Isolating the Role of the Node-Linker Bond in the Compression of UiO-66 Metal-Organic Frameworks

Louis R. Redfern; Maxime Ducamp; Megan C. Wasson; Lee Robison; Florencia A. Son; François Xavier Coudert; Omar K. Farha

doi:10.1021/acs.chemmater.0c01922

Isolating the Role of the Node-Linker Bond in the Compression of UiO-66 Metal-Organic Frameworks

Louis R. Redfern, Maxime Ducamp, Megan C. Wasson, Lee Robison, Florencia A. Son, François Xavier Coudert^*, Omar K. Farha

^*Corresponding author for this work

Chemistry

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

31 Scopus citations

Abstract

Understanding the mechanical properties of metal-organic frameworks (MOFs) is essential to the fundamental advancement and practical implementations of porous materials. Recent computational and experimental efforts have revealed correlations between mechanical properties and pore size, topology, and defect density. These results demonstrate the important role of the organic linker in the response of these materials to physical stresses. However, the impact of the coordination bond between the inorganic node and organic linker on the mechanical stability of MOFs has not been thoroughly studied. Here, we isolate the role of this node-linker coordination bond to systematically study the effect it plays in the compression of a series of isostructural MOFs, M-UiO-66 (M = Zr, Hf, or Ce). The bulk modulus (i.e., the resistance to compression under hydrostatic pressure) of each MOF is determined by in situ diamond anvil cell (DAC) powder X-ray diffraction measurements and density functional theory (DFT) simulations. These experiments reveal the distinctive behavior of Ce-UiO-66 in response to pressures under 1 GPa. In situ DAC Raman spectroscopy and DFT calculations support the observed differences in compressibility between Zr-UiO-66 and the Ce analogue. Monitoring changes in bond lengths as a function of pressure through DFT simulations provides a clear picture of those which shorten more drastically under pressure and those which resist compression. We hypothesize that the presence of â10% Ce3+ in the nodes of Ce-UiO-66 may contribute to the weakening of the node-linker coordination, manifesting in the distinct behavior under pressure. This study demonstrates that changes to the node-linker bond can have significant ramifications on the mechanical properties of MOFs.

Original language	English (US)
Pages (from-to)	5864-5871
Number of pages	8
Journal	Chemistry of Materials
Volume	32
Issue number	13
DOIs	https://doi.org/10.1021/acs.chemmater.0c01922
State	Published - Jul 14 2020

Funding

O.K.F. gratefully acknowledges support from the Defense Threat Reduction Agency (HDTRA1-19-1-0007). M.D. and F.-X.C. acknowledge financial support from the Agence Nationale de la Recherche under project \u201CMATAREB\u201D (ANR-18-CE29-0009-01) and access to high-performance computing platforms provided by GENCI grant A0070807069. Portions of this work were performed at GeoSoilEnviroCARS (The University of Chicago, Sector 13), Advanced Photon Source (APS), Argonne National Laboratory. GeoSoilEnviroCARS is supported by the National Science Foundation\u2013Earth Sciences (EAR \u2013 1634415) and Department of Energy\u2013GeoSciences (DE-FG02-94ER14466). This research used resources of the Advanced Photon Source, a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under Contract No. DE-AC02-06CH11357. Use of the GSECARS Raman Lab System was supported by the NSF MRI Proposal (EAR-1531583). This work made use of the IMSERC at Northwestern University, which has received support from the Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF ECCS-1542205), the State of Illinois, and the International Institute for Nanotechnology (IIN). This work made use of the SPID facility of Northwestern University\u2019s NUANCE Center, which has received support from the Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF ECCS-1542205); the MRSEC program (NSF DMR-1720139) at the Materials Research Center; the International Institute for Nanotechnology (IIN); the Keck Foundation; the State of Illinois, through the IIN. This work made use of the Keck-II facility of Northwestern University\u2019s NUANCE Center, which has received support from the Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF ECCS-1542205); the MRSEC program (NSF DMR-1720139) at the Materials Research Center; the International Institute for Nanotechnology (IIN); the Keck Foundation; the State of Illinois, through the IIN. M.C.W. is supported by the NSF Graduate Research Fellowship under grant DGE-1842165.

ASJC Scopus subject areas

General Chemistry
General Chemical Engineering
Materials Chemistry

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10.1021/acs.chemmater.0c01922

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title = "Isolating the Role of the Node-Linker Bond in the Compression of UiO-66 Metal-Organic Frameworks",

abstract = "Understanding the mechanical properties of metal-organic frameworks (MOFs) is essential to the fundamental advancement and practical implementations of porous materials. Recent computational and experimental efforts have revealed correlations between mechanical properties and pore size, topology, and defect density. These results demonstrate the important role of the organic linker in the response of these materials to physical stresses. However, the impact of the coordination bond between the inorganic node and organic linker on the mechanical stability of MOFs has not been thoroughly studied. Here, we isolate the role of this node-linker coordination bond to systematically study the effect it plays in the compression of a series of isostructural MOFs, M-UiO-66 (M = Zr, Hf, or Ce). The bulk modulus (i.e., the resistance to compression under hydrostatic pressure) of each MOF is determined by in situ diamond anvil cell (DAC) powder X-ray diffraction measurements and density functional theory (DFT) simulations. These experiments reveal the distinctive behavior of Ce-UiO-66 in response to pressures under 1 GPa. In situ DAC Raman spectroscopy and DFT calculations support the observed differences in compressibility between Zr-UiO-66 and the Ce analogue. Monitoring changes in bond lengths as a function of pressure through DFT simulations provides a clear picture of those which shorten more drastically under pressure and those which resist compression. We hypothesize that the presence of {\^a}10% Ce3+ in the nodes of Ce-UiO-66 may contribute to the weakening of the node-linker coordination, manifesting in the distinct behavior under pressure. This study demonstrates that changes to the node-linker bond can have significant ramifications on the mechanical properties of MOFs.",

author = "Redfern, {Louis R.} and Maxime Ducamp and Wasson, {Megan C.} and Lee Robison and Son, {Florencia A.} and Coudert, {Fran{\c c}ois Xavier} and Farha, {Omar K.}",

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AU - Redfern, Louis R.

AU - Ducamp, Maxime

AU - Wasson, Megan C.

AU - Robison, Lee

AU - Son, Florencia A.

AU - Coudert, François Xavier

AU - Farha, Omar K.

PY - 2020/7/14

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AB - Understanding the mechanical properties of metal-organic frameworks (MOFs) is essential to the fundamental advancement and practical implementations of porous materials. Recent computational and experimental efforts have revealed correlations between mechanical properties and pore size, topology, and defect density. These results demonstrate the important role of the organic linker in the response of these materials to physical stresses. However, the impact of the coordination bond between the inorganic node and organic linker on the mechanical stability of MOFs has not been thoroughly studied. Here, we isolate the role of this node-linker coordination bond to systematically study the effect it plays in the compression of a series of isostructural MOFs, M-UiO-66 (M = Zr, Hf, or Ce). The bulk modulus (i.e., the resistance to compression under hydrostatic pressure) of each MOF is determined by in situ diamond anvil cell (DAC) powder X-ray diffraction measurements and density functional theory (DFT) simulations. These experiments reveal the distinctive behavior of Ce-UiO-66 in response to pressures under 1 GPa. In situ DAC Raman spectroscopy and DFT calculations support the observed differences in compressibility between Zr-UiO-66 and the Ce analogue. Monitoring changes in bond lengths as a function of pressure through DFT simulations provides a clear picture of those which shorten more drastically under pressure and those which resist compression. We hypothesize that the presence of â10% Ce3+ in the nodes of Ce-UiO-66 may contribute to the weakening of the node-linker coordination, manifesting in the distinct behavior under pressure. This study demonstrates that changes to the node-linker bond can have significant ramifications on the mechanical properties of MOFs.

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Isolating the Role of the Node-Linker Bond in the Compression of UiO-66 Metal-Organic Frameworks

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