A Computational and Experimental Approach Linking Disorder, High-Pressure Behavior, and Mechanical Properties in UiO Frameworks

Claire L. Hobday, Ross J. Marshall, Colin F. Murphie, Jorge Sotelo, Tom Richards, David R. Allan, Tina Dueren, Francois-Xavier Coudert, Ross S. Forgan, Carole A. Morrison, Stephen A. Moggach, Thomas D. Bennett

Research output: Contribution to journalArticle

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Abstract

Whilst many metal-organic frameworks possess the chemical stability needed to be used as functional materials, they often lack the physical strength required for industrial applications. Herein, we have investigated the mechanical properties of two UiO-topology Zr-MOFs, the planar UiO-67 ([Zr6O4(OH) 4(bpdc) 6], bpdc: 4,4'-biphenyl dicarboxylate) and UiO-abdc ([Zr6O4(OH) 4(abdc) 6], abdc: 4,4'-azobenzene dicarboxylate) by single-crystal nanoindentation, high-pressure X-ray diffraction, density functional theory calculations, and first-principles molecular dynamics. On increasing pressure, both UiO-67 and UiO-abdc were found to be incompressible when filled with methanol molecules within a diamond anvil cell. Stabilization in both cases is attributed to dynamical linker disorder. The diazo-linker of UiO-abdc possesses local site disorder, which, in conjunction with its longer nature, also decreases the capacity of the framework to compress and stabilizes it against direct compression, compared to UiO-67, characterized by a large elastic modulus. The use of non-linear linkers in the synthesis of UiO-MOFs therefore creates MOFs that have more rigid mechanical properties over a larger pressure range.

Original languageEnglish
Pages (from-to)2401-2405
Number of pages5
JournalANGEWANDTE CHEMIE-INTERNATIONAL EDITION
Volume55
Issue number7
DOIs
Publication statusPublished - 12 Feb 2016
Externally publishedYes

Cite this

Hobday, C. L., Marshall, R. J., Murphie, C. F., Sotelo, J., Richards, T., Allan, D. R., ... Bennett, T. D. (2016). A Computational and Experimental Approach Linking Disorder, High-Pressure Behavior, and Mechanical Properties in UiO Frameworks. ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 55(7), 2401-2405. https://doi.org/10.1002/anie.201509352
Hobday, Claire L. ; Marshall, Ross J. ; Murphie, Colin F. ; Sotelo, Jorge ; Richards, Tom ; Allan, David R. ; Dueren, Tina ; Coudert, Francois-Xavier ; Forgan, Ross S. ; Morrison, Carole A. ; Moggach, Stephen A. ; Bennett, Thomas D. / A Computational and Experimental Approach Linking Disorder, High-Pressure Behavior, and Mechanical Properties in UiO Frameworks. In: ANGEWANDTE CHEMIE-INTERNATIONAL EDITION. 2016 ; Vol. 55, No. 7. pp. 2401-2405.
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abstract = "Whilst many metal-organic frameworks possess the chemical stability needed to be used as functional materials, they often lack the physical strength required for industrial applications. Herein, we have investigated the mechanical properties of two UiO-topology Zr-MOFs, the planar UiO-67 ([Zr6O4(OH) 4(bpdc) 6], bpdc: 4,4'-biphenyl dicarboxylate) and UiO-abdc ([Zr6O4(OH) 4(abdc) 6], abdc: 4,4'-azobenzene dicarboxylate) by single-crystal nanoindentation, high-pressure X-ray diffraction, density functional theory calculations, and first-principles molecular dynamics. On increasing pressure, both UiO-67 and UiO-abdc were found to be incompressible when filled with methanol molecules within a diamond anvil cell. Stabilization in both cases is attributed to dynamical linker disorder. The diazo-linker of UiO-abdc possesses local site disorder, which, in conjunction with its longer nature, also decreases the capacity of the framework to compress and stabilizes it against direct compression, compared to UiO-67, characterized by a large elastic modulus. The use of non-linear linkers in the synthesis of UiO-MOFs therefore creates MOFs that have more rigid mechanical properties over a larger pressure range.",
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Hobday, CL, Marshall, RJ, Murphie, CF, Sotelo, J, Richards, T, Allan, DR, Dueren, T, Coudert, F-X, Forgan, RS, Morrison, CA, Moggach, SA & Bennett, TD 2016, 'A Computational and Experimental Approach Linking Disorder, High-Pressure Behavior, and Mechanical Properties in UiO Frameworks' ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, vol. 55, no. 7, pp. 2401-2405. https://doi.org/10.1002/anie.201509352

A Computational and Experimental Approach Linking Disorder, High-Pressure Behavior, and Mechanical Properties in UiO Frameworks. / Hobday, Claire L.; Marshall, Ross J.; Murphie, Colin F.; Sotelo, Jorge; Richards, Tom; Allan, David R.; Dueren, Tina; Coudert, Francois-Xavier; Forgan, Ross S.; Morrison, Carole A.; Moggach, Stephen A.; Bennett, Thomas D.

In: ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, Vol. 55, No. 7, 12.02.2016, p. 2401-2405.

Research output: Contribution to journalArticle

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T1 - A Computational and Experimental Approach Linking Disorder, High-Pressure Behavior, and Mechanical Properties in UiO Frameworks

AU - Hobday, Claire L.

AU - Marshall, Ross J.

AU - Murphie, Colin F.

AU - Sotelo, Jorge

AU - Richards, Tom

AU - Allan, David R.

AU - Dueren, Tina

AU - Coudert, Francois-Xavier

AU - Forgan, Ross S.

AU - Morrison, Carole A.

AU - Moggach, Stephen A.

AU - Bennett, Thomas D.

PY - 2016/2/12

Y1 - 2016/2/12

N2 - Whilst many metal-organic frameworks possess the chemical stability needed to be used as functional materials, they often lack the physical strength required for industrial applications. Herein, we have investigated the mechanical properties of two UiO-topology Zr-MOFs, the planar UiO-67 ([Zr6O4(OH) 4(bpdc) 6], bpdc: 4,4'-biphenyl dicarboxylate) and UiO-abdc ([Zr6O4(OH) 4(abdc) 6], abdc: 4,4'-azobenzene dicarboxylate) by single-crystal nanoindentation, high-pressure X-ray diffraction, density functional theory calculations, and first-principles molecular dynamics. On increasing pressure, both UiO-67 and UiO-abdc were found to be incompressible when filled with methanol molecules within a diamond anvil cell. Stabilization in both cases is attributed to dynamical linker disorder. The diazo-linker of UiO-abdc possesses local site disorder, which, in conjunction with its longer nature, also decreases the capacity of the framework to compress and stabilizes it against direct compression, compared to UiO-67, characterized by a large elastic modulus. The use of non-linear linkers in the synthesis of UiO-MOFs therefore creates MOFs that have more rigid mechanical properties over a larger pressure range.

AB - Whilst many metal-organic frameworks possess the chemical stability needed to be used as functional materials, they often lack the physical strength required for industrial applications. Herein, we have investigated the mechanical properties of two UiO-topology Zr-MOFs, the planar UiO-67 ([Zr6O4(OH) 4(bpdc) 6], bpdc: 4,4'-biphenyl dicarboxylate) and UiO-abdc ([Zr6O4(OH) 4(abdc) 6], abdc: 4,4'-azobenzene dicarboxylate) by single-crystal nanoindentation, high-pressure X-ray diffraction, density functional theory calculations, and first-principles molecular dynamics. On increasing pressure, both UiO-67 and UiO-abdc were found to be incompressible when filled with methanol molecules within a diamond anvil cell. Stabilization in both cases is attributed to dynamical linker disorder. The diazo-linker of UiO-abdc possesses local site disorder, which, in conjunction with its longer nature, also decreases the capacity of the framework to compress and stabilizes it against direct compression, compared to UiO-67, characterized by a large elastic modulus. The use of non-linear linkers in the synthesis of UiO-MOFs therefore creates MOFs that have more rigid mechanical properties over a larger pressure range.

KW - gas separation

KW - high-pressure chemistry

KW - metalorganic frameworks

KW - structure elucidation

KW - X-ray crystallography

KW - METAL-ORGANIC FRAMEWORKS

KW - ZEOLITIC IMIDAZOLATE FRAMEWORKS

KW - NEGATIVE THERMAL-EXPANSION

KW - SINGLE-CRYSTAL

KW - PORE-SIZE

KW - FLEXIBILITY

KW - STABILITY

KW - CHEMISTRY

KW - TOPOLOGY

KW - MOF-5

U2 - 10.1002/anie.201509352

DO - 10.1002/anie.201509352

M3 - Article

VL - 55

SP - 2401

EP - 2405

JO - Angewandte Chemie - International Edition

JF - Angewandte Chemie - International Edition

SN - 1433-7851

IS - 7

ER -