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Plutonium and Cerium Perrhenate/Pertechnetate Coordination Polymers and Frameworks
Abstract
Spent nuclear fuel (SNF) contains transuranic and lanthanide species, which are sometimes recovered and repurposed. One particularly problematic fission product, 99TcO4–, hampers this recovery via coextraction with high valence metals, perhaps by complexation during aqueous reprocessing of SNF. There is limited molecular-level knowledge concerning the coordination chemistry between TcO4– or its well-known surrogate ReO4– and transuranic/lanthanide species. In the current study, we investigated the coordination of ReO4–/TcO4– with plutonium and cerium cations by structural and chemical characterization of a series of isolated extended solids. In this study, Ce represents both trivalent lanthanides and is considered a surrogate for Pu, respectively, in its common trivalent and tetravalent oxidation states. The structural elucidation of the seven isolated crystalline solids revealed that ReO4–/TcO4– directly connects to PuIV, PuVIO2 2+, CeIII, and CeIV in the terminal and bridging coordination modes, leading to 1-, 2-, and 3-dimensional frameworks. For example, ReO4– coordination to Pu(IV) formed a 1D chain or 2D framework, isostructural with previously isolated Th(IV) compounds. However, PuVIO2 2+ alternating with ReO4– led to a unique 1D chain, different from the prior-reported U(VI)/Np(VI)-ReO4–/TcO4– structures. Coordination of ReO4–/TcO4– with Ce(III) promotes the assembly of 3D frameworks. Finally, attempted synthesis of a Ce(IV)-ReO4– compound resulted inmore »
- Authors:
-
[2];
[2];
[1]
- Oregon State University, Corvallis, OR (United States)
- University of Notre Dame, IN (United States)
- Publication Date:
- Research Org.:
- University of Notre Dame, IN (United States)
- Sponsoring Org.:
- USDOE National Nuclear Security Administration (NNSA)
- OSTI Identifier:
- 2299507
- Grant/Contract Number:
- NA0003763
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Inorganic Chemistry
- Additional Journal Information:
- Journal Volume: 63; Journal Issue: 4; Journal ID: ISSN 0020-1669
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY; Chemical structure; Crystals; Materials; Organic polymers; Vinyl
Citation Formats
Shohel, Mohammad, Sockwell, A. Kirstin, Hixon, Amy E., and Nyman, May. Plutonium and Cerium Perrhenate/Pertechnetate Coordination Polymers and Frameworks. United States: N. p., 2024.
Web. doi:10.1021/acs.inorgchem.3c03846.
Shohel, Mohammad, Sockwell, A. Kirstin, Hixon, Amy E., & Nyman, May. Plutonium and Cerium Perrhenate/Pertechnetate Coordination Polymers and Frameworks. United States. https://doi.org/10.1021/acs.inorgchem.3c03846
Shohel, Mohammad, Sockwell, A. Kirstin, Hixon, Amy E., and Nyman, May. Wed .
"Plutonium and Cerium Perrhenate/Pertechnetate Coordination Polymers and Frameworks". United States. https://doi.org/10.1021/acs.inorgchem.3c03846.
@article{osti_2299507,
title = {Plutonium and Cerium Perrhenate/Pertechnetate Coordination Polymers and Frameworks},
author = {Shohel, Mohammad and Sockwell, A. Kirstin and Hixon, Amy E. and Nyman, May},
abstractNote = {Spent nuclear fuel (SNF) contains transuranic and lanthanide species, which are sometimes recovered and repurposed. One particularly problematic fission product, 99TcO4–, hampers this recovery via coextraction with high valence metals, perhaps by complexation during aqueous reprocessing of SNF. There is limited molecular-level knowledge concerning the coordination chemistry between TcO4– or its well-known surrogate ReO4– and transuranic/lanthanide species. In the current study, we investigated the coordination of ReO4–/TcO4– with plutonium and cerium cations by structural and chemical characterization of a series of isolated extended solids. In this study, Ce represents both trivalent lanthanides and is considered a surrogate for Pu, respectively, in its common trivalent and tetravalent oxidation states. The structural elucidation of the seven isolated crystalline solids revealed that ReO4–/TcO4– directly connects to PuIV, PuVIO2 2+, CeIII, and CeIV in the terminal and bridging coordination modes, leading to 1-, 2-, and 3-dimensional frameworks. For example, ReO4– coordination to Pu(IV) formed a 1D chain or 2D framework, isostructural with previously isolated Th(IV) compounds. However, PuVIO2 2+ alternating with ReO4– led to a unique 1D chain, different from the prior-reported U(VI)/Np(VI)-ReO4–/TcO4– structures. Coordination of ReO4–/TcO4– with Ce(III) promotes the assembly of 3D frameworks. Finally, attempted synthesis of a Ce(IV)-ReO4– compound resulted in a 2D framework with a mixed-valence CeIII/IV. The highly acidic reaction conditions supported the reduction of both CeIV and TcVII, challenging isolation of compounds featuring these species. Only one TcO4-containing structure was obtained in this study (CeIII–TcO4 3D framework), vs the six total Ce/Pu-ReO4 compounds. Furthermore, our three Pu-ReO4 crystal structures are the first reported and translated to atomic-level information about Pu-TcO4 coordination in nuclear fuel reprocessing scenarios, in addition to broadening our knowledge of bonding trends in the early, high-valence actinides.},
doi = {10.1021/acs.inorgchem.3c03846},
journal = {Inorganic Chemistry},
number = 4,
volume = 63,
place = {United States},
year = {Wed Jan 17 00:00:00 EST 2024},
month = {Wed Jan 17 00:00:00 EST 2024}
}
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Works referenced in this record:
The structural and spectroscopic characterisation of three actinyl complexes with coordinated and uncoordinated perrhenate: [UO 2 (ReO 4 ) 2 (TPPO) 3 ], [{(UO 2 )(TPPO) 3 } 2 (µ 2 -O 2 )][ReO 4 ] 2 and [NpO 2 (TPPO) 4 ][ReO 4 ]
journal, January 2004
- John, Gordon H.; May, Iain; Sarsfield, Mark J.
- Dalton Trans., Issue 5
Reduction of Np(VI) and Pu(VI) by Organic Chelating Agents
journal, January 1998
- Reed, D. T.; Wygmans, D. G.; Aase, S. B.
- Radiochimica Acta, Vol. 82, Issue s1
Structural and Spectroscopic Characterization of Plutonyl(VI) Nitrate under Acidic Conditions
journal, May 2011
- Gaunt, Andrew J.; May, Iain; Neu, Mary P.
- Inorganic Chemistry, Vol. 50, Issue 10
Structure of the Aqueous Pertechnetate Ion by Raman and Infrared Spectroscopy. Raman and Infrared Spectra of Crystalline KTcO 4 , KReO 4 , Na 2 MoO 4 , Na 2 WO 4 , Na 2 MoO 4 ·2H 2 O, and Na 2 WO 4 ·2H 2 O
journal, July 1964
- Busey, R. H.; Keller, O. L.
- The Journal of Chemical Physics, Vol. 41, Issue 1
A short history of SHELX
journal, December 2007
- Sheldrick, George M.
- Acta Crystallographica Section A Foundations of Crystallography, Vol. 64, Issue 1, p. 112-122
Neptunyl Compounds: Polyhedron Geometries, Bond-Valence Parameters, and Structural Hierarchy
journal, December 2008
- Forbes, T. Z.; Wallace, C.; Burns, P. C.
- The Canadian Mineralogist, Vol. 46, Issue 6
Raman analysis of perrhenate and pertechnetate in alkali salts and borosilicate glasses: Raman analysis of perrhenate and pertechnetate
journal, January 2014
- Gassman, Paul L.; McCloy, John S.; Soderquist, Chuck Z.
- Journal of Raman Spectroscopy, Vol. 45, Issue 1
Crystal structure of tetraaquatris(perrhenate)cerium(III), Ce(ReO4)3(H2O)4
journal, September 2009
- Mujica, Carlos; Jimenez, Daniela; Cardoso-Gil, Raúl
- Zeitschrift für Kristallographie - New Crystal Structures, Vol. 224, Issue 3
Synthesis, Structure, and Properties of Actinide(VII) Compounds
journal, November 2021
- Krot, N. N.; Charushnikova, I. A.
- Radiochemistry, Vol. 63, Issue 6
Structural Units in Three Uranyl Perrhenates
journal, October 2007
- Karimova, Oxana V.; Burns, Peter C.
- Inorganic Chemistry, Vol. 46, Issue 24
Investigation of the UO22+ / ReO4 / TPPO reaction system; the first characterised actinide-perrhenate complex, [UO2(ReO4)2(TPPO)3].
journal, November 2002
- John, Gordon H.; Collison, David; May, Iain
- Journal of Nuclear Science and Technology, Vol. 39, Issue sup3
Theoretical Study of Plutonium(IV) Complexes Formed within the PUREX Process: A Proposal of a Plutonium Surrogate in Fire Conditions
journal, October 2014
- Šulka, Martin; Cantrel, Laurent; Vallet, Valérie
- The Journal of Physical Chemistry A, Vol. 118, Issue 43
Properties of Pertechnic Acid
journal, September 2019
- Soderquist, Chuck; Weaver, Jamie; Cho, Herman
- Inorganic Chemistry, Vol. 58, Issue 20
Fuel cycle strategies and plutonium management in Europe
journal, November 2007
- Haas, D.; Hamilton, D. J.
- Progress in Nuclear Energy, Vol. 49, Issue 8, p. 574-582
Raman Spectroscopic Detection for Perchlorate at Low Concentrations
journal, June 2004
- Gu, Baohua; Tio, Jacqueline; Wang, Wei
- Applied Spectroscopy, Vol. 58, Issue 6
A review of technetium and zirconium extraction into tributyl phosphate in the PUREX process
journal, May 2022
- George, Kathryn; Masters, Andrew J.; Livens, Francis R.
- Hydrometallurgy, Vol. 211
The Synthesis, Structural, and Spectroscopic Characterization of Uranium(IV) Perrhenate Complexes
journal, October 2005
- John, Gordon H.; May, Iain; Sharrad, Clint A.
- Inorganic Chemistry, Vol. 44, Issue 21
Coordination of pertechnetate [TcO4]? to actinides
journal, January 2004
- Sarsfield, Mark J.; Sutton, Andrew D.; May, Iain
- Chemical Communications, Issue 20
Structural Periodicity in Plutonium(IV) Sulfates
journal, June 2011
- Wilson, Richard E.
- Inorganic Chemistry, Vol. 50, Issue 12
Spectroscopic Evidence for the Direct Coordination of the Pertechnetate Anion to the Uranyl Cation in [UO 2 (TcO 4 )(DPPMO 2 ) 2 ] +
journal, September 2004
- Sutton, Andrew D.; John, Gordon H.; Sarsfield, Mark J.
- Inorganic Chemistry, Vol. 43, Issue 18
Role of Anions and Reaction Conditions in the Preparation of Uranium(VI), Neptunium(VI), and Plutonium(VI) Borates
journal, March 2011
- Wang, Shuao; Villa, Eric M.; Diwu, Juan
- Inorganic Chemistry, Vol. 50, Issue 6
Synthesis and characterization of new families of lanthanide perrhenate complexes
journal, February 2022
- Decoteau, Elizabeth A.; Polinski, Matthew J.
- Journal of Solid State Chemistry, Vol. 306
Raman spectral titration method: an informative technique for studying the complexation of uranyl with uranyl( vi )–DPA/oxalate systems as examples
journal, January 2017
- Liu, Qian; Zhang, Qianci; Yang, Suliang
- Dalton Transactions, Vol. 46, Issue 39
Theoretical Prediction of Rhenium Separation from Ammonium Perrhenate by Phonon–Photon Resonance Absorption
journal, February 2022
- Li, Miao-Miao; Cao, Jing-Wen; Qin, Xiao-Ling
- ACS Omega, Vol. 7, Issue 6
OLEX2 : a complete structure solution, refinement and analysis program
journal, January 2009
- Dolomanov, Oleg V.; Bourhis, Luc J.; Gildea, Richard J.
- Journal of Applied Crystallography, Vol. 42, Issue 2
Temperature-resolved study of three [M(M′O4)4(TBPO)4] complexes (MM′ = URe, ThRe, ThTc)
journal, January 2006
- Helliwell, Madeleine; Collison, David; John, Gordon H.
- Acta Crystallographica Section B Structural Science, Vol. 62, Issue 1
Synthesis and properties of neptunium(VI,V) and plutonium(VI) pertechnetates
journal, March 2003
- Fedosseev, A. M.; Budantseva, N. A.; Grigoriev, M. S.
- Radiochimica Acta, Vol. 91, Issue 3
Role of Metal Selection in the Radiation Stability of Isostructural M-UiO-66 Metal–Organic Frameworks
journal, September 2022
- Hastings, Ashley M.; Fairley, Melissa; Wasson, Megan C.
- Chemistry of Materials, Vol. 34, Issue 18
Raman and optical spectra of magnesia-supported perrhenates
journal, August 1987
- Gazzoli, D.; Valigi, M.; Vielhaber, B.
- Journal of the Less Common Metals, Vol. 134, Issue 1
Plutonium and Reprocessing of Spent Nuclear Fuel
journal, September 2001
- von Hippel, Frank N.
- Science, Vol. 293, Issue 5539
Elucidating Actinide–Pertechnetate and Actinide–Perrhenate Bonding via a Family of Th–TcO4 and Th–ReO4 Frameworks and Solutions
journal, June 2023
- Shohel, Mohammad; Bustos, Jenna; Stroscio, Gautam D.
- Inorganic Chemistry, Vol. 62, Issue 26
SHELXT – Integrated space-group and crystal-structure determination
journal, January 2015
- Sheldrick, George M.
- Acta Crystallographica Section A Foundations and Advances, Vol. 71, Issue 1, p. 3-8
Structural Role of Isonicotinic Acid in U(VI), Np(VI), and Pu(VI) Complexes with TcO 4 – , ReO 4 – , and ClO 4 – Ions
journal, September 2017
- Budantseva, Nina; Andreev, Grigory; Fedoseev, Aleksander
- Inorganic Chemistry, Vol. 56, Issue 20
Anion Exchange Resins for the Selective Separation of Technetium from Uranium in Carbonate Solutions
journal, July 2012
- Long, Kristy M.; Goff, George S.; Ware, Stuart D.
- Industrial & Engineering Chemistry Research, Vol. 51, Issue 31
Raman spectroscopy of neptunyl and plutonyl ions in aqueous solution: hydrolysis of neptunium(VI) and plutonium(VI) and disproportionation of plutonium(V)
journal, June 1984
- Madic, C.; Begun, G. M.; Hobart, D. E.
- Inorganic Chemistry, Vol. 23, Issue 13