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Intercalation of Ethylene Glycol in Smectites: Several Molecular Simulation Models Verified by X-Ray Diffraction Data

Published online by Cambridge University Press:  01 January 2024

Marek Szczerba  and
Andrey G. Kalinichev
Marek Szczerba*
Affiliation:
Institute of Geological Sciences, Polish Academy of Sciences, Kraków, Poland
Andrey G. Kalinichev
Affiliation:
Laboratoire SUBATECH (UMR 6457), Ecole des Mines de Nantes, Nantes, France
*
*E-mail address of corresponding author: ndszczer@cyf-kr.edu.pl
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Abstract

Organo-clays represent a special challenge for molecular simulations because they require accurate representation of the clay and the organic/aqueous sections of the model system and accurate representation of the interactions between them. Due to the broad range of force-field models available, an important question to ask is which sets of parameters will best suit the molecular modeling of the organo-intercalated smectites? To answer this question, the structure of the ethylene glycol (EG)-smectite complex is used here as a testing model because the intercalation of EG in smectites provides a stable interlayer complex with relatively constant basal spacing.

Three smectite samples with substantially different layer charge and charge localization were selected for X-ray diffraction (XRD) measurements. Their molecular models were built and molecular-dynamics simulations performed using various combinations of the organic force fields (CGenFF, GAFF, CVFF, and OPLS-aa) with ClayFF and INTERFACE force fields used to describe smectites. The simulations covered a range of different EG and water contents. For every structure, the density distribution of interlayer species along the direction perpendicular to the layer plane was calculated and then used to optimize the XRD patterns for these simulated models.

A comparison of these results with experimental XRD patterns shows very large discrepancies in the structures and basal spacings obtained for different layer charges as well as for different force fields and their combinations. The most significant factor affecting the accuracy of the calculated XRD patterns was the selection of the clay-mineral force-field parameters. The second important conclusion is that a slight modification of the basal oxygen parameters for non-electrostatic interactions (increase of their effective atomic diameters) may be a simple and straightforward way to improve significantly the agreement between the modeled XRD patterns with experiments, especially for high-charge smectites. Generally, among organic force fields, the least accurate results were obtained with CGenFF. For unmodified ClayFF, its combination with GAFF gave the best results, while the two other sets (OPLS-aa and CVFF) gave the best results in combination with ClayFFmod. The INTERFACE and INTERFACEmod produced much better results for low-charge montmorillonite than for high-charge smectites.

Keywords

Ethylene GlycolMolecular DynamicsSmectiteX-ray Diffraction
Type
Article
Information
Clays and Clay Minerals , Volume 64 , Issue 4 , August 2016 , pp. 488 - 502
Copyright
Copyright © The Clay Minerals Society 2016

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Footnotes

This paper is published as part of a special issue on the subject of ‘Computational Molecular Modeling.’ Some of the papers were presented during the 2015 Clay Minerals Society-Euroclay Conference held in Edinburgh, UK.

References

Allen, M.P. and Tildesley, D.J., 1987 Computer Simulation of Liquids New York Oxford University Press 385 pp..Google Scholar
Berendsen, H.J.C. Postma, J.P.M. van Gunsteren, W.F. Hermans, J., Pullman, B., 1981 Interaction models for water in relation to protein hydration Intermolecular Forces Dordrecht, The Netherlands D. Reidel 331–342.CrossRefGoogle Scholar
Brindley, G.W., 1966 Ethylene glycol and glycerol complexes of smectite and vermiculites Clay Minerals 6 237–259.CrossRefGoogle Scholar
Cornell, W.D. Cieplak, P. Bayly, C.I. Gould, I.R. Merz, K.M. Jr. Ferguson, D.M. Spellmeyer, D.C. Fox, T. Caldwell, J.W. and Kollman, P.A., 1995 A second generation force field for the simulation of proteins, nucleic acids and organic molecules Journal of the American Chemical Society 117 5179–5197.CrossRefGoogle Scholar
Cygan, R.T. Liang, J.J. and Kalinichev, A.G., 2004 Molecular models of hydroxide, oxyhydroxide, and clay phases and the development of a general force field Journal of Physical Chemistry B 108 1255–1266.CrossRefGoogle Scholar
Cygan, R.T. Greathouse, J.A. Heinz, H. and Kalinichev, A.G., 2009 Molecular models and simulation of layered minerals Journal of Materials Chemistry 19 2470–2481.CrossRefGoogle Scholar
Dauber-Osguthorpe, P. Roberts, V.A. Osguthorpe, D.J. Wolff, J. Genest, M. and Hagler, A.T., 1988 Structure and energetics of ligand binding to proteins: E. coli dihydrofolate reductase-trimethoprim, a drug-receptor system Proteins: Structure, Function and Genetics 4 31–47.CrossRefGoogle ScholarPubMed
Drits, V. and Tchoubar, C., 1990 X-ray Diffraction by Disordered Lamellar Structures. Theory and Applications to Microdivided Silicates and Carbons Berlin, Heidelberg Springer-Verlag.Google Scholar
Duque-Redondo, E. Manzano, H. Epelde-Elezcano, N. Martínez-Martínez, V. and Lopez-Arbeloa, I., 2014 Molecular forces governing shear and tensile failure in clay-dye hybrid materials Chemistry of Materials 26 4338–4345.CrossRefGoogle Scholar
Eberl, D.D. Środoń, J. Northrop, H.R., Davis, J.A. and Hayes, K.F., 1986 Potassium fixation in smectite by wetting and drying Geochemical Processes at Mineral Surfaces 296–326.CrossRefGoogle Scholar
Eberl, D.D. Środoń, J. Lee, M. Nadeau, P.H. and Northrop, H.R., 1987 Sericite from the Silverton caldera, Colorado: Correlation among structure, composition, origin, and particle thickness American Mineralogist 72 914–934.Google Scholar
Ferrage, E. Sakharov, B.A. Michot, L.J. Delville, A. Bauer, A. Lanson, B. Grangeon, S. Frapper, G. Jimenez-Ruiz, M. and Cuello, G.J., 2011 Hydration properties and interlayer organization of water and ions in synthetic Nasmectite with tetrahedral layer charge. Part 2. Toward a precise coupling between molecular simulations and diffraction data Journal of Physical Chemistry C 115 1867–1881.CrossRefGoogle Scholar
Frisch, M.J. Trucks, G.W. Schlegel, H.B. Scuseria, G.E. Robb, M.A. Cheeseman, J.R.T. Montgomery, J.A. Vreven, J.T. Kudin, K.N. Burant, J.C. Millam, J.M. Iyengar, S.S. Tomasi, J. Barone, V. Mannucci, B. Cossi, M. Scalmani, G. Rega, N. Petersson, G.A. Nakatsuji, H. Hada, M. Ehara, M. Toyota, K. Fukuda, F. Hasegawa, J. Ishida, M. Nakajima, T. Honda, Y. Kitao, O. Nakai, H. Klene, M. Li, X. Knox, J.E. Hratchian, H.P. Cross, J.B. Bakken, V. Adamo, C. Jramillo, J. Gomperts, R. Stratmann, R.E. Yazyev, O. Austin, A.J. Cammi, R. Pomelli, C. Ochterski, J.W. Ayala, P.Y. Morokuma, K. Voth, G.A. Salvador, P. Dannenberg, J.J. Zakrzewski, V.G. Dapprich, S. Daniels, A.D. Strain, M.C. Frakas, O. Malick, D.K. Rabuck, A.D. Raghavachari, K. Foresman, J.B. Ortiz, J.V. Cui, Q. Baboul, A.G. Clifford, S. Cislowski, J. Stefanov, B.B. Liu, G. Liashenko, A. Piskorz, P. Komaromi, I. Martin, R.L. Fox, D.J. Keith, T. Al-Laham, M.A. Peng, C.Y. Nanayakkara, A. Challacombe, M. Gill, P.M.W. Johnson, B. Chen, W. Wong, M.W. Gonzalez, C. and Pople, J.A., 2004 Gaussian-94, Revision C.3 Pennsylvania, USA Gaussian, Inc. Pittsburgh.Google Scholar
Greathouse, J.A. Hart, D.B. Bowers, G.M. Kirkpatrick, R.J. and Cygan, R.T., 2015 Molecular simulation of structure and diffusion at smectite-water interfaces: Using expanded clay interlayers as model nanopores Journal of Physical Chemistry C 119 17126–17136.CrossRefGoogle Scholar
Greathouse, J.A. Johnson, K.L. and Greenwell, H.C., 2014 Interaction of natural organic matter with layered minerals: Recent developments in computational methods at the nanoscale Minerals 4 519–540.CrossRefGoogle Scholar
Guillot, B., 2002 A reappraisal of what we have learnt during three decades of computer simulations on water Journal of Molecular Liquids 101 219–260.CrossRefGoogle Scholar
Guvench, O. MacKerell, A.D. Jr., 2008 Comparison of protein force fields for molecular dynamics simulations Methods in Molecular Biology 443 63–88.CrossRefGoogle ScholarPubMed
Harward, M.E. and Brindley, G.W., 1965 Swelling properties of synthetic smectite in relation to lattice substitutions Clays and Clay Minerals 13 209–222.CrossRefGoogle Scholar
Harward, M.E. Carstea, D.D. and Sayegh, A.H., 1969 Properties of vermiculite and smectites: Expansion and collapse Clays and Clay Minerals 16 437–447.CrossRefGoogle Scholar
Heinz, H. Koerner, H. Anderson, K.L. Vaia, R.A. and Farmer, B.L., 2005 Force field for mica-type silicates and dynamics of octadecylammonium chains grafted to montmorillonite Chemistry of Materials 17 5658–5669.CrossRefGoogle Scholar
Heinz, H. Lin, T.J. Mishra, R.K. and Emami, F.S., 2013 Thermodynamically consistent force fields for the assembly of inorganic, organic, and biological nanostructures: The INTERFACE force field Langmuir 29 1754–1765.CrossRefGoogle ScholarPubMed
Heinz, H. and Ramezani-Dakhel, H., 2016 Simulations of inorganic-bioorganic interfaces to discover new materials: insights, comparisons to experiment, challenges, and opportunities Chemical Society Reviews 45 412–448.CrossRefGoogle ScholarPubMed
Hill, J.-R. and Sauer, J., 1995 Molecular mechanics potential for silica and zeolite catalysts based on ab initio calculations. 2. Aluminosilicates Journal of Physical Chemistry 99 9536–9550.CrossRefGoogle Scholar
Humphrey, W. Dalke, A. and Schulten, K., 1996 VMD — Visual Molecular Dynamics Journal of Molecular Graphics 14 33–38.CrossRefGoogle ScholarPubMed
Jorgensen, W.L. and Gao, J., 1986 Monte Carlo simulations of the hydration of ammonium and carboxylate ions The Journal of Physical Chemistry 90 2174–2182.CrossRefGoogle Scholar
Jorgensen, W.L. Maxwell, D.S. and Tirado-Rives, J., 1996 Development and testing of the OPLS all-atom force field on conformational energetics and properties of organic liquids Journal of the American Chemical Society 118 11225–11236.CrossRefGoogle Scholar
Kalinichev, A.G., 2001 Molecular simulations of liquid and supercritical water: Thermodynamics, structure, and hydrogen bonding Molecular Modeling Theory: Applications in the Geosciences 42 83–129.CrossRefGoogle Scholar
Kalinichev, A.G. Kumar, P.P. and Kirkpatrick, R.J., 2010 Molecular dynamics computer simulations of the effects of hydrogen bonding on the properties of layered double hydroxides intercalated with organic acids Philosophical Magazine 90 2475–2488.CrossRefGoogle Scholar
Kumar, P.P. Kalinichev, A.G. and Kirkpatrick, R.J., 2006 Hydration, swelling, interlayer structure, and hydrogen bonding in organolayered double hydroxides: Insights from molecular dynamics simulation of citrate-intercalated hydrotalcite Journal of Physical Chemistry B 110 3841–3844.CrossRefGoogle Scholar
Lee, J.H. and Guggenheim, S., 1981 Single crystal X-ray refinement of pyrophyllite-1Tc American Mineralogist 66 350–357.Google Scholar
Liu, X. Lu, X. Wang, R. Zhou, H. and Xu, S., 2007 Interlayer structure and dynamics of alkylammonium-intercalated smectites with and without water: A molecular dynamics study Clays and Clay Minerals 55 554–564.CrossRefGoogle Scholar
MacKerell, A.D. Jr. Bashford, D. Bellott, M. Dunbrack, R.L. Evanseck, J.D. Field, M.J. Fischer, S. G. J, Guo, H. Ha, S. Joseph-McCarthy, D. Kuchnir, L. Kuczera, K. Lau, F.T.K. Mattos, C. Michnick, S. Ngo, T. Nguyen, D.T. Prodhom, B. Reiher, I.I.I. W.E, R. B, S. M, S. J.C, S. R, Straub, J. Watanabe, M. Wiórkiewicz-Kuczera, J. Yin, D. and Karplus, M., 1998 All-atom empirical potential for molecular modeling and dynamics studies of proteins Journal of Physical Chemistry B 102 3586–3616.CrossRefGoogle ScholarPubMed
Manevitch, O.L. and Rutledge, G.C., 2004 Elastic properties of a single lamella of montmorillonite by molecular dynamics simulation Journal of Physical Chemistry B 108 1428–1435.CrossRefGoogle Scholar
Morrow, C.P. Yazaydin, A. Krishnan, M. Bowers, G.M. Kalinichev, A.G. and Kirkpatrick, R.J., 2013 Structure, energetics, and dynamics of smectite clay interlayer hydration: Molecular dynamics and metadynamics investigation of Na-hectorite Journal of Physical Chemistry C 117 5172–5187.CrossRefGoogle Scholar
Mosser-Ruck, R. Devineau, K. Charpentier, D. and Cathelineau, M., 2005 Effects of ethylene glycol saturation protocols on XRD patterns: A critical review and discussion Clays and Clay Minerals 53 631–638.CrossRefGoogle Scholar
Mukherjee, G. Patra, N. Barua, P. and Jayaram, B., 2011 A fast empirical GAFF compatible partial atomic charge assignment scheme for modeling interactions of small molecules with biomolecular targets (TPACM4) Journal of Computational Chemistry 32 893–907.CrossRefGoogle Scholar
Ngouana Wakou, B.F. and Kalinichev, A.G., 2014 Structural arrangements of isomorphic substitutions in smectites: Molecular simulation of the swelling properties, interlayer structure, and dynamics of hydrated Cs-montmorillonite revisited with new clay models Journal of Physical Chemistry C 118 12758–12773.CrossRefGoogle Scholar
Ortega-Castro, J. Hernández-Haro, N. Dove, M.T. Hernández-Laguna, A. and Saínz-Diaz, C.I., 2010 Density functional theory and Monte Carlo study of octahedral cation ordering of Al/Fe/Mg cations in dioctahedral 2:1 phyllosilicates American Mineralogist 95 209–220.CrossRefGoogle Scholar
Pintore, M. Deiana, S. Demontis, P. Manunza, B. Suffritti, G.B. and Gessa, C., 2001 Simulations of interlayer methanol in Ca-and Na-saturated montmorillonites using molecular dynamics Clays and Clay Minerals 49 255–262.CrossRefGoogle Scholar
Plimpton, S., 1995 Fast parallel algorithms for short-range molecular dynamics Journal of Computational Physics 117 1–19.CrossRefGoogle Scholar
Reynolds, R.C., 1965 An X-ray study of an ethylene glycolmontmorillonite complex American Mineralogist 50 990–1001.Google Scholar
Reynolds, R.C., 1986 The Lorentz-polarization factor and preferred orientation in oriented clay aggregates Clays and Clay Minerals 34 359.CrossRefGoogle Scholar
Sato, T. Watanabe, T. and Otsuka, R., 1992 Effects of layer charge, charge location, and energy change on expansion properties of dioctahedral smectites Clays and Clay Minerals 40 103–113.CrossRefGoogle Scholar
Sato, H. Yamagishi, A. and Kawamura, K., 2001 Molecular simulation for flexibility of a single clay layer Journal of Physical Chemistry B 105 7990–7997.CrossRefGoogle Scholar
Schampera, B. Solc, R. Woche, S.K. Mikutta, R. Dultz, S. Guggenberger, G. and Tunega, D., 2015 Surface structure of organoclays as examined by X-ray photoelectron spectroscopy and molecular dynamics simulations Clay Minerals 50 353–367.CrossRefGoogle Scholar
Skipper, N.T. Refson, K. and McConnell, J.D.C., 1991 Computer simulation of interlayer water in 2:1 clays Journal of Chemical Physics 94 7434–7445.CrossRefGoogle Scholar
Skipper, N.T. Chang, F.R.C. and Sposito, G., 1995 Monte Carlo simulation of interlayer molecular structure in swelling clay minerals. I: Methodology Clays and Clay Minerals 43 285–293.CrossRefGoogle Scholar
Smith, D.E., 1998 Molecular computer simulations of the swelling properties and interlayer structure of cesium montmorillonite Langmuir 14 5959–5967.CrossRefGoogle Scholar
Svensson, P.D. and Hansen, S., 2010 Intercalation of smectite with liquid ethylene glycol u` Resolved in time and space by synchrotron X-ray diffraction Applied Clay Science 48 358–367.CrossRefGoogle Scholar
Suter, J.L. and Coveney, P.V., 2009 Computer simulation study of the materials properties of intercalated and exfoliated poly (ethylene) glycol clay nanocomposites Soft Matter 5 2239–2251.CrossRefGoogle Scholar
Suter, J.L. Coveney, P.V. Anderson, R.L. Greenwell, H.C. and Cliffe, S., 2011 Rule based design of clay-swelling inhibitors Energy & Environmental Science 4 4572–4586.CrossRefGoogle Scholar
Suter, J.L. Groen, D. and Coveney, P.V., 2015 Chemically specific multiscale modeling of clay-polymer nanocomposites reveals intercalation dynamics, tactoid self-assembly and emergent materials properties Advanced Materials 27 966–984.CrossRefGoogle ScholarPubMed
Swadling, J.B. Coveney, P.V. and Greenwell, H.C., 2010 Clay minerals mediate folding and regioselective interactions of RNA: a large-scale atomistic simulation study Journal of the American Chemical Society 132 13750–13764.CrossRefGoogle ScholarPubMed
Szczerba, M. Kłapyta, Z. and Kalinichev, A.G., 2014 Ethylene glycol intercalation in smectites. Molecular dynamics simulation studies Applied Clay Science 91-92 87–97.CrossRefGoogle Scholar
Szczerba, M. Kuligiewicz, A. Derkowski, A. Gionis, V. Chryssikos, G.D. and Kalinichev, A.G., 2016 Structure and dynamics of water-smectite interfaces: Hydrogen bonding and the origin of the sharp O-Dw/O-Hw infrared band from molecular simulations Clays and Clay Minerals 64 452–471.CrossRefGoogle Scholar
Środoń, J., 1980 Precise identification of illite/smectite interstratification by X-ray powder diffraction Clay and Clay Minerals 28 401–411.CrossRefGoogle Scholar
Tambach, T.J. Bolhuis, P.G. Hensen, E.J. and Smit, B., 2006 Hysteresis in clay swelling induced by hydrogen bonding: accurate prediction of swelling states Langmuir 22 1223–1234.CrossRefGoogle ScholarPubMed
Teppen, B.J. Rasmussen, K.R. Bertsch, P.M. Miller, D.M. and Schafer, L., 1997 Molecular dynamics modeling of clay minerals. 1. Gibbsite, kaolinite, pyrophillite, and beidellite The Journal of Physical Chemistry B 101 1579–1587.CrossRefGoogle Scholar
Vanommeslaeghe, K. Hatcher, E. Acharya, C. Kundu, S. Zhong, S. Shim, J. Darian, E. Guvench, O. Lopes, P. Vorobyov, I. Mackerell, A.D. Jr., 2009 CHARMM general force field: A force field for drug-like molecules compatible with the CHARMM all-atom additive biological force fields Journal of Computational Chemistry 31 671–90.Google Scholar
Wallqvist, A. and Mountain, R.D., 1999 Molecular models of water: Derivation and description Reviews in Computational Chemistry 13 183–247.CrossRefGoogle Scholar
Wang, J. Wolf, R.M. Caldwell, J.W. Kollman, P.A. and Case, D.A., 2004 Development and testing of a general amber force field Journal of Computational Chemistry 25 1157–74.CrossRefGoogle ScholarPubMed
Wang, Y. Wohlert, J. Bergenstrahle-Wohlert, M. Kochumalayil, J.J. Berglund, L.A. Tu, Y. and Ågren, H., 2014 Molecular adhesion at clay nanocomposite interfaces depends on counterion hydration-molecular dynamics simulation of montmorillonite / xyloglucan Biomacromolecules 16 257–265.CrossRefGoogle ScholarPubMed
Zeng, Q.H. Yu, A.B. Lu, G.Q. and Standish, R.K., 2003 Molecular dynamics simulation of organic-inorganic nanocomposites: Layering behavior and interlayer structure of organoclays Chemistry of Materials 15 4732–4738.CrossRefGoogle Scholar