In situ Raman spectroscopy of uranyl peroxide nanoscale cage clusters under hydrothermal conditions

Aqueous solutions containing the nanoscale uranyl peroxide cage clusters U60, [(UO2)(O2)(OH)]6060-, and U60Ox30, [{(UO2)(O2)}60(C2O4)30]60-, were monitored by in situ Raman spectroscopy during stepwise heating to 180 °C. In solutions containing U60, clusters persist to 120 °C, although conversion of...

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Bibliographic Details
Published in:Dalton transactions : an international journal of inorganic chemistry 2019, Vol.48 (22), p.7755-7765
Main Authors: Lobeck, Haylie L, Traustason, Hrafn, Julien, Patrick A, FitzPatrick, John R, Mana, Sara, Szymanowski, Jennifer E S, Burns, Peter C
Format: Article
Language:English
Subjects:
Aqueous solutions
Cages
Clusters
Conversion
Heating
High temperature
INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
NANOSCIENCE AND NANOTECHNOLOGY
Polytetrafluoroethylene
RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY
Raman spectroscopy
Sapphire
Scanning electron microscopy
Spectrum analysis
Uranium
Uranium dioxide
Uranium oxides
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Summary:Aqueous solutions containing the nanoscale uranyl peroxide cage clusters U60, [(UO2)(O2)(OH)]6060-, and U60Ox30, [{(UO2)(O2)}60(C2O4)30]60-, were monitored by in situ Raman spectroscopy during stepwise heating to 180 °C. In solutions containing U60, clusters persist to 120 °C, although conversion of U60 to U24, [(UO2)(O2)(OH)]2424-, occurs above 100 °C. U60Ox30 persisted in solutions heated to 150 °C, although partial conversion to smaller uranyl peroxide clusters species was observed beginning at 100 °C. Upon breakdown of the uranyl peroxide cage clusters, uranium precipitated as a compreignacite-like phase, K2[(UO2)3O2(OH)3]2(H2O)7, and metaschoepite, [(UO2)8O2(OH)12](H2O)10. The role of the countercations, oxalate bridge, and solution pH are examined in order to better understand the mobility of these species at elevated temperatures.
ISSN:1477-9226
1477-9234
DOI:10.1039/c9dt01529a