Hostname: page-component-745bb68f8f-lrblm Total loading time: 0 Render date: 2025-01-12T01:47:02.573Z Has data issue: false hasContentIssue false
  • English
  • Français

Molecular Dynamics Simulations of the Adsorption of Methylene Blue at Clay Mineral Surfaces

Published online by Cambridge University Press:  28 February 2024

Ching-Hsing Yu ,
Susan Q. Newton ,
Mya A. Norman ,
David M. Miller ,
Lothar Schäfer  and
Brian J. Teppen
Ching-Hsing Yu
Affiliation:
Department of Chemistry, University of Arkansas, Fayetteville, Arkansas 72701 USA
Susan Q. Newton
Affiliation:
Department of Chemistry, University of Arkansas, Fayetteville, Arkansas 72701 USA
Mya A. Norman
Affiliation:
Department of Chemistry, University of Arkansas, Fayetteville, Arkansas 72701 USA
David M. Miller
Affiliation:
Department of Chemistry, University of Arkansas, Fayetteville, Arkansas 72701 USA
Lothar Schäfer*
Affiliation:
Department of Crop, Soil, and Environmental Sciences, University of Arkansas, Fayetteville, Arkansas 72701, USA
Brian J. Teppen
Affiliation:
Department of Crop and Soil Sciences, Michigan State University, East Lansing, Michigan 48824-1325, USA
*
E-mail of corresponding author: schafer@protein.uark.edu
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.

Molecular dynamics simulations were performed of the adsorption of methylene blue (MB) on model beidellite, montmorillonite, and muscovite mica surfaces, using a previously determined empirical force field developed for dioctahedral clays. The simulations show that the adsorption of MB on mineral surfaces can result in a variety of configurations, including single and double layers of MB parallel to the basal surface, and irregular clusters. The d(001) values of ~12.3 and ~15.7 Å are assigned to dry phases with parallel single and double layers of MB, respectively, in agreement with X-ray studies. At intermediate MB loadings, stacks inclined to basal surfaces are formed. The stacks of MB ions inclined by 65–70° relative to the (001) plane of muscovite are not found on dry surfaces, in contrast to previous studies. Configurations similar to those proposed by others form spontaneously in the presence of H2O, but the ions in the model systems are not quite as ordered and not ordered in exactly the same way as the ones previously described, and they display a mobility that is not compatible with strict atomic order. The formation of a triple layer of H2O interspersed with ions may occur in the interlayer. Overall, the results of the simulations confirm that the MB-ion method must be used with great caution in surface-area determinations, because of the multiplicity of possible configurations. At the same time, the ability for adsorption to occur as either single or multiple MB layers is useful to determine cation-exchange capacity over a wide range of surface-charge densities.

Keywords

Adsorption of Methylene BlueClay Cation-Exchange Capacity DeterminationClay Surface-Area DeterminationMolecular Dynamics Simulations
Type
Research Article
Information
Clays and Clay Minerals , Volume 48 , Issue 6 , December 2000 , pp. 665 - 681
Copyright
Copyright © 2000, The Clay Minerals Society

References

Arbeloa, F.L. Arbeloa, T.L. and Arbeloa, I.L., (1997) Spectroscopy of rhodamine 6G adsorbed on sepiolite aqueous suspensions Journal of Colloid and Interface Science 187 105–112 10.1006/jcis.1996.4672.CrossRefGoogle ScholarPubMed
Bensted, J., (1985) Application of the methylene blue test to cement raw materials Journal of Chemical Technology and Biotechnology 35A 181–184.CrossRefGoogle Scholar
Bergmann, K. and O’Konski, C.T., (1963) A spectroscopic study of methylene blue monomer, dimer, and complexes with montmorillonite Journal of Physical Chemistry 67 2169–2177 10.1021/j100804a048.CrossRefGoogle Scholar
Bodenheimer, W. and Heller, L., (1968) Sorption of methylene blue by montmorillonite saturated with different cations Israel Journal of Chemistry 6 307–314 10.1002/ijch.196800040.CrossRefGoogle Scholar
Breen, C. and Loughlin, H., (1994) The competitive adsorption of methylene blue on to Na-montmorillonite from binary solution with n-alkylytrimethylammonium surfactants Clay Minerals 29 775–783.CrossRefGoogle Scholar
Breen, C. and Rock, B., (1994) The competitive adsorption of methylene blue on to montmorillonite from binary solution with thioflavin T, proflavine and acridine yellow. Steadystate and dynamic studies Clay Minerals 29 179–189 10.1180/claymin.1994.029.2.04.CrossRefGoogle Scholar
Brindley, G.W. and Thompson, T.D., (1970) Methylene blue adsorption by montmorillonites. Determinations of surface areas and exchange capacities with different initial cation saturations Israel Journal of Chemistry 8 409–415 10.1002/ijch.197000047.CrossRefGoogle Scholar
Bujdâk, J. and Komadel, P., (1997) Interaction of methylene blue with reduced charge montmorillonite Journal of Physical Chemistry B 101 9065–9068 10.1021/jp9718515.CrossRefGoogle Scholar
Bujdâk, J. Janek, M. Madejova, J. and Komadel, P., (1998) Influence of the layer charge density of smectites on the interaction with methylene blue Journal of Chemical Society-Faraday Transactions 94 3487–3492 10.1039/a805341c.CrossRefGoogle Scholar
Cenens, J. and Schoonheydt, R.A., (1988) Visible spectroscopy of methylene blue on hectorite, laponite B, and barasym in aqueous suspension Clays and Clay Minerals 36 214–224 10.1346/CCMN.1988.0360302.CrossRefGoogle Scholar
Cenens, J. Schoonheydt, R.A., Farmer, V.C. and Tardy, Y., (1990) Quantitative absorption spectroscopy of cationic dyes on clays Proceedings of the 9th International Clay Conference, Strasbourg 1989 15–23.Google Scholar
Chu, C.H. and Johnson, L.J., (1979) Cation exchange behavior of clays and synthetic aluminosilica gels Clays and Clay Minerals 27 87–90 10.1346/CCMN.1979.0270202.CrossRefGoogle Scholar
Comodi, P. and Zanazzi, P.F., (1995) High-pressure structural study of muscovite Physics and Chemistry of Minerals 22 170–177 10.1007/BF00202297.CrossRefGoogle Scholar
De, D.K. das Kanugo, J.L. and Chakravarti, S.K., (1973) Studies on the adsorption of methylene blue on and from Vermiculite and asbestos Journal of Indian Chemical Society 507–510.Google Scholar
De, D.K. das Kanugo, J.L. and Chakravarti, S.K., (1974) Adsorption of methylene blue, crystal violet and malachite green on bentonite, vermiculite, kaolinite, asbestos, and feldspar Indian Journal of Chemistry 12 1187–1189.Google Scholar
Fischer, D. Caseri, W.R. and Hähner, G., (1998) Orientation and electronic structure of ion exchanged dye molecules on mica: An X-ray absorption study Journal of Colloid and Interface Science 198 337–346 10.1006/jcis.1997.5296.CrossRefGoogle Scholar
Garfinkel-Shweky, D. and Yariv, S., (1997) Metachromasy in clay-dye systems: The adsorption of acridine orange by Na-saponite Clay Minerals 32 653–663 10.1180/claymin.1997.032.4.15.CrossRefGoogle Scholar
Garfinkel-Shweky, D. and Yariv, S., (1997) The determination of surface basicity of the oxygen planes of expanding clay minerals by acridine orange Journal of Colloid and Interface Science 188 168–175 10.1006/jcis.1996.4712.CrossRefGoogle Scholar
Gessner, F. Schmitt, C.C. and Neumann, M.G., (1994) Timedependent spectroscopic study of the interaction of basic dyes with clays. 1. Methylene blue and neutral red on montmorillonite and hectorite Langmuir 10 3749–3753 10.1021/la00022a059.CrossRefGoogle Scholar
Hähner, G. Marti, A. Spencer, N.D. and Caseri, W.R., (1996) Orientation and electronic structure of methylene blue on mica: A near edge X-ray absorption fine structure spectroscopic study Journal of Chemical Physics 104 7749–7757 10.1063/1.471451.CrossRefGoogle Scholar
Hang, P.T. and Brindley, G.W., (1970) Methylene blue adsorption by clay minerals. Determination of surface areas and cation exchange capacities Clays and Clay Minerals 18 203–212 10.1346/CCMN.1970.0180404.CrossRefGoogle Scholar
Inel, O. and Askin, A., (1996) Adsorption of monovalent cationic dyes on some silicates Turkish Journal of Chemistry 20 276–282.Google Scholar
Karasawa, N. and Goddard, W.A. III, (1989) Acceleration of convergence for lattice sums Journal of Physical Chemistry 93 7320–7327 10.1021/j100358a012.CrossRefGoogle Scholar
Lagaly, G., (1981) Characterization of clays by organic compounds Clay Minerals 16 1–21 10.1180/claymin.1981.016.1.01.CrossRefGoogle Scholar
Lee, J.H. and Guggenheim, S., (1981) Single crystal X-ray refinement of pyrophyllite-1Tc American Mineralogist 66 350–357.Google Scholar
MSI, (1996) Insight II/Discover Users Guides, Version 4.0.0 California Molecular Simulations Inc., San Diego.Google Scholar
Mishael, Y.G. Rytwo, G. Nir, S. Crespin, M. Annabi-Bergaya, F. and Van Damme, H., (1999) Interactions of monovalent organic cations with pillared clays Journal of Colloid and Interface Science 209 123–128 10.1006/jcis.1998.5896.CrossRefGoogle ScholarPubMed
Neumann, M.G. Schmitt, C.C. and Gessner, F., (1996) Timedependent spectrophotometric study of the interaction of basic dyes with clays. 2. Thionine on natural and synthetic montmorillonites and hectorites Journal of Colloid and Interface Science 177 495–501 10.1006/jcis.1996.0063.CrossRefGoogle Scholar
Rytwo, G. Nir, S. and Margulies, L., (1996) A model for adsorption of divalent organic cations to montmorillonite Journal of Colloid and Interface Science 181 551–560 10.1006/jcis.1996.0412.CrossRefGoogle Scholar
Rytwo, G. Nir, S. Margulies, L. Casai, B. Merino, J. Ruiz-Hitzky, E. and Serratosa, J.M., (1998) Adsorption of monovalent organic cations on sepiolite: Experimental results and model calculations Clays and Clay Minerals 46 340–348 10.1346/CCMN.1998.0460313.CrossRefGoogle Scholar
Saehr, D. LeDred, R. and Hoffner, D., (1978) Contribution on a l’etude des Interactions Vermiculite-Colorants Cationiques Clay Minerals 13 411–425 10.1180/claymin.1978.013.4.06.CrossRefGoogle Scholar
Schoonheydt, R.A. and Mashuhara, H., (1994) Organization and spectroscopy of dyes on submicron-sized crystalline solids Microchemistry: Spectroscopy and Chemistry in Small Domains Amsterdam Elsevier Science 469–482 10.1016/B978-0-444-81513-2.50039-9.CrossRefGoogle Scholar
Schoonheydt, R.A. and Heughebaert, L., (1992) Clay adsorbed dyes: Methylene blue on Laponite Clay Minerals 27 91–100 10.1180/claymin.1992.027.1.09.CrossRefGoogle Scholar
Schramm, L.L. Yariv, S. Ghosh, D.K. and Hepler, L.G., (1997) Electrokinetic study of the adsorption of ethyl violet and crystal violet by montmorillonite clay particles Canadian Journal of Chemistry 75 1868–1877 10.1139/v97-620.CrossRefGoogle Scholar
Shariatmadari, H. Mermut, A.R. and Benke, M.B., (1999) Sorption of selected cationic and neutral organic molecules on palygorskite and sepiolite Clays and Clay Minerals 47 44–53 10.1346/CCMN.1999.0470105.CrossRefGoogle Scholar
Shelden, R.A. Caseri, W.R. and Suter, U.W., (1993) Ion exchange on muscovite mica with ultrahigh specific surface area Journal of Colloid and Interface Science 157 318–327 10.1006/jcis.1993.1192.CrossRefGoogle Scholar
Taylor, R.K., (1985) Cation exchange in clays and mudrocks by methylene blue Journal of Chemical Technology and Biotechnology 35A 195–207.CrossRefGoogle Scholar
Teppen, B.J. Rasmussen, K. Bertsch, P.M. Miller, D.M. and Schäfer, L., (1997) Molecular dynamics modeling of clay minerals. 1. Gibbsite, kaolinite, pyrophyllilte, and beidellite Journal of Physical Chemistry B 101 1579–1587 10.1021/jp961577z.CrossRefGoogle Scholar
Teppen, B.J. Yu, C.H. Miller, D.M. and Schafer, L., (1998) Molecular dynamics simulations of sorption of organic compounds at the clay mineral / aqueous solution interface Journal of Computational Chemistry 19 144–153 10.1002/(SICI)1096-987X(19980130)19:2<144::AID-JCC7>3.0.CO;2-U.3.0.CO;2-U>CrossRefGoogle Scholar
Viseras, C. and Lopez-Galindo, A., (1999) Pharmaceutical applications of some Spanish clays (sepiolite, palygorskite, bentonite): Some preformulation studies Applied Clay Science 14 69–82 10.1016/S0169-1317(98)00050-7.CrossRefGoogle Scholar
Xeidakis, G.S., (1996) Stabilization of swelling clays by Mg(OH)2. Changes in clay properties after addition of Mg-hydroxide Engineering Geology 44 107–120 10.1016/S0013-7952(96)00047-6.CrossRefGoogle Scholar
Xeidakis, G.S., (1996) Stabilization of swelling clays by Mg(OH)2. Factors affecting hydroxy-Mg-interlayering in swelling clays Engineering Geology 44 93–106 10.1016/S0013-7952(96)00046-4.CrossRefGoogle Scholar
Yariv, S. and Lurie, D., (1971) Metachromasy in clay minerals. Part 1. Sorption of methylene blue by montmorillonite Israel Journal of Chemistry 9 537–552 10.1002/ijch.197100070.CrossRefGoogle Scholar
Yool, A.I.G. Lees, T.P. and Fried, A., (1998) Improvements to the methylene blue dye test for harmful clay in aggregates for concrete and mortar Cement and Concrete Research 28 1417–1428 10.1016/S0008-8846(98)00114-8.CrossRefGoogle Scholar