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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

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