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Polarized ATR-FTIR investigation of Fe reduction in the Uley nontronites

Published online by Cambridge University Press:  01 January 2024

Bryan R. Bzdek  and
Molly M. McGuire
Bryan R. Bzdek
Affiliation:
Department of Chemistry, Bucknell University, Lewisburg, PA 17837, USA
Molly M. McGuire*
Affiliation:
Department of Chemistry, Bucknell University, Lewisburg, PA 17837, USA
*
* E-mail address of corresponding author: mmcguire@bucknell.edu
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Abstract

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Reduction of structural Fe in smectites affects the surface chemical behavior of the clay, but the underlying mechanism and changes in clay structure are still in need of investigation, particularly with respect to changes in the tetrahedral sheet. The purpose of this study was to probe changes in the tetrahedral sheet that occur when structural Fe is reduced in the Uley nontronites, NAu-1 and NAu-2, using polarized attenuated total internal reflection Fourier-transform infrared spectroscopy. Despite the differences in their structures — NAu-2 has tetrahedral Fe3+ while NAu-1 does not — the changes observed in the Si-O stretching region were quite similar. Reduction results in a shift of the in-plane Si-O stretching modes to lower frequencies, while the out-of-plane Si-O stretch shifts to higher frequencies. The magnitude of these shifts is greater in NAu-2 than in NAu-1, but the crystallinity of the tetrahedral silicate sheet of NAu-2 is preserved upon reduction. In both nontronites, the orientation of the out-of-plane Si-O bond changes and becomes completely perpendicular to the basal (001) surface of the clay, indicating the formation of trioctahedral domains wherein the individual tetrahedra reorient relative to the plane of the clay layer.

Keywords

ATR-FTIRInfrared SpectroscopyNAu-1NAu-2NontroniteReduction
Type
Article
Information
Clays and Clay Minerals , Volume 57 , Issue 2 , April 2009 , pp. 227 - 233
Copyright
Copyright © The Clay Minerals Society 2009

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