Structural transformation of metal oxo species within UiO-66 type metal-organic frameworks

Megan C. Wasson; Haomiao Xie; Xingjie Wang; Joshua S. Duncan; Omar K. Farha

doi:10.1039/d2ce00650b

Structural transformation of metal oxo species within UiO-66 type metal-organic frameworks

Megan C. Wasson, Haomiao Xie, Xingjie Wang, Joshua S. Duncan, Omar K. Farha^*

^*Corresponding author for this work

Chemistry

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

5 Scopus citations

Abstract

Studying the coordination of actinide-based metal oxo clusters can provide valuable insights for nuclear energy technologies and radioactive waste containment. Metal-organic frameworks serve as a platform to directly interrogate the structure and properties of understudied actinide elements, including thorium. Examples of structural evolutions within Th oxo species within MOFs are rare yet relevant for nuclear waste speciation in solution. Herein, we report the serendipitous discovery of the structural evolution of Th-UiO-66 containing a hexanuclear Th node to a mononuclear Th(bdc)₂(dmf)₂ upon the evaporation of solvent from the reaction. We observe a partial reversal of Th(bdc)₂(dmf)₂ back to Th-UiO-66 upon hydrothermal treatment, indicating the complex dynamics of Th oxo species in solution. We report that isolated Ce-UiO-66 similarly transforms to a newly isolated 1D Ce^III carboxylate chain MOF named NU-351 under the same conditions as Th-UiO-66, while Zr-UiO-66 and Hf-UiO-66 retain their structures.

Original language	English (US)
Pages (from-to)	5135-5140
Number of pages	6
Journal	CrystEngComm
Volume	24
Issue number	28
DOIs	https://doi.org/10.1039/d2ce00650b
State	Published - Jun 30 2022

ASJC Scopus subject areas

General Chemistry
General Materials Science
Condensed Matter Physics

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10.1039/d2ce00650b

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title = "Structural transformation of metal oxo species within UiO-66 type metal-organic frameworks",

abstract = "Studying the coordination of actinide-based metal oxo clusters can provide valuable insights for nuclear energy technologies and radioactive waste containment. Metal-organic frameworks serve as a platform to directly interrogate the structure and properties of understudied actinide elements, including thorium. Examples of structural evolutions within Th oxo species within MOFs are rare yet relevant for nuclear waste speciation in solution. Herein, we report the serendipitous discovery of the structural evolution of Th-UiO-66 containing a hexanuclear Th node to a mononuclear Th(bdc)2(dmf)2 upon the evaporation of solvent from the reaction. We observe a partial reversal of Th(bdc)2(dmf)2 back to Th-UiO-66 upon hydrothermal treatment, indicating the complex dynamics of Th oxo species in solution. We report that isolated Ce-UiO-66 similarly transforms to a newly isolated 1D CeIII carboxylate chain MOF named NU-351 under the same conditions as Th-UiO-66, while Zr-UiO-66 and Hf-UiO-66 retain their structures.",

author = "Wasson, {Megan C.} and Haomiao Xie and Xingjie Wang and Duncan, {Joshua S.} and Farha, {Omar K.}",

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AU - Wasson, Megan C.

AU - Xie, Haomiao

AU - Wang, Xingjie

AU - Duncan, Joshua S.

AU - Farha, Omar K.

PY - 2022/6/30

Y1 - 2022/6/30

N2 - Studying the coordination of actinide-based metal oxo clusters can provide valuable insights for nuclear energy technologies and radioactive waste containment. Metal-organic frameworks serve as a platform to directly interrogate the structure and properties of understudied actinide elements, including thorium. Examples of structural evolutions within Th oxo species within MOFs are rare yet relevant for nuclear waste speciation in solution. Herein, we report the serendipitous discovery of the structural evolution of Th-UiO-66 containing a hexanuclear Th node to a mononuclear Th(bdc)2(dmf)2 upon the evaporation of solvent from the reaction. We observe a partial reversal of Th(bdc)2(dmf)2 back to Th-UiO-66 upon hydrothermal treatment, indicating the complex dynamics of Th oxo species in solution. We report that isolated Ce-UiO-66 similarly transforms to a newly isolated 1D CeIII carboxylate chain MOF named NU-351 under the same conditions as Th-UiO-66, while Zr-UiO-66 and Hf-UiO-66 retain their structures.

AB - Studying the coordination of actinide-based metal oxo clusters can provide valuable insights for nuclear energy technologies and radioactive waste containment. Metal-organic frameworks serve as a platform to directly interrogate the structure and properties of understudied actinide elements, including thorium. Examples of structural evolutions within Th oxo species within MOFs are rare yet relevant for nuclear waste speciation in solution. Herein, we report the serendipitous discovery of the structural evolution of Th-UiO-66 containing a hexanuclear Th node to a mononuclear Th(bdc)2(dmf)2 upon the evaporation of solvent from the reaction. We observe a partial reversal of Th(bdc)2(dmf)2 back to Th-UiO-66 upon hydrothermal treatment, indicating the complex dynamics of Th oxo species in solution. We report that isolated Ce-UiO-66 similarly transforms to a newly isolated 1D CeIII carboxylate chain MOF named NU-351 under the same conditions as Th-UiO-66, while Zr-UiO-66 and Hf-UiO-66 retain their structures.

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Structural transformation of metal oxo species within UiO-66 type metal-organic frameworks

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CCDC 2167180: Experimental Crystal Structure Determination

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Structural transformation of metal oxo species within UiO-66 type metal-organic frameworks

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CCDC 2167180: Experimental Crystal Structure Determination

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