Pertechnetate/perrhenate–capped Zr/Hf–Dihydroxide Dimers: Elucidating Zr–TcO4 Co–Mobility in the Nuclear Fuel Cycle

Shohel, Mohammad; Bustos, Jenna; Roseborough, Alexander; Nyman, May

doi:10.1002/chem.202303218

Pertechnetate/perrhenate–capped Zr/Hf–Dihydroxide Dimers: Elucidating Zr–TcO₄ Co–Mobility in the Nuclear Fuel Cycle

Journal Article · Mon Dec 18 00:00:00 EST 2023 · Chemistry - A European Journal

DOI:https://doi.org/10.1002/chem.202303218· OSTI ID:2279027

^[1]; ^[2]; Roseborough, Alexander ^[2]; ^[2]

Oregon State University, Corvallis, OR (United States); University of Notre Dame
Oregon State University, Corvallis, OR (United States)

Spent nuclear fuel contains heavy element fission products that must be separated for effective reprocessing for a safe and sustainable nuclear fuel cycle. ⁹³Zr and ⁹⁹Tc are high-yield fission products that co-transport in liquid-liquid extraction processes. Here we seek atomic-level information of this co-extraction process, as well as fundamental knowledge about Zr^IV (and Hf^IV) aqueous speciation in the presence of topology-directing ligands such as pertechnetate (TcO₄^–) and non-radioactive surrogate perrhenate (ReO₄^–). In this context, we show that the flat tetrameric oxyhydroxyl-cluster [M^IV₄(OH)₈(H₂O)₁₆]⁸⁺ (and related polymers) is dissociated by perrhenate/pertechnetate to yield isostructural dimers, M₂(OH)₂(XO₄^–)₆(H₂O)₆ • 3H₂O (M=Zr/Hf^IV; X=Re/Tc^VII), elucidated by single-crystal X-ray diffraction. We used these model compounds to understand the pervasive ⁹³Zr-⁹⁹Tc coextraction with further speciation studies in water, nitric acid, and tetrabutylphosphate (TBP) -kerosene; where the latter two media are relevant to nuclear fuel reprocessing. SAXS (small angle X-ray scattering), compositional evaluation, and where experimentally feasible, ESI-MS (electrospray ionization mass spectrometry) showed that perrhenate/pertechnetate influence Zr/Hf^IV-speciation in water. Here, in Zr-XO₄ solvent extraction studies to simulate fuel reprocessing, we provide evidence that TcO₄^– enhances extraction of Zr^IV, and compositional analysis of the extracted metal-complexes (Zr-ReO₄ study) is consistent with the crystallized Zr^IV₂(OH)₂(Re^VIIO₄^–)₆(H₂O)₆•dimer.

View Accepted Manuscript (DOE)

Research Organization:: University of Notre Dame, IN (United States)

Sponsoring Organization:: Murdock Charitable Trust; USDOE; USDOE National Nuclear Security Administration (NNSA)

Grant/Contract Number:: NA0003763

OSTI ID:: 2279027

Alternate ID(s):: OSTI ID: 2274837

Journal Information:: Chemistry - A European Journal, Journal Name: Chemistry - A European Journal Journal Issue: 10 Vol. 30; ISSN 0947-6539

Publisher:: WileyCopyright Statement

Country of Publication:: United States

Language:: English

References (61)

Amphoteric Aqueous Hafnium Cluster Chemistry Goberna-Ferrón, Sara; Park, Deok-Hie; Amador, Jenn M. Angewandte Chemie International Edition, Vol. 55, Issue 21 https://doi.org/10.1002/anie.201601134	journal	April 2016
Discrete Hf ₁₈ Metal‐oxo Cluster as a Heterogeneous Nanozyme for Site‐Specific Proteolysis Moons, Jens; Azambuja, Francisco; Mihailovic, Jelena Angewandte Chemie International Edition, Vol. 59, Issue 23 https://doi.org/10.1002/anie.202001036	journal	March 2020
A Toroidal Zr ₇₀ Oxysulfate Cluster and Its Diverse Packing Structures Øien‐Ødegaard, Sigurd; Bazioti, Calliope; Redekop, Evgeniy A. Angewandte Chemie International Edition, Vol. 59, Issue 48 https://doi.org/10.1002/anie.202010847	journal	November 2020
Aqueous Isolation of 17-Nuclear Zr/Hf Oxide Clusters during the Hydrothermal Synthesis of ZrO ₂ /HfO ₂ Sun, Qing; Liu, Caiyun; Zhang, Guanyun Chemistry - A European Journal, Vol. 24, Issue 55 https://doi.org/10.1002/chem.201801267	journal	September 2018
Capture of Gaseous Iodine in Isoreticular Zirconium‐Based UiO‐n Metal‐Organic Frameworks: Influence of Amino Functionalization, DFT Calculations, Raman and EPR Spectroscopic Investigation Leloire, Maeva; Walshe, Catherine; Devaux, Philippe Chemistry – A European Journal, Vol. 28, Issue 14 https://doi.org/10.1002/chem.202104437	journal	February 2022
Structural Analysis of Zirconium Hydroxide Nitrate Monohydrates by X-Ray Powder Diffraction Bénard-Rocherullé, Patricia; Rius, Jordi; Louër, Daniel Journal of Solid State Chemistry, Vol. 128, Issue 2 https://doi.org/10.1006/jssc.1996.7226	journal	February 1997
X-ray diffraction investigation of some zirconium, hafnium and tetravalent cerium sulfates Rogachev, D. L.; Antsyshkina, A. S.; Porai-Koshits, M. A. Journal of Structural Chemistry, Vol. 13, Issue 2 https://doi.org/10.1007/BF00744494	journal	January 1972
Coextraction of pertechnetate and zirconium by tri-n-butyl phosphate Garraway, J.; Wilson, P. D. Journal of the Less Common Metals, Vol. 106, Issue 1 https://doi.org/10.1016/0022-5088(85)90379-0	journal	March 1985
Mainstreaming inorganic metal-oxide resists for high-resolution lithography Olynick, Deirdre; Schwartzberg, Adam; Keszler, Douglas A. Materials and Processes for Next Generation Lithography https://doi.org/10.1016/B978-0-08-100354-1.00010-7	book	January 2016
The forgotten chemistry of group(IV) metals: A survey on the synthesis, structure, and properties of discrete Zr(IV), Hf(IV), and Ti(IV) oxo clusters Zhang, Yujie; de Azambuja, Francisco; Parac-Vogt, Tatjana N. Coordination Chemistry Reviews, Vol. 438 https://doi.org/10.1016/j.ccr.2021.213886	journal	July 2021
A review of technetium and zirconium extraction into tributyl phosphate in the PUREX process George, Kathryn; Masters, Andrew J.; Livens, Francis R. Hydrometallurgy, Vol. 211 https://doi.org/10.1016/j.hydromet.2022.105892	journal	May 2022
Countercation-Controlled Nuclearity of Zr/Hf Peroxo Oxalates Kozma, Karoly; Zakharov, Lev N.; Nyman, May Crystal Growth & Design, Vol. 20, Issue 10 https://doi.org/10.1021/acs.cgd.0c00713	journal	August 2020
A Decade of UiO-66 Research: A Historic Review of Dynamic Structure, Synthesis Mechanisms, and Characterization Techniques of an Archetypal Metal–Organic Framework Winarta, Joseph; Shan, Bohan; Mcintyre, Sean M. Crystal Growth & Design, Vol. 20, Issue 2 https://doi.org/10.1021/acs.cgd.9b00955	journal	December 2019
Efficient Capture of Perrhenate and Pertechnetate by a Mesoporous Zr Metal–Organic Framework and Examination of Anion Binding Motifs Drout, Riki J.; Otake, Kenichi; Howarth, Ashlee J. Chemistry of Materials, Vol. 30, Issue 4 https://doi.org/10.1021/acs.chemmater.7b04619	journal	January 2018
Radioactive Transition Metals for Imaging and Therapy Boros, Eszter; Packard, Alan B. Chemical Reviews, Vol. 119, Issue 2 https://doi.org/10.1021/acs.chemrev.8b00281	journal	September 2018
Differentiating Zr/Hf ^IV Aqueous Polyoxocation Chemistry with Peroxide Ligation Sommers, James A.; Hutchison, Danielle C.; Martin, Nicolas P. Inorganic Chemistry, Vol. 60, Issue 3 https://doi.org/10.1021/acs.inorgchem.0c03128	journal	January 2021
Structure, Properties, and Reactivity of Polyoxocationic Zirconium and Hafnium Clusters: A Computational Investigation Bhattacharjee, Rameswar; Hare, Ethan T.; Miró, Pere Inorganic Chemistry, Vol. 62, Issue 13 https://doi.org/10.1021/acs.inorgchem.2c04142	journal	March 2023
Elucidating Actinide–Pertechnetate and Actinide–Perrhenate Bonding via a Family of Th–TcO₄ and Th–ReO₄ Frameworks and Solutions Shohel, Mohammad; Bustos, Jenna; Stroscio, Gautam D. Inorganic Chemistry, Vol. 62, Issue 26 https://doi.org/10.1021/acs.inorgchem.3c01430	journal	June 2023
Intramolecular Re···O Nonvalent Interactions as a Stabilizer of the Polyoxorhenate(VII) Volkov, Mikhail A.; Novikov, Anton P.; Borisova, Nataliya E. Inorganic Chemistry, Vol. 62, Issue 33 https://doi.org/10.1021/acs.inorgchem.3c01863	journal	August 2023
Modulated Hydrothermal Synthesis of UiO-66(Hf)-Type Metal–Organic Frameworks for Optimal Carbon Dioxide Separation Hu, Zhigang; Nalaparaju, Anjaiah; Peng, Yongwu Inorganic Chemistry, Vol. 55, Issue 3 https://doi.org/10.1021/acs.inorgchem.5b02312	journal	January 2016
Structural Evolution of Aqueous Zirconium Acetate by Time-Resolved Small-Angle X-ray Scattering and Rheology Bremholm, Martin; Birkedal, Henrik; Iversen, Bo Brummerstedt The Journal of Physical Chemistry C, Vol. 119, Issue 22 https://doi.org/10.1021/acs.jpcc.5b00698	journal	May 2015
Theoretical Prediction of Rhenium Separation from Ammonium Perrhenate by Phonon–Photon Resonance Absorption Li, Miao-Miao; Cao, Jing-Wen; Qin, Xiao-Ling ACS Omega, Vol. 7, Issue 6 https://doi.org/10.1021/acsomega.1c06744	journal	February 2022
Chemistry of Technetium and Rhenium Species during Low-Level Radioactive Waste Vitrification Darab, John G.; Smith, Peter A. Chemistry of Materials, Vol. 8, Issue 5, p. 1004-1021 https://doi.org/10.1021/cm950418	journal	May 1996
Solution and Solid-State Structural Chemistry of Actinide Hydrates and Their Hydrolysis and Condensation Products Knope, Karah E.; Soderholm, L. Chemical Reviews, Vol. 113, Issue 2 https://doi.org/10.1021/cr300212f	journal	October 2012
Synthesis and characterization of bis(.mu.-hydroxo)tetraaquadiplutonium(IV) sulfate, Pu2(OH)2(SO4)3.4H2O, a novel compound containing hydrolyzed plutonium(IV) Wester, Dennis W. Inorganic Chemistry, Vol. 21, Issue 9 https://doi.org/10.1021/ic00139a022	journal	September 1982
Crystal structure of a complex basic zirconium sulfate Squattrito, Philip J.; Rudolf, Philip R.; Clearfield, Abraham Inorganic Chemistry, Vol. 26, Issue 25 https://doi.org/10.1021/ic00272a020	journal	December 1987
Spectroscopic Evidence for the Direct Coordination of the Pertechnetate Anion to the Uranyl Cation in [UO ₂ (TcO ₄ )(DPPMO ₂ ) ₂ ] ⁺ Sutton, Andrew D.; John, Gordon H.; Sarsfield, Mark J. Inorganic Chemistry, Vol. 43, Issue 18 https://doi.org/10.1021/ic049588r	journal	September 2004
The Crystal Structure of Zr ₂ (OH) ₂ (SO ₄ ) ₃ (H ₂ O) ₄ McWhan, D. B.; Lundgren, Georg Inorganic Chemistry, Vol. 5, Issue 2 https://doi.org/10.1021/ic50036a027	journal	February 1966
Hafnium Sulfate Prenucleation Clusters and the Hf ₁₈ Polyoxometalate Red Herring Ruther, Rose E.; Baker, Brenna M.; Son, Jung-Ho Inorganic Chemistry, Vol. 53, Issue 8 https://doi.org/10.1021/ic500375v	journal	March 2014
Understanding the Role of Aqueous Solution Speciation and Its Application to the Directed Syntheses of Complex Oxidic Zr Chlorides and Sulfates Hu, Yung-Jin; Knope, Karah E.; Skanthakumar, S. Journal of the American Chemical Society, Vol. 135, Issue 38 https://doi.org/10.1021/ja405555h	journal	September 2013
Zirconium(IV) Tetramer/Octamer Hydrolysis Equilibrium in Aqueous Hydrochloric Acid Solution Singhal, A.; Toth, L. M.; Lin, J. S. Journal of the American Chemical Society, Vol. 118, Issue 46 https://doi.org/10.1021/ja9602399	journal	January 1996
Oxo-Cluster-Based Zr/Hf ^IV Separation: Shedding Light on a 70-Year-Old Process Sommers, James A.; Palys, Lauren; Martin, Nicolas P. Journal of the American Chemical Society, Vol. 144, Issue 6 https://doi.org/10.1021/jacs.1c13338	journal	February 2022
Single-Site Cobalt Catalysts at New Zr ₈ (μ ₂ -O) ₈ (μ ₂ -OH) ₄ Metal-Organic Framework Nodes for Highly Active Hydrogenation of Alkenes, Imines, Carbonyls, and Heterocycles Ji, Pengfei; Manna, Kuntal; Lin, Zekai Journal of the American Chemical Society, Vol. 138, Issue 37 https://doi.org/10.1021/jacs.6b06759	journal	September 2016
Metal–Organic Nanosheets Formed via Defect-Mediated Transformation of a Hafnium Metal–Organic Framework Cliffe, Matthew J.; Castillo-Martínez, Elizabeth; Wu, Yue Journal of the American Chemical Society, Vol. 139, Issue 15 https://doi.org/10.1021/jacs.7b00106	journal	April 2017
Single-Site Cobalt Catalysts at New Zr ₁₂ (μ ₃ -O) ₈ (μ ₃ -OH) ₈ (μ ₂ -OH) ₆ Metal–Organic Framework Nodes for Highly Active Hydrogenation of Nitroarenes, Nitriles, and Isocyanides Ji, Pengfei; Manna, Kuntal; Lin, Zekai Journal of the American Chemical Society, Vol. 139, Issue 20 https://doi.org/10.1021/jacs.7b02394	journal	May 2017
Superactivity of MOF-808 toward Peptide Bond Hydrolysis Ly, Hong Giang T.; Fu, Guangxia; Kondinski, Aleksandar Journal of the American Chemical Society, Vol. 140, Issue 20 https://doi.org/10.1021/jacs.8b01902	journal	April 2018
Zirconium-Formate Macrocycles and Supercage: Molecular Packing versus MOF-like Network for Water Vapor Sorption Choi, Jong In; Chun, Hyungphil; Lah, Myoung Soo Journal of the American Chemical Society, Vol. 140, Issue 34 https://doi.org/10.1021/jacs.8b06757	journal	August 2018
Peroxide-Promoted Disassembly Reassembly of Zr-Polyoxocations Sommers, James A.; Hutchison, Danielle C.; Martin, Nicolas P. Journal of the American Chemical Society, Vol. 141, Issue 42 https://doi.org/10.1021/jacs.9b08627	journal	September 2019
Syntheses and crystal structures of supramolecular compounds of tetranuclear Zr^IVand Hf^IVaqua hydroxo complexes with macrocyclic cavitand cucurbituril Mit"kina, T. V.; Gerasko, O. A.; Sokolov, M. N. Russian Chemical Bulletin, Vol. 53, Issue 1 https://doi.org/10.1023/B:RUCB.0000024833.64526.ba	journal	January 2004
Water in minerals? A peak in the infrared Aines, Roger D.; Rossman, George R. Journal of Geophysical Research: Solid Earth, Vol. 89, Issue B6 https://doi.org/10.1029/JB089iB06p04059	journal	June 1984
Destruction of chemical warfare agents using metal–organic frameworks Mondloch, Joseph E.; Katz, Michael J.; Isley III, William C. Nature Materials, Vol. 14, Issue 5 https://doi.org/10.1038/nmat4238	journal	March 2015
Grafting alkylamine in UiO-66 by charge-assisted coordination bonds for carbon dioxide capture from high-humidity flue gas Li, Lu-Jian; Liao, Pei-Qin; He, Chun-Ting Journal of Materials Chemistry A, Vol. 3, Issue 43 https://doi.org/10.1039/C5TA05997F	journal	January 2015
Applications of water stable metal–organic frameworks Wang, Chenghong; Liu, Xinlei; Keser Demir, Nilay Chemical Society Reviews, Vol. 45, Issue 18 https://doi.org/10.1039/C6CS00362A	journal	January 2016
The chemistry of PET imaging with zirconium-89 Dilworth, Jonathan R.; Pascu, Sofia I. Chemical Society Reviews, Vol. 47, Issue 8 https://doi.org/10.1039/C7CS00014F	journal	January 2018
Interplay between structural parameters and reactivity of Zr₆-based MOFs as artificial proteases Loosen, Alexandra; de Azambuja, Francisco; Smolders, Simon Chemical Science, Vol. 11, Issue 26 https://doi.org/10.1039/D0SC02136A	journal	January 2020
Fatty acid capped, metal oxo clusters as the smallest conceivable nanocrystal prototypes Van den Eynden, Dietger; Pokratath, Rohan; Mathew, Jikson Pulparayil Chemical Science, Vol. 14, Issue 3 https://doi.org/10.1039/D2SC05037D	journal	January 2023
Coordination of pertechnetate [TcO4]? to actinides Sarsfield, Mark J.; Sutton, Andrew D.; May, Iain Chemical Communications, Issue 20 https://doi.org/10.1039/b404424j	journal	January 2004
The coordination of perrhenate and pertechnetate to thorium(iv) in the presence of phosphine oxide or phosphate ligands Sutton, Andrew D.; May, Iain; Sharrad, Clint A. Dalton Transactions, Issue 48 https://doi.org/10.1039/b611046k	journal	January 2006
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 Busey, R. H.; Keller, O. L. The Journal of Chemical Physics, Vol. 41, Issue 1 https://doi.org/10.1063/1.1725625	journal	July 1964
X-ray diffraction "fingerprinting" of DNA structure in solution for quantitative evaluation of molecular dynamics simulation Zuo, X.; Cui, G.; Merz, K. M. Proceedings of the National Academy of Sciences, Vol. 103, Issue 10 https://doi.org/10.1073/pnas.0600022103	journal	February 2006
Detection of Polynuclear Zirconium Hydroxide Species in Aqueous Solution by Desktop ESI-MS Sasaki, Takayuki; Nakaoka, Osamu; Arakawa, Ryuichi Journal of Nuclear Science and Technology, Vol. 47, Issue 12 https://doi.org/10.1080/18811248.2010.9720988	journal	December 2010
Structural determination of a highly stable metal-organic framework with possible application to interim radioactive waste scavenging: Hf-UiO-66 Jakobsen, Søren; Gianolio, Diego; Wragg, David S. Physical Review B, Vol. 86, Issue 12 https://doi.org/10.1103/PhysRevB.86.125429	journal	September 2012
OLEX2 : a complete structure solution, refinement and analysis program Dolomanov, Oleg V.; Bourhis, Luc J.; Gildea, Richard J. Journal of Applied Crystallography, Vol. 42, Issue 2 https://doi.org/10.1107/S0021889808042726	journal	January 2009
Irena : tool suite for modeling and analysis of small-angle scattering Ilavsky, Jan; Jemian, Peter R. Journal of Applied Crystallography, Vol. 42, Issue 2 https://doi.org/10.1107/S0021889809002222	journal	February 2009
Approximations Leading to a Unified Exponential/Power-Law Approach to Small-Angle Scattering Beaucage, G. Journal of Applied Crystallography, Vol. 28, Issue 6 https://doi.org/10.1107/S0021889895005292	journal	December 1995
A short history of SHELX Sheldrick, George M. Acta Crystallographica Section A Foundations of Crystallography, Vol. 64, Issue 1, p. 112-122 https://doi.org/10.1107/S0108767307043930	journal	December 2007
The crystal structure of zirconyl chloride octahydrate and zirconyl bromide octahydrate Clearfield, A.; Vaughan, P. A. Acta Crystallographica, Vol. 9, Issue 7 https://doi.org/10.1107/S0365110X56001558	journal	July 1956
Crystal structure refinement with SHELXL Sheldrick, George M. Acta Crystallographica Section C Structural Chemistry, Vol. 71, Issue 1, p. 3-8 https://doi.org/10.1107/S2053229614024218	journal	January 2015
Interaction of zirconium with pertechnetic acid in the course of extraction from nitric acid solutions with tributyl phosphate in diluent in the presence of uranyl nitrate at various temperatures and its mathematical description Puzikov, E. A.; Zilberman, B. Ya.; Fedorov, Yu. S. Radiochemistry, Vol. 57, Issue 3 https://doi.org/10.1134/S106636221503008X	journal	May 2015
Aqueous Reprocessing of Used Nuclear Fuel Law, Jack D. Nuclear Fuel Reprocessing and Waste Management https://doi.org/10.1142/9789813271371_0001	book	August 2018
Electrospray Ionization Mass Spectrometry: A Technique to Access the Information beyond the Molecular Weight of the Analyte Banerjee, Shibdas; Mazumdar, Shyamalava International Journal of Analytical Chemistry, Vol. 2012 https://doi.org/10.1155/2012/282574	journal	January 2012

Similar Records

Synthesis and Characterization of 5- and 6- Coordinated Alkali Pertechnetates

Journal Article · Wed Jan 11 19:00:00 EST 2017 · MRS Advances · OSTI ID:1959968

Synthesis and Characterization of 5- and 6- Coordinated Alkali Pertechnetates

Journal Article · Sat Dec 31 23:00:00 EST 2016 · MRS Advances · OSTI ID:1372995

Related Subjects

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY
Hafnium
Nuclear Fuel
Technetium
Zirconium

CSD 2263497: Experimental Crystal Structure Determination Mohammad, Shohel,; Jenna, Bustos,; Alexander, Roseborough, https://doi.org/10.25505/fiz.icsd.cc2fzc1v The current record is supplemented by this dataset	dataset	January 2023
CSD 2263498: Experimental Crystal Structure Determination Mohammad, Shohel,; Jenna, Bustos,; Alexander, Roseborough, https://doi.org/10.25505/fiz.icsd.cc2fzc2w The current record is supplemented by this dataset	dataset	January 2023
CSD 2263499: Experimental Crystal Structure Determination Mohammad, Shohel,; Jenna, Bustos,; Alexander, Roseborough, https://doi.org/10.25505/fiz.icsd.cc2fzc3x The current record is supplemented by this dataset	dataset	January 2023
CSD 2263500: Experimental Crystal Structure Determination Mohammad, Shohel,; Jenna, Bustos,; Alexander, Roseborough, https://doi.org/10.25505/fiz.icsd.cc2fzc4y The current record is supplemented by this dataset	dataset	January 2023

Pertechnetate/perrhenate–capped Zr/Hf–Dihydroxide Dimers: Elucidating Zr–TcO4 Co–Mobility in the Nuclear Fuel Cycle

Citation Formats

References (61)

Linked Research (4)

Similar Records

Related Subjects

Pertechnetate/perrhenate–capped Zr/Hf–Dihydroxide Dimers: Elucidating Zr–TcO₄ Co–Mobility in the Nuclear Fuel Cycle