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Computational Study of the Bulk and Surface Properties of Minor Actinide Dioxides MAnO2 (MAn = Np, Am, and Cm); Water Adsorption on Stoichiometric and Reduced {111}, {110}, and {100} Surfaces

Cite this: J. Phys. Chem. C 2019, 123, 25, 15540–15550
Publication Date (Web):June 3, 2019
https://doi.org/10.1021/acs.jpcc.9b02324
Copyright © 2019 American Chemical Society

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    Abstract

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    Hubbard U-corrected generalized gradient approximation density functional theory is used to study the bulk and surface properties of minor actinide dioxides NpO2, AmO2, and CmO2. Comparison of lattice parameters, band gaps, and density of states with experimental data indicates that PBE + U (U = 4.50 eV, J = 0.50 eV) is the best approach of those considered. Stoichiometric and oxygen vacancy defect {111}, {110}, and {100} surfaces are investigated, including the molecular and dissociative adsorptions of water. Comparison with previous work by our group on UO2 and PuO2 leads to the conclusion that the oxygen defect generation energy is essentially linearly correlated with the An(IV)/(III) redox potential across the AnO2 series from U to Cm. The geometries of water adsorption are similar across the series, whereas adsorption energies generally decrease, with the exception of certain PuO2 surfaces, in agreement with the very hygroscopic nature of PuO2. Surface defects promote dissociative water adsorption.

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    The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.jpcc.9b02324.

    • Dependence on U of the band gap of MAnO2 (MAn = Np, Am, and Cm), images of the stoichiometric and reduced {111}, {110}, and {100} surfaces of AmO2 and CmO2, images of water adsorption on the stoichiometric {111}, {110}, and {100} surfaces of AmO2 and CmO2, bond length water adsorption on the stoichiometric {111}, {110}, and {100} surfaces of MAnO2 (MAn = Np, Am, and Cm), images of water adsorption on the reduced {111}, {110}, and {100} surfaces of MAnO2 (MAn = Np, Am, and Cm), and energies for molecular and dissociative water adsorptions on reduced NpO2 and AmO2 surfaces (PDF)

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    Cited By

    This article is cited by 14 publications.

    1. Jia-Li Chen, Peter Blaha, Nikolas Kaltsoyannis. DFT + U Simulation of the X-ray Absorption Near-Edge Structure of Bulk UO2 and PuO2. The Journal of Physical Chemistry C 2023, 127 (36) , 17994-18000. https://doi.org/10.1021/acs.jpcc.3c03143
    2. Jia-Li Chen, Nikolas Kaltsoyannis. DFT + U Study of Uranium Dioxide and Plutonium Dioxide with Occupation Matrix Control. The Journal of Physical Chemistry C 2022, 126 (27) , 11426-11435. https://doi.org/10.1021/acs.jpcc.2c03804
    3. Jia-Li Chen, Nikolas Kaltsoyannis. Computational Study of Plutonium–Americium Mixed Oxides (Pu0.92Am0.08O2–x); Water Adsorption on {111}, {110}, and {100} Surfaces. The Journal of Physical Chemistry C 2020, 124 (12) , 6646-6658. https://doi.org/10.1021/acs.jpcc.9b11601
    4. Sergei M. Butorin, David K. Shuh. Chemical bonding in americium oxides probed by X-ray spectroscopy. Scientific Reports 2023, 13 (1) https://doi.org/10.1038/s41598-023-38505-y
    5. Le Zhang, Bo Sun, Qili Zhang, Haifeng Liu, Haifeng Song. Theoretical insights into the hydroxyl-promoted H2 releasing reaction after H2O splitting on Pu-oxide surfaces. Journal of Nuclear Materials 2023, 585 , 154642. https://doi.org/10.1016/j.jnucmat.2023.154642
    6. Xiaoyu Han, Nathan M. Alcock, Nikolas Kaltsoyannis. Effect of Point Defects on Water Adsorption on the ThO2{111} Surface: a First-principles Computational Study. Journal of Nuclear Materials 2023, 221 , 154763. https://doi.org/10.1016/j.jnucmat.2023.154763
    7. Xiaoyu Han, Nikolas Kaltsoyannis. Reactions of NO and H2O on the PuO2 {111} surface: A DFT study. Journal of Nuclear Materials 2023, 575 , 154240. https://doi.org/10.1016/j.jnucmat.2023.154240
    8. Jia-Li Chen, Nikolas Kaltsoyannis. Hybrid functional/embedded cluster study of uranium and actinide (actinide = Np, Pu, Am or Cm) mixed dioxides bulk and {110} surfaces. Journal of Nuclear Materials 2022, 560 , 153490. https://doi.org/10.1016/j.jnucmat.2021.153490
    9. Le Zhang, Bo Sun, Qili Zhang, Haifeng Liu, Kezhao Liu, Haifeng Song. Unravelling the chemical heterogeneity of α-Pu2O3(111) surface with the site-selective adsorption of H2O and CO2. Journal of Alloys and Compounds 2021, 870 , 159371. https://doi.org/10.1016/j.jallcom.2021.159371
    10. Jonathan Collard, Jia-Li Chen, Helen Steele, Nikolas Kaltsoyannis. Embedded Cluster Study of the Co-Adsorption of HCl and H2O on PuO2 Surfaces. Journal of Nuclear Materials 2021, 545 , 152623. https://doi.org/10.1016/j.jnucmat.2020.152623
    11. Le Zhang, Bo Sun, Qili Zhang, Haifeng Liu, Kezhao Liu, Haifeng Song. The adsorption thermodynamics of H2O and CO2 on PuO2(1 1 1) surface: A comparative study based on DFT+U-D3. Applied Surface Science 2021, 537 , 147882. https://doi.org/10.1016/j.apsusc.2020.147882
    12. Jia-Li Chen, Nikolas Kaltsoyannis. DFT + U study of U1-An O2- (An = Np, Pu, Am and Cm) {1 1 1}, {1 1 0} and {1 0 0} surfaces. Applied Surface Science 2021, 537 , 147972. https://doi.org/10.1016/j.apsusc.2020.147972
    13. Gaoxue Wang, Enrique R. Batista, Ping Yang. Water on Actinide Dioxide Surfaces: A Review of Recent Progress. Applied Sciences 2020, 10 (13) , 4655. https://doi.org/10.3390/app10134655
    14. Le Zhang, Bo Sun, Qili Zhang, Haifeng Liu, Kezhao Liu, Haifeng Song. Polaron modulation mechanism of H2O and CO2 adsorption on PuO2(111) surface. Applied Surface Science 2020, 516 , 146164. https://doi.org/10.1016/j.apsusc.2020.146164

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