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Mass Changes during Adsorption of Metal Bipyridyl Complexes by Clay Films Monitored with an Electrochemical Quartz Crystal Microbalance

Published online by Cambridge University Press:  01 January 2024

Laisheng Sun  and
Gilles Villemure
Laisheng Sun
Affiliation:
Department of Chemistry, University of New Brunswick, PO Box #45222, Fredericton, New Brunswick E2B 6E2, Canada
Gilles Villemure*
Affiliation:
Department of Chemistry, University of New Brunswick, PO Box #45222, Fredericton, New Brunswick E2B 6E2, Canada
*
*E-mail address of corresponding author: gvd@unb.ca
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Abstract

The adsorption of [M(bpy)3]2+ ions (M = Ru or Os) by clay films immersed in pure water and in electrolyte solutions was investigated by electrochemical quartz crystal microbalance (EQCM), UV-visible spectroscopy and powder X-ray diffraction. In water, the adsorption of the cations resulted in a decrease in the mass of the films. This decrease in mass is attributed to the expulsion of some 50 water molecules from the clay interlayer spaces for each cation adsorbed. Water is lost to make room for the large metal complex cations in the interlayer spaces, and because of decreases in the volume of the interlayer spaces during adsorption of the cations. In 0.05 M NaCl or 0.05 M Na2SO4, UV-visible measurements show a rapid initial adsorption of the cations by ion exchange, followed by a slower additional adsorption of the cations above the clay’s CEC, presumably as ion pairs with the electrolyte counter ions. The EQCM show initial reductions in the mass of the films that were two to three times larger in pure water. These initial mass decreases were followed by smaller mass ‘re-increases’ at longer times that were not observed in water. The larger initial mass losses are attributed to the loss of more water from the clay interlayer spaces. In 0.5 M Na2SO4 or 1.0 M NaCl, adsorption of the cations never exceeded the clay’s CEC. The initial decreases in mass upon addition of the cations all but disappeared, leaving only the smaller positive mass changes at longer times.

Keywords

Clay-modified ElectrodesClay FilmsEQCMIon ExchangeMicrogravimetryUV-visible Spectroscopy
Type
Research Article
Information
Clays and Clay Minerals , Volume 52 , Issue 1 , February 2004 , pp. 31 - 39
Copyright
Copyright © 2004, The Clay Minerals Society

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References

Breen, C. Zahoor, F.D. Madejová, J. and Komadel, P., (1997) Characterization and catalytic activity of acid-treated, size-fractionated smectites Journal of Physical Chemistry 101 5324–5331 10.1021/jp963287o.CrossRefGoogle Scholar
Buttry, D.A. and Bard, A.J., (1991) Applications of the quartz crystal microbalance to electrochemistry Electrochemical Analysis New York Marcel Decker 1–85 Vol. 17.Google Scholar
Buttry, D.A. and Ward, M.D., (1992) Measurement of interfacial processes at electrode surfaces with the electrochemical quartz crystal microbalance Chemical Reviews 92 1355–1379 10.1021/cr00014a006.CrossRefGoogle Scholar
Creutz, C. Chou, M. Netzel, T.L. Okumura, M. and Sutin, N., (1980) Lifetimes, spectra and quenching of the excited states of polypyridine complexes of iron(II), ruthenium(II) and osmium(II) Journal of the American Chemical Society 102 1309–1318 10.1021/ja00524a014.CrossRefGoogle Scholar
Falaras, P. and Lezou, F., (1998) Electrochemical behavior of acid activated montmorillonite modified electrodes Journal of Electroanalytical Chemistry 455 169–179 10.1016/S0022-0728(98)00272-1.CrossRefGoogle Scholar
Graham, J.S. Rosseinsky, D.R. Slocombe, J.D. Barrett, S. and Francis, S.R., (1995) Electrochemistry of clay electro-deposition from sols: electro-transfer, deposition and microgravimetry studies Colloids and Surfaces A: Physical and Engineering Aspects 94 177–188 10.1016/0927-7757(94)02982-2.CrossRefGoogle Scholar
Gaudiello, J.G. Bradley, P.G. Norton, K.A. Woodruff, W.H. and Bard, A.J., (1984) Electrochemistry in Liquid Sulfur Dioxide. 5. Oxidation of bipyridine and phenanthroline complexes of osmium, ruthenium and iron Inorganic Chemistry 23 3–10 10.1021/ic00169a003.CrossRefGoogle Scholar
Hillman, A.R., (1997) Mobile species populations and viscoelastic effects in electroactive polymer films Solid State Ionics 94 151–160 10.1016/S0167-2738(96)00502-4.CrossRefGoogle Scholar
Hillman, A.R. Loveday, D.C. and Bruckenstein, S., (1989) Thermodynamic changes in ion and solvent populations accompanying redox switching in polyvinylferrocene films Journal of Electroanalytical Chemistry 274 157–166 10.1016/0022-0728(89)87037-8.CrossRefGoogle Scholar
Hotta, Y. Inukai, K. Taniguchi, M. and Yamagishi, A., (1997) A clay self assembled on a gold surface as studied by atomic force microscopy Journal of Colloid and Interface Science 188 404–408 10.1006/jcis.1996.4754.CrossRefGoogle Scholar
Hotta, Y. Inukai, K. Taniguchi, M. Nakata, M. and Yamagishi, A., (1997) A clay self assembled on a gold surface as studied by atomic force microscopy and electrochemistry Langmuir 13 6697–6703 10.1021/la970333i.CrossRefGoogle Scholar
Jackson, M.L. Wittig, L.D. and Pennington, R.P., (1949) Segregation procedure for the mineralogical analysis of soils Soil Science Society of America Proceedings 14 77–81 10.2136/sssaj1950.036159950014000C0017x.CrossRefGoogle Scholar
Jozefaciuk, G. and Bowanko, G., (2002) Effect of acid and alkali treatments on surface areas and adsorption energies of selected minerals Clays and Clay Minerals 50 771–783 10.1346/000986002762090308.CrossRefGoogle Scholar
Jureviciute, I. Bruckenstein, S. and Hillman, A.R., (2000) Counter-ion specific effects on charge and solvent trapping in poly(vinylferrocene) Journal of Electroanalytical Chemistry 488 73–81 10.1016/S0022-0728(00)00190-X.CrossRefGoogle Scholar
Kalyanasundaram, K., (1982) Photophysics, photochemistry and solar energy conversion with tris (bipyridyl) ruthenium(II) and its analogues Coordination Chemistry Reviews 46 159–244 10.1016/0010-8545(82)85003-0.CrossRefGoogle Scholar
Lasky, S.J. and Buttry, D.A., (1988) Mass measurements using isotopically labelled solvents reveal the extend of solvent transport during redox in thin films on electrodes Journal of American Chemical Society 110 6258–6260 10.1021/ja00226a058.CrossRefGoogle Scholar
Newman, A.C.D. and Newman, A.C.D., (1987) The interaction of water with clay mineral surfaces Chemistry of Clays and Clay Minerals London Mineralogical Society 237–274.Google Scholar
Norrish, K., (1954) The swelling of montmorillonite Discussions of the Faraday Society 18 120–133 10.1039/df9541800120.CrossRefGoogle Scholar
Oyama, N. and Ohsaka, T., (1995) Coupling between electron and mass transfer kinetics in electroactive polymer films an application of the in situ quartz crystal electrodes Progress in Polymer Science 20 761–85 10.1016/0079-6700(95)00006-2.CrossRefGoogle Scholar
Shang, C. Thompson, M.L. and Laird, D.A., (1995) Transmission X-ray diffraction techniques for measuring crystalline swelling of smectites in electrolyte solutions Clays and Clay Minerals 43 128–130 10.1346/CCMN.1995.0430115.CrossRefGoogle Scholar
Shi, M. and Anson, F.C., (1997) Dehydration of protonated Nafion coatings induced by cation exchange and monitored by quartz crys tal microgravimetry Journal of Electroanalytical Chemistry 425 117–123 10.1016/S0022-0728(96)04945-5.CrossRefGoogle Scholar
Shirtcliffe, N., (1999) Deposition of clays onto a rotating, electrochemical, quartz crystal microbalance Colloids and Surfaces A: Physical and Engineering Aspects 155 277–285 10.1016/S0927-7757(98)00915-7.CrossRefGoogle Scholar
Tanner, C.G. and Jackson, M.L., (1947) Nomographs of sedimentation times for soil particles under gravity or centrifugal acceleration Soil Science Society of America Proceedings 12 60–65 10.2136/sssaj1948.036159950012000C0014x.CrossRefGoogle Scholar
Van Olphen, H., (1977) An Introduction to Clay Colloid Chemistry New York John Wiley and Sons 249–253.Google Scholar
Varineau, P.T. and Buttry, D.A., (1987) Applications of the quartz crys tal microbalance to electrochemistry. Measurement of ion and solvent populations in thin films of poly(vinylferrocene) as functions of redox state Journal of Physical Chemistry 91 1292–1295 10.1021/j100290a003.CrossRefGoogle Scholar
Villemure, G., (1990) Effect of negative surface charge densities of smectites clays on the adsorption isotherms of racemic and enantiomeric tris(2,2′-bipyridyl) ruthenium(II) chloride Clays and Clay Minerals 38 623–630 10.1346/CCMN.1990.0380608.CrossRefGoogle Scholar
Villemure, G., (1991) X-ray diffraction patterns of montmorillonite oriented films exchanged with enantiomeric and racemic tris(2,2′-bipyridyl) ruthenium(II) Clays and Clay Minerals 39 580–585 10.1346/CCMN.1991.0390603.CrossRefGoogle Scholar
Yao, K. Shimazu, K. and Yamagishi, A., (1995) Mass transport on clay-modified electrodes as studied by the quartz crystal microbalance method Chemistry Letters 161–162.CrossRefGoogle Scholar
Yao, K. Shimazu, K. Nakata, M. and Yamagishi, A., (1998) Clay-modified electrodes as studied by the quartz crystal microbalance: adsorption of ruthenium complexes Journal of Electroanalytical Chemistry 442 235–242 10.1016/S0022-0728(97)00445-2.CrossRefGoogle Scholar
Yao, K. Shimazu, K. Nakata, M. and Yamagishi, A., (1998) Clay-modified electrodes as studied by the quartz crystal microbalance: redox processes of ruthenium and iron complexes Journal of Electroanalytical Chemistry 443 253–261 10.1016/S0022-0728(97)00549-4.CrossRefGoogle Scholar