journal article·2021-12-14Open access

Linker Contribution toward Stability of Metal–Organic Frameworks under Ionizing Radiation

Melissa Fairley, Sara E. Gilson, Sylvia L. Hanna, Anushrut Mishra, Julia G. Knapp, Karam B. Idrees, Saumil Chheda, Hrafn Traustason, Timur Islamoglu, Peter C. Burns, Laura Gagliardi, Omar K. Farha, Jay A. LaVerne

Chemistry of Materials· Volume 33· Issue 23

Abstract

The effects of radiation on a series of UiO derivative metal–organic frameworks (MOFs) that contain the same zirconium hexamer node and similar organic linkers, UiO-66, UiO-66–NH2, UiO-66–OH, and NU-403, were examined using γ-rays and 5 MeV He ions. UiO-66, UiO-66–NH2, and UiO-66–OH contain aromatic linkers and are significantly more stable to radiation than NU-403. Of these, UiO-66 is the most radiation resistant, displaying crystalline features up to 47 MGy of He-ion irradiation. MOFs containing aromatic linkers functionalized by electron-donating groups, UiO-66–NH2 and UiO-66–OH, retained crystalline features up to 19 MGy. NU-403 contains aliphatic rings and is the least radiation-resistant MOF studied here. NU-403 exhibits small changes in infrared spectra upon 3 MGy of γ-irradiation and significant damage upon 10 MGy of He-ion irradiation. Diffraction data revealed radiation-induced defect formation. Structural locations of radiation-induced breakdown were interrogated experimentally and via density functional theory. The results indicated changes in the carboxylate (−OCO) of the linker and μ3-OH vibrational modes, suggesting that introduction of an aliphatic linker into the MOF renders the connection between the linker and metal node most susceptible to radiation damage. This study reveals that the choice of the linker is crucial in designing a radiation-resistant MOF.
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Research context

OpenAlex topics: Metal-Organic Frameworks: Synthesis and Applications · Radioactive element chemistry and processing · X-ray Diffraction in Crystallography

SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.

Affiliations

Radiation Laboratory, University of Notre Dame, Notre Dame, Indiana 46556, United States

Department of Chemistry and Biochemistry, University of Notre Dame, Notre Dame, Indiana 46556, United States

Department of Chemistry and International Institute of Nanotechnology, Northwestern University, Evanston, Illinois 60208, United States

Department of Chemical Engineering and Materials Science, Chemical Theory Center, Minnesota Supercomputing Institute, University of Minnesota-Twin Cities, Minneapolis, Minnesota 55455, United States

Department of Civil and Environmental Engineering and Earth Sciences, University of Notre Dame, Notre Dame, Indiana 46556, United States

Department of Chemistry, Pritzker School of Molecular Engineering, Chicago Center for Theoretical Chemistry, University of Chicago, Chicago, Illinois 60637, United States

Department of Chemical and Biological Engineering, Northwestern University, 2145 Sheridan Road, Evanston, Illinois 60208, United States

Department of Physics, University of Notre Dame, Notre Dame, Indiana 46556, United States

Funding

National Nuclear Security Administration

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