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Title: Evidence of a Nonphotochemical Mechanism for the Solid-State Formation of Uranyl Peroxide

Here, we have demonstrated the solid-state formation of a uranyl peroxide (UP) species from hydrated uranyl fluoride via a uranyl hydroxide intermediate, the first observation of a UP species formed in a solid-state reaction. Water vapor pressure is shown to be a driving factor of both the loss of fluorine and the subsequent formation of peroxo units. We have ruled out a photochemical mechanism for formation of the UP species by demonstrating that the same reaction occurs in the dark. A radiolytic mechanism is unlikely because of the low radioactivity of the sample material, suggesting the existence of a novel UP formation mechanism.
Authors:
 [1] ; ORCiD logo [2] ; ORCiD logo [2] ; ORCiD logo [1]
  1. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Univ. of Tennessee, Knoxville, TN (United States)
  2. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Publication Date:
Grant/Contract Number:
AC05-00OR22725
Type:
Accepted Manuscript
Journal Name:
Inorganic Chemistry
Additional Journal Information:
Journal Volume: 57; Journal Issue: 10; Journal ID: ISSN 0020-1669
Publisher:
American Chemical Society (ACS)
Research Org:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org:
USDOE National Nuclear Security Administration (NNSA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
OSTI Identifier:
1440829

Kirkegaard, Marie C., Miskowiec, Andrew J., Ambrogio, Michael W., and Anderson, Brian B.. Evidence of a Nonphotochemical Mechanism for the Solid-State Formation of Uranyl Peroxide. United States: N. p., Web. doi:10.1021/acs.inorgchem.8b00512.
Kirkegaard, Marie C., Miskowiec, Andrew J., Ambrogio, Michael W., & Anderson, Brian B.. Evidence of a Nonphotochemical Mechanism for the Solid-State Formation of Uranyl Peroxide. United States. doi:10.1021/acs.inorgchem.8b00512.
Kirkegaard, Marie C., Miskowiec, Andrew J., Ambrogio, Michael W., and Anderson, Brian B.. 2018. "Evidence of a Nonphotochemical Mechanism for the Solid-State Formation of Uranyl Peroxide". United States. doi:10.1021/acs.inorgchem.8b00512.
@article{osti_1440829,
title = {Evidence of a Nonphotochemical Mechanism for the Solid-State Formation of Uranyl Peroxide},
author = {Kirkegaard, Marie C. and Miskowiec, Andrew J. and Ambrogio, Michael W. and Anderson, Brian B.},
abstractNote = {Here, we have demonstrated the solid-state formation of a uranyl peroxide (UP) species from hydrated uranyl fluoride via a uranyl hydroxide intermediate, the first observation of a UP species formed in a solid-state reaction. Water vapor pressure is shown to be a driving factor of both the loss of fluorine and the subsequent formation of peroxo units. We have ruled out a photochemical mechanism for formation of the UP species by demonstrating that the same reaction occurs in the dark. A radiolytic mechanism is unlikely because of the low radioactivity of the sample material, suggesting the existence of a novel UP formation mechanism.},
doi = {10.1021/acs.inorgchem.8b00512},
journal = {Inorganic Chemistry},
number = 10,
volume = 57,
place = {United States},
year = {2018},
month = {5}
}