Reactivity, formation, and solubility of polyoxometalates pprobed by calorimetry

Traustason, H., Bell, N. L. , Caranto, K., Auld, D. C., Lockey, D. T., Kokot, A., Szymanowski, J. E.S., Cronin, L. and Burns, P. C. (2020) Reactivity, formation, and solubility of polyoxometalates pprobed by calorimetry. Journal of the American Chemical Society, 142(48), pp. 20463-20469. (doi: 10.1021/jacs.0c10133) (PMID:33203207)

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Abstract

Room temperature calorimetry methods were developed to describe the energy landscapes of six polyoxometalates (POMs), Li-U , Li-U , K-U , Li/K-U , Mo , and Mo , in terms of three components: enthalpy of dissolution (Δ ), enthalpy of formation of aqueous POMs (Δ ), and enthalpy of formation of POM crystals (Δ ). Δ 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 Δ and are more stable than those containing only peroxide bridges. 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 Δ can be accurately estimated using only Δ values owing to the dominance of the clusters in determining the energetics of POM crystals.

Item Type:Articles
Status:Published
Refereed:Yes
Glasgow Author(s) Enlighten ID:Bell, Dr Nicola and Cronin, Professor Lee and Lockey, David
Authors: Traustason, H., Bell, N. L., Caranto, K., Auld, D. C., Lockey, D. T., Kokot, A., Szymanowski, J. E.S., Cronin, L., and Burns, P. C.
College/School:College of Science and Engineering > School of Chemistry
Journal Name:Journal of the American Chemical Society
Publisher:American Chemical Society
ISSN:0002-7863
ISSN (Online):1520-5126
Published Online:17 November 2020
Copyright Holders:Copyright © 2020 American Chemical Society
First Published:First published in Journal of the American Chemical Society 142(48): 20463-20469
Publisher Policy:Reproduced in accordance with the publisher copyright policy

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Project CodeAward NoProject NamePrincipal InvestigatorFunder's NameFunder RefLead Dept
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167864Energy and the Physical Sciences: Hydrogen Production using a Proton Electron BufferLeroy CroninEngineering and Physical Sciences Research Council (EPSRC)EP/K023004/1Chemistry
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172151SMARTPOM: Artificial-Intelligence Driven Discovery and Synthesis of Polyoxometalate ClustersLeroy CroninEuropean Research Council (ERC)670467Chemistry