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Title: 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*

Abstract

Uranyl-peroxide capsules are the newest family of polyoxometalates. Although discovered 13 years prior with over 70 topologies reported, we lack fundamental understanding of assembly mechanisms, particularly the role of the alkali countercations. Herein, we report the reaction pathway and assembly of uranyl peroxide capsules by tracking the conversion from K+ uranyl triperoxide monomer to the K+ uranyl-peroxide U28 capsule via Small Angle X-Ray Scattering and Raman Spectroscopy. For the first time, the K+ uranyl-peroxide pentamer face is isolated and structurally characterized, giving credence to the long-held belief that these geometric faces serve as building blocks to the fully formed capsules. Once isolated and redissolved, the pentamer face undergoes rapid conversion to capsule forms, underlining its high reactivity that challenges its isolation. Calorimetric measurements of the studied species confirms the pentamer lies on the energy landscape between the monomer and capsule.

Authors:
 [1];  [2];  [2];  [2];  [2];  [1]
  1. Oregon State Univ., Corvallis, OR (United States). Dept. of Chemistry
  2. Univ. of Notre Dame, Notre Dame, IN (United States). Dept. of Civil and Environmental Engineering and Earth Sciences
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Materials Science of Actinides (MSA); Univ. of Notre Dame, Notre Dame, IN (United States)
Sponsoring Org.:
USDOE National Nuclear Security Administration (NNSA); USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1502931
Alternate Identifier(s):
OSTI ID: 1503928
Grant/Contract Number:  
NA0003763; SC0001089
Resource Type:
Accepted Manuscript
Journal Name:
Chemistry - A European Journal
Additional Journal Information:
Journal Volume: 25; Journal Issue: 24; Journal ID: ISSN 0947-6539
Publisher:
ChemPubSoc Europe
Country of Publication:
United States
Language:
English
Subject:
77 NANOSCIENCE AND NANOTECHNOLOGY; 38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; uranyl; Polyoxometalates; X-ray scattering; Calorimetry; crystal structure

Citation Formats

Arteaga, Ana, Zhang, Lei, Hickam, Sarah, Dembowski, Mateusz, Burns, Peter, and Nyman, May. 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*. United States: N. p., 2019. Web. doi:10.1002/chem.201806227.
Arteaga, Ana, Zhang, Lei, Hickam, Sarah, Dembowski, Mateusz, Burns, Peter, & Nyman, May. 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*. United States. doi:10.1002/chem.201806227.
Arteaga, Ana, Zhang, Lei, Hickam, Sarah, Dembowski, Mateusz, Burns, Peter, and Nyman, May. Wed . "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*". United States. doi:10.1002/chem.201806227. https://www.osti.gov/servlets/purl/1502931.
@article{osti_1502931,
title = {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*},
author = {Arteaga, Ana and Zhang, Lei and Hickam, Sarah and Dembowski, Mateusz and Burns, Peter and Nyman, May},
abstractNote = {Uranyl-peroxide capsules are the newest family of polyoxometalates. Although discovered 13 years prior with over 70 topologies reported, we lack fundamental understanding of assembly mechanisms, particularly the role of the alkali countercations. Herein, we report the reaction pathway and assembly of uranyl peroxide capsules by tracking the conversion from K+ uranyl triperoxide monomer to the K+ uranyl-peroxide U28 capsule via Small Angle X-Ray Scattering and Raman Spectroscopy. For the first time, the K+ uranyl-peroxide pentamer face is isolated and structurally characterized, giving credence to the long-held belief that these geometric faces serve as building blocks to the fully formed capsules. Once isolated and redissolved, the pentamer face undergoes rapid conversion to capsule forms, underlining its high reactivity that challenges its isolation. Calorimetric measurements of the studied species confirms the pentamer lies on the energy landscape between the monomer and capsule.},
doi = {10.1002/chem.201806227},
journal = {Chemistry - A European Journal},
number = 24,
volume = 25,
place = {United States},
year = {2019},
month = {3}
}

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Cited by: 3 works
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Works referenced in this record:

Time-Resolved X-ray Scattering and Raman Spectroscopic Studies of Formation of a Uranium-Vanadium-Phosphorus-Peroxide Cage Cluster
journal, June 2016


A comprehensive comparison of transition-metal and actinyl polyoxometalates
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Hybrid Uranium–Transition-Metal Oxide Cage Clusters
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Complexity of Uranyl Peroxide Cluster Speciation from Alkali-Directed Oxidative Dissolution of Uranium Dioxide
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Closing Uranyl Polyoxometalate Capsules with Bismuth and Lead Polyoxocations
journal, September 2016

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Solid-State Dynamics of Uranyl Polyoxometalates
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Probing the Nature of Chemical Bonding in Uranyl(VI) Complexes with Quantum Chemical Methods
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Uranyl-Promoted Peroxide Generation: Synthesis and Characterization of Three Uranyl Peroxo [(UO 2 ) 2 (O 2 )] Complexes
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Captivation with encapsulation: a dozen years of exploring uranyl peroxide capsules
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Studtite, [(UO 2 )(O 2 )(H 2 O) 2 ](H 2 O) 2 : The first structure of a peroxide mineral
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The Key Role of U 28 in the Aqueous Self-Assembly of Uranyl Peroxide Nanocages
journal, August 2016


Thermodynamic studies of studtite thermal decomposition pathways via amorphous intermediates UO3, U2O7, and UO4
journal, September 2016


Uranyl peroxide enhanced nuclear fuel corrosion in seawater
journal, January 2012

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  • DOI: 10.1073/pnas.1119758109

Computationally-Guided Assignment of Unexpected Signals in the Raman Spectra of Uranyl Triperoxide Complexes
journal, January 2017


Actinyl Peroxide Nanospheres
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Role of Ammonium Ions in the Formation of Ammonium Uranyl Peroxides and Uranyl Peroxo-oxalates
journal, November 2015

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The Energy Landscape of Uranyl-Peroxide Species
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Rapid Self-Assembly of Uranyl Polyhedra into Crown Clusters
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Self-Assembly of Alkali-Uranyl-Peroxide Clusters
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The U28 Nanosphere: What's Inside?
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Closing Uranyl Polyoxometalate Capsules with Bismuth and Lead Polyoxocations
journal, September 2016

  • Renier, Olivier; Falaise, Clément; Neal, Harrison
  • Angewandte Chemie, Vol. 128, Issue 43
  • DOI: 10.1002/ange.201607151

Clusters of Actinides with Oxide, Peroxide, or Hydroxide Bridges
journal, October 2012

  • Qiu, Jie; Burns, Peter C.
  • Chemical Reviews, Vol. 113, Issue 2
  • DOI: 10.1021/cr300159x

On the Origin of the Cation Templated Self-Assembly of Uranyl-Peroxide Nanoclusters
journal, December 2010

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  • Journal of the American Chemical Society, Vol. 132, Issue 50
  • DOI: 10.1021/ja1053175

Resolving Confined 7 Li Dynamics of Uranyl Peroxide Capsule U 24
journal, April 2018


Understanding the Structure and Formation of Uranyl Peroxide Nanoclusters by Quantum Chemical Calculations
journal, October 2010

  • Vlaisavljevich, Bess; Gagliardi, Laura; Burns, Peter C.
  • Journal of the American Chemical Society, Vol. 132, Issue 41
  • DOI: 10.1021/ja104964x

Charge Density Influence on Enthalpy of Formation of Uranyl Peroxide Cage Cluster Salts
journal, August 2018


Sandwich-type Uranium-Substituted of Bismuthotungstate: Synthesis and Structure Determination of [Na(UO2)2(H2O)4(BiW9O33)2]13−
journal, April 2008


Uranyl-Peroxide Clusters Incorporating Iron Trimers and Bridging by Bisphosphonate- and Carboxylate-Containing Ligands
journal, March 2017


Alkali-Driven Disassembly and Reassembly of Molecular Niobium Oxide in Water
journal, July 2018

  • Sures, Dylan; Segado, Mireia; Bo, Carles
  • Journal of the American Chemical Society, Vol. 140, Issue 34
  • DOI: 10.1021/jacs.8b05015

Dynamics of Uranyl Peroxide Nanocapsules
journal, November 2012

  • Nyman, May; Alam, Todd M.
  • Journal of the American Chemical Society, Vol. 134, Issue 49
  • DOI: 10.1021/ja308673f

Syntheses and structures determination of new polytungstoarsenates [Na2As2W18U2O72]12− and [MAs2W18U2O72]13− ()
journal, June 2006


A new structural family of heteropolytungstate lacunary complexes with the uranyl, UO22+, cation
journal, January 2003

  • Gaunt, Andrew J.; May, Iain; Copping, Roy
  • Dalton Transactions, Issue 15
  • DOI: 10.1039/b302955g

Hybrid uranyl–vanadium nano-wheels
journal, January 2015

  • Senchyk, G. A.; Wylie, E. M.; Prizio, S.
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Actinyl Peroxide Nanospheres
journal, March 2005

  • Burns, Peter C.; Kubatko, Karrie-Ann; Sigmon, Ginger
  • Angewandte Chemie International Edition, Vol. 44, Issue 14
  • DOI: 10.1002/anie.200462445

Energetics of metastudtite and implications for nuclear waste alteration
journal, November 2014

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  • Proceedings of the National Academy of Sciences, Vol. 111, Issue 50
  • DOI: 10.1073/pnas.1421144111

The crystal and molecular structure of sodium uranyl triperoxide
journal, January 1968

  • Alcock, N. W.
  • Journal of the Chemical Society A: Inorganic, Physical, Theoretical
  • DOI: 10.1039/j19680001588

Structure and Reactivity of X-ray Amorphous Uranyl Peroxide, U 2 O 7
journal, March 2016


Uranyl-Peroxide Nanocapsules: Electronic Structure and Cation Complexation in [(UO 2 ) 20 (μ-O 2 ) 30 ] 20–
journal, March 2012

  • Miro, Pere; Bo, Carles
  • Inorganic Chemistry, Vol. 51, Issue 6
  • DOI: 10.1021/ic300029d

    Works referencing / citing this record:

    CSD 1882899: Experimental Crystal Structure Determination
    dataset, January 2019

    • Arteaga, Ana; Zhang, Lei; Hickam, Sarah
    • FIZ Karlsruhe – Leibniz Institute for Information Infrastructure
    • DOI: 10.25505/fiz.icsd.cc2169p8

    Actinyl Peroxide Nanospheres
    journal, March 2005

    • Burns, Peter C.; Kubatko, Karrie-Ann; Sigmon, Ginger
    • Angewandte Chemie, Vol. 117, Issue 14
    • DOI: 10.1002/ange.200462445

    Closing Uranyl Polyoxometalate Capsules with Bismuth and Lead Polyoxocations
    journal, September 2016

    • Renier, Olivier; Falaise, Clément; Neal, Harrison
    • Angewandte Chemie, Vol. 128, Issue 43
    • DOI: 10.1002/ange.201607151

    Actinyl Peroxide Nanospheres
    journal, March 2005

    • Burns, Peter C.; Kubatko, Karrie-Ann; Sigmon, Ginger
    • Angewandte Chemie International Edition, Vol. 44, Issue 14
    • DOI: 10.1002/anie.200462445

    Closing Uranyl Polyoxometalate Capsules with Bismuth and Lead Polyoxocations
    journal, September 2016

    • Renier, Olivier; Falaise, Clément; Neal, Harrison
    • Angewandte Chemie International Edition, Vol. 55, Issue 43
    • DOI: 10.1002/anie.201607151

    The Energy Landscape of Uranyl-Peroxide Species
    journal, March 2014

    • Tiferet, Eitan; Gil, Adrià; Bo, Carles
    • Chemistry - A European Journal, Vol. 20, Issue 13
    • DOI: 10.1002/chem.201304076

    Solid-State Dynamics of Uranyl Polyoxometalates
    journal, May 2014

    • Alam, Todd M.; Liao, Zuolei; Zakharov, Lev N.
    • Chemistry - A European Journal, Vol. 20, Issue 27
    • DOI: 10.1002/chem.201402351

    The Key Role of U 28 in the Aqueous Self-Assembly of Uranyl Peroxide Nanocages
    journal, August 2016


    The U28 Nanosphere: What's Inside?
    journal, March 2011

    • Nyman, May; Rodriguez, Mark A.; Alam, Todd M.
    • European Journal of Inorganic Chemistry, Vol. 2011, Issue 14
    • DOI: 10.1002/ejic.201001355

    Sandwich-type Uranium-Substituted of Bismuthotungstate: Synthesis and Structure Determination of [Na(UO2)2(H2O)4(BiW9O33)2]13−
    journal, April 2008


    Thermodynamic studies of studtite thermal decomposition pathways via amorphous intermediates UO3, U2O7, and UO4
    journal, September 2016


    Syntheses and structures determination of new polytungstoarsenates [Na2As2W18U2O72]12− and [MAs2W18U2O72]13− ()
    journal, June 2006


    Role of Ammonium Ions in the Formation of Ammonium Uranyl Peroxides and Uranyl Peroxo-oxalates
    journal, November 2015

    • Blanchard, Florent; Ellart, Marine; Rivenet, Murielle
    • Crystal Growth & Design, Vol. 16, Issue 1
    • DOI: 10.1021/acs.cgd.5b01090

    Structure and Reactivity of X-ray Amorphous Uranyl Peroxide, U 2 O 7
    journal, March 2016


    Time-Resolved X-ray Scattering and Raman Spectroscopic Studies of Formation of a Uranium-Vanadium-Phosphorus-Peroxide Cage Cluster
    journal, June 2016


    Computationally-Guided Assignment of Unexpected Signals in the Raman Spectra of Uranyl Triperoxide Complexes
    journal, January 2017


    Uranyl-Peroxide Clusters Incorporating Iron Trimers and Bridging by Bisphosphonate- and Carboxylate-Containing Ligands
    journal, March 2017


    Resolving Confined 7 Li Dynamics of Uranyl Peroxide Capsule U 24
    journal, April 2018


    Complexity of Uranyl Peroxide Cluster Speciation from Alkali-Directed Oxidative Dissolution of Uranium Dioxide
    journal, July 2018


    Charge Density Influence on Enthalpy of Formation of Uranyl Peroxide Cage Cluster Salts
    journal, August 2018


    Clusters of Actinides with Oxide, Peroxide, or Hydroxide Bridges
    journal, October 2012

    • Qiu, Jie; Burns, Peter C.
    • Chemical Reviews, Vol. 113, Issue 2
    • DOI: 10.1021/cr300159x

    Self-Assembly of Alkali-Uranyl-Peroxide Clusters
    journal, September 2010

    • Nyman, May; Rodriguez, Mark A.; Campana, Charles F.
    • Inorganic Chemistry, Vol. 49, Issue 17
    • DOI: 10.1021/ic1005192

    Uranyl-Peroxide Nanocapsules: Electronic Structure and Cation Complexation in [(UO 2 ) 20 (μ-O 2 ) 30 ] 20–
    journal, March 2012

    • Miro, Pere; Bo, Carles
    • Inorganic Chemistry, Vol. 51, Issue 6
    • DOI: 10.1021/ic300029d

    Elucidating Self-Assembly Mechanisms of Uranyl–Peroxide Capsules from Monomers
    journal, September 2014

    • Liao, Zuolei; Deb, Tapash; Nyman, May
    • Inorganic Chemistry, Vol. 53, Issue 19
    • DOI: 10.1021/ic501587g

    Hybrid Uranium–Transition-Metal Oxide Cage Clusters
    journal, November 2014

    • Ling, Jie; Hobbs, Franklin; Prendergast, Steven
    • Inorganic Chemistry, Vol. 53, Issue 24
    • DOI: 10.1021/ic5018449

    Uranyl-Promoted Peroxide Generation: Synthesis and Characterization of Three Uranyl Peroxo [(UO 2 ) 2 (O 2 )] Complexes
    journal, April 2015

    • Thangavelu, Sonia G.; Cahill, Christopher L.
    • Inorganic Chemistry, Vol. 54, Issue 9
    • DOI: 10.1021/ic502767k

    Understanding the Structure and Formation of Uranyl Peroxide Nanoclusters by Quantum Chemical Calculations
    journal, October 2010

    • Vlaisavljevich, Bess; Gagliardi, Laura; Burns, Peter C.
    • Journal of the American Chemical Society, Vol. 132, Issue 41
    • DOI: 10.1021/ja104964x

    On the Origin of the Cation Templated Self-Assembly of Uranyl-Peroxide Nanoclusters
    journal, December 2010

    • Miró, Pere; Pierrefixe, Simon; Gicquel, Mickaël
    • Journal of the American Chemical Society, Vol. 132, Issue 50
    • DOI: 10.1021/ja1053175

    Rapid Self-Assembly of Uranyl Polyhedra into Crown Clusters
    journal, June 2011

    • Sigmon, Ginger E.; Burns, Peter C.
    • Journal of the American Chemical Society, Vol. 133, Issue 24
    • DOI: 10.1021/ja2013449

    Dynamics of Uranyl Peroxide Nanocapsules
    journal, November 2012

    • Nyman, May; Alam, Todd M.
    • Journal of the American Chemical Society, Vol. 134, Issue 49
    • DOI: 10.1021/ja308673f

    Alkali-Driven Disassembly and Reassembly of Molecular Niobium Oxide in Water
    journal, July 2018

    • Sures, Dylan; Segado, Mireia; Bo, Carles
    • Journal of the American Chemical Society, Vol. 140, Issue 34
    • DOI: 10.1021/jacs.8b05015

    Probing the Nature of Chemical Bonding in Uranyl(VI) Complexes with Quantum Chemical Methods
    journal, November 2012

    • Vallet, Valérie; Wahlgren, Ulf; Grenthe, Ingmar
    • The Journal of Physical Chemistry A, Vol. 116, Issue 50
    • DOI: 10.1021/jp3091123

    A new structural family of heteropolytungstate lacunary complexes with the uranyl, UO22+, cation
    journal, January 2003

    • Gaunt, Andrew J.; May, Iain; Copping, Roy
    • Dalton Transactions, Issue 15
    • DOI: 10.1039/b302955g

    A comprehensive comparison of transition-metal and actinyl polyoxometalates
    journal, January 2012

    • Nyman, May; Burns, Peter C.
    • Chemical Society Reviews, Vol. 41, Issue 22
    • DOI: 10.1039/c2cs35136f

    The crystal and molecular structure of sodium uranyl triperoxide
    journal, January 1968

    • Alcock, N. W.
    • Journal of the Chemical Society A: Inorganic, Physical, Theoretical
    • DOI: 10.1039/j19680001588

    Uranyl peroxide enhanced nuclear fuel corrosion in seawater
    journal, January 2012

    • Armstrong, C. R.; Nyman, M.; Shvareva, T.
    • Proceedings of the National Academy of Sciences, Vol. 109, Issue 6
    • DOI: 10.1073/pnas.1119758109

    Energetics of metastudtite and implications for nuclear waste alteration
    journal, November 2014

    • Guo, Xiaofeng; Ushakov, Sergey V.; Labs, Sabrina
    • Proceedings of the National Academy of Sciences, Vol. 111, Issue 50
    • DOI: 10.1073/pnas.1421144111

    Studtite, [(UO 2 )(O 2 )(H 2 O) 2 ](H 2 O) 2 : The first structure of a peroxide mineral
    journal, July 2003

    • Burns, Peter C.; Hughes, Karrie-Ann
    • American Mineralogist, Vol. 88, Issue 7
    • DOI: 10.2138/am-2003-0725