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First Evidence of Multiple Octahedral Al Sites in Na-Montmorillonite by 27Al Multiple Quantum MAS NMR

Published online by Cambridge University Press:  01 January 2024

Takafumi Takahashi ,
Koji Kanehashi  and
Koji Saito
Takafumi Takahashi*
Affiliation:
Advanced Technology Research Laboratories, Nippon Steel Corporation, 20-1 Shintomi, Futtsu, 293-8511 Japan
Koji Kanehashi
Affiliation:
Advanced Technology Research Laboratories, Nippon Steel Corporation, 20-1 Shintomi, Futtsu, 293-8511 Japan
Koji Saito
Affiliation:
Advanced Technology Research Laboratories, Nippon Steel Corporation, 20-1 Shintomi, Futtsu, 293-8511 Japan
*
* E-mail address of corresponding author: [email protected]
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Abstract

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The configuration of hydroxyl groups around the octahedral cations of 2:1 phyllosilicate minerals has long been an important question in clay science. In the present study, 27Al multiple quantum (MQ) magic angle spinning nuclear magnetic resonance (MAS NMR) was applied to the local structural analysis of octahedral Al positions in a purified Na-montmorillonite. Three octahedral Al sites ([6]Ala, [6]Alb, and [6]Alc) are distinguished by 27Al 5QMAS NMR, whereas these sites are not differentiated by 27Al MAS and 3QMAS NMR. The isotropic chemical shift (δcs) and the quadrupolar product (PQ) were estimated to be 5.8 ppm and 2.6 MHz for [6]Ala, 6.2 ppm and 3.0 MHz for [6]Alb, and 6.7 ppm and 3.7 MHz for [6]Alc, respectively. The three Al sites originated from geometric isomers with cis and trans structures, which have mutually different configurations of the OH groups around the central Al3+ ions. From the view point of symmetry for the OH groups, [6]Ala and [6]Alb in the upfield region were assigned to cis sites, and [6]Alc in the downfield region was assigned to a trans site. The occurrence of multiple Al sites implies that Na-montmorillonite used in the present study has cis-vacant structure in the octahedral sheet. This is a reasonable insight, supported by the chemical composition and the differential thermal analysis data of the Na-montmorillonite.

Keywords

CisHydroxylMQMAS NMRNa-montmorilloniteOctahedral AlTrans
Type
Article
Information
Clays and Clay Minerals , Volume 56 , Issue 5 , October 2008 , pp. 520 - 525
Copyright
Copyright © The Clay Minerals Society 2009

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