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Methylene Blue Interactions with Reduced-Charge Smectites

Published online by Cambridge University Press:  28 February 2024

Juraj Bujdák,
Marián Janek,
Jana Madejová and
Peter Komadel
Juraj Bujdák
Affiliation:
Institute of Inorganic Chemistry, Slovak Academy of Sciences, SK-842 36, Bratislava, Slovakia
Marián Janek
Affiliation:
Institute of Inorganic Chemistry, Slovak Academy of Sciences, SK-842 36, Bratislava, Slovakia
Jana Madejová
Affiliation:
Institute of Inorganic Chemistry, Slovak Academy of Sciences, SK-842 36, Bratislava, Slovakia
Peter Komadel
Affiliation:
Institute of Inorganic Chemistry, Slovak Academy of Sciences, SK-842 36, Bratislava, Slovakia
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Abstract

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The objective of this work was to prepare series of reduced-charge materials from different parent Li-saturated dioctahedral smectites, to investigate the effects of temperature, chemical composition and charge location in smectites on the charge reduction and to characterize reduced-charge smectites (RCSs) using methylene blue (MB) adsorption. The layer charge decrease, induced by Li fixation, is correlated with the trends in the spectra of MB-RCS dispersions in the visible region (VIS) spectra. Distribution of the negative surface charge of the clay minerals controls the distance between the adsorbed MB cations and thus affects the formation of MB dimers and higher agglomerates. Because each form of MB (monomer, dimer, higher agglomerate, J-aggregates) absorbs light at a different wavelength, the VIS spectra of MB depend sensitively on the charge density at the clay surface. Both cation exchange capacity (CEC) values and spectra of MB-clay dispersions clearly detect extensive reduction of the layer-charge density in reduced-charge montmorillonites (RCMs) upon Li-thermal treatment. The extent of charge reduction depends on the temperature of the thermal treatment, as well as on the octahedral charge of the montmorillonite. Reduction of the layer charge proceeds to a much lesser extent for smectites with mainly tetrahedral charge and high Fe content (Fe-rich beidellite and ferruginous smectite). Both CEC data and MB spectra detect only a slight decrease of the layer charge density, which relates to the low octahedral charge of these minerals. Following heating at higher temperatures (120-160°C), slightly higher Li fixation is indicated by CEC values; however, no charge reduction is confirmed by MB spectra. Release of protons accompanying Li+ fixation in Fe-rich smectites heated at 180 or 200°C was detected in the spectra of MB-clay dispersions and confirmed by potentiometric titrations.

Keywords

Cation Exchange CapacityDye Cation AgglomeratesJ-AggregatesLayer Charge ReductionMethylene BlueMontmorilloniteSmectite

Information

Type
Research Article
Information
Clays and Clay Minerals , Volume 49 , Issue 3 , June 2001, pp. 244 - 254
Copyright
Copyright © 2001, The Clay Minerals Society

References

Bergman, 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
Braswell, E., 1968 Evidence for the trimerisation in aqueous solutions of methylene blue Journal of Physical Chemistry 72 2477–2483 10.1021/j100853a035.CrossRefGoogle Scholar
Breen, C. and Loughlin, H., 1994 The competitive adsorption of methylene blue on to Na-montmorillonite from binary solution with n-alkylammonium 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, steady state and dynamic studies Clay Minerals 29 179–189 10.1180/claymin.1994.029.2.04.CrossRefGoogle Scholar
Brindley, G.W. and Ertem, G., 1971 Preparation and solvation properties of some variable charge montmorillonites Clays and Clay Minerals 19 399–404 10.1346/CCMN.1971.0190608.CrossRefGoogle Scholar
Brindley, G.W. and Thompson, T.D., 1970 Methylene blue absorption by montmorillonites. Determinations of surface areas and exchange capacities with different initial cation saturations (Clay-organic studies XIX) Israel Journal of Chemistry 8 409–415 10.1002/ijch.197000047.CrossRefGoogle Scholar
Bujdák, 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
Bujdák, J. Slosiariková, H. Nováková, L. and Číčel, B., 1991 Fixation of lithium cations in montmorillonite Chemical Papers 45 499–507.Google Scholar
Bujdák, J. Petrovičová, I. and Slosiariková, H., 1992 Study of water-reduced charge montmorillonite system Geologica Carpathica, Series Clays 43 109–111.Google Scholar
Bujdák, J. Janek, M. Madejovâ, J. and Komadel, P., 1998 Influence of the layer charge density of smectites on the interaction with methylene blue Journal of the Royal Society of Chemistry, Faraday Transactions 94 3487–3492 10.1039/a805341c.CrossRefGoogle Scholar
Calvet, R. and Prost, R., 1971 Cation migration into empty octahedral sites and surface properties of clays Clays and Clay Minerals 19 175–186 10.1346/CCMN.1971.0190306.CrossRefGoogle Scholar
Cenens, J. and Schoonheydt, R.A., 1988 Visible spectroscopy of methylene blue on hectorite, Laponite B and Barasym in aqueous suspensions Clays and Clay Minerals 36 214–224 10.1346/CCMN.1988.0360302.CrossRefGoogle Scholar
Číčel, B. Komadel, P., Amonette, J.E. and Zelazny, L.W., 1994 Structural formulae of layer silicates Quantitative Methods in Soil Mineralogy Madison, Wisconsin Soil Science Society of America 114–136.Google Scholar
Ci’cel, B. Komadel, P. Lego, S. Madejovâ, J. and Vlckovâ, L., 1992 Iron-rich beidellite in bentonite from Stebno Geologica Carpathica, Series Clays 43 121–124.Google Scholar
del Monte, F. and Levy, D., 1999 Identification of oblique and coplanar inclined fluorescent J-dimers in rhodamine 110 doped sol-gel-glasses Journal of Physical Chemistry B 103 8080–8086 10.1021/jp991491g.CrossRefGoogle Scholar
Ertem, G., 1972 Irreversible collapse of montmorillonite Clays and Clay Minerals 20 199–205 10.1346/CCMN.1972.0200403.CrossRefGoogle Scholar
Farmer, V.C. and Russell, J.D., 1967 Infrared adsorption spectrometry in clay studies Clays and Clay Minerals 15 121–142 10.1346/CCMN.1967.0150112.CrossRefGoogle Scholar
Gessner, F. Schmitt, C.C. and Neumann, M.G., 1994 Time-dependent 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
Glaeser, R. and Mering, J., 1967 Effet du chauffage sur les montmorillonites saturées de cations de petit rayon Comptes Rendus de l’Académie des Sciences-Paris 265 833–835.Google Scholar
Greene-Kelly, R., 1953 The identification of montmorillon-oids in clays Journal of Soil Science 4 233–237 10.1111/j.1365-2389.1953.tb00657.x.CrossRefGoogle Scholar
Greene-Kelly, R., 1955 Dehydration of montmorillonite minerals Mineralogical Magazine 30 604–615 10.1180/minmag.1955.030.228.06.CrossRefGoogle Scholar
Grim, R.E. Allaway, W.H. and Cuthbert, E.L., 1947 Reaction of different clay minerals with some organic cations Journal of the American Chemical Society 30 137 42.Google 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 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 (Clay-Organic Studies XVIII) Clays and Clay Minerals 18 203–212 10.1346/CCMN.1970.0180404.CrossRefGoogle Scholar
Hofmann, U. and Kiemen, R., 1950 Verlust der Austauschfähigkeit von Lithiuminonen an Bentonit durch Erhitzung Zeitschrift für anorganische und allgemeine Chemie 262 95–99 10.1002/zaac.19502620114.CrossRefGoogle Scholar
Jaynes, W.F. and Bigham, J.M., 1987 Charge reduction, octahedral charge, and lithium retention in heated, Li-saturated smectites Clays and Clay Minerals 35 440–448 10.1346/CCMN.1987.0350604.CrossRefGoogle Scholar
Kahr, G. and Madsen, E.T., 1995 Determination of the cation exchange capacity and the surface area of bentonite, illite and kaolinite by methylene blue adsorption Applied Clay Science 9 327–336 10.1016/0169-1317(94)00028-O.CrossRefGoogle Scholar
Kawano, M. and Tornita, K., 1989 X-ray studies of rehydration behaviors for montmorillonite Clay Science 7 277–287.Google Scholar
Komadel, P. Bujdâk, J. Madejovâ, J. Sucha, V. and Elsass, E., 1996 Effect of non-swelling layers on the dissolution of reduced-charge montmorillonite in hydrochloric acid Clay Minerals 31 333–345 10.1180/claymin.1996.031.3.04.CrossRefGoogle Scholar
Lewis, G.N. and Bigeleisen, J., 1943 Methylene blue and other indicators in general acids. The acidity function Journal of the American Chemical Society 65 1144–1150 10.1021/ja01246a036.CrossRefGoogle Scholar
Lim, C.H. and Jackson, M.L., 1986 Expandable phyllosili-cate reactions with lithium on heating Clays and Clay Minerals 34 346–352 10.1346/CCMN.1986.0340316.CrossRefGoogle Scholar
Luca, V. Cardile, C.M. and Meinhold, R.H., 1989 High-resolution multinuclear NMR study of cation migration in montmorillonite Clay Minerals 24 115–119 10.1180/claymin.1989.024.1.10.CrossRefGoogle Scholar
Madejovâ, J. Bujdâk, J. Gates, W.R. and Komadel, P., 1996 Preparation and infrared spectroscopic characterization of reduced-charge montmorillonite with various Li content Clay Minerals 31 233–241 10.1180/claymin.1996.031.2.09.CrossRefGoogle Scholar
Madejovâ, J. Arvaiovâ, B. and Komadel, P., 1999 FTIR spectroscopic characterization of thermally treated Cu2+, Cd2+ and Li+ montmorillonites Spectrochimica Acta A 55 2467–2476 10.1016/S1386-1425(99)00039-6.CrossRefGoogle Scholar
Margulies, L. Rozen, H. and Nir, S., 1988 Model for competitive adsorption of organic cations on clay Clays and Clay Minerals 36 270–276 10.1346/CCMN.1988.0360309.CrossRefGoogle Scholar
Miyamoto, N. Kawai, R. Kuroda, K. and Ogawa, M., 2000 Adsorption and aggregation of a cationic cyanine dye on layered clay minerals Applied Clay Science 16 161–170 10.1016/S0169-1317(99)00051-4.CrossRefGoogle Scholar
Russell, J.D., 1979 An infrared spectroscopic study on the interaction of nontronite and ferruginous montmorillonites with alkali metal hydroxides Clay Minerals 14 127–137 10.1180/claymin.1979.014.2.05.CrossRefGoogle Scholar
Russell, J.D. and Farmer, V.C., 1964 Infrared spectroscopic study of the dehydration of montmorillonite and saponite Clay Minerals Bulletin 5 443–464 10.1180/claymin.1964.005.32.04.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
Schultz, L.G., 1969 Lithium and potassium absorption, de-hydroxylation temperature and structural water content in aluminous smectites Clays and Clay Minerals 17 115–149 10.1346/CCMN.1969.0170302.CrossRefGoogle Scholar
Sposito, G. Prost, R. and Gaultier, J.P., 1983 Infrared spectroscopic study of adsorbed water on reduced-charge Na/Li montmorillonites Clays and Clay Minerals 31 9–16 10.1346/CCMN.1983.0310102.CrossRefGoogle Scholar
Srasra, E. Bergaya, E. and Fripiat, J.J., 1994 Infrared spectroscopy study of tetrahedral and octahedral substitutions in an interstratified illite-smectite clay Clays and Clay Minerals 42 237–241 10.1346/CCMN.1994.0420301.CrossRefGoogle Scholar
Tettenhorst, R., 1962 Cation migration in montmorillonites American Mineralogist 47 769–773.Google Scholar
Trillo, J.M. Alba, M.D. Alvero, R. and Castro, M.A., 1994 Reversible migration of lithium in montmorillonite Journal of Physical Chemistry 98 7848–7853 10.1021/j100083a017.Google Scholar
Vansant, E.E. and Uytterhoeven, J.B., 1972 Thermodynamics of the exchange of n-alkylammonium ions on Na-mont-morillonite Clays and Clay Minerals 20 47–54 10.1346/CCMN.1972.0200106.CrossRefGoogle Scholar
Williams, J. Pumell, J.H. and Ballantine, J.A., 1991 The mechanism of layer charge reduction and regeneration in Unexchanged montmorillonite Catalysis Letters 9 115–120 10.1007/BF00769089.CrossRefGoogle Scholar
Yao, H. Sugiyama, S. Kawabata, R. Ikeda, H. Matsuoka, O. Yamamoto, S. and Kitamura, N., 1999 Spectroscopic and AFM studies on the structures of pseudoisocyanine J aggregates at a mica water interface Journal of Physical Chemistry B 103 4452–4456 10.1021/jp990127e.CrossRefGoogle Scholar
Yariv, S. and Lune, D., 1971 Metachromasy in clay minerals. Part I. Sorption of methylene-blue by montmorillonite Israel Journal of Chemistry 9 537–552 10.1002/ijch.197100070.CrossRefGoogle Scholar