Journal article
Utilizing Autoxidation of Solvents To Promote the Formation of Uranyl Peroxide Materials
Crystal growth & design, Vol.19(3), pp.1756-1766
03/06/2019
DOI: 10.1021/acs.cgd.8b01735
Abstract
Uranyl peroxide compounds are important to the nuclear fuel cycle and are typically formed from the direct addition of hydrogen peroxide or through photochemical pathways that utilize a sacrificial solvent. In this study, we explore the use of THF as a peroxide forming solvent that could be used to promote the crystallization of uranyl peroxide materials. Compound 1 (Li(H 2 O) 2 (UO 2 )(C 7 H 3 NO 4 )(C 4 H 5 NO 4 )·2H 2 O) was originally crystallized after aging for 10 days at room temperature and was characterized by X-ray diffraction, elemental analysis, Raman spectroscopy, and UV/vis spectroscopy. Exposure to ambient light for one month led to the complete transformation of 1 to compound 2 ((C 5 NH 6 ) 2 [(UO 2 ) 2 (μ-O 2 )(H 2 O) 2 (C 7 NO 4 H 3 ) 2 ]·4H 2 O). Oxidation of the THF molecule was proposed as the major mechanism for the formation of the secondary uranyl peroxide compound, which was accelerated in the presence of the UO 22+ cation and light. Presence of THF hydrogen peroxide was confirmed by spectral (NMR and Raman) analysis of the mother liquor. Compound 3 ((C 4 N 2 H 12 )[(UO 2 ) 2 (μ-O 2 )(H 2 O) 2 (C 7 NO 4 H 3 ) 2 ]·2.75H 2 O) formed in the presence of transition metal cations and additional experiments indicated that photoexcitation was not necessary to create free peroxide in this system. Autoxidation of the THF molecule is the most likely mechanism for peroxide formation and indicates that judicial choice of solvent can lead to the formation of new uranyl peroxide materials. ©
Details
- Title: Subtitle
- Utilizing Autoxidation of Solvents To Promote the Formation of Uranyl Peroxide Materials
- Creators
- Ashini S Jayasinghe - Department of Chemistry, University of Iowa, Iowa City, Iowa 52242, United StatesLindsey C Applegate - Department of Chemistry, University of Iowa, Iowa City, Iowa 52242, United StatesDaniel K Unruh - Department of Chemistry, University of Iowa, Iowa City, Iowa 52242, United StatesJeremy Hutton - Department of Chemistry, University of Iowa, Iowa City, Iowa 52242, United StatesTori Z Forbes - Department of Chemistry, University of Iowa, Iowa City, Iowa 52242, United States
- Resource Type
- Journal article
- Publication Details
- Crystal growth & design, Vol.19(3), pp.1756-1766
- DOI
- 10.1021/acs.cgd.8b01735
- ISSN
- 1528-7483
- eISSN
- 1528-7505
- Grant note
- DOI: 10.13039/100000078, name: Division of Materials Research, award: DMR1252831
- Language
- English
- Date published
- 03/06/2019
- Academic Unit
- Chemistry; Core Research Facilities; Civil and Environmental Engineering
- Record Identifier
- 9984216676102771
Metrics
6 Record Views