Reactivity, Formation, and Solubility of Polyoxometalates Probed by Calorimetry

Traustason, Hrafn; Bell, Nicola L.; Caranto, Kiana; Auld, David C.; Lockey, David T.; Kokot, Alex; Szymanowski, Jennifer E. S.; Cronin, Leroy; Burns, Peter C.

doi:10.1021/jacs.0c10133

Reactivity, Formation, and Solubility of Polyoxometalates Probed by Calorimetry

Journal Article · Tue Nov 17 00:00:00 EST 2020 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/jacs.0c10133· OSTI ID:1725816

Traustason, Hrafn ^[1]; ^[2]; Caranto, Kiana ^[3]; Auld, David C. ^[2]; Lockey, David T. ^[2]; Kokot, Alex ^[3]; Szymanowski, Jennifer E. S. ^[3]; ^[2]; ^[3]

Univ. of Notre Dame, IN (United States); University of Notre Dame
Univ. of Glasgow (United Kingdom)
Univ. of Notre Dame, IN (United States)

Room temperature calorimetry methods were developed to describe the energy landscapes of six polyoxometalates (POMs), Li–U₂₄, Li–U₂₈, K–U₂₈, Li/K–U₆₀, Mo₁₃₂, and Mo₁₅₄, in terms of three components: enthalpy of dissolution (ΔH_diss), enthalpy of formation of aqueous POMs (ΔH_f,(aq)), and enthalpy of formation of POM crystals (ΔH_f,(c)). ΔH_diss is controlled by a combination of cation solvation enthalpy and the favorability of cation interactions with binding sites on the POM. In the case of the four uranyl peroxide POMs studied, clusters with hydroxide bridges have lower ΔH_f,(aq) and are more stable than those containing only peroxide bridges. Here, in general for POMs, the combination of calorimetric results and synthetic observations suggest that spherical topologies may be more stable than wheel-like clusters, and ΔH_f,(aq) can be accurately estimated using only ΔH_f,(c) values owing to the dominance of the clusters in determining the energetics of POM crystals.

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:: 1725816

Journal Information:: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 48 Vol. 142; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (50)

Organizational Forms of Matter: An Inorganic Super Fullerene and Keplerate Based on Molybdenum Oxide Müller, Achim; Krickemeyer, Erich; Bögge, Hartmut Angewandte Chemie International Edition, Vol. 37, Issue 24 https://doi.org/10.1002/(SICI)1521-3773(19981231)37:24<3359::AID-ANIE3359>3.0.CO;2-J	journal	December 1998
[Mo154(NO)14O420(OH)28(H2O)70](25± 5)−: A Water-Soluble Big Wheel with More than 700 Atoms and a Relative Molecular Mass of About 24000 Müller, Achim; Krickemeyer, Erich; Meyer, Jochen Angewandte Chemie International Edition in English, Vol. 34, Issue 19 https://doi.org/10.1002/anie.199521221	journal	October 1995
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
Exploring the Molecular Growth of Two Gigantic Half‐Closed Polyoxometalate Clusters {Mo ₁₈₀ } and {Mo ₁₃₀ Ce ₆ } Xuan, Weimin; Pow, Robert; Long, De‐Liang Angewandte Chemie International Edition, Vol. 56, Issue 33 https://doi.org/10.1002/anie.201702957	journal	August 2017
Ligand‐Directed Template Assembly for the Construction of Gigantic Molybdenum Blue Wheels Xuan, Weimin; Pow, Robert; Zheng, Qi Angewandte Chemie International Edition, Vol. 58, Issue 32 https://doi.org/10.1002/anie.201901818	journal	August 2019
Beyond Charge Balance: Counter‐Cations in Polyoxometalate Chemistry Misra, Archismita; Kozma, Karoly; Streb, Carsten Angewandte Chemie International Edition, Vol. 59, Issue 2 https://doi.org/10.1002/anie.201905600	journal	January 2020
The Energy Landscape of Uranyl-Peroxide Species Tiferet, Eitan; Gil, Adrià; Bo, Carles Chemistry - A European Journal, Vol. 20, Issue 13 https://doi.org/10.1002/chem.201304076	journal	March 2014
Selective Permeability of Uranyl Peroxide Nanocages to Different Alkali Ions: Influences from Surface Pores and Hydration Shells Gao, Yunyi; Haso, Fadi; Szymanowski, Jennifer E. S. Chemistry - A European Journal, Vol. 21, Issue 51 https://doi.org/10.1002/chem.201503773	journal	November 2015
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
Isotope and Hydrogen‐Bond Effects on the Self‐Assembly of Macroions in Dilute Solution Li, Hui; Shen, Yidan; Yang, Peng Chemistry – A European Journal, Vol. 25, Issue 71 https://doi.org/10.1002/chem.201902444	journal	November 2019
Controlling the Molecular Assembly of Polyoxometalates from the Nano to the Micron Scale: Molecules to Materials Hutin, Marie; Long, De-Liang; Cronin, Leroy Israel Journal of Chemistry, Vol. 51, Issue 2 https://doi.org/10.1002/ijch.201100008	journal	February 2011
Enthalpies de dissolution du fluorure et de l'hydrogenofluorure d'ammonium dans l'eau Thourey, J.; Bendaoud, S.; Perachon, G. Journal of Fluorine Chemistry, Vol. 23, Issue 4 https://doi.org/10.1016/S0022-1139(00)81217-8	journal	October 1983
Experimental measurements of U60 nanocluster stability in aqueous solution Flynn, Shannon L.; Szymanowski, Jennifer E. S.; Gao, Yunyi Geochimica et Cosmochimica Acta, Vol. 156 https://doi.org/10.1016/j.gca.2015.02.021	journal	May 2015
Thermodynamic properties of ammonium sulfamate Kosova, Daria A.; Druzhinina, Anna I.; Tiflova, Lyudmila A. The Journal of Chemical Thermodynamics, Vol. 132 https://doi.org/10.1016/j.jct.2019.01.021	journal	May 2019
Processing used nuclear fuel with nanoscale control of uranium and ultrafiltration Wylie, Ernest M.; Peruski, Kathryn M.; Prizio, Sarah E. Journal of Nuclear Materials, Vol. 473 https://doi.org/10.1016/j.jnucmat.2016.02.013	journal	May 2016
The energetics of lanthanum tantalate materials Forbes, Tori Z.; Nyman, May; Rodriguez, Mark A. Journal of Solid State Chemistry, Vol. 183, Issue 11 https://doi.org/10.1016/j.jssc.2010.08.024	journal	November 2010
Uranyl Peroxide Cage Cluster Solubility in Water and the Role of the Electrical Double Layer Peruski, Kathryn M.; Bernales, Varinia; Dembowski, Mateusz Inorganic Chemistry, Vol. 56, Issue 3 https://doi.org/10.1021/acs.inorgchem.6b02435	journal	January 2017
The Propensity of Uranium-Peroxide Systems to Preserve Nanosized Assemblies Dembowski, Mateusz; Colla, Christopher A.; Yu, Ping Inorganic Chemistry, Vol. 56, Issue 16 https://doi.org/10.1021/acs.inorgchem.7b01095	journal	July 2017
Complexity of Uranyl Peroxide Cluster Speciation from Alkali-Directed Oxidative Dissolution of Uranium Dioxide Hickam, Sarah; Aksenov, Sergey M.; Dembowski, Mateusz Inorganic Chemistry, Vol. 57, Issue 15 https://doi.org/10.1021/acs.inorgchem.8b01299	journal	July 2018
Charge Density Influence on Enthalpy of Formation of Uranyl Peroxide Cage Cluster Salts Sharifironizi, Melika; Szymanowski, Jennifer E. S.; Qiu, Jie Inorganic Chemistry, Vol. 57, Issue 18 https://doi.org/10.1021/acs.inorgchem.8b01300	journal	August 2018
The Role of the Organic Solvent Polarity in Isolating Uranyl Peroxide Capsule Fragments Arteaga, Ana; Ray, Debmalya; Glass, Elliot Inorganic Chemistry, Vol. 59, Issue 3 https://doi.org/10.1021/acs.inorgchem.9b02660	journal	January 2020
Dynamics of Cation-Induced Conformational Changes in Nanometer-Sized Uranyl Peroxide Clusters Dembowski, Mateusz; Pilgrim, Corey D.; Hickam, Sarah Inorganic Chemistry, Vol. 59, Issue 4 https://doi.org/10.1021/acs.inorgchem.9b03390	journal	February 2020
Ultrafiltration of Uranyl Peroxide Nanoclusters for the Separation of Uranium from Aqueous Solution Wylie, Ernest M.; Peruski, Kathryn M.; Weidman, Jacob L. ACS Applied Materials & Interfaces, Vol. 6, Issue 1 https://doi.org/10.1021/am404520b	journal	December 2013
Clusters of Actinides with Oxide, Peroxide, or Hydroxide Bridges Qiu, Jie; Burns, Peter C. Chemical Reviews, Vol. 113, Issue 2 https://doi.org/10.1021/cr300159x	journal	October 2012
Crown and Bowl-Shaped Clusters of Uranyl Polyhedra Sigmon, Ginger E.; Weaver, Brittany; Kubatko, Karrie-Ann Inorganic Chemistry, Vol. 48, Issue 23 https://doi.org/10.1021/ic9020355	journal	December 2009
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
Time-Resolved Self-Assembly of a Fullerene-Topology Core–Shell Cluster Containing 68 Uranyl Polyhedra Qiu, Jie; Ling, Jie; Sui, Audrey Journal of the American Chemical Society, Vol. 134, Issue 3 https://doi.org/10.1021/ja210163b	journal	January 2012
Alkali-Driven Disassembly and Reassembly of Molecular Niobium Oxide in Water Sures, Dylan; Segado, Mireia; Bo, Carles Journal of the American Chemical Society, Vol. 140, Issue 34 https://doi.org/10.1021/jacs.8b05015	journal	July 2018
Stereoselective Assembly of Gigantic Chiral Molybdenum Blue Wheels Using Lanthanide Ions and Amino Acids Xuan, Weimin; Pow, Robert; Watfa, Nancy Journal of the American Chemical Society, Vol. 141, Issue 3 https://doi.org/10.1021/jacs.8b09750	journal	November 2018
Supramolecular Assembly of Geometrically Unstable Hybrid Organic–Inorganic Uranyl Peroxide Cage Clusters and Their Transformations Xu, Mengyu; Traustason, Hrafn; Bo, Fabrice Dal Journal of the American Chemical Society, Vol. 141, Issue 32 https://doi.org/10.1021/jacs.9b05599	journal	July 2019
Enhancing coherence in molecular spin qubits via atomic clock transitions Shiddiq, Muhandis; Komijani, Dorsa; Duan, Yan Nature, Vol. 531, Issue 7594 https://doi.org/10.1038/nature16984	journal	March 2016
Polyoxometalate clusters, nanostructures and materials: From self assembly to designer materials and devices Long, De-Liang; Burkholder, Eric; Cronin, Leroy Chem. Soc. Rev., Vol. 36, Issue 1 https://doi.org/10.1039/B502666K	journal	January 2007
Polyoxometalate – conductive polymer composites for energy conversion, energy storage and nanostructured sensors Herrmann, Sven; Ritchie, Chris; Streb, Carsten Dalton Transactions, Vol. 44, Issue 16 https://doi.org/10.1039/C4DT03763D	journal	January 2015
Polyoxometalate-functionalized nanocarbon materials for energy conversion, energy storage and sensor systems Ji, Yuanchun; Huang, Lujiang; Hu, Jun Energy & Environmental Science, Vol. 8, Issue 3 https://doi.org/10.1039/C4EE03749A	journal	January 2015
Neodymium uranyl peroxide synthesis by ion exchange on ammonium uranyl peroxide nanoclusters Blanchard, F.; Ellart, M.; Rivenet, M. Chemical Communications, Vol. 52, Issue 20 https://doi.org/10.1039/C5CC09527A	journal	January 2016
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
The lithium–water configuration encapsulated by uranyl peroxide cage cluster U ₂₄ Traustason, H.; Aksenov, S. M.; Burns, P. C. CrystEngComm, Vol. 21, Issue 3 https://doi.org/10.1039/C8CE01774C	journal	January 2019
Functionalization of polyoxometalates: towards advanced applications in catalysis and materials science Proust, Anna; Thouvenot, René; Gouzerh, Pierre Chemical Communications, Issue 16 https://doi.org/10.1039/b715502f	journal	January 2008
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
Solution behaviors and self-assembly of polyoxometalates as models of macroions and amphiphilic polyoxometalate–organic hybrids as novel surfactants Yin, Panchao; Li, Dong; Liu, Tianbo Chemical Society Reviews, Vol. 41, Issue 22 https://doi.org/10.1039/c2cs35176e	journal	January 2012
Polyoxometalate water oxidation catalysts and the production of green fuel Lv, Hongjin; Geletii, Yurii V.; Zhao, Chongchao Chemical Society Reviews, Vol. 41, Issue 22, p. 7572-7589 https://doi.org/10.1039/c2cs35292c	journal	January 2012
Use of ion-mobility mass spectrometry (IMS-MS) to map polyoxometalate Keplerate clusters and their supramolecular assemblies Robbins, Philip J.; Surman, Andrew J.; Thiel, Johannes Chemical Communications, Vol. 49, Issue 19 https://doi.org/10.1039/c3cc38615e	journal	January 2013
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
Polyoxometalate clusters in minerals: review and complexity analysis Krivovichev, Sergey V. Acta Crystallographica Section B Structural Science, Crystal Engineering and Materials, Vol. 76, Issue 4 https://doi.org/10.1107/S2052520620007131	journal	July 2020
Complex minerals preserve natural geochemically important nanoscale metal oxide clusters Burns, Peter C. Acta Crystallographica Section B Structural Science, Crystal Engineering and Materials, Vol. 76, Issue 4 https://doi.org/10.1107/S2052520620010045	journal	July 2020
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
Niobium Is Highly Mobile As a Polyoxometalate Ion During Natural Weathering Friis, Henrik; Casey, William H. The Canadian Mineralogist, Vol. 56, Issue 6 https://doi.org/10.3749/canmin.1800058	journal	November 2018

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