Uranyl Peroxide Capsule Self-assembly in Slow Motion Ana Arteaga,1 Lei Zhang,2 Sarah Hickam,2 Mateusz Dembowski,2,3 Peter C. Burns 2 and May Nyman1*

Arteaga, Ana; Zhang, Lei; Hickam, Sarah; Dembowski, Mateusz; Burns, Peter; Nyman, May

doi:10.1002/chem.201806227

Uranyl Peroxide Capsule Self-assembly in Slow Motion Ana Arteaga,1 Lei Zhang,2 Sarah Hickam,2 Mateusz Dembowski,2,3 Peter C. Burns 2 and May Nyman1*

Journal Article · Wed Mar 06 04:00:00 EST 2019 · Chemistry - A European Journal

DOI:https://doi.org/10.1002/chem.201806227· OSTI ID:1502931

Arteaga, Ana ^[1]; Zhang, Lei ^[2]; Hickam, Sarah ^[2]; Dembowski, Mateusz ^[2]; Burns, Peter ^[2]; Nyman, May ^[3]

Oregon State Univ., Corvallis, OR (United States). Dept. of Chemistry; University of Notre Dame
Univ. of Notre Dame, Notre Dame, IN (United States). Dept. of Civil and Environmental Engineering and Earth Sciences
Oregon State Univ., Corvallis, OR (United States). Dept. of Chemistry

Uranyl-peroxide capsules are the newest family of polyoxometalates. Although discovered 13 years prior with over 70 topologies reported, we lack fundamental understanding of assembly mechanisms, particularly the role of the alkali countercations. Herein, we report the reaction pathway and assembly of uranyl peroxide capsules by tracking the conversion from K⁺ uranyl triperoxide monomer to the K⁺ uranyl-peroxide U28 capsule via Small Angle X-Ray Scattering and Raman Spectroscopy. For the first time, the K⁺ uranyl-peroxide pentamer face is isolated and structurally characterized, giving credence to the long-held belief that these geometric faces serve as building blocks to the fully formed capsules. Once isolated and redissolved, the pentamer face undergoes rapid conversion to capsule forms, underlining its high reactivity that challenges its isolation. Calorimetric measurements of the studied species confirms the pentamer lies on the energy landscape between the monomer and capsule.

View Accepted Manuscript (DOE)

Research Organization:: Energy Frontier Research Centers (EFRC) (United States). Materials Science of Actinides (MSA); Univ. of Notre Dame, Notre Dame, IN (United States)

Sponsoring Organization:: USDOE National Nuclear Security Administration (NNSA); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: NA0003763

OSTI ID:: 1502931

Alternate ID(s):: OSTI ID: 1503928
OSTI ID: 22972097

Journal Information:: Chemistry - A European Journal, Journal Name: Chemistry - A European Journal Journal Issue: 24 Vol. 25; ISSN 0947-6539

Publisher:: ChemPubSoc EuropeCopyright Statement

Country of Publication:: United States

Language:: English

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Uranyl Peroxide Capsule Self-assembly in Slow Motion Ana Arteaga,1 Lei Zhang,2 Sarah Hickam,2 Mateusz Dembowski,2,3 Peter C. Burns 2 and May Nyman1*

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