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Natural and Synthetic Copper Phyllosilicates Studied by XPS

Published online by Cambridge University Press:  28 February 2024

Christine Mosser ,
Aimé Mosser ,
Michelangelo Romeo ,
Sabine Petit  and
Alain Decarreau
Christine Mosser
Affiliation:
Centre de Géochimie de la Surface, CNRS, 1 rue Blessig 67084 Strasbourg, France
Aimé Mosser
Affiliation:
Institut de Physique et Chimie des Matériaux de Strasbourg, 4 rue Blaise Pascal, 67070 Strasbourg Cedex, France
Michelangelo Romeo
Affiliation:
Institut de Physique et Chimie des Matériaux de Strasbourg, 4 rue Blaise Pascal, 67070 Strasbourg Cedex, France
Sabine Petit
Affiliation:
Laboratoire de Pétrologie de la Surface, URA 721 du CNRS, Université de Poitiers, 40 Avenue du Recteur Pineau, 86022 Poitiers Cedex, France
Alain Decarreau
Affiliation:
Laboratoire de Pétrologie de la Surface, URA 721 du CNRS, Université de Poitiers, 40 Avenue du Recteur Pineau, 86022 Poitiers Cedex, France
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Abstract

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X-ray photoelectron spectroscopy (XPS) has been used to characterize the bonding state of Cu2+, Si4+, Al3+, and O2− ions in structural (octahedral and interlamellar) or adsorbed position in phyllosilicates. Five smectites, 5 kaolinites, and 1 chrysocolla with Cu(II) in known positions (octahedral, interlamellar, or surface adsorbed) have been investigated. Their spectra were compared with those of pure Cu metal and of pure Cu(I) and Cu(II) oxides.

The line for Cu 2p3/2 (binding energy of 935.4 eV) and well-defined shake-up lines (binding energy of about 943 eV) observed after 1 hr of X-ray irradiation are characteristic of Cu(II) in phyllosilicate octahedral sites. But due to the photoreduction effect, they show Cu(I) oxidation states (Cu 2p3/2, binding energy of 933.2 eV and near absence of shake-up lines) for the phyllosilicates with adsorbed Cu or in interlamellar positions. The kinetics of photoreduction distinguishes octahedral from interlamellar positions, and the latter from a surface adsorbed position. The enlargement of the FWHM (full width at half maximum) of XPS lines has been used to describe crystallochemical parameters linked to local ordering around the probe cations. Crystallization produces decreasing O 1 s and Cu 2p (octahedral cation) line widths but has no effect on the Si 2p (tetrahedral cation) line width. The enlargement of FWHM for all ion lines of the lattice is linked to the nature (Cu > Mg > Al) and the number and amount of structural cations in the phyllosilicates.

Keywords

ChrysocollaCuESCAKaoliniteSmectiteXPS
Type
Research Article
Information
Clays and Clay Minerals , Volume 40 , Issue 5 , October 1992 , pp. 593 - 599
Copyright
Copyright © 1992, The Clay Minerals Society

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