Reaction of CO2 with UO3 Nanoclusters

Flores, Luis A.; Murphy, Julia G.; Copeland, William B.; Dixon, David A.

doi:10.1021/acs.jpca.7b09107

Reaction of CO₂ with UO₃ Nanoclusters

Journal Article · Fri Oct 13 00:00:00 EDT 2017 · Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory

DOI:https://doi.org/10.1021/acs.jpca.7b09107· OSTI ID:1470291

Flores, Luis A. ^[1]; Murphy, Julia G. ^[1]; Copeland, William B. ^[1]; ^[1]

Univ. of Alabama, Tuscaloosa, AL (United States)

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 indicated 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 bound to convert (UO₃)_n to uranyl carbonates.

View Accepted Manuscript (DOE)

Research Organization:: Georgia Inst. of Technology, Atlanta, GA (United States). Energy Frontier Research Center (EFRC) Center for Understanding and Control of Acid Gas-induced Evolution of Materials for Energy (UNCAGE-ME)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: SC0012577

OSTI ID:: 1470291

Journal Information:: Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory, Journal Name: Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory Journal Issue: 44 Vol. 121; ISSN 1089-5639

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Cited By (1)

Mononuclear Hydroxo Carbonato Complexes of Np(V), Np(VI), and U(VI): A Density Functional Study: Mononuclear Hydroxo Carbonato Complexes of Np(V), Np(VI), and U(VI): A Density Functional Study Gray, Andrew; Chiorescu, Ion; Krüger, Sven European Journal of Inorganic Chemistry, Vol. 2019, Issue 42 https://doi.org/10.1002/ejic.201900759	journal	November 2019

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