Benchmarking Uranyl Peroxide Capsule Chemistry in Organic Media

Neal, Harrison A.; Szymanowski, Jennifer; Fein, Jeremy B.; Burns, Peter C.; Nyman, May

doi:10.1002/ejic.201601219

Benchmarking Uranyl Peroxide Capsule Chemistry in Organic Media

Journal Article · Tue Nov 29 04:00:00 EST 2016 · European Journal of Inorganic Chemistry

DOI:https://doi.org/10.1002/ejic.201601219· OSTI ID:1401247

Neal, Harrison A. ^[1]; ^[2]; Fein, Jeremy B. ^[2]; Burns, Peter C. ^[2]; ^[1]

Department of Chemistry Oregon State University Corvallis 97331 OR USA
Department of Civil &, Environmental Engineering &, Earth Sciences University of Notre Dame 46556 Notre Dame IN USA

Uranyl peroxide capsules are a recent addition to polyoxometalate (POM) chemistry. Ten years of development has ensued only in water, while transition metal POMs are commonly exploited in aqueous and organic media, controlled by counterions or ligation to render the clusters hydrophilic or hydrophobic. Here, new uranyl POM behavior is recognized in organic media, including (1) stabilization and immobilization of encapsulated hydrophilic countercations, identified by Li nuclear magnetic resonance (NMR) spectroscopy, (2) formation of new cluster species upon phase transfer, (3) extraction of uranyl clusters from different starting materials including simulated spent nuclear fuel, (4) selective phase transfer of one cluster type from a mixture, and (5) phase transfer of clusters from both acidic and alkaline media. The capsule morphology of the uranyl POMs renders accurate characterization by X‐ray scattering, including the distinction of geometrically similar clusters. Compositional analysis of the aqueous phase post‐extraction provided a quantitative determination of the ion exchange process that enables transfer of the clusters into the organic phase. Preferential partitioning of uranyl POMs into organic media presents new frontiers in metal ion behavior and chemical reactions in the confined space of the cluster capsules in hydrophobic media, as well as the reactivity of clusters at the organic/aqueous interface.

View Accepted Manuscript (Publisher)

Sponsoring Organization:: USDOE

Grant/Contract Number:: NONE; SC0001089

OSTI ID:: 1401247

Alternate ID(s):: OSTI ID: 22659559
OSTI ID: 1388537

Journal Information:: European Journal of Inorganic Chemistry, Journal Name: European Journal of Inorganic Chemistry Journal Issue: 1 Vol. 2017; ISSN 1434-1948

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

Country of Publication:: Germany

Language:: English

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