The Role of the Organic Solvent Polarity in Isolating Uranyl Peroxide Capsule Fragments

Arteaga, Ana; Ray, Debmalya; Glass, Elliot; Martin, Nicolas P.; Zakharov, Lev N.; Gagliardi, Laura; Nyman, May

doi:10.1021/acs.inorgchem.9b02660

The Role of the Organic Solvent Polarity in Isolating Uranyl Peroxide Capsule Fragments

Journal Article · Tue Jan 21 00:00:00 EST 2020 · Inorganic Chemistry

DOI:https://doi.org/10.1021/acs.inorgchem.9b02660· OSTI ID:1593800

Arteaga, Ana ^[1]; ^[2]; Glass, Elliot ^[3]; ^[4]; Zakharov, Lev N. ^[3]; ^[2]; ^[3]

Oregon State Univ., Corvallis, OR (United States). Dept. of Chemistry; University of Notre Dame
Univ. of Minnesota, Minneapolis, MN (United States). Dept. of Chemistry, Chemical Theory Center, and Minnesota Supercomputing Inst.
Oregon State Univ., Corvallis, OR (United States). Dept. of Chemistry
Department of Chemistry, Oregon State University, Corvallis, Oregon 97331, United States

Uranyl peroxide capsules are a fascinating class of polyoxometalates (POMs), discovered only in the 21st century. Understanding the reactivity between peroxide, alkali cations, and uranyl in alkaline solutions is important in nuclear science disciplines including mineralogy, nuclear energy, and legacy nuclear wastes. In this work, we have developed a general procedure to isolate different fragments of the uranyl-peroxide POM capsules, using organic solvents to partially remove K⁺ salts from crude solids of the monomer building block UO₂(O₂)₃^4– (K–U₁), leading to stabilization of these reactive fragments. Higher polarity organic solvents remove more K⁺ salts from the crude solid, owed to higher solubility, resulting in more extensive linking of uranyl peroxide building units. By this strategy we have isolated and structurally characterized a dimer K₆[(UO₂)₂(O₂)₄(OH)₂]·7H₂O (K–U₂) and a hexamer face frequently observed in the capsules, K₁₂[(UO₂)₆(O₂)₉(OH)₆]$·x$H₂O(K–U₆). Comparing experimental and computed Raman spectra shows that these intermediates crystallize by a solid-to-solid transformation, via polymerization of the monomer building block. By small-angle X-ray scattering (SAXS), we track the conversion of the fragments to POM capsules; the reaction rate increases from K–U₁ (days) < K–U₂ (hours) < K–U₆ (instantaneous). This study provides a general synthetic procedure to isolate metastable uranyl peroxide oligomers and control the oligomerization, which will be later applied to systems with the heavier alkalis that are even less stable.

View Accepted Manuscript (DOE)

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

Sponsoring Organization:: USDOE National Nuclear Security Administration (NNSA)

Grant/Contract Number:: NA0003763

OSTI ID:: 1593800

Journal Information:: Inorganic Chemistry, Journal Name: Inorganic Chemistry Journal Issue: 3 Vol. 59; ISSN 0020-1669

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (51)

Actinyl Peroxide Nanospheres Burns, Peter C.; Kubatko, Karrie-Ann; Sigmon, Ginger Angewandte Chemie International Edition, Vol. 44, Issue 14 https://doi.org/10.1002/anie.200462445	journal	March 2005
Symmetry versus Minimal Pentagonal Adjacencies in Uranium-Based Polyoxometalate Fullerene Topologies Sigmon, Ginger E.; Unruh, Daniel K.; Ling, Jie Angewandte Chemie International Edition, Vol. 48, Issue 15 https://doi.org/10.1002/anie.200805870	journal	March 2009
In Situ Generation of Organic Peroxide to Create a Nanotubular Uranyl Peroxide Phosphate Kravchuk, Dmytro V.; Forbes, Tori Z. Angewandte Chemie International Edition, Vol. 58, Issue 51 https://doi.org/10.1002/anie.201910287	journal	November 2019
A Journey inside the U28 Nanocapsule Gil, Adrià; Karhánek, David; Miró, Pere Chemistry - A European Journal, Vol. 18, Issue 27 https://doi.org/10.1002/chem.201200801	journal	May 2012
Solid-State Dynamics of Uranyl Polyoxometalates Alam, Todd M.; Liao, Zuolei; Zakharov, Lev N. Chemistry - A European Journal, Vol. 20, Issue 27 https://doi.org/10.1002/chem.201402351	journal	May 2014
Self-Assembly of Uranyl-Peroxide Nanocapsules in Basic Peroxidic Environments Miró, Pere; Vlaisavljevich, Bess; Gil, Adria Chemistry - A European Journal, Vol. 22, Issue 25 https://doi.org/10.1002/chem.201600390	journal	May 2016
The Key Role of U ₂₈ in the Aqueous Self-Assembly of Uranyl Peroxide Nanocages Falaise, Clément; Nyman, May Chemistry - A European Journal, Vol. 22, Issue 41 https://doi.org/10.1002/chem.201602130	journal	August 2016
Uranyl–Peroxide Capsule Self‐Assembly in Slow Motion Arteaga, Ana; Zhang, Lei; Hickam, Sarah Chemistry – A European Journal, Vol. 25, Issue 24 https://doi.org/10.1002/chem.201806227	journal	February 2019
The U28 Nanosphere: What's Inside? Nyman, May; Rodriguez, Mark A.; Alam, Todd M. European Journal of Inorganic Chemistry, Vol. 2011, Issue 14 https://doi.org/10.1002/ejic.201001355	journal	March 2011
Potassium-Sodium Cobaltinitrite Precipitate Robinson, Rex J.; Hauschildt, James D. Industrial & Engineering Chemistry Analytical Edition, Vol. 12, Issue 11 https://doi.org/10.1021/ac50151a018	journal	November 1940
Role of Ammonium Ions in the Formation of Ammonium Uranyl Peroxides and Uranyl Peroxo-oxalates Blanchard, Florent; Ellart, Marine; Rivenet, Murielle Crystal Growth & Design, Vol. 16, Issue 1 https://doi.org/10.1021/acs.cgd.5b01090	journal	November 2015
Utilizing Autoxidation of Solvents To Promote the Formation of Uranyl Peroxide Materials Jayasinghe, Ashini S.; Applegate, Lindsey C.; Unruh, Daniel K. Crystal Growth & Design, Vol. 19, Issue 3 https://doi.org/10.1021/acs.cgd.8b01735	journal	January 2019
Cation Templating and Electronic Structure Effects in Uranyl Cage Clusters Probed by the Isolation of Peroxide-Bridged Uranyl Dimers Qiu, Jie; Vlaisavljevich, Bess; Jouffret, Laurent Inorganic Chemistry, Vol. 54, Issue 9 https://doi.org/10.1021/acs.inorgchem.5b00248	journal	April 2015
Structure and Reactivity of X-ray Amorphous Uranyl Peroxide, U ₂ O ₇ Odoh, Samuel O.; Shamblin, Jacob; Colla, Christopher A. Inorganic Chemistry, Vol. 55, Issue 7 https://doi.org/10.1021/acs.inorgchem.6b00017	journal	March 2016
Computationally-Guided Assignment of Unexpected Signals in the Raman Spectra of Uranyl Triperoxide Complexes Dembowski, Mateusz; Bernales, Varinia; Qiu, Jie Inorganic Chemistry, Vol. 56, Issue 3 https://doi.org/10.1021/acs.inorgchem.6b02666	journal	January 2017
Resolving Confined ⁷ Li Dynamics of Uranyl Peroxide Capsule U ₂₄ Xie, Jing; Neal, Harrison A.; Szymanowski, Jennifer Inorganic Chemistry, Vol. 57, Issue 9 https://doi.org/10.1021/acs.inorgchem.8b00474	journal	April 2018
Energetic Trends in Monomer Building Blocks for Uranyl Peroxide Clusters Zhang, Lei; Dembowski, Mateusz; Arteaga, Ana Inorganic Chemistry, Vol. 58, Issue 1 https://doi.org/10.1021/acs.inorgchem.8b02661	journal	December 2018
Neptunyl Peroxide Chemistry: Synthesis and Spectroscopic Characterization of a Neptunyl Triperoxide Compound, Ca ₂ [NpO ₂ (O ₂ ) ₃ ]·9H ₂ O Hickam, Sarah; Ray, Debmalya; Szymanowski, Jennifer E. S. Inorganic Chemistry, Vol. 58, Issue 18 https://doi.org/10.1021/acs.inorgchem.9b01712	journal	August 2019
SM6: A Density Functional Theory Continuum Solvation Model for Calculating Aqueous Solvation Free Energies of Neutrals, Ions, and Solute−Water Clusters Kelly, Casey P.; Cramer, Christopher J.; Truhlar, Donald G. Journal of Chemical Theory and Computation, Vol. 1, Issue 6 https://doi.org/10.1021/ct050164b	journal	November 2005
Formation of Studtite during the Oxidative Dissolution of UO ₂ by Hydrogen Peroxide: A SFM Study Clarens, F.; de Pablo, J.; Díez-Pérez, I. Environmental Science & Technology, Vol. 38, Issue 24 https://doi.org/10.1021/es0492891	journal	December 2004
Expanding the Crystal Chemistry of Uranyl Peroxides: Synthesis and Structures of Di- and Triperoxodioxouranium(VI) Complexes Kubatko, Karrie-Ann; Forbes, Tori Z.; Klingensmith, Amanda L. Inorganic Chemistry, Vol. 46, Issue 9 https://doi.org/10.1021/ic070118h	journal	April 2007
Self-Assembly of Alkali-Uranyl-Peroxide Clusters Nyman, May; Rodriguez, Mark A.; Campana, Charles F. Inorganic Chemistry, Vol. 49, Issue 17 https://doi.org/10.1021/ic1005192	journal	September 2010
Uranyl-Peroxide Nanocapsules: Electronic Structure and Cation Complexation in [(UO ₂ ) ₂₀ (μ-O ₂ ) ₃₀ ] ^20– Miro, Pere; Bo, Carles Inorganic Chemistry, Vol. 51, Issue 6 https://doi.org/10.1021/ic300029d	journal	March 2012
Elucidating Self-Assembly Mechanisms of Uranyl–Peroxide Capsules from Monomers Liao, Zuolei; Deb, Tapash; Nyman, May Inorganic Chemistry, Vol. 53, Issue 19 https://doi.org/10.1021/ic501587g	journal	September 2014
Uranyl-Promoted Peroxide Generation: Synthesis and Characterization of Three Uranyl Peroxo [(UO ₂ ) ₂ (O ₂ )] Complexes Thangavelu, Sonia G.; Cahill, Christopher L. Inorganic Chemistry, Vol. 54, Issue 9 https://doi.org/10.1021/ic502767k	journal	April 2015
Understanding the Structure and Formation of Uranyl Peroxide Nanoclusters by Quantum Chemical Calculations Vlaisavljevich, Bess; Gagliardi, Laura; Burns, Peter C. Journal of the American Chemical Society, Vol. 132, Issue 41 https://doi.org/10.1021/ja104964x	journal	October 2010
On the Origin of the Cation Templated Self-Assembly of Uranyl-Peroxide Nanoclusters Miró, Pere; Pierrefixe, Simon; Gicquel, Mickaël Journal of the American Chemical Society, Vol. 132, Issue 50 https://doi.org/10.1021/ja1053175	journal	December 2010
Rapid Self-Assembly of Uranyl Polyhedra into Crown Clusters Sigmon, Ginger E.; Burns, Peter C. Journal of the American Chemical Society, Vol. 133, Issue 24 https://doi.org/10.1021/ja2013449	journal	June 2011
Dynamics of Uranyl Peroxide Nanocapsules Nyman, May; Alam, Todd M. Journal of the American Chemical Society, Vol. 134, Issue 49 https://doi.org/10.1021/ja308673f	journal	November 2012
Aqueous Solvation Free Energies of Ions and Ion−Water Clusters Based on an Accurate Value for the Absolute Aqueous Solvation Free Energy of the Proton Kelly, Casey P.; Cramer, Christopher J.; Truhlar, Donald G. The Journal of Physical Chemistry B, Vol. 110, Issue 32 https://doi.org/10.1021/jp063552y	journal	August 2006
Universal Solvation Model Based on Solute Electron Density and on a Continuum Model of the Solvent Defined by the Bulk Dielectric Constant and Atomic Surface Tensions Marenich, Aleksandr V.; Cramer, Christopher J.; Truhlar, Donald G. The Journal of Physical Chemistry B, Vol. 113, Issue 18, p. 6378-6396 https://doi.org/10.1021/jp810292n	journal	May 2009
Captivation with encapsulation: a dozen years of exploring uranyl peroxide capsules Burns, Peter C.; Nyman, May Dalton Transactions, Vol. 47, Issue 17 https://doi.org/10.1039/C7DT04245K	journal	January 2018
A comprehensive comparison of transition-metal and actinyl polyoxometalates Nyman, May; Burns, Peter C. Chemical Society Reviews, Vol. 41, Issue 22 https://doi.org/10.1039/c2cs35136f	journal	January 2012
The crystal and molecular structure of sodium uranyl triperoxide Alcock, N. W. Journal of the Chemical Society A: Inorganic, Physical, Theoretical https://doi.org/10.1039/j19680001588	journal	January 1968
Valence basis sets for relativistic energy-consistent small-core actinide pseudopotentials Cao, Xiaoyan; Dolg, Michael; Stoll, Hermann The Journal of Chemical Physics, Vol. 118, Issue 2 https://doi.org/10.1063/1.1521431	journal	January 2003
Self‐Consistent Molecular‐Orbital Methods. IX. An Extended Gaussian‐Type Basis for Molecular‐Orbital Studies of Organic Molecules Ditchfield, R.; Hehre, W. J.; Pople, J. A. The Journal of Chemical Physics, Vol. 54, Issue 2 https://doi.org/10.1063/1.1674902	journal	January 1971
A new local density functional for main-group thermochemistry, transition metal bonding, thermochemical kinetics, and noncovalent interactions Zhao, Yan; Truhlar, Donald G. The Journal of Chemical Physics, Vol. 125, Issue 19, Article No. 194101 https://doi.org/10.1063/1.2370993	journal	November 2006
Assessment of the Perdew–Burke–Ernzerhof exchange-correlation functional Ernzerhof, Matthias; Scuseria, Gustavo E. The Journal of Chemical Physics, Vol. 110, Issue 11 https://doi.org/10.1063/1.478401	journal	March 1999
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
Uranyl peroxide enhanced nuclear fuel corrosion in seawater Armstrong, C. R.; Nyman, M.; Shvareva, T. Proceedings of the National Academy of Sciences, Vol. 109, Issue 6 https://doi.org/10.1073/pnas.1119758109	journal	January 2012
Energetics of metastudtite and implications for nuclear waste alteration Guo, Xiaofeng; Ushakov, Sergey V.; Labs, Sabrina Proceedings of the National Academy of Sciences, Vol. 111, Issue 50 https://doi.org/10.1073/pnas.1421144111	journal	November 2014
Density-functional approximation for the correlation energy of the inhomogeneous electron gas Perdew, John P. Physical Review B, Vol. 33, Issue 12 https://doi.org/10.1103/PhysRevB.33.8822	journal	June 1986
Generalized Gradient Approximation Made Simple Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868 https://doi.org/10.1103/PhysRevLett.77.3865	journal	October 1996
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
SHELXT – Integrated space-group and crystal-structure determination Sheldrick, George M. Acta Crystallographica Section A Foundations and Advances, Vol. 71, Issue 1, p. 3-8 https://doi.org/10.1107/S2053273314026370	journal	January 2015
Stability of Peroxide-Containing Uranyl Minerals Kubatko, K. -A. H. Science, Vol. 302, Issue 5648 https://doi.org/10.1126/science.1090259	journal	November 2003
Nuclear Fuel in a Reactor Accident Burns, Peter C.; Ewing, Rodney C.; Navrotsky, Alexandra Science, Vol. 335, Issue 6073 https://doi.org/10.1126/science.1211285	journal	March 2012
Contrary effects of the water radiolysis product H2O2 upon th dissolution of nuclear fuel in natural ground water and deionized water Amme, M. Radiochimica Acta, Vol. 90, Issue 7 https://doi.org/10.1524/ract.2002.90.7_2002.399	journal	January 2002
Corrosion of commercial spent nuclear fuel. 1. Formation of studtite and metastudtite Hanson, Brady D.; McNamara, Bruce; Buck, Edgar C. Radiochimica Acta, Vol. 93, Issue 3 https://doi.org/10.1524/ract.93.3.159.61613	journal	January 2005
Observation of Studtite and Metastudtite on Spent Fuel McNamara, Bruce; Buck, Edgar; Hanson, Brady MRS Proceedings, Vol. 757 https://doi.org/10.1557/PROC-757-II9.7	journal	January 2002
Studtite, [(UO ₂ )(O ₂ )(H ₂ O) ₂ ](H ₂ O) ₂ : The first structure of a peroxide mineral Burns, Peter C.; Hughes, Karrie-Ann American Mineralogist, Vol. 88, Issue 7 https://doi.org/10.2138/am-2003-0725	journal	July 2003

Similar Records

Energetic Trends in Monomer Building Blocks for Uranyl Peroxide Clusters

Journal Article · Sun Dec 23 19:00:00 EST 2018 · Inorganic Chemistry · OSTI ID:1489654

Uranyl Peroxide Capsule Self-assembly in Slow Motion Ana Arteaga,1 Lei Zhang,2 Sarah Hickam,2 Mateusz Dembowski,2,3 Peter C. Burns 2 and May Nyman1*

Journal Article · Tue Mar 05 19:00:00 EST 2019 · Chemistry - A European Journal · OSTI ID:1502931

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY
77 NANOSCIENCE AND NANOTECHNOLOGY

The Role of the Organic Solvent Polarity in Isolating Uranyl Peroxide Capsule Fragments

Citation Formats

References (51)

Linked Research (1)

Similar Records

Related Subjects