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Electrodes Modified with Synthetic Clay Minerals: Electrochemistry of Cobalt Smectites

Published online by Cambridge University Press:  28 February 2024

Yan Xiang
Affiliation:
Department of Chemistry, University of New Brunswick, Bag Service #45222, Fredericton New Brunswick E2B 6E2, Canada
Gilles Villemure
Affiliation:
Department of Chemistry, University of New Brunswick, Bag Service #45222, Fredericton New Brunswick E2B 6E2, Canada
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Abstract

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Hydrothermal treatment of a mixture of silicic acid, cobalt chloride, sodium dithionite and sodium hydroxide at 250 °C under 500 psi of argon produced a pink solid. X-ray powder diffraction (XRD), transmission electron microscopy (TEM) and electron diffraction data showed the product to be a well-crystallized smectite. SEM/EDX analysis gave a unit cell formula of [(Si8.05)(Co5.58)O20(OH)4]Na066. Heating the same mixture at 150 °C without argon gave a less well ordered smectite of composition [(Si7.93)(CO5.92)O20(OH)4]Na0.42. Two peaks were observed in the cyclic voltammograms of electrodes modified with films of these two clays recorded for the blank electrolytes in the absence of any adsorbed electroactive species. The first peak was attributed to the oxidation of a small fraction of the Co2+ sites within the clay lattices to Co3+. The second peak was assigned to further oxidation of these Co3+ to Co4+.

Type
Research Article
Copyright
Copyright © 1996, The Clay Minerals Society

References

Bard, A.J. and Mallouk, T.E.. 1992. Electrodes modified with clays, zeolite and related microporous solids. Technique of chemistry molecular design of electrode surfaces 22: 271312.Google Scholar
Brindley, G.W. and Brown, G.. 1980. X-ray diffraction procedures for clay minerals identification. In: Brindley, G.W., Brown, G., editors. Crystal structures of clay minerals and their X-ray identification. London: Mineralogical Society. p 305360.CrossRefGoogle Scholar
Bruce, L.A., Sanders, J.V. and Turney, T.W.. 1986. Hydrothermal synthesis and characterization of cobalt clays. Clays & Clay Miner 34: 2536.CrossRefGoogle Scholar
Burke, L.D., Lyons, M.E. and Murphy, O.J.. 1982. Formation of hydrous oxide films on cobalt under potential cycling conditions. J Electroanal Chem 132: 247261.CrossRefGoogle Scholar
Castro-Martins, S de, Tuel, A. and Ben Taârit, Y.. 1994. Cyclic voltammetric characterization of titanium silicalite TS-1. Zeolites 14: 130136.CrossRefGoogle Scholar
Castro-Martins, S de, Tuel, A. and Ben Taârit, Y.. 1993. Characterization of titanium silicalite using TS-1-modified carbon paste electrodes. J Electroanal Chem 350: 1528.CrossRefGoogle Scholar
Davies, G. and Watkins, K.O.. 1970. The kinetic of some oxidation-reduction reactions involving cobalt(III) in aqueous perchloric acid. J Phys Chem 74: 33883392.CrossRefGoogle Scholar
Faye, G.H. and Nickel, E.H.. 1968. The origin of pleochroism in erythrite. Can Miner 9: 493504.Google Scholar
Fitch, A.. 1990. Clay-modified electrodes: A review. Clays & Clay Miner 38: 391400.CrossRefGoogle Scholar
Fitch, A. and Lee, S.A.. 1993. Effect of clay charge on Cr(bpy)33+ reaction mechanism at clay-modified electrodes. J Electroanal Chem 344: 4559.CrossRefGoogle Scholar
Guven, N.. 1988. Smectites. In: Bailey, S.W., editor. Hydrous phyllosilicates (exclusive of micas) reviews in mineralogy Chelsea: Mineralogical Society of America 19: 497552.CrossRefGoogle Scholar
Jackson, M.L., Wittig, L.D. and Pennington, R.P.. 1949. Segregation procedure for the mineralogical analysis of soils. Soil Sci Soc Am Proc 14: 7781.CrossRefGoogle Scholar
Jaynes, W.F. and Bigham, J.M.. 1986. Multiple cation-exchange capacity measurements on standard clays using a commercial mechanical extractor. Clays & Clay Miner 34: 9398.CrossRefGoogle Scholar
Kaviratna, P de S and Pinnavaia, T.J.. 1992. Electroactive Ru(NH3)63+ gallery cations in clay-modified electrodes. J Electroanal Chem 332: 135145.CrossRefGoogle Scholar
Kessler, T., Visintin, A., Triaca, W.E., Arvia, A.J. and Gennero De Chialvo, M.R.. 1991. Preparation and modification of hydrous thick cobalt oxide layers: Voltammetric characteristic of rough Co3O4-spinel-type electrodes. J Appl Electrochem 21: 516523.CrossRefGoogle Scholar
King, R.D., Nocera, D.G. and Pinnavaia, T.J.. 1987. On the nature of electroactive sites in clay-modified electrodes. J Electroanal Chem 236: 4353.CrossRefGoogle Scholar
Malla, P.B., Robert, M., Douglas, L.A., Tessier, D. and Komarneni, S.. 1993. Charge heterogeneity and nanostructure of 2: 1 layer silicates by high-resolution transmission electron microscopy. Clays & Clay Miner 41: 412422.CrossRefGoogle Scholar
Methikos-Hukovic, M., Stupnisek-Lisac, E. and Sokolean, D.. 1991. Surface properties of the system: hard metal/Co coating/electrolyte. J Appl Electochem 21: 619624.CrossRefGoogle Scholar
Milazzo, G. and Caroli, S.. 1978. Tables of standard electrode potentials. New York: John Wiley & Sons, Ltd. p 336343.Google Scholar
Mizutani, T., Fukushima, Y., Okada, A., Kamigaito, O. and Kobayashi, T.. 1991. Synthesis of 1: 1 and 2: 1 iron phyllosilicates and characterization of their iron state by Mössbauer spectroscopy. Clays & Clay Miner 39: 381386.CrossRefGoogle Scholar
Newman, A.C.D. and Brown, G.. 1987. The chemical constitution of clays. In: Newman, A.C.D., editor. Chemistry of clays and clay minerals. New York: Mineralogical Society. p 1129.Google Scholar
Ohsaka, T., Yamguchi, Y. and Oyama, N.. 1990. A new amperometric glucose sensor base on bilayer film coating of redox-active clay film and glucose oxidase enzyme film. Bull Chem Soc Jpn 63: 26462652.CrossRefGoogle Scholar
Oyama, N. and Anson, F.C.. 1986. Catalysis of the electroreduction of hydrogen peroxide by montmorillonite clay coatings on graphite electrodes. J Electroanal Chem 199: 467470.CrossRefGoogle Scholar
Qiu, J. and Villemure, G.. 1995. Anionic clay modified electrodes: electrochemical activity of nickel(II) sites in layered double hydroxide films. J Electroanal Chem 395: 159166.CrossRefGoogle Scholar
Rossman, G.R.. 1988. Optical spectroscopy. In: Hawthorne, F.C., editor. Spectroscopic methods in mineralogy and geology, Reviews in mineralogy Chelsea: Mineralogical Society of America. 18: 207243.CrossRefGoogle Scholar
Rudzinski, W.E. and Bard, A.J.. 1986. Clay modified electrodes part VI. Aluminum and silicon pillared clay modified electrodes. J Electroanal Chem 199: 323340.CrossRefGoogle Scholar
Shaw, B.R.. 1989. Modification of solid electrodes in electro-analytical chemistry 1978-1988. In: Stock, J.T., Orna, M.V., editors. Electrochemistry past and present, ACS Symposium Series 390. Washington: American Chemical Society. p 318338.CrossRefGoogle Scholar
Simmons, G.W., Kellerman, E. and Leidheiser, H. Jr. 1976. In situ studies of the passivation and anodic oxidation of cobalt by emission Mössbauer spectroscopy. J Electrochem Soc 123: 12761284.CrossRefGoogle Scholar
Simmons, G.W., Vértes, A., Varsanyi, M.L. and Leidheiser, H. Jr. 1979. Emission Mössbauer studies of anodically formed CoO2. J Electrochem Soc 126: 187189.CrossRefGoogle Scholar
Stucki, J.W.. 1981. The quantitative assay of minerals for Fe2+ and Fe3+ using 1,10-phenanthroline: II. A photochemical method. Soil Sci Soc Am J 45: 638640.CrossRefGoogle Scholar
Villemure, G. and Bard, A.J.. 1990. Clay modified electrodes part 9: Electrochemical studies of the electroactive fraction of adsorbed species in reduced-charge and preadsorbed clay films. J Electroanal Chem 282: 107121.CrossRefGoogle Scholar
Villemure, G., Kodama, H. and Detellier, C.. 1985. Photoreduction of water by visible light in the presence of montmorillonite. Can J Chem 63: 11391142.CrossRefGoogle Scholar
Xiang, Y. and Villemure, G.. 1995. Electrodes modified with synthetic clay minerals: Evidence of direct electron transfer from structural iron sites in the clay lattice. J Electroanal Chem 381: 2127.CrossRefGoogle Scholar
Xiang, Y. and Villemure, G.. 1992. Electron transport in clay-modified electrodes: study of electron transfer between electro-chemically oxidized tris (2,2'-bipyridyl)iron cations and clay structural iron(II) sites. Can J Chem 70: 18331837.CrossRefGoogle Scholar
Wang, D., Yu, W. and Zhu, B.. 1989. A special solid electrolyte-montmorillonite. Solid State Ionics 34: 219223.CrossRefGoogle Scholar