Reaction of CO2 with UO3 Nanoclusters

Adsorption of CO2 to uranium oxide, (UO3) n , clusters was modeled using density functional theory (DFT) and coupled cluster theory (CCSD­(T)). Geometries and reaction energies were predicted for carbonate formation (chemisorption) and Lewis acid–base addition of CO2 (physisorption) to these (UO3) n...

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Bibliographic Details
Published in:The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Molecules, spectroscopy, kinetics, environment, & general theory, 2017-11, Vol.121 (44), p.8518-8524
Main Authors: Flores, Luis A, Murphy, Julia G, Copeland, William B, Dixon, David A
Format: Article
Language:English
Subjects:
INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
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Summary:Adsorption of CO2 to uranium oxide, (UO3) n , clusters was modeled using density functional theory (DFT) and coupled cluster theory (CCSD­(T)). Geometries and reaction energies were predicted for carbonate formation (chemisorption) and Lewis acid–base addition of CO2 (physisorption) to these (UO3) n clusters. Chemisorption of multiple CO2 moieties was also modeled for dimer and trimer clusters. Physisorption and chemisorption were both predicted to be thermodynamically allowed for (UO3) n clusters, with chemisorption being more thermodynamically favorable than physisorption. The most energetically favored (UO3)3(CO2) m clusters contain tridentate carbonates, which is consistent with solid-state and solution structures for uranyl carbonates. The calculations show that CO2 exposure is likely to convert (UO3) n to uranyl carbonates.
ISSN:1089-5639
1520-5215
DOI:10.1021/acs.jpca.7b09107