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Title: The Energy Landscape of Uranyl-Peroxide Species

Abstract

Nanoscale uranyl peroxide clusters containing UO22+ groups bonded through peroxide bridges to form polynuclear molecular species (polyoxometalates) exist both in solution and in the solid state. There is an extensive family of clusters containing 28 uranium atoms (U28 clusters), with an encapsulated anion in the center, for example, [UO2(O2)3-x(OH)x4-], [Nb(O2)43-], or [Ta(O2)43-]. The negative charge of these clusters is balanced by alkali ions, both encapsulated, and located exterior to the cluster. The present study reports measurement of enthalpy of formation for two such U28 compounds, one of which is uranyl centered and the other is peroxotantalate centered. The [(Ta(O2)4]-centered U28 capsule is energetically more stable than the [(UO2)(O2)3]-centered capsule. These data, along with our prior studies on other uranyl–peroxide solids, are used to explore the energy landscape and define thermochemical trends in alkali–uranyl–peroxide systems. It was suggested that the energetic role of charge-balancing alkali ions and their electrostatic interactions with the negatively charged uranyl–peroxide species is the dominant factor in defining energetic stability. These experimental data were supported by DFT calculations, which agree that the [(Ta(O2)4]-centered U28 capsule is more stable than the uranyl-centered capsule. Moreover, the relative stability is controlled by the interactions of the encapsulated alkalis with themore » encapsulated anion. Thus, the role of alkali-anion interactions was shown to be important at all length scales of uranyl–peroxide species: in both comparing clusters to clusters; and clusters to monomers or extended solids.« less

Authors:
; ; ; ; ;
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Materials Science of Actinides (MSA)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1385696
DOE Contract Number:  
SC0001089
Resource Type:
Journal Article
Journal Name:
Chemistry - A European Journal
Additional Journal Information:
Journal Volume: 20; Journal Issue: 13; Related Information: MSA partners with University of Notre Dame (lead); University of California, Davis; Florida State University; George Washington University; University of Michigan; University of Minnesota; Oak Ridge National Laboratory; Oregon state University; Rensselaer Polytechnic Institute; Savannah River National Laboratory; Journal ID: ISSN 0947-6539
Publisher:
ChemPubSoc Europe
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; nuclear (including radiation effects), materials and chemistry by design, synthesis (novel materials), synthesis (self-assembly)

Citation Formats

Tiferet, Eitan, Gil, Adrià, Bo, Carles, Shvareva, Tatiana Y., Nyman, May, and Navrotsky, Alexandra. The Energy Landscape of Uranyl-Peroxide Species. United States: N. p., 2014. Web. doi:10.1002/chem.201304076.
Tiferet, Eitan, Gil, Adrià, Bo, Carles, Shvareva, Tatiana Y., Nyman, May, & Navrotsky, Alexandra. The Energy Landscape of Uranyl-Peroxide Species. United States. doi:10.1002/chem.201304076.
Tiferet, Eitan, Gil, Adrià, Bo, Carles, Shvareva, Tatiana Y., Nyman, May, and Navrotsky, Alexandra. Thu . "The Energy Landscape of Uranyl-Peroxide Species". United States. doi:10.1002/chem.201304076.
@article{osti_1385696,
title = {The Energy Landscape of Uranyl-Peroxide Species},
author = {Tiferet, Eitan and Gil, Adrià and Bo, Carles and Shvareva, Tatiana Y. and Nyman, May and Navrotsky, Alexandra},
abstractNote = {Nanoscale uranyl peroxide clusters containing UO22+ groups bonded through peroxide bridges to form polynuclear molecular species (polyoxometalates) exist both in solution and in the solid state. There is an extensive family of clusters containing 28 uranium atoms (U28 clusters), with an encapsulated anion in the center, for example, [UO2(O2)3-x(OH)x4-], [Nb(O2)43-], or [Ta(O2)43-]. The negative charge of these clusters is balanced by alkali ions, both encapsulated, and located exterior to the cluster. The present study reports measurement of enthalpy of formation for two such U28 compounds, one of which is uranyl centered and the other is peroxotantalate centered. The [(Ta(O2)4]-centered U28 capsule is energetically more stable than the [(UO2)(O2)3]-centered capsule. These data, along with our prior studies on other uranyl–peroxide solids, are used to explore the energy landscape and define thermochemical trends in alkali–uranyl–peroxide systems. It was suggested that the energetic role of charge-balancing alkali ions and their electrostatic interactions with the negatively charged uranyl–peroxide species is the dominant factor in defining energetic stability. These experimental data were supported by DFT calculations, which agree that the [(Ta(O2)4]-centered U28 capsule is more stable than the uranyl-centered capsule. Moreover, the relative stability is controlled by the interactions of the encapsulated alkalis with the encapsulated anion. Thus, the role of alkali-anion interactions was shown to be important at all length scales of uranyl–peroxide species: in both comparing clusters to clusters; and clusters to monomers or extended solids.},
doi = {10.1002/chem.201304076},
journal = {Chemistry - A European Journal},
issn = {0947-6539},
number = 13,
volume = 20,
place = {United States},
year = {2014},
month = {3}
}

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