Expansion of the Na 3 M III (Ln/An) 6 F 30 Series: Incorporation of Plutonium into a Highly Robust and Stable Framework
[1];
[2];
[1]
- Center for Hierarchical Waste form Materials Columbia SC 29208 USA, Department of Chemistry and Biochemistry University of South Carolina Columbia SC 29208 USA
- Department of Chemistry and Biochemistry University of South Carolina Columbia SC 29208 USA
- Savannah River National Laboratory Aiken SC 29803 USA
- Center for Hierarchical Waste form Materials Columbia SC 29208 USA, Savannah River National Laboratory Aiken SC 29803 USA
Abstract Na n MAn 6 F 30 is an extremely versatile framework structure for incorporating tetravalent actinides (An) and cerium along with divalent or trivalent d‐metals (M); moreover, the structure exhibits a high resistance to harsh chemical conditions. This extreme robustness can potentially be exploited for the sequestration of plutonium in a stable matrix; however, no Na n MPu 6 F 30 compounds have been reported so far. Herein, we present four new plutonium fluorides that have been prepared as single crystals by mild hydrothermal synthesis methods. Structural characterizations revealed their compositions to be Na 3 AlPu 6 F 30 , Na 3 FePu 6 F 30 , Na 3 CoPu 6 F 30 , and Na 2.4 Mn 1.6 Pu 6 F 30 . Surprisingly, in the plutonium series, it was found that Co 2+ and Mn 2+ precursors oxidized to form Na 3 Co III Pu 6 F 30 and Na 2.4 Mn II/III 1.6 Pu 6 F 30 , whereas the analogous reactions for cerium result in reduction of the transition metal, even when beginning with a M 3+ precursor. While cerium is often used as a surrogate for plutonium, this work serves as an example that deviations between their chemistries do occur.
- Sponsoring Organization:
- USDOE
- Grant/Contract Number:
- AC09-08SR22470; SC0014664; SC0016574
- OSTI ID:
- 1671350
- Journal Information:
- Chemistry - A European Journal, Journal Name: Chemistry - A European Journal Journal Issue: 57 Vol. 26; ISSN 0947-6539
- Publisher:
- Wiley Blackwell (John Wiley & Sons)Copyright Statement
- Country of Publication:
- Germany
- Language:
- English
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