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

preprint
submitted on 11.05.2020 and posted on 13.05.2020 by Louis Redfern, Maxime Ducamp, Megan C. Wasson, Lee Robison, Florencia Son, François-Xavier Coudert, Omar Farha
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 distinctive behavior of Ce-UiO-66 in response to pressures under one 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. This study demonstrates that changes to the node–linker bond can have significant ramifications on the mechanical properties of MOFs.

Funding

HDTRA1-19-1-0007

ANR-18-CE29-0009-01

A0070807069

History

Email Address of Submitting Author

o-farha@northwestern.edu

Institution

Northwestern University

Country

United States

ORCID For Submitting Author

0000-0002-9904-9845

Declaration of Conflict of Interest

No conflict of interest

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