Dynamics of Uranyl Peroxide Nanocapsules

Journal Article · Fri Nov 30 04:00:00 EST 2012 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/ja308673f· OSTI ID:1386701

Nyman, May ^[1]; Alam, Todd M. ^[2]

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1. Sandia National Laboratories, Albuquerque, New Mexico 87185, United States; Department of Chemistry, Oregon State University, Corvallis, Oregon 97331, United States
2. Sandia National Laboratories, Albuquerque, New Mexico 87185, United States

Discrete aqueous metal oxide polyionic clusters that include aluminum polycations, transition-metal polyoxometalates, and the actinyl peroxide clusters have captivated the interest of scientists in the realm of both their fundamental and applied chemistries. Yet the counterions for these polycations or polyanions are often ignored, even though they are imperative for solubility, crystallization, purification, and even templating cluster formation. The actinyl peroxide clusters have counterions not only external, but internal to the hollow peroxide capsules. In this study, we reveal the dynamic behavior of these internal alkali counterions via solid-state and liquid NMR experiments. These studies on two select cluster geometries, those containing 24 and 28 uranyl polyhedra, respectively, show that the capsules-like clusters are not rigid entities. Rather, the internal alkalis both have mobility inside the capsules, as well as exchange with species in the media in which they are dissolved. The alkali mobilities are affected by both what is inside the clusters as well as the composition of the dissolving medium.

• Research Organization: Energy Frontier Research Centers (EFRC) (United States). Materials Science of Actinides (MSA)
• Sponsoring Organization: USDOE SC Office of Basic Energy Sciences (SC-22)
• DOE Contract Number: SC0001089
• OSTI ID: 1386701
• Journal Information: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 49 Vol. 134; ISSN 0002-7863
• Publisher: American Chemical Society (ACS)
• Country of Publication: United States
• Language: English

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