Reactivity, Formation, and Solubility of Polyoxometalates Probed by Calorimetry

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

doi:10.1021/jacs.0c10133

Reactivity, Formation, and Solubility of Polyoxometalates Probed by Calorimetry

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

Research output: Contribution to journal › Article › peer-review

34 Scopus citations

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. 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.

Original language	English
Pages (from-to)	20463-20469
Number of pages	7
Journal	Journal of the American Chemical Society
Volume	142
Issue number	48
DOIs	https://doi.org/10.1021/jacs.0c10133
State	Published - Dec 2 2020
Externally published	Yes

Funding

This work was supported by the National Nuclear Security Administration, Department of Energy, under Award No. DE-NA0003763. This work was supported by LCs EPSRC grants (No. EP/J015156/1; EP/L023652/1; EP/I033459/1; EP/J015156/1; EP/K023004/1; and EP/L023652/1) and the ERC Advanced Grant (ERC-ADG, 670467 SMART-POM). The Material Characterization Facility of the Center for Sustainable Energy at Notre Dame provided thermogravimetric analysis instrumentation.

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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. 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.",

author = "Hrafn Traustason and Bell, \{Nicola L.\} and Kiana Caranto and Auld, \{David C.\} and Lockey, \{David T.\} and Alex Kokot and Szymanowski, \{Jennifer E.S.\} and Leroy Cronin and Burns, \{Peter C.\}",

year = "2020",

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doi = "10.1021/jacs.0c10133",

language = "English",

volume = "142",

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journal = "Journal of the American Chemical Society",

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T1 - Reactivity, Formation, and Solubility of Polyoxometalates Probed by Calorimetry

AU - Traustason, Hrafn

AU - Bell, Nicola L.

AU - Caranto, Kiana

AU - Auld, David C.

AU - Lockey, David T.

AU - Kokot, Alex

AU - Szymanowski, Jennifer E.S.

AU - Cronin, Leroy

AU - Burns, Peter C.

PY - 2020/12/2

Y1 - 2020/12/2

N2 - 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. 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.

AB - 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. 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.

UR - https://www.scopus.com/pages/publications/85096559442

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DO - 10.1021/jacs.0c10133

M3 - Article

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AN - SCOPUS:85096559442

SN - 0002-7863

VL - 142

SP - 20463

EP - 20469

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

IS - 48

ER -

Reactivity, Formation, and Solubility of Polyoxometalates Probed by Calorimetry

Abstract

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