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A Mössbauer Spectroscopic Study of Aluminum- and Iron-Pillared Clay Minerals

Published online by Cambridge University Press:  01 January 2024

Amina Aouad ,
Alexandre S. Anastácio ,
Faïza Bergaya  and
Joseph W. Stucki
Amina Aouad
Affiliation:
Department of Natural Resources and Environmental Sciences, University of Illinois, 1102 South Goodwin Avenue, Urbana, Illinois 61801, USA CRMD CNRS-Université d’Orléans, 1b Rue de la Férollerie, 45071 Orléans, France
Alexandre S. Anastácio
Affiliation:
Department of Natural Resources and Environmental Sciences, University of Illinois, 1102 South Goodwin Avenue, Urbana, Illinois 61801, USA
Faïza Bergaya
Affiliation:
CRMD CNRS-Université d’Orléans, 1b Rue de la Férollerie, 45071 Orléans, France
Joseph W. Stucki*
Affiliation:
Department of Natural Resources and Environmental Sciences, University of Illinois, 1102 South Goodwin Avenue, Urbana, Illinois 61801, USA
*
* E-mail address of corresponding author: jstucki@illinois.edu
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Abstract

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The placement of metal oxide pillars between clay mineral layers modifies their physical-chemical properties, including surface area, acidity, and catalytic activity. Aluminum is the most commonly used pillar cation, but the use of Fe offers a distinct opportunity to expand the range of catalytic behavior. The purpose of this study was to prepare Fe-pillared Laponite and montmorillonite and to characterize the resulting Fe phase(s). Laponite or montmorillonite suspension was mixed with different pillaring solutions containing Al oligomer and/or Fe oligomer with Fe:(Al+Fe) percent ratios ranging from 0 to 100%. The Al oligomer was obtained by hydrolysis of A1C13·6H2O with NaOH at pH 4.4 and the Fe oligomer was prepared by FeCl3 hydrolysis with Na2CO3 at pH 2.2. The pillared clay was obtained by adding the oligomer to the clay suspension, then heating to 300°C for 3 h. The Fe oligomer and the pillared clay minerals were characterized by variable-temperature Mössbauer spectroscopy, X-ray powder diffraction, and chemical analysis. The unheated Fe oligomer was akaganeite, an Fe oxyhydroxide phase. Heating the Fe oligomer to 300°C transformed the akaganeite to hematite, but heating it in the presence of the clay protected it, at least partially, from this transformation, creating instead a phase which resembled a more poorly ordered akaganeite or a mixture of akaganeite and poorly ordered hematite. Mixing of Al and Fe oligomers in the pillaring solution had no effect on the magnetic hyperfine field of the Fe pillars, indicating that Al forms separate pillars rather than substituting for Fe in the pillar. A small fraction (4%) of the Fe pillar resisted reductive dissolution by citrate-bicarbonate-dithionite.

Keywords

AkaganeiteAluminumIronLaponiteMontmorilloniteMössbauer SpectroscopyPillared Clay
Type
Article
Information
Clays and Clay Minerals , Volume 58 , Issue 2 , April 2010 , pp. 164 - 173
Copyright
Copyright © Clays and Clay Minerals 2010

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