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

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

Research output: Contribution to journalArticlepeer-review

6 Citations (Scopus)


The adsorption sites of Cs on montmorillonite clays were investigated by theoretical 133 Cs chemical shift calculations, 133 Cs 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 133 Cs chemical shifts were highly sensitive to the tetrahedral Al (Al T )-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 Al T and on the surface in the open nanospace. In a series of 133 Cs MAS NMR spectral changes for partial Cs substituted samples, the Cs atoms are preferentially adsorbed at sites near Al T 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
Issue number48
Publication statusPublished - 2018 Dec 6

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry


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