Prediction of Solution Behavior via Calorimetric Measurements Allows for Detailed Elucidation of Polyoxometalate Transformation

Traustason, Hrafn; Lobeck, Haylie L.; Julien, Patrick A.; Xu, Mengyu; Dembowski, Mateusz; Burns, Peter C.

doi:10.1021/acs.inorgchem.1c00587

Prediction of Solution Behavior via Calorimetric Measurements Allows for Detailed Elucidation of Polyoxometalate Transformation

Journal Article · Thu Apr 15 00:00:00 EDT 2021 · Inorganic Chemistry

DOI:https://doi.org/10.1021/acs.inorgchem.1c00587· OSTI ID:1782109

Traustason, Hrafn ^[1]; Lobeck, Haylie L. ^[2]; Julien, Patrick A. ^[2]; Xu, Mengyu ^[2]; ^[2]; ^[2]

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

The solution behavior of a polyoxometalate cluster, LiNa-U₂₄Pp₁₂ (Li₂₄Na₂₄[(UO₂O₂)₂₄(P₂O₇)₁₂]) that consists of 24 uranyl ions, peroxide groups, and 12 pyrophosphate linkers, was successfully predicted based on new thermodynamic results using a calorimetric method recently described for uranyl peroxide nanoclusters (UPCs), molybdenum blues, and molybdenum browns. The breakdown of LiNa-U₂₄Pp₁₂ and formation of U₂₄ (Li₂₄[UO₂O₂OH]₂₄) was monitored in situ via Raman spectroscopy using a custom heating apparatus. A combination of analytical techniques confirmed the simultaneous existence of U₂₄Pp₁₂ and U₂₄ midway through the conversion process and U₂₄ as the single end product. The application of a molecular weight filter resulted in a complete and successful separation of UPCs from solution and, in conjunction with DOSY results, confirmed the presence of large intermediate cluster building blocks.

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:: 1782109

Journal Information:: Inorganic Chemistry, Journal Name: Inorganic Chemistry Journal Issue: 9 Vol. 60; ISSN 0020-1669

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (49)

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
Hybrid Uranium-Oxalate Fullerene Topology Cage Clusters Ling, Jie; Wallace, Christine M.; Szymanowski, Jennifer E. S. Angewandte Chemie International Edition, Vol. 49, Issue 40 https://doi.org/10.1002/anie.201003197	journal	August 2010
Dynamics of a Nanometer-Sized Uranyl Cluster in Solution Johnson, Rene L.; Ohlin, C. André; Pellegrini, Kristi Angewandte Chemie International Edition, Vol. 52, Issue 29 https://doi.org/10.1002/anie.201301973	journal	June 2013
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
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
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
A one-shot sequence for high-resolution diffusion-ordered spectroscopy Pelta, Michelle D.; Morris, Gareth A.; Stchedroff, Marc J. Magnetic Resonance in Chemistry, Vol. 40, Issue 13 https://doi.org/10.1002/mrc.1107	journal	January 2002
Simultaneous three-dimensional visualization of mineralized and soft skeletal tissues by a novel microCT contrast agent with polyoxometalate structure Kerckhofs, Greet; Stegen, Steve; van Gastel, Nick Biomaterials, Vol. 159 https://doi.org/10.1016/j.biomaterials.2017.12.016	journal	March 2018
Detection and identification of solids, surfaces, and solutions of uranium using vibrational spectroscopy Lu, Grace; Haes, Amanda J.; Forbes, Tori Z. Coordination Chemistry Reviews, Vol. 374 https://doi.org/10.1016/j.ccr.2018.07.010	journal	November 2018
Recent advances in POM-organic frameworks and POM-organic polyhedra Li, Xin-Xiong; Zhao, Dan; Zheng, Shou-Tian Coordination Chemistry Reviews, Vol. 397 https://doi.org/10.1016/j.ccr.2019.07.005	journal	October 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
Time-Resolved X-ray Scattering and Raman Spectroscopic Studies of Formation of a Uranium-Vanadium-Phosphorus-Peroxide Cage Cluster Qiu, Jie; Dembowski, Mateusz; Szymanowski, Jennifer E. S. Inorganic Chemistry, Vol. 55, Issue 14 https://doi.org/10.1021/acs.inorgchem.6b00918	journal	June 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
Hierarchy of Pyrophosphate-Functionalized Uranyl Peroxide Nanocluster Synthesis Dembowski, Mateusz; Colla, Christopher A.; Hickam, Sarah Inorganic Chemistry, Vol. 56, Issue 9 https://doi.org/10.1021/acs.inorgchem.7b00649	journal	April 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
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
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
Raman Spectroscopic and ESI-MS Characterization of Uranyl Peroxide Cage Clusters McGrail, Brendan T.; Sigmon, Ginger E.; Jouffret, Laurent J. Inorganic Chemistry, Vol. 53, Issue 3 https://doi.org/10.1021/ic402570b	journal	January 2014
Uranium Pyrophosphate/Methylenediphosphonate Polyoxometalate Cage Clusters Ling, Jie; Qiu, Jie; Sigmon, Ginger E. Journal of the American Chemical Society, Vol. 132, Issue 38 https://doi.org/10.1021/ja1048219	journal	September 2010
Observing Assembly of Complex Inorganic Materials from Polyoxometalate Building Blocks Hou, Yu; Zakharov, Lev N.; Nyman, May Journal of the American Chemical Society, Vol. 135, Issue 44 https://doi.org/10.1021/ja4086484	journal	October 2013
Synthesis, Assembly, and Sizing of Neutral, Lanthanide Substituted Molybdenum Blue Wheels {Mo ₉₀ Ln ₁₀ } Garrido Ribó, Eduard; Bell, Nicola L.; Xuan, Weimin Journal of the American Chemical Society, Vol. 142, Issue 41 https://doi.org/10.1021/jacs.0c07146	journal	September 2020
Reactivity, Formation, and Solubility of Polyoxometalates Probed by Calorimetry Traustason, Hrafn; Bell, Nicola L.; Caranto, Kiana Journal of the American Chemical Society, Vol. 142, Issue 48 https://doi.org/10.1021/jacs.0c10133	journal	November 2020
Hierarchical Self-Assembly of Polyoxometalate-Based Hybrids Driven by Metal Coordination and Electrostatic Interactions: From Discrete Supramolecular Species to Dense Monodisperse Nanoparticles Izzet, Guillaume; Abécassis, Benjamin; Brouri, Dalil Journal of the American Chemical Society, Vol. 138, Issue 15 https://doi.org/10.1021/jacs.6b00972	journal	April 2016
Solution ³¹ P NMR Study of the Acid-Catalyzed Formation of a Highly Charged {U ₂₄ Pp ₁₂ } Nanocluster, [(UO ₂ ) ₂₄ (O ₂ ) ₂₄ (P ₂ O ₇ ) ₁₂ ] ^48– , and Its Structural Characterization in the Solid State Using Single-Crystal Neutron Diffraction Dembowski, Mateusz; Olds, Travis A.; Pellegrini, Kristi L. Journal of the American Chemical Society, Vol. 138, Issue 27 https://doi.org/10.1021/jacs.6b04028	journal	June 2016
Reduction-Triggered Self-Assembly of Nanoscale Molybdenum Oxide Molecular Clusters Yin, Panchao; Wu, Bin; Li, Tao Journal of the American Chemical Society, Vol. 138, Issue 33 https://doi.org/10.1021/jacs.6b05882	journal	August 2016
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
Water-soluble multi-cage super tetrahedral uranyl peroxide phosphate clusters Qiu, Jie; Ling, Jie; Jouffret, Laurent Chem. Sci., Vol. 5, Issue 1 https://doi.org/10.1039/C3SC52357H	journal	January 2014
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
Solution behaviour of a polymer with polyoxometalate inorganic molecular clusters in its main chain Haso, Fadi; Wang, Ruixin; He, Jiazhi New Journal of Chemistry, Vol. 40, Issue 2 https://doi.org/10.1039/C5NJ01326G	journal	January 2016
A highly stable polyoxometalate-based metal–organic framework with an ABW zeolite-like structure Li, Xiao-Xin; Shen, Feng-Cui; Liu, Jiang Chemical Communications, Vol. 53, Issue 72 https://doi.org/10.1039/C7CC05552H	journal	January 2017
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
In situ Raman spectroscopy of uranyl peroxide nanoscale cage clusters under hydrothermal conditions Lobeck, Haylie L.; Traustason, Hrafn; Julien, Patrick A. Dalton Transactions, Vol. 48, Issue 22 https://doi.org/10.1039/C9DT01529A	journal	January 2019
Raman spectroscopy of aqueous phosphate solutions at temperatures up to 450 °C. Two liquid phases, supercritical fluids, and pyro- to ortho-phosphate conversions Marshall, William L.; Begun, G. M. J. Chem. Soc., Faraday Trans. 2, Vol. 85, Issue 12 https://doi.org/10.1039/F29898501963	journal	January 1989
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
On the “yl” bond weakening in uranyl(VI) coordination complexes Tsushima, Satoru Dalton Transactions, Vol. 40, Issue 25 https://doi.org/10.1039/c1dt10481k	journal	January 2011
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
From linking of metal-oxide building blocks in a dynamic library to giant clusters with unique properties and towards adaptive chemistry Müller, Achim; Gouzerh, Pierre Chemical Society Reviews, Vol. 41, Issue 22 https://doi.org/10.1039/c2cs35169b	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
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
An empirical correction for the influence of low-energy contamination Krause, Lennard; Herbst-Irmer, Regine; Stalke, Dietmar Journal of Applied Crystallography, Vol. 48, Issue 6 https://doi.org/10.1107/S1600576715020440	journal	November 2015
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
Carrier-envelope phase dynamics of octave-spanning dispersion-managed Ti: sapphire lasers Sander, Michelle Y.; Ippen, Erich P.; Kärtner, Franz X. Optics Express, Vol. 18, Issue 5 https://doi.org/10.1364/OE.18.004948	journal	January 2010

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