Improving understanding of NpO2 and Np2O5 through vibrational spectroscopy

Gilson, Sara E.; Sadergaski, Luke R.; Parkison, Adam J.

doi:10.1016/j.jssc.2024.124954

Improving understanding of NpO₂ and Np₂O₅ through vibrational spectroscopy

Journal Article · Thu Aug 15 00:00:00 EDT 2024 · Journal of Solid State Chemistry

DOI:https://doi.org/10.1016/j.jssc.2024.124954· OSTI ID:2438871

^[1]; ^[1]; Parkison, Adam J. ^[1]

Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Raman spectra of three NpO₂ samples and two samples produced from a modified direct denitration (MDD) process were collected. The spectral features of the NpO₂ samples were consistent and indicated only NpO₂. The spectra of the MDD samples indicated the presence of NpO₂ and an additional phase attributed to the neptunium binary oxide Np₂O₅. These Raman spectra are the first reported of Np₂O₅, and the proportions of these neptunium oxide phases varied within the samples, suggesting significant sample inhomogeneity. Peaks in the Raman spectra of Np₂O₅ at 569 and 782 cm^–1 were tentatively assigned to concerted, symmetric stretches of the neptunyl cations. Finally, laser-induced heating of regions in the MDD samples that were rich in Np₂O₅ showed spectral features that indicated conversion to NpO₂.

View Accepted Manuscript (DOE)

Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: USDOE Office of Nuclear Energy (NE)

Grant/Contract Number:: AC05-00OR22725

OSTI ID:: 2438871

Journal Information:: Journal of Solid State Chemistry, Journal Name: Journal of Solid State Chemistry Vol. 339; ISSN 0022-4596

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

References (30)

Amorphous to crystalline transformation in Ta2O5 studied by Raman spectroscopy: Amorphous to crystalline transformation in Ta2O5 studied by Raman spectroscopy Joseph, C.; Bourson, P.; Fontana, M. D. Journal of Raman Spectroscopy, Vol. 43, Issue 8 https://doi.org/10.1002/jrs.3142	journal	June 2012
Raman spectroscopy: A tool to investigate alpha decay damage in a PuO ₂ crystal lattice and determining sample age since calcination Villa‐Aleman, Eliel; Houk, Amanda L.; Bridges, Nicholas J. Journal of Raman Spectroscopy, Vol. 50, Issue 6 https://doi.org/10.1002/jrs.5591	journal	March 2019
Raman spectra of some actinide dioxides and of EuF2 Begun, G. M.; Haire, R. G.; Wilmarth, W. R. Journal of the Less Common Metals, Vol. 162, Issue 1 https://doi.org/10.1016/0022-5088(90)90465-V	journal	August 1990
Advanced thermal denitration conversion processes for aqueous-based reprocessing and recycling of spent nuclear fuels Collins, Emory D. Reprocessing and Recycling of Spent Nuclear Fuel https://doi.org/10.1016/B978-1-78242-212-9.00012-5	book	January 2015
Covalency in f-element complexes Neidig, Michael L.; Clark, David L.; Martin, Richard L. Coordination Chemistry Reviews, Vol. 257, Issue 2 https://doi.org/10.1016/j.ccr.2012.04.029	journal	January 2013
Detection and identification of solids, surfaces, and solutions of uranium using vibrational spectroscopy Lu, Grace; Haes, Amanda J.; Forbes, Tori Z. Coordination Chemistry Reviews, Vol. 374 https://doi.org/10.1016/j.ccr.2018.07.010	journal	November 2018
The crystal and coordination chemistry of neptunium in all its oxidation states: An expanded structural hierarchy of neptunium compounds Gilson, Sara E.; Burns, Peter C. Coordination Chemistry Reviews, Vol. 445 https://doi.org/10.1016/j.ccr.2021.213994	journal	October 2021
Raman spectroscopy of plutonium dioxide and related materials Sarsfield, Mark J.; Taylor, Robin J.; Puxley, Christopher Journal of Nuclear Materials, Vol. 427, Issue 1-3 https://doi.org/10.1016/j.jnucmat.2012.04.034	journal	August 2012
Raman microspectroscopy of PuO2 particulate aggregates Villa-Aleman, Eliel; Bridges, Nicholas J.; Shehee, Thomas C. Journal of Nuclear Materials, Vol. 515 https://doi.org/10.1016/j.jnucmat.2018.12.022	journal	March 2019
Optoelectronic and thermodynamic properties, infrared and Raman spectra of NbO2 and Nb2O5 from DFT formalism Carvalho, R. C.; Mendonça, M. E. V.; Tavares, M. S. Journal of Physics and Chemistry of Solids, Vol. 163 https://doi.org/10.1016/j.jpcs.2021.110549	journal	April 2022
Search for octupolar order in NpO2 by neutron powder diffraction Frontzek, Matthias D.; Sadergaski, Luke R.; Cary, Samantha K. Journal of Solid State Chemistry, Vol. 321 https://doi.org/10.1016/j.jssc.2023.123875	journal	May 2023
Synthesis of Single Crystal Li₂NpO₄ and Li₄NpO₅ from Aqueous Lithium Hydroxide Solutions under Mild Hydrothermal Conditions Hutchison, Danielle C.; Kravchuk, Dmytro V.; Rajapaksha, Harindu Inorganic Chemistry, Vol. 62, Issue 40 https://doi.org/10.1021/acs.inorgchem.3c02460	journal	September 2023
Three-Dimensional Network of Cation–Cation-Bound Neptunyl(V) Squares: Synthesis and in Situ Raman Spectroscopy Studies Jin, Geng Bang Inorganic Chemistry, Vol. 55, Issue 5 https://doi.org/10.1021/acs.inorgchem.5b02955	journal	February 2016
Unraveling the Structure–Raman Spectra Relationships in V ₂ O ₅ Polymorphs via a Comprehensive Experimental and DFT Study Smirnov, Mikhail B.; Roginskii, Evgenii M.; Smirnov, Konstantin S. Inorganic Chemistry, Vol. 57, Issue 15 https://doi.org/10.1021/acs.inorgchem.8b01212	journal	July 2018
Raman Scattering from Decoupled Phonon and Electron States in NpO ₂ Naji, M.; Magnani, N.; Colle, J. -Y. The Journal of Physical Chemistry C, Vol. 120, Issue 9 https://doi.org/10.1021/acs.jpcc.5b12068	journal	February 2016
Cation−Cation Interactions and Antiferromagnetism in Na[Np(V)O ₂ (OH) ₂ ]: Synthesis, Structure, and Magnetic Properties Almond, Philip M.; Skanthakumar, S.; Soderholm, L. Chemistry of Materials, Vol. 19, Issue 2 https://doi.org/10.1021/cm0621040	journal	January 2007
Fabrication of Targets for Neutron Irradiation of Neptunium Dioxide Myrick, R. E.; Folger, R. L. Industrial & Engineering Chemistry Process Design and Development, Vol. 3, Issue 4 https://doi.org/10.1021/i260012a006	journal	October 1964
Raman spectrometric studies of "cation-cation" complexes of pentavalent actinides in aqueous perchlorate solutions Guillaume, B.; Begun, G. M.; Hahn, R. L. Inorganic Chemistry, Vol. 21, Issue 3 https://doi.org/10.1021/ic00133a055	journal	March 1982
Mixed-Valent Neptunium(IV/V) Compound with Cation–Cation-Bound Six-Membered Neptunyl Rings Jin, Geng Bang Inorganic Chemistry, Vol. 52, Issue 21 https://doi.org/10.1021/ic4021492	journal	October 2013
Specific Interaction between Np(V) and U(VI) in Aqueous Perchloric Acid Media ¹ Sullivan, J. C.; Hindman, J. C.; Zielen, A. J. Journal of the American Chemical Society, Vol. 83, Issue 16 https://doi.org/10.1021/ja01477a004	journal	August 1961
Synthesis, Structure, and Magnetism of Np ₂ O ₅ Forbes, Tori Z.; Burns, Peter C.; Skanthakumar, S. Journal of the American Chemical Society, Vol. 129, Issue 10 https://doi.org/10.1021/ja069250r	journal	March 2007
In Situ Formation of Unprecedented Neptunium-Oxide Wheel Clusters Stabilized in a Metal–Organic Framework Gilson, Sara E.; Li, Peng; Szymanowski, Jennifer E. S. Journal of the American Chemical Society, Vol. 141, Issue 30 https://doi.org/10.1021/jacs.9b06187	journal	July 2019
Raman study of laser-induced heating effects in free-standing silicon nanocrystals Han, Lihao; Zeman, Miro; Smets, Arno H. M. Nanoscale, Vol. 7, Issue 18 https://doi.org/10.1039/C5NR00468C	journal	January 2015
Use of vibrational spectroscopy to identify the formation of neptunyl–neptunyl interactions: a paired density functional theory and Raman spectroscopy study Pyrch, Mikaela M.; Augustine, Logan J.; Williams, James M. Dalton Transactions, Vol. 51, Issue 12 https://doi.org/10.1039/D2DT00200K	journal	January 2022
517. Neptunium pentoxide Cohen, Donald; Walter, A. J. Journal of the Chemical Society (Resumed) https://doi.org/10.1039/jr9640002696	journal	January 1964
Cation–cation interaction in crystalline actinide compounds Krot, Nikolai N.; Grigoriev, Mikhail S. Russian Chemical Reviews, Vol. 73, Issue 1 https://doi.org/10.1070/RC2004v073n01ABEH000852	journal	January 2004
Plutonium-238 Production Program Results, Implications, and Projections from Irradiation and Examination of Initial NpO₂ Test Targets for Improved Production Collins, Emory D.; Morris, Robert N.; McDuffee, Joel L. Nuclear Technology, Vol. 208, Issue sup1 https://doi.org/10.1080/00295450.2021.2021769	journal	April 2022
Analysis of radial breathing-mode of nanostructures with various morphologies: a critical review Ghavanloo, E.; A. Fazelzadeh, S.; Rafii-Tabar, H. International Materials Reviews, Vol. 60, Issue 6 https://doi.org/10.1179/1743280415Y.0000000002	journal	May 2015
CURIES: Compendium of uranium Raman and infrared experimental spectra Spano, Tyler L.; Olds, Travis A.; McDonnell, Marshall American Mineralogist, Vol. 108, Issue 12, p. 2219-2233 https://doi.org/10.2138/am-2022-8738	journal	December 2023
Neptunyl Compounds: Polyhedron Geometries, Bond-Valence Parameters, and Structural Hierarchy Forbes, T. Z.; Wallace, C.; Burns, P. C. The Canadian Mineralogist, Vol. 46, Issue 6 https://doi.org/10.3749/canmin.46.6.1623	journal	December 2008

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Improving understanding of NpO₂ and Np₂O₅ through vibrational spectroscopy