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Hydrothermal Synthesis (250°C) of Copper-Substituted Kaolinites

Published online by Cambridge University Press:  28 February 2024

Sabine Petit ,
Alain Decarreau ,
Christine Mosser ,
Gabrielle Ehret  and
Olivier Grauby
Sabine Petit
Affiliation:
"Argiles, Sols & Atérations", URA CNRS 721, Université de Poitiers, 40 Avenue du Recteur Pineau, F-86022, Poitiers Cedex, France
Alain Decarreau
Affiliation:
"Argiles, Sols & Atérations", URA CNRS 721, Université de Poitiers, 40 Avenue du Recteur Pineau, F-86022, Poitiers Cedex, France
Christine Mosser
Affiliation:
Centre de Géochimie de la surface, UPR CNRS 6251, 1 rue Blessig, 67084 Strasbourg Cedex, France
Gabrielle Ehret
Affiliation:
IPCMS, CNRS, 23, rue du loess, F-67037, Strasbourg Cedex, France
Olivier Grauby
Affiliation:
Centre de Recherche sur les Mécanismes de la Croissance Cristalline, UPR CNRS 7251, Campus de Luminy, Case 913, F-13288 Marseille, France
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Abstract

To obtain Cu-kaolinites with a controlled range of chemical compositions, syntheses were performed by hydrothermally ageing gels with kaolinite stoichiometric compositions. Gels were prepared with sodium metasilicate and nitrates of octahedral cations. Temperature of synthesis was 250°C with a corresponding equilibrium water pressure of 38 bars.

Three samples with copper contents ranging from 0.1 to 7% and another one with the chemical composition of the Cu end-member were synthesized. While this fourth sample led to tenorite after the hydrothermal treatment, the three others crystallized well into kaolinite.

Up to almost 1% CuO was measured by TEM in some isolated ‘clean’ and hexagonal kaolinite particles. EPR and XPS spectroscopies were consistent with an octahedral position of Cu2+. In IR spectra, vAl-OH-Cu absorption bands were not observed, but vAl2OH bands appeared more and more blurred when Cu content of samples increased. Weak bands situated at 868 cm−1 and 840 cm−1 are tentatively attributed to δAlCuOH. By differential thermal analysis, a downward shift of 20°C in temperature of the endothermic peak from the less Cu-rich sample to the most Cu-rich one, argued for the existence of some Al-OH-Cu bonds, whose binding energies are presumed to be less than the Al-OH-Al ones.

In view of these results, Cu2+ appears incorporated in the octahedral sheet of kaolinite. Moreover, this incorporation is made without major perturbation of the kaolinite structure.

Keywords

Cu2+KaoliniteOctahedral substitutionSynthesis
Type
Research Article
Information
Clays and Clay Minerals , Volume 43 , Issue 4 , August 1995 , pp. 482 - 494
Copyright
Copyright © 1995, The Clay Minerals Society

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