Journal article
Formation of U(VI) peroxide nanoclusters from cascade reactions with a persulfate radical initiator
Dalton transactions : an international journal of inorganic chemistry, Vol.54(35), pp.13129-13142
09/21/2025
DOI: 10.1039/D5DT00785B
Appears in UI Libraries Support Open Access
Abstract
Radiolysis of water in high radiation fields generates a variety of reactive oxygen species that influence the chemical behavior and complexation of hexavalent uranium. This study investigates the behavior of interaction of uranyl cation (UO22+(VI)) with series of free radicals that are formed in situ via activation of the free radical initiator persulphate (S2O82-), which releases both SO4-• and •OH species in the solution. Electron Paramagnetic Resonance (EPR) and Raman spectroscopy were used to evaluate the presence of hydroperoxyl radical (HO2.) and superoxide radicals (O2.-) that are formed within the solution through radical cascade reactions. In addition, a uranyl peroxide cluster (NaU24) cluster solid was crystallized and characterized using single crystal x-ray diffraction (SCXRD), vibrational spectroscopy, and EPR spectroscopy. Presence of the hydroperoxyl radical (HO2.) and superoxide radicals (O2.-) were also observed in the solid-state compound, but spectroscopic evidence suggest that it was associated with the Na+ network and not the cluster itself. Density functional theory (DFT) calculations were also utilized to further confirm the radical species produced and determine the potential stabilization of radicals detected within the cluster and lattice.
Details
- Title: Subtitle
- Formation of U(VI) peroxide nanoclusters from cascade reactions with a persulfate radical initiator
- Creators
- Vidumini S. Samarasiri - University of IowaHarindu Rajapaksha - University of IowaSarah McGee - University of IowaSara E. Mason - Brookhaven National LaboratoryTori Forbes - University of Iowa
- Resource Type
- Journal article
- Publication Details
- Dalton transactions : an international journal of inorganic chemistry, Vol.54(35), pp.13129-13142
- DOI
- 10.1039/D5DT00785B
- ISSN
- 1477-9226
- eISSN
- 1477-9234
- Publisher
- Royal Society of Chemistry
- Language
- English
- Electronic publication date
- 07/29/2025
- Date published
- 09/21/2025
- Academic Unit
- Civil and Environmental Engineering; Core Research Facilities; Chemistry
- Record Identifier
- 9984927083602771
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