Hostname: page-component-cd9895bd7-dzt6s Total loading time: 0 Render date: 2024-12-28T19:20:55.817Z Has data issue: false hasContentIssue false
  • English
  • Français

Solid-State 1H and 27Al NMR Studies of DMSO-Kaolinite Intercalates

Published online by Cambridge University Press:  01 January 2024

Jonathan Fafard ,
Victor Terskikh  and
Christian Detellier
Jonathan Fafard
Affiliation:
Center for Catalysis Research and Innovation and Department of Chemistry and Biomolecular Sciences, University of Ottawa, K1N 6N5, Ottawa, Ontario, Canada
Victor Terskikh
Affiliation:
Center for Catalysis Research and Innovation and Department of Chemistry and Biomolecular Sciences, University of Ottawa, K1N 6N5, Ottawa, Ontario, Canada
Christian Detellier*
Affiliation:
Center for Catalysis Research and Innovation and Department of Chemistry and Biomolecular Sciences, University of Ottawa, K1N 6N5, Ottawa, Ontario, Canada
*
*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.

Nuclear magnetic resonance (NMR) provides a powerful tool to describe local nuclear environments. In this work, unique structural information on kaolinite and on kaolinite dimethylsulfoxide (DMSO) intercalate were provided by solid-state 1H and 27Al magic-angle spinning (MAS) NMR. The interlayer chemistry of kaolinite (K) was examined by intercalating a select group of highly polar organic molecules or salts into kaolinite as a first step. Once the interlayer space is expanded, the intercalated compounds can be replaced in a second step. Intercalating DMSO into kaolinite to form the DMSO-K intercalate is, thus, a particularly useful first step toward the intercalation of a large variety of molecules, including polymers and ionic liquids. Well developed characterization methods are essential to define the structural modifications of kaolinite, and MAS NMR is a useful complement to other techniques. The use of 1H and 27Al MAS NMR for this purpose has been relatively rare. 1H NMR, nevertheless, can give unique information about kaolinite hydroxyls. Because quadrupolar interactions are sensitive to the local octahedral Al(III) geometry, solid-state 27Al NMR can follow subtle structural modifications in the octahedral sheet. In the present work, the 1H MAS NMR chemical shifts of KGa-1b were unambiguously attributed to the internal surface hydroxyls at 2.7 ppm and to the internal hydroxyls at 1.7 ppm. The 1H MAS NMR chemical shifts of the two methyl groups in DMSO-K are not equivalent and can be attributed to the 2.9 and 4.2 ppm peaks. The 27Al MAS NMR spectra of KGa-1b obtained under different magnetic fields revealed that most of the quadrupolar effects were highly reduced at 21.1 T, whereas the spectra at lower field, 4.7 T, were dominated by quadrupolar effects. The two octahedral Al(III) sites are not equivalent and can be distinguished in the low-field spectral simulation. Increased quadrupolar constants were observed and showed the major perturbations of the local Al symmetry that resulted from DMSO intercalation. Both the 1H and 27Al MAS NMR studies at different magnetic fields afforded important information about the local environments of the kaolinite hydroxyl groups and structural Al(III).

Keywords

27Al MAS NMRDeconvolutionDMSO1H MASIntercalationKaoliniteQuadrupolar InteractionsSolid-State NMR
Type
Article
Information
Clays and Clay Minerals , Volume 65 , Issue 3 , June 2017 , pp. 206 - 219
Copyright
Copyright © Clay Minerals Society 2017

References

Abou-El-Sherbini, K.S. Elzahany, E.A.M. Wahba, M.A. Drweesh, S.A., and Youssef, N.S., 2017 Evaluation of some intercalation methods of dimethylsulfoxide onto HCltreated and untreated Egyptian kaolinite Applied Clay Science 137 33–42.CrossRefGoogle Scholar
Alba, M.D. Becerro, A.I. Castro, M.A. and Perdigón, A.C., 2000 High-resolution 1H MAS NMR spectra of 2:1 phyllosilicates Chemical Communications 37–38.CrossRefGoogle Scholar
Armstrong, B.H., 1967 Spectrum line profiles: the Voigt function Journal of Quantitative Spectroscopy and Radiative Transfer 7 61–88.CrossRefGoogle Scholar
Ashbrook, S.E. McManus, J. MacKenzie, K.J.D. and Wimperis, S., 2000 Multiple-quantum and cross-polarized 27Al MAS NMR of mechanically treated mixtures of kaolinite and gibbsite Journal of Physical Chemistry B 104 6408–6416.CrossRefGoogle Scholar
Bish, DL D ^RB, 1989 Rietveld refinement of non-hydrogen atomic positions in kaolinite Clays and Clay Minerals 37 289–296.CrossRefGoogle Scholar
Bish, D.L., 1993 Rietveld refinement of the kaolinite structure at 1.5K Clays and Clay Minerals 41 738–744.CrossRefGoogle Scholar
Barron, P.F. Frost, R.L. and Skjemstad, J.O., 1983 Detection of two silicon environments in kaolins via solid-state 29Si NMR Nature 302 49–50.CrossRefGoogle Scholar
Bergaya, F. Lagaly, G., Bergaya, F., and Lagaly, G., 2013 General Introduction: Clays, Clay Minerals, and Clay Science Handbook of Clay Science 2nd ed. Amsterdam Elsevier.Google Scholar
Brack, A., Bergaya, F., and Lagaly, G., 2013 Clay minerals and the origin of life Handbook of Clay Science 2nd ed. Amsterdam. Elsevier 507–522.CrossRefGoogle Scholar
Brigatti, M.F. Galän, E. Theng, B.K.G., Bergaya, F., and Lagaly, G., 2013 Structure and mineralogy of clay minerals Handbook of Clay Science 2nd ed. Amsterdam Elsevier 29–35.Google Scholar
Cheng, H. Hou, X. Liu, Q. Li, X., and Frost, R.L., 2015 New insights into the molecular structure of kaolinite methanol intercalation complexes Applied Clay Science 109-110 55–63.CrossRefGoogle Scholar
Crosson, G.S. Choi, S.Y. Chorover, J. Amistadi, M.K. O’Day, P.A., and Mueller, K.T., 2006 Solid-state NMR identification and quantification of newly formed aluminosilicate phases in weathered kaolinite systems Journal of Physical Chemistry B 110 723–732.CrossRefGoogle ScholarPubMed
Dedzo, G.K., and Detellier, C., 2016 Functional nanohybrid materials derived from kaolinite Applied Clay Science 130 33–39.CrossRefGoogle Scholar
Detellier, C., and Schoonheydt, R.A., 2014 From Platy Kaolinite to Nanorolls Elements 10 201–206.CrossRefGoogle Scholar
Detellier, C., Letaief, S., Fafard, J., and Dedzo, G.K. (2015) Desorption of bitumen from clay particles and mature fine tailings, US Patent application No 14/083,824; US 2015/0136651 A1: published May 21, 2015.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
Duer, M.J., and Rocha, J., 1992 A two-dimensional solid-state exchange NMR study of the molecular motion in the kaolinite: DMSO intercalation compound Journal of Magnetic Resonance 98 524–533.Google Scholar
Frost, R.L. Kristof, J. Paroz, G.N., and Kloprogge, J.T., 1998 Molecular structure of dimethyl sulfoxide intercalated kaolinites The Journal of Physical Chemistry B 102 8519–8532.CrossRefGoogle Scholar
Galimberti, M. Cipolletti, V.R. Coombs, M., Bergaya, F., and Lagaly, G., 2013 Applications of clay-polymer nanocomposites Handbook of Clay Science 2nd edition Amsterdam Elsevier 539–586.CrossRefGoogle Scholar
Gerstein, B.C., 2009.CRAMPS: High-Resolution NMR of High-γ Nuclei in SolidsCrossRefGoogle Scholar
Ghose, S. and Tsang, T., 1973 Structural Dependence of Quadrupole Coupling Constant e2qQ/h for 27Al and Crystal Field Parameter D for Fe3+ in Aluminosilicates American Mineralogist 58 748–755.Google Scholar
Giese, R.F., 1982 Theoretical studies of the kaolin minerals electrostatic calculations Bulletin de Minéralogie 105 417–424.CrossRefGoogle Scholar
Gullion, T., 1995 Measurement of dipolar interactions between spin-1/2 and quadrupolar nuclei by rotational-echo, adiabatic-passage, double-resonance NMR Chemical Physics Letters 246 325–330.CrossRefGoogle Scholar
Hayashi, S. Ueda, T. Hayamizu, K., and Akiba, E., 1992 NMR study of kaolinite Journal of Physical Chemistry 96 10922–10928.CrossRefGoogle Scholar
Hayashi, S. Ueda, T. Hayamizu, K. and Akiba, E., 1992 NMR study of kaolinite. 2. 1H, 27Al, and 29Si spin-lattice relaxations Journal of Physical Chemistry 96 10928–10933.CrossRefGoogle Scholar
Hayashi, S., and Akiba, E., 1995 Nuclear spin-lattice relaxation mechanisms in kaolinite confirmed by magicangle spinning Solid State Nuclear Magnetic Resonance 4 331–340.CrossRefGoogle ScholarPubMed
Hayashi, S., 1997 NMR study of dynamics and evolution of guest molecules in kaolinite /dimethylsulfoxide intercalation compound Clays and Clay Minerals 45 724–732.CrossRefGoogle Scholar
Hirsemann, D. Köster, TK-J Wack, J v W ^L Breu, J., and Senker, J., 2011 Covalent grafting to μ hydroxy-capped surfaces? A kaolinite case study Chemistry of Materials 23 3152–3158.CrossRefGoogle Scholar
Horvath, E. Kristof, J., and Frost, R.L., 2010 Vibrational spectroscopy of intercalated kaolinite. Part I. Applied Spectroscopy Reviews 45 130–147.CrossRefGoogle Scholar
Jeffries, C.D., and Jackson, M.L., 1949 Mineralogical analysis of soils Soil Science 68 57–74.CrossRefGoogle Scholar
Johansson, U. Holmgren, A. Forsling, W., and Frost, R., 1998 Isotopic exchange of kaolinite hydroxyl protons: a diffuse reflectance infrared Fourier transform spectroscopy study Analyst 123 641–645.CrossRefGoogle Scholar
Johnston, C.T. Sposito, G. Bocian, D.F., and Birge, R.R., 1984 Vibrational spectroscopic study of the interlamellar kaolinite-dimethylsulfoxide complex Journal of Physical Chemistry 88 5959–5964.CrossRefGoogle Scholar
Johnston, C.T. Agnew, S.F., and Bish, D.L., 1990 Polarized single-crystal Fourier-transform infrared microscopy of Ouray dickite and Keokuk kaolinite Clays and Clay Minerals 38 573–583.CrossRefGoogle Scholar
Johnston, C.T., 2010 Probing the nanoscale architecture of clay minerals Clay Minerals 45 245–279.CrossRefGoogle Scholar
Kittel, C., and Abrahams, E., 1953 Dipolar broadening of magnetic resonance lines in magnetically diluted crystals Physical Review 90 238–239.CrossRefGoogle Scholar
Lagaly, G. Ogawa, M. Dékäny, I., Bergaya, F., and Lagaly, G., 2013 Intercalation reactions of kaolinite Handbook of Clay Science 2nd edition Amsterdam Elsevier 437–445.Google Scholar
Langford, J.I., 1978 A rapid method for analysing the breadths of diffraction and spectral lines using the Voigt function Journal of Applied Crystallography 11 10–14.CrossRefGoogle Scholar
Laszlo, P., 1986 Catalysis of organic reactions by inorganic solids Accounts of Chemical Research 19 121–127.CrossRefGoogle Scholar
Ledoux, R.L., and White, J.L., 1964 Infrared study of selective deuteration of kaolinite and halloysite at room temperature Science 145 47–49.CrossRefGoogle ScholarPubMed
Letaief, S. Diaco, T. Pell, W. Gorelsky, S.I., and Detellier, C., 2008 Ionic conductivity of nanostructured hybrid materials designed from imidazolium ionic liquids and kaolinite Chemistry of Materials 20 7136–7142.CrossRefGoogle Scholar
Letaief, S., and Detellier, C., 2009 Clay-polymer nanocomposite material from the delamination of kaolinite in the presence of sodium polyacrylate Langmuir 25 10975–10979.CrossRefGoogle ScholarPubMed
Letaief, S., and Detellier, C., 2011 Application of thermal analysis for the characterisation of intercalated and grafted organo-kaolinite nanohybrid materials Journal of Thermal and Analytical Calorimetry 104 831–839.CrossRefGoogle Scholar
Li, S. Zheng, A. Su, Y. Fang, H. Shen, W. Yu, Z. Chen, L., and Deng, F., 2010 Extra-framework aluminium species in hydrated faujasite zeolite as investigated by two-dimensional solid-state NMR spectroscopy and theoretical calculations Physical Chemistry Chemical Physics 12 3895–3903.CrossRefGoogle ScholarPubMed
Lin, F. He, L. Hou, J. Masliyah, J., and Xu, Z., 2016 Role of ethyl cellulose in bitumen extraction from oil sands ores using an aqueous-nonaqueous hybrid process Energy & Fuels 30 121–129.CrossRefGoogle Scholar
MacKenzie, K.J.D. Smith, M.E., Cahn, R.W., 2002 Physical Background Multinuclear Solid-state Nuclear Magnetic Resonance of Inorganic Materials Oxford, UK Elsevier Science Ltd 21–108.Google Scholar
Mansa, R. Piegang, G B N, and Detellier, C., 2017 Kaolinite aggregation in book-like structures from nonaqueous media Clays and Clay Minerals 65 193–205.CrossRefGoogle Scholar
Massiot, D. Fayon, F. Capron, M. King, I L C ^S Alonso, B. Hoatson, G. Durand, J. Bujoli, B. Gan, Z., and Hoatson, G., 2002 Modelling one- and two -dimensional solid-state NMR spectra Magnetic Resonance in Chemistry 40 70–76.CrossRefGoogle Scholar
Mccabe, R.W. Adams, J.M., Bergaya, F., and Lagaly, G., 2013 Clay minerals as catalysts Handbook of Clay Science 2nd ed Amsterdam Elsevier 491–523.CrossRefGoogle Scholar
Michalkovä, A., and Tunega, D., 2007 Kaolinite:dimethylsulfoxide intercalate A theoretical study Journal of Physical Chemistry C 111 11259–11266.CrossRefGoogle Scholar
Millot, Y., and Man, P.P., 2002 Procedures for labeling the high-resolution axis of two-dimensional MQ-MAS NMR spectra of half-integer quadrupole spins Solid State Nuclear Magnetic Resonance 21 21–43.CrossRefGoogle ScholarPubMed
Murray, H.H. Keller, W.D., H.H, M. W.M, B., and C.C, H., 1993 Kaolins, kaolins, and kaolins Kaolin Genesis and Utilization Boulder, Colorado, USA The Clay Minerals Society 1–24.CrossRefGoogle Scholar
Murray, H.H., 2007 Applied Clay Mineralogy Oxford Elsevier.Google Scholar
Ngnie, G. Dedzo, G.K., and Detellier, C., 2016 Synthesis and catalytic application of palladium nanoparticles supported on kaolini te-based nanohybrid materials Dalton Transactions 45 9065–9072.CrossRefGoogle Scholar
Olejnik, S. Aylmore, L.A.G. Posner, A.M., and Quirk, J.P., 1968 Infrared spectra of kaolin mineral dimethylsulfoxide complexes Journal of Physical Chemistry 72 241–249.CrossRefGoogle Scholar
Paris, M., 2014 The two aluminum sites in the 27Al MAS NMR spectrum of kaolinite: Accurate determination of isotropic chemical shifts and quadrupolar interaction parameters American Mineralogist 99 393–400.CrossRefGoogle Scholar
Pruett, R.J., and Webb, H.L., 1993 Sampling and analysis of KGa-1b well crystallized kaolin source clay Clays and Clay Minerals 41 514–519.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
Rocha, J. and Pedrosa de Jesus, D., 1994 27Al satellite transition MAS-NMR spectroscopy of kaolinite Clay Minerals 29 287–291.CrossRefGoogle Scholar
Romo, L.A., 1956 The exchange of hydrogen by deuterium in hydroxyls of kaolinite Journal of Physical Chemistry 60 987–989.CrossRefGoogle Scholar
Scholtzova, E., and Smrcok, L., 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
Schroeder, P.A., and Erickson, G., 2014 Kaolin: from ancient porcelains to nanocomposites Elements 10 177–182.CrossRefGoogle Scholar
Thompson, J.G., 1985 Interpretation of solid state 13C and 29Si nuclear magnetic resonance spectra of kaolinite intercalates Clays and Clay Minerals 33 173–180.CrossRefGoogle Scholar
Thompson, J.G., and Cuff, C., 1985 Crystal structure of kaolinite: dimethylsulfoxide intercalate Clays and Clay Minerals 33 490–500.CrossRefGoogle Scholar
Tonlé, I.K. Letaief, S. Ngameni, E., and Detellier, C., 2009 Nanohybrid materials from the grafting of imidazolium cations on the interlayer surfaces of kaolinite Application as electrode modifier. Journal of Material Chemistry 19 5996–6003.Google Scholar
Tonlé, I.K. Letaief, S. Ngameni, E. Walcarius, A., and Detellier, C., 2011 Square wave voltammetric determination of lead(II) ions using a carbon paste electrode modified by a thiol-functionalized kaolinite Electroanalysis 23 245–252.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., 1994 Preparation and characterization of two distinct ethylene glycol derivatives of kaolinite Clays and Clay Minerals 42 552–560.CrossRefGoogle Scholar
Van Vleck, J.H., 1948 The dipolar broadening of magnetic resonance lines in crystals Physical Review 74 1168–1183.CrossRefGoogle Scholar
Wang, L. Wu, D. Yuan, P. Chen, Z. and Chen, Z., 2002 1H MAS NMR spectra of kaolinite/formamide intercalation compound Chinese Science Bulletin 47 504–508.CrossRefGoogle Scholar
Wasylishen, R.E. Ashbrook, S.E. and Wimperis, S., 2012.NMR of Quadrupolar Nuclei in Solid MaterialsGoogle Scholar
Wojdyr, M., 2010 Fityk: a general-purpose peak fitting program Journal of Applied Crystallography 43 1126–1128.CrossRefGoogle Scholar
Yariv, S., and Lapides, I., 2008 Thermo-infrared spectroscopy analysis of dimethylsulfoxide-kaolinite intercalation complexes Journal of Thermal Analysis and Calorimetry 94 433–440.CrossRefGoogle Scholar
Yong, R.N., and Mourato, D., 1990 Influence of polysaccharides on kaolinite structure and properties in a kaolinitewater system Canadian Geotechnical Journal 27 774–788.CrossRefGoogle Scholar
Zhou, B. Sherriff, B.L. and Wang, T., 2009 27Al NMR spectroscopy at multiple magnetic fields and ab initio quantum modeling for kaolinite American Mineralogist 94 865–871.CrossRefGoogle Scholar
Zhu, X. Zhu, Z. Lei, X., and Yan, C., 2016 Defects in structure as the sources of the surface charges of kaolinite Applied Clay Science 124–125 127–136.CrossRefGoogle Scholar