Resolving Confined 7Li Dynamics of Uranyl Peroxide Capsule U24

Xie, Jing; Neal, Harrison A.; Szymanowski, Jennifer; Burns, Peter C.; Alam, Todd M.; Nyman, May; Gagliardi, Laura

doi:10.1021/acs.inorgchem.8b00474

Title: Resolving Confined ⁷Li Dynamics of Uranyl Peroxide Capsule U₂₄

Journal Article · Wed Apr 18 00:00:00 EDT 2018 · Inorganic Chemistry

DOI: https://doi.org/10.1021/acs.inorgchem.8b00474 · OSTI ID:1457405

^[1]; Neal, Harrison A. ^[2]; Szymanowski, Jennifer ^[3];

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Univ. of Minnesota, Minneapolis, MN (United States)
Oregon State Univ., Corvallis, OR (United States)
Univ. of Notre Dame, Notre Dame, IN (United States)
Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)

Here, we obtained a kerosene-soluble form of the lithium salt [UO₂(O₂)(OH)₂]₂₄ phase (Li-U₂₄), by adding cetyltrimethylammonium bromide surfactant to aqueous Li-U₂₄. Interestingly, its variable-temperature solution ⁷Li NMR spectroscopy resolves two narrowly spaced resonances down to –10 °C, which shift upfield with increasing temperature, and finally coalesce at temperatures > 85 °C. Comparison with solid-state NMR demonstrates that the Li dynamics in the Li-U₂₄-CTA phase involves only exchange between different local encapsulated environments. This behavior is distinct from the rapid Li exchange dynamics observed between encapsulated and external Li environments for Li-U₂₄ in both the aqueous and the solid-state phases. Density functional theory calculations suggest that the two experimental ⁷Li NMR chemical shifts are due to Li cations coordinated within the square and hexagonal faces of the U₂₄ cage, and they can undergo exchange within the confined environment, as the solution is heated. Very different than U₂₄ in aqueous media, there is no evidence that the Li cations exit the cage, and therefore, this represents a truly confined space.

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Research Organization:: Sandia National Laboratories (SNL-NM), Albuquerque, NM (United States); Energy Frontier Research Centers (EFRC) (United States). Materials Science of Actinides (MSA)

Sponsoring Organization:: USDOE Office of Science (SC)

Grant/Contract Number:: AC04-94AL85000

OSTI ID:: 1457405

Report Number(s):: SAND--2018-1993J; 660910

Journal Information:: Inorganic Chemistry, Journal Name: Inorganic Chemistry Journal Issue: 9 Vol. 57; ISSN 0020-1669

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Title: Resolving Confined ⁷Li Dynamics of Uranyl Peroxide Capsule U₂₄