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Polarized ATR-FTIR Investigation of Fe Reduction in the Uley Nontronites


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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.
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Document Type: Research Article

Publication date: April 1, 2009

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  • The JOURNAL publishes articles of interest to the international community of clay scientists, including but not limited to areas in mineralogy, crystallography, geology, geochemistry, sedimentology, soil science, agronomy, physical chemistry, colloid chemistry, ceramics, petroleum engineering, foundry engineering, and soil mechanics. Clays and Clay Minerals exists to disseminate to its worldwide readership the most recent developments in all of these aspects of clay materials. Manuscripts are welcome from all countries.

    Clays and Clay Minerals is the official publication of The Clay Minerals Society.

    The Editor-in-Chief is Professor Joseph W. Stucki [email protected]

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