New Insights into the Cs Adsorption on Montmorillonite Clay from 133Cs Solid-State NMR and Density Functional Theory Calculations

Takahiro Ohkubo, Takuya Okamoto, Katsuyuki Kawamura, Regis Guegan, Kenzo Deguchi, Shinobu Ohki, Tadashi Shimizu, Yukio Tachi, Yasuhiko Iwadate

Research output: Contribution to journalArticle

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Abstract

The adsorption sites of Cs on montmorillonite clays were investigated by theoretical 133Cs chemical shift calculations, 133Cs magic-angle-spinning nuclear magnetic resonance (MAS NMR) spectroscopy, and X-ray diffraction under controlled relative humidity. The theoretical calculations were carried out for structures with three stacking variations in the clay layers, where hexagonal cavities formed with Si-O bonds in the tetrahedral layers were aligned as monoclinic, parallel, alternated; with various d-spacings. After structural optimization, all Cs atoms were positioned around the center of hexagonal cavities in the upper or lower tetrahedral sheets. The calculated 133Cs chemical shifts were highly sensitive to the tetrahedral Al (AlT)-Cs distance and d-spacing, rather than to the Cs coordination number. Accordingly, three peaks observed in our theoretical spectra were interpreted to be adsorbed Cs around the center of hexagonal cavity with or without AlT and on the surface in the open nanospace. In a series of 133Cs MAS NMR spectral changes for partial Cs substituted samples, the Cs atoms are preferentially adsorbed at sites near AlT for low Cs substituted montmorillonites. The presence of nonhydrated Cs was also confirmed in partially Cs substituted samples, even after being hydrated under high relative humidity.

Original languageEnglish
Pages (from-to)9326-9337
Number of pages12
JournalJournal of Physical Chemistry A
Volume122
Issue number48
DOIs
Publication statusPublished - 2018 Dec 6

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Bentonite
Magic angle spinning
Chemical shift
montmorillonite
clays
Density functional theory
Atmospheric humidity
Nuclear magnetic resonance
density functional theory
solid state
Adsorption
Atoms
metal spinning
nuclear magnetic resonance
cavities
adsorption
chemical equilibrium
humidity
Structural optimization
spacing

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

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New Insights into the Cs Adsorption on Montmorillonite Clay from 133Cs Solid-State NMR and Density Functional Theory Calculations. / Ohkubo, Takahiro; Okamoto, Takuya; Kawamura, Katsuyuki; Guegan, Regis; Deguchi, Kenzo; Ohki, Shinobu; Shimizu, Tadashi; Tachi, Yukio; Iwadate, Yasuhiko.

In: Journal of Physical Chemistry A, Vol. 122, No. 48, 06.12.2018, p. 9326-9337.

Research output: Contribution to journalArticle

Ohkubo, Takahiro ; Okamoto, Takuya ; Kawamura, Katsuyuki ; Guegan, Regis ; Deguchi, Kenzo ; Ohki, Shinobu ; Shimizu, Tadashi ; Tachi, Yukio ; Iwadate, Yasuhiko. / New Insights into the Cs Adsorption on Montmorillonite Clay from 133Cs Solid-State NMR and Density Functional Theory Calculations. In: Journal of Physical Chemistry A. 2018 ; Vol. 122, No. 48. pp. 9326-9337.
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