Benchmarking Uranyl Peroxide Capsule Chemistry in Organic Media
Abstract
Uranyl peroxide capsules are a recent addition to polyoxometalate (POM) chemistry. Ten years of development has ensued only in water, while transition metal POMs are commonly exploited in aqueous and organic media, controlled by counterions or ligation to render the clusters hydrophilic or hydrophobic. Here, new uranyl POM behavior is recognized in organic media, including (1) stabilization and immobilization of encapsulated hydrophilic countercations, identified by Li nuclear magnetic resonance (NMR) spectroscopy, (2) formation of new cluster species upon phase transfer, (3) extraction of uranyl clusters from different starting materials including simulated spent nuclear fuel, (4) selective phase transfer of one cluster type from a mixture, and (5) phase transfer of clusters from both acidic and alkaline media. The capsule morphology of the uranyl POMs renders accurate characterization by X‐ray scattering, including the distinction of geometrically similar clusters. Compositional analysis of the aqueous phase post‐extraction provided a quantitative determination of the ion exchange process that enables transfer of the clusters into the organic phase. Preferential partitioning of uranyl POMs into organic media presents new frontiers in metal ion behavior and chemical reactions in the confined space of the cluster capsules in hydrophobic media, as well as the reactivity of clusters atmore »
- Authors:
-
[2];
[1]
- Department of Chemistry Oregon State University Corvallis 97331 OR USA
- Department of Civil &, Environmental Engineering &, Earth Sciences University of Notre Dame 46556 Notre Dame IN USA
- Publication Date:
- Sponsoring Org.:
- USDOE
- OSTI Identifier:
- 1401247
- Resource Type:
- Publisher's Accepted Manuscript
- Journal Name:
- European Journal of Inorganic Chemistry
- Additional Journal Information:
- Journal Name: European Journal of Inorganic Chemistry Journal Volume: 2017 Journal Issue: 1; Journal ID: ISSN 1434-1948
- Publisher:
- Wiley Blackwell (John Wiley & Sons)
- Country of Publication:
- Germany
- Language:
- English
Citation Formats
Neal, Harrison A., Szymanowski, Jennifer, Fein, Jeremy B., Burns, Peter C., and Nyman, May. Benchmarking Uranyl Peroxide Capsule Chemistry in Organic Media. Germany: N. p., 2016.
Web. doi:10.1002/ejic.201601219.
Neal, Harrison A., Szymanowski, Jennifer, Fein, Jeremy B., Burns, Peter C., & Nyman, May. Benchmarking Uranyl Peroxide Capsule Chemistry in Organic Media. Germany. https://doi.org/10.1002/ejic.201601219
Neal, Harrison A., Szymanowski, Jennifer, Fein, Jeremy B., Burns, Peter C., and Nyman, May. Tue .
"Benchmarking Uranyl Peroxide Capsule Chemistry in Organic Media". Germany. https://doi.org/10.1002/ejic.201601219.
@article{osti_1401247,
title = {Benchmarking Uranyl Peroxide Capsule Chemistry in Organic Media},
author = {Neal, Harrison A. and Szymanowski, Jennifer and Fein, Jeremy B. and Burns, Peter C. and Nyman, May},
abstractNote = {Uranyl peroxide capsules are a recent addition to polyoxometalate (POM) chemistry. Ten years of development has ensued only in water, while transition metal POMs are commonly exploited in aqueous and organic media, controlled by counterions or ligation to render the clusters hydrophilic or hydrophobic. Here, new uranyl POM behavior is recognized in organic media, including (1) stabilization and immobilization of encapsulated hydrophilic countercations, identified by Li nuclear magnetic resonance (NMR) spectroscopy, (2) formation of new cluster species upon phase transfer, (3) extraction of uranyl clusters from different starting materials including simulated spent nuclear fuel, (4) selective phase transfer of one cluster type from a mixture, and (5) phase transfer of clusters from both acidic and alkaline media. The capsule morphology of the uranyl POMs renders accurate characterization by X‐ray scattering, including the distinction of geometrically similar clusters. Compositional analysis of the aqueous phase post‐extraction provided a quantitative determination of the ion exchange process that enables transfer of the clusters into the organic phase. Preferential partitioning of uranyl POMs into organic media presents new frontiers in metal ion behavior and chemical reactions in the confined space of the cluster capsules in hydrophobic media, as well as the reactivity of clusters at the organic/aqueous interface.},
doi = {10.1002/ejic.201601219},
journal = {European Journal of Inorganic Chemistry},
number = 1,
volume = 2017,
place = {Germany},
year = {Tue Nov 29 00:00:00 EST 2016},
month = {Tue Nov 29 00:00:00 EST 2016}
}
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Works referenced in this record:
Sustained epoxidation of olefins by oxygen donors catalyzed by transition metal-substituted polyoxometalates, oxidatively resistant inorganic analogs of metalloporphyrins
journal, February 1986
- Hill, Craig L.; Brown, Robert B.
- Journal of the American Chemical Society, Vol. 108, Issue 3
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
X-ray Studies of Interfacial Strontium–Extractant Complexes in a Model Solvent Extraction System
journal, October 2014
- Bu, Wei; Mihaylov, Miroslav; Amoanu, Daniel
- The Journal of Physical Chemistry B, Vol. 118, Issue 43
Hybrid Uranium-Oxalate Fullerene Topology Cage Clusters
journal, August 2010
- Ling, Jie; Wallace, Christine M.; Szymanowski, Jennifer E. S.
- Angewandte Chemie International Edition, Vol. 49, Issue 40
Solution and Solid-State Structural Chemistry of Actinide Hydrates and Their Hydrolysis and Condensation Products
journal, October 2012
- Knope, Karah E.; Soderholm, L.
- Chemical Reviews, Vol. 113, Issue 2
Observation of a Rare Earth Ion–Extractant Complex Arrested at the Oil–Water Interface During Solvent Extraction
journal, August 2014
- Bu, Wei; Yu, Hao; Luo, Guangming
- The Journal of Physical Chemistry B, Vol. 118, Issue 36
B-α-[AsW 9 O 33 ] 9− polyoxometalates incorporating hexanuclear uranium {U 6 O 8 }-like clusters bearing the U IV form or unprecedented mixed valence U IV /U VI involving direct U VI O–U IV bonding
journal, January 2015
- Duval, Sylvain; Sobanska, Sophie; Roussel, Pascal
- Dalton Transactions, Vol. 44, Issue 46
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
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
Micelle-mediated separation and cloud-point extraction
journal, May 2005
- Paleologos, Evangelos K.; Giokas, Dimosthenis L.; Karayannis, Miltiades I.
- TrAC Trends in Analytical Chemistry, Vol. 24, Issue 5
Onionlike Hybrid Assemblies Based on Surfactant-Encapsulated Polyoxometalates
journal, February 2007
- Li, Haolong; Sun, Hang; Qi, Wei
- Angewandte Chemie International Edition, Vol. 46, Issue 8
Structural study of trivalent lanthanide and actinide complexes formed upon solvent extraction
journal, January 2006
- Gannaz, Beno?t; Antonio, Mark R.; Chiarizia, Renato
- Dalton Transactions, Issue 38
Polyoxometalate-based functional nanostructured films: Current progress and future prospects
journal, August 2010
- Liu, Shaoqin; Tang, Zhiyong
- Nano Today, Vol. 5, Issue 4
A Highly Transparent and Luminescent Hybrid Based on the Copolymerization of Surfactant-Encapsulated Polyoxometalate and Methyl Methacrylate
journal, November 2005
- Li, H.; Qi, W.; Li, W.
- Advanced Materials, Vol. 17, Issue 22
The Key Role of U 28 in the Aqueous Self-Assembly of Uranyl Peroxide Nanocages
journal, August 2016
- Falaise, Clément; Nyman, May
- Chemistry - A European Journal, Vol. 22, Issue 41
Toward Nanodevices: Synthesis and Characterization of the Nanoporous Surfactant-Encapsulated Keplerate (DODA) 40 (NH 4 ) 2 [(H 2 O) n ⊂Mo 132 O 372 (CH 3 COO) 30 (H 2 O) 72 ]
journal, March 2000
- Volkmer, Dirk; Du Chesne, Alexander; Kurth, Dirk G.
- Journal of the American Chemical Society, Vol. 122, Issue 9
Anisotropic ionic liquids built from nonmesogenic cation surfactants and Keggin-type polyoxoanions
journal, January 2011
- Jiang, Yunxia; Liu, Shuxia; Li, Shujun
- Chemical Communications, Vol. 47, Issue 37
Neodymium uranyl peroxide synthesis by ion exchange on ammonium uranyl peroxide nanoclusters
journal, January 2016
- Blanchard, F.; Ellart, M.; Rivenet, M.
- Chemical Communications, Vol. 52, Issue 20
Processing used nuclear fuel with nanoscale control of uranium and ultrafiltration
journal, May 2016
- Wylie, Ernest M.; Peruski, Kathryn M.; Prizio, Sarah E.
- Journal of Nuclear Materials, Vol. 473
Binary Superlattices from {Mo 132 } Polyoxometalates and Maghemite Nanocrystals: Long-Range Ordering and Fine-Tuning of Dipole Interactions
journal, November 2015
- Breitwieser, Romain; Auvray, Thomas; Volatron, Florence
- Small, Vol. 12, Issue 2
Actinyl Peroxide Nanospheres
journal, March 2005
- Burns, Peter C.; Kubatko, Karrie-Ann; Sigmon, Ginger
- Angewandte Chemie, Vol. 117, Issue 14
Water Radiolysis: Influence of Oxide Surfaces on H2 Production under Ionizing Radiation
journal, February 2011
- Le Caër, Sophie
- Water, Vol. 3, Issue 1
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
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
Evolution of Actinyl Peroxide Clusters U 28 in Dilute Electrolyte Solution: Exploring the Transition from Simple Ions to Macroionic Assemblies
journal, January 2014
- Li, Dong; Simotwo, Silas; Nyman, May
- Chemistry - A European Journal, Vol. 20, Issue 6
Molecular Probe Location in Reverse Micelles Determined by NMR Dipolar Interactions
journal, April 2006
- Crans, Debbie C.; Rithner, Christopher D.; Baruah, Bharat
- Journal of the American Chemical Society, Vol. 128, Issue 13
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
Chemical equilibria in the UO22+–H2O2–F−/OH− systems and possible solution precursors for the formation of [Na6(OH2)8]@[UO2(O2)F]2418− and [Na6(OH2)8]@[UO2(O2)OH]2418− clusters
journal, January 2013
- Zanonato, Pier Luigi; Di Bernardo, Plinio; Fischer, Andreas
- Dalton Transactions, Vol. 42, Issue 28
Closing Uranyl Polyoxometalate Capsules with Bismuth and Lead Polyoxocations
journal, September 2016
- Renier, Olivier; Falaise, Clément; Neal, Harrison
- Angewandte Chemie, Vol. 128, Issue 43
Alkali–metal ion coordination in uranyl( vi ) poly-peroxo complexes in solution, inorganic analogues to crown-ethers. Part 2. Complex formation in the tetramethyl ammonium-, Li + -, Na + - and K + -uranyl( vi )–peroxide–carbonate systems
journal, January 2015
- Zanonato, Pier Luigi; Szabó, Zoltán; Vallet, Valerie
- Dalton Transactions, Vol. 44, Issue 37
Mixed-Valent Uranium(IV,VI) Diphosphonate: Synthesis, Structure, and Spectroscopy
journal, March 2012
- Diwu, Juan; Albrecht-Schmitt, Thomas E.
- Inorganic Chemistry, Vol. 51, Issue 8
Hybrid Uranium-Oxalate Fullerene Topology Cage Clusters
journal, August 2010
- Ling, Jie; Wallace, Christine M.; Szymanowski, Jennifer E. S.
- Angewandte Chemie, Vol. 122, Issue 40
Clusters of Actinides with Oxide, Peroxide, or Hydroxide Bridges
journal, October 2012
- Qiu, Jie; Burns, Peter C.
- Chemical Reviews, Vol. 113, Issue 2
The Anderson–Evans polyoxometalate: From inorganic building blocks via hybrid organic–inorganic structures to tomorrows “Bio-POM”
journal, January 2016
- Blazevic, Amir; Rompel, Annette
- Coordination Chemistry Reviews, Vol. 307
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
Irena : tool suite for modeling and analysis of small-angle scattering
journal, February 2009
- Ilavsky, Jan; Jemian, Peter R.
- Journal of Applied Crystallography, Vol. 42, Issue 2
Onionlike Hybrid Assemblies Based on Surfactant-Encapsulated Polyoxometalates
journal, February 2007
- Li, Haolong; Sun, Hang; Qi, Wei
- Angewandte Chemie, Vol. 119, Issue 8
Single Crystal Growth and Structural Characterization of a Novel Mixed-Valent Ternary Uranium Oxide, K8U7O24
journal, October 2014
- Read, Cory M.; Smith, Mark D.; zur Loye, Hans-Conrad
- Journal of Chemical Crystallography, Vol. 44, Issue 11-12
Highly oxidation resistant inorganic-porphyrin analog polyoxometalate oxidation catalysts. 1. The synthesis and characterization of aqueous-soluble potassium salts of .alpha.2-P2W17O61(Mn+.cntdot.OH2)(n-10) and organic solvent soluble tetra-n-butylammonium salts of .alpha.2-P2W17O61(Mn+.cntdot.Br)(n-11) (M = Mn3+,Fe3+,Co2+,Ni2+,Cu2+)
journal, September 1991
- Lyon, David K.; Miller, Warren K.; Novet, Thomas
- Journal of the American Chemical Society, Vol. 113, Issue 19
Self-Assembly of Organic−Inorganic Hybrid Amphiphilic Surfactants with Large Polyoxometalates as Polar Head Groups
journal, November 2008
- Zhang, Jie; Song, Yu-Fei; Cronin, Leroy
- Journal of the American Chemical Society, Vol. 130, Issue 44
Recovery of Uranium from Wet Phosphoric Acid by Solvent Extraction Processes
journal, November 2014
- Beltrami, Denis; Cote, Gérard; Mokhtari, Hamid
- Chemical Reviews, Vol. 114, Issue 24
Probing protein fine structures by wide angle solution X-ray scattering
journal, June 2000
- Zhang, R.; Thiyagarajan, P.; Tiede, D. M.
- Journal of Applied Crystallography, Vol. 33, Issue 3
The First Structural and Spectroscopic Characterization of a Neptunyl Polyoxometalate Complex
journal, November 2002
- Gaunt, Andrew J.; May, Iain; Helliwell, Madeleine
- Journal of the American Chemical Society, Vol. 124, Issue 45
Dynamics of Uranyl Peroxide Nanocapsules
journal, November 2012
- Nyman, May; Alam, Todd M.
- Journal of the American Chemical Society, Vol. 134, Issue 49
Reverse micelles as microreactors
journal, July 1993
- Pileni, M. P.
- The Journal of Physical Chemistry, Vol. 97, Issue 27
Actinyl Peroxide Nanospheres
journal, March 2005
- Burns, Peter C.; Kubatko, Karrie-Ann; Sigmon, Ginger
- Angewandte Chemie International Edition, Vol. 44, Issue 14
Interaction of sulfur dioxide with heteropolyanions in nonpolar solvents. Evidence for complex formation
journal, January 1987
- Katsoulis, Dimitris E.; Tausch, Valerie S.; Pope, Michael T.
- Inorganic Chemistry, Vol. 26, Issue 1