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Preparation, Characterization and Electrochemistry of Synthetic Copper Clays

Published online by Cambridge University Press:  28 February 2024

Jun Xiao  and
Gilles Villemure
Jun Xiao
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 aqueous mixtures of sodium hydroxide, copper chloride and excess sodium silicate (Si/Cu ≥ 2) at 150 °C produced blue powders. Scanning electron microscopy/energy dispersive X-ray (SEM/EDX) analysis of the products show they all had similar chemical compositions, with Si/Cu ratios of approximately 1.33, the value expected for 2:1 trioctahedral phyllosilicates. Their X-ray diffraction (XRD) patterns were consistent with that of swelling smectite-type clays. Reaction mixtures that did not contain excess Si (Si/Cu ≤ 1.33) did not produce smectites. They gave gray mixtures of amorphous silicates and copper oxides, with some phyllosilicates. A mixture containing a Si/Cu ratio of 5.2 heated at 250 °C under 500 psi of Ar gave a pale blue solid containing a Si/Cu ratio of approximately 1, the value expected for chrysocolla. Transmission electron microscopy (TEM) showed this product had a well-ordered layered structure. Its XRD powder pattern was consistent with that of chrysocolla. This clay did not swell very much on exposure to glycol vapors. Peaks were observed in the cyclic voltam-mogram of electrodes modified with films of these synthetic Cu-clays. They were attributed to electrochemical activity of Cu(II) centers in the lattice of the clays. The presence of these redox active Cu(II) sites greatly improved charge transport in the films. Much larger voltametric waves were observed for [Os(bpy)3]2+ ions (“bpy” = the ligand 2,2′bipyridyl) adsorbed in films of the synthetic Cu-clays than in films of a natural montmorillonite. The larger peak currents obtained corresponded to 10- to 15-fold increases in the fractions of the adsorbed ions that were electrochemically oxidizable in the modified electrodes.

Keywords

ChrysocollaClay-modified ElectrodesCopper SmectitesCyclic VoltammetrySynthetic Clay
Type
Research Article
Information
Clays and Clay Minerals , Volume 46 , Issue 2 , April 1998 , pp. 195 - 203
Copyright
Copyright © 1998, The Clay Minerals Society

References

Baker, M.D. and Senaratne, C., 1993 Electrochemistry with clays and zeolites Frontiers of electrochemistry. The electrochemistry of novel materials 3 339–380.Google Scholar
Breu, J. Richard, C. and Catlow, A., 1995 Chiral recognition among tris(diimine)-metal complexes 4. Atomistic computer modeling of a monolayer of [Ru(bpy)3]2+ intercalated into a smectite clay Inorg Chem 34 4504–4510 10.1021/ic00121a032.CrossRefGoogle Scholar
Brindley, G.W., Brindley, G.W. and Brown, G., 1980 Order-disorder in clay mineral structure Crystal structures of clay minerals and their X-ray identification London Mineral Soc 125–195.CrossRefGoogle Scholar
Brindley, G.W. Brown, G., Brindley, G.W. and Brown, G., 1980 X-ray diffraction procedures for clay minerals identification Crystal structures of clay minerals and their X-ray identification London Mineral Soc 305–360.CrossRefGoogle Scholar
Carriat, J.Y. Che, M. Kermarec, M. and Decarreau, A., 1994 Influence of order-disorder parameters on the reducibility of Ni-and Cu-containing silicates: Application to talc and chrysocolla Catal Lett 25 147–149 10.1007/BF00815422.CrossRefGoogle Scholar
Colon, L.A. Dadoo, R. and Zare, R.N., 1993 Determination of carbonhydrates by capillary zone electrophoresis with amper-ometric detection at a copper microelectrode Anal Chem 65 476–481 10.1021/ac00052a027.CrossRefGoogle Scholar
Decarreau, A., 1980 Cristallogene expérimentale des smectites magnésiennes: Hectorite, stevensite Bull Mineral 103 579–590.Google Scholar
Decarreau, A., 1981 Cristallogenese a basse temperature de smectites trioctahedrique par vieillisement de coprecipites silico métallique de formule(Si4-x)M3O10·nH2O C. R. Acad Sci Paris 292 61–64.Google Scholar
Decarreau, A., 1983 Etude experimental de la cristallogenese des smectites. Mesure des coefficients de partage smectite trioctaedrique-solution acqueuse pour les metaux M2+ de la premiere serie de transition Mem Sci Geol 74 1–191.Google Scholar
Decarreau, A., 1985 Partitioning of divalent transition elements between octahedral sheets of trioctahedral smectites and water Geochim Cosmochim Acta 49 1537–1544 10.1016/0016-7037(85)90258-3.CrossRefGoogle Scholar
Decarreau, A. Grauby, O. and Petit, S., 1992 The actual distribution of octahedral cations in 2:1 clay minerals: Results from clay synthesis Appl Clay Sci. 7 147–167 10.1016/0169-1317(92)90036-M.CrossRefGoogle Scholar
De Vynck, I., 1980 Synthese de phyllosilicates de cobalt, de nickel, de cuivre et de zinc Silicates Industriels 3 51–66.Google Scholar
Farmer, V.C. and Farmer, V.C., 1974 The layer silicates Infrared spectra of minerals London Mineral Soc 331–363 10.1180/mono-4.15.CrossRefGoogle Scholar
Ildefonse, P. Manceau, A. Prost, D. and Groke, M.C.T., 1986 Hydroxy-Cu-vermiculite formed by the weathering of Fe-biotites at salobo, Carajas, Brazil Clays Clay Miner 34 338–345 10.1346/CCMN.1986.0340315.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 77–81 10.2136/sssaj1950.036159950014000C0017x.CrossRefGoogle Scholar
Jaynes, W.F. and Bigham, J.M., 1986 Multiple cation-exchange capacity measurement on standard clays using a commercial mechanical extractor Clays Clay Miner 34 93–98 10.1346/CCMN.1986.0340112.CrossRefGoogle Scholar
de Kaviratana P, S. and Pinnavaia, T.J., 1992 Electroactive Ru(NH3)6 3+ gallery cations in clay-modified electrodes J Electroanal Chem 332 135–145 10.1016/0022-0728(92)80346-6.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 43–53 10.1016/0022-0728(87)88017-8.CrossRefGoogle Scholar
Li, J. and Calzaferri, G., 1994 Copper-zeolite-modified electrodes: An intrazeolite ion transport mechanism J Electroanal Chem 377 163–175 10.1016/0022-0728(94)03455-9.CrossRefGoogle Scholar
Luo, P. Prabhu, S.V. and Baldwin, R.P., 1990 Constant potential amperometric detection at a copper-based electrode: Electrode formation and operation Anal Chem 62 752–755 10.1021/ac00206a021.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 41 412–422 10.1346/CCMN.1993.0410402.CrossRefGoogle Scholar
Mosser, C. Mestdagh, M. Decarreau, A. and Herbillon, A., 1990 Spectroscopic (ESR, EXAFS) evidence of Cu for (Al-Mg) substitution in octahedral sheets of smectites Clay Miner 25 271–281 10.1180/claymin.1990.025.3.03.CrossRefGoogle Scholar
Mosser, C. Mosser, A. Romeo, A. Petit, S. and Decarreau, A., 1992 Natural and synthetic copper phyllosilicates studied by XPS Clays Clay Miner 40 593–599 10.1346/CCMN.1992.0400514.CrossRefGoogle Scholar
Newman, A.C.D. Brown, G. and Newman, A.C.D., 1987 The chemical constitution of clays Chemistry of clays and clay minerals New York Mineral Soc 1–29.Google 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 199 467–470 10.1016/0022-0728(86)80020-1.CrossRefGoogle Scholar
Petit, S. Decarreau, A. Mosser, C. Ehret, G. and Grauby, O., 1995 Hydrothermal synthesis (250 °C) of copper-substituted ka-olinites Clays Clay Miner 43 482–494 10.1346/CCMN.1995.0430413.CrossRefGoogle Scholar
Petridis, D. Falaras, F. and Pinnavaia, T.J., 1994 Self-assembly of ion-paired electron-transfer centers in a clay-modified electrode Inorg Chem 31 3530–3533 10.1021/ic00043a010.CrossRefGoogle Scholar
Prabhu, S.V. and Baldwin, R.P., 1989 Constant potential amperometric detection of carbonhydrates at a copper-based chemically modified electrode Anal Chem 61 852–856 10.1021/ac00183a014.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 395 159–166 10.1016/0022-0728(95)04070-5.CrossRefGoogle Scholar
Qiu, J. and Villemure, G., 1997 Anionic clay modified electrodes: Electron transfer mediated by electroactive nickel, cobalt or manganese sites in layered double hydroxide films J Electroanal Chem 428 165–172 10.1016/S0022-0728(96)05070-X.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 199 323–340 10.1016/0022-0728(86)80007-9.CrossRefGoogle Scholar
Tanner, C.G. and Jackson, M.L., 1947 Nomographs of sedimentation times for soil particles under gravity or centrifugal acceleration Soil Sei Soc Am Proc 12 60–65 10.2136/sssaj1948.036159950012000C0014x.CrossRefGoogle Scholar
Traynor, M.F. Mortland, M.M. and Pinnavaia, T.J., 1978 Ion exchange and intersalation reactions of hectorite with tris-bipyridyl metal complexes Clays Clay Miner 26 318–326 10.1346/CCMN.1978.0260502.CrossRefGoogle Scholar
Senaratne, C. Zhang, J. Baker, M.D. Bessel, C.A. and Rolison, R., 1996 Zeolite-modified electrodes: Intra-versus extrazeolite electron transfer J Phys Chem 100 5849–5862 10.1021/jp951923x.CrossRefGoogle Scholar
Shaw, B.R., Stock, J.T. and Orna, M.V., 1989 Modification of solid electrodes in electro-analytical chemistry 1978–1988 Electrochemistry past and present, ACS Symposium Series 390 318–338 10.1021/bk-1989-0390.ch022.CrossRefGoogle Scholar
Sun, M.S., 1963 The natural of chrysocolla from Inspiration mine, Arizona Am Miner 48 469–658.Google Scholar
Van Oosterwyck-Gastuche, M.C., 1970 La structure de la chrysocolle CR Acad Sci Paris 271 1837–1840.Google Scholar
Villemure, G., 1991 X-ray diffraction of montmorillonite oriented films exchanged with enantiomeric and racemic tris(2,2’-bipyridyl)ruthenium(II) Clays Clay Miner 39 580–585 10.1346/CCMN.1991.0390603.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 282 107–121 10.1016/0022-0728(91)85092-4.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 1139–1142 10.1139/v85-193.CrossRefGoogle Scholar
Wang, D. Yu, W. and Zhu, B., 1989 A special solid electrolyte-montmorillonite Solid State Ionics 34 219–223 10.1016/0167-2738(89)90445-1.CrossRefGoogle Scholar
Wilkins, R.W.T. and Ito, J., 1967 Infrared spectra of some synthetic talc Am Miner 52 1649–1661.Google 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 1833–1837 10.1139/v92-227.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 21–27 10.1016/0022-0728(94)03629-H.CrossRefGoogle Scholar
Xiang, Y. and Villemure, G., 1996 Electrodes modified with synthetic clay minerals: Electrochemistry of cobalt smectites Clays Clay Miner 44 515–521 10.1346/CCMN.1996.0440410.CrossRefGoogle Scholar
Xiang, Y. and Villemure, G., 1996 Electrodes modified with synthetic clay minerals: Electron transfer between adsorbed tris(2,2′-bipyridyl) metal cations and electroactive cobalt centers in synthetic smectites J Phys Chem 100 7143–7147 10.1021/jp952865i.CrossRefGoogle Scholar