., 1992 Accurate and simple analytic representation of the electron-gas correlation energy Physical Review B 45 13244–13249.CrossRefGoogle ScholarPubMed
Perdew, J.P. and Zunger, A., 1981 Self-interaction correction to density-functional approximations for many-electron systems Physical Review B 23 5048–5079.CrossRefGoogle Scholar
Raupach, M. Barron, P.F. and Thompson, J.G., 1987 Nuclear magnetic resonance, infrared, and X-ray powder diffraction study of dimethylsulfoxide and dimethylselenoxide intercalates with kaolinite Clays and Clay Minerals 35 208–219.CrossRefGoogle Scholar
Scholtzová, E. Smrčok, , 2009 Hydrogen bonding and vibrational spectra in kaolinite-dimethylsulfoxide and -dimethylselenoxide intercalates - a solid-state computational study Clays and Clay Minerals 57 54–71.CrossRefGoogle Scholar
Scholtzová, E. Benco, L. and Tunega, D., 2008 A model study of dickite intercalated with formamide and N-methylformamide Physics and Chemistry of Minerals 35 299–309.CrossRefGoogle Scholar
Smrčok, Tunega, D. Ramirez-Cuesta, A.J. and Scholtzová, E., 2010 The combined inelastic neutron scattering and solid state DFT study of hydrogen atoms dynamics in a highly ordered kaolinite Physics and Chemistry of Minerals 37 571–579.CrossRefGoogle Scholar
Steiner, T., 2002 The hydrogen bond in the solid state Angewandte Chemie International Edition 41 48–76.3.0.CO;2-U>CrossRefGoogle ScholarPubMed
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
Tunney, J.J. and Detellier, C., 1993 Interlamellar covalent grafting of organic units on kaolinite Chemistry of Materials 5 747–748.CrossRefGoogle Scholar
Tunney, J.J. and Detellier, C., 1996 Chemically modified kaolinite. Grafting of methoxy groups on the interlamellar aluminol surface of kaolinite Journal of Materials Chemistry 6 1679–1685.CrossRefGoogle Scholar
Wada, K., 1961 Lattice expansion of kaolin minerals by treatment with potassium acetate American Mineralogist 46 78–91.Google Scholar