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Title: Reactivity, Formation, and Solubility of Polyoxometalates Probed by Calorimetry

Abstract

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 (ΔHdiss), enthalpy of formation of aqueous POMs (ΔHf,(aq)), and enthalpy of formation of POM crystals (ΔHf,(c)). ΔHdiss 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 ΔHf,(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 ΔHf,(aq) can be accurately estimated using only ΔHf,(c) values owing to the dominance of the clusters in determining the energetics of POM crystals.

Authors:
 [1]; ORCiD logo [2];  [1];  [2];  [2];  [1];  [1]; ORCiD logo [2]; ORCiD logo [1]
  1. Univ. of Notre Dame, IN (United States)
  2. Univ. of Glasgow (United Kingdom)
Publication Date:
Research Org.:
Univ. of Notre Dame, IN (United States)
Sponsoring Org.:
USDOE National Nuclear Security Administration (NNSA)
OSTI Identifier:
1725816
Grant/Contract Number:  
NA0003763
Resource Type:
Accepted Manuscript
Journal Name:
Journal of the American Chemical Society
Additional Journal Information:
Journal Name: Journal of the American Chemical Society; Journal ID: ISSN 0002-7863
Publisher:
American Chemical Society (ACS)
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; Anions; Solution chemistry; Cluster chemistry; Cations; Enthalpy

Citation Formats

Traustason, Hrafn, Bell, Nicola L., Caranto, Kiana, Auld, David C., Lockey, David T., Kokot, Alex, Szymanowski, Jennifer E. S., Cronin, Leroy, and Burns, Peter C. Reactivity, Formation, and Solubility of Polyoxometalates Probed by Calorimetry. United States: N. p., 2020. Web. doi:10.1021/jacs.0c10133.
Traustason, Hrafn, Bell, Nicola L., Caranto, Kiana, Auld, David C., Lockey, David T., Kokot, Alex, Szymanowski, Jennifer E. S., Cronin, Leroy, & Burns, Peter C. Reactivity, Formation, and Solubility of Polyoxometalates Probed by Calorimetry. United States. doi:10.1021/jacs.0c10133.
Traustason, Hrafn, Bell, Nicola L., Caranto, Kiana, Auld, David C., Lockey, David T., Kokot, Alex, Szymanowski, Jennifer E. S., Cronin, Leroy, and Burns, Peter C. Tue . "Reactivity, Formation, and Solubility of Polyoxometalates Probed by Calorimetry". United States. doi:10.1021/jacs.0c10133.
@article{osti_1725816,
title = {Reactivity, Formation, and Solubility of Polyoxometalates Probed by Calorimetry},
author = {Traustason, Hrafn and Bell, Nicola L. and Caranto, Kiana and Auld, David C. and Lockey, David T. and Kokot, Alex and Szymanowski, Jennifer E. S. and Cronin, Leroy and Burns, Peter C.},
abstractNote = {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 (ΔHdiss), enthalpy of formation of aqueous POMs (ΔHf,(aq)), and enthalpy of formation of POM crystals (ΔHf,(c)). ΔHdiss 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 ΔHf,(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 ΔHf,(aq) can be accurately estimated using only ΔHf,(c) values owing to the dominance of the clusters in determining the energetics of POM crystals.},
doi = {10.1021/jacs.0c10133},
journal = {Journal of the American Chemical Society},
number = ,
volume = ,
place = {United States},
year = {2020},
month = {11}
}

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This content will become publicly available on November 17, 2021
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