The Key Role of U 28 in the Aqueous Self‐Assembly of Uranyl Peroxide Nanocages

Falaise, Clément; Nyman, May

doi:10.1002/chem.201602130

Title: The Key Role of U ₂₈ in the Aqueous Self‐Assembly of Uranyl Peroxide Nanocages

Journal Article · Fri Aug 19 00:00:00 EDT 2016 · Chemistry - A European Journal

DOI:https://doi.org/10.1002/chem.201602130· OSTI ID:1400785

Falaise, Clément ^[1];

^[1]

Energy Frontier Research Center Materials Science of Actinides Department of Chemistry Oregon State University Gilbert Hall Corvallis Oregon 97331 United States

Abstract For 11 years now, the structural diversity and aesthetic beauty of uranyl–peroxide capsules have fascinated researchers from the diverse fields of mineralogy, polyoxometalate chemistry, and nuclear fuel technologies. There is still much to be learned about the mechanisms of the self‐assembly process, and the role of solution parameters including pH, alkali template, temperature, time, and others. Here we have exploited the high solubility of the UO ₂ ²⁺ /H ₂ O ₂ /LiOH aqueous system to address the effect of the hydroxide concentration. Important techniques of this study are single‐crystal X‐ray diffraction, small‐angle X‐ray scattering, and Raman spectroscopy. Three key phases dominate the solution speciation as a function of time and the LiOH/UO ₂ ²⁺ ratio: the uranyl–triperoxide monomer [UO ₂ (O ₂ ) ₃ ] ⁴⁻ and the two capsules [(UO ₂ )(O ₂ )(OH)] ₂₄ ²⁴⁻ (U ₂₄ ) and [(UO ₂ )(O ₂ ) _1.5 ] ₂₈ ²⁸⁻ (U ₂₈ ). When the LiOH/U ratio is around three, U ₂₈ forms rapidly and this cluster can be isolated in high yield and purity. This result was most surprising and challenges the hypothesis that alkali templating is the most important determinant in the cluster geometry. Moreover, analogous experiments with KOH, NH ₄ OH, and TEAOH (TEA=tetraethylammonium) also rapidly yield U ₂₈ , which suggests that U ₂₈ is the kinetically favored species. Complete mapping of the pH–time phase space reveals only a narrow window of the U ₂₈ dominance, which is why it was previously overlooked as an important kinetic species in this chemical system, as well as others with different counterions.

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Sponsoring Organization:: USDOE

OSTI ID:: 1400785

Journal Information:: Chemistry - A European Journal, Journal Name: Chemistry - A European Journal Vol. 22 Journal Issue: 41; ISSN 0947-6539

Publisher:: Wiley Blackwell (John Wiley & Sons)Copyright Statement

Country of Publication:: Germany

Language:: English

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Cited by: 41 works

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