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

doi:10.1021/acs.chemmater.1c02999

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

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

23 Scopus citations

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.

Original language	English
Pages (from-to)	9285-9294
Number of pages	10
Journal	Chemistry of Materials
Volume	33
Issue number	23
DOIs	https://doi.org/10.1021/acs.chemmater.1c02999
State	Published - Dec 14 2021
Externally published	Yes

Funding

This work was supported by the Department of Energy, National Nuclear Security Administration, under award number DE-NA0003763. S.E.G., H.T., and P.C.B. were funded under this award until December 2020 and then by University funds. S.L.H. acknowledges support from the U.S. Department of Energy National Nuclear Security Administration Stewardship Science Graduate Fellowship 20 (DOE NNSA SSGF) under award number DE-NA0003960. The authors thank Debmalya Ray for computational support and advice. The authors acknowledge the Center for Sustainable Energy at Notre Dame (ND Energy) Materials Characterization Facilities for the use of the Bruker D8 Advance Davinci powder X-ray diffractometer and NRS-5100 Jasco confocal Raman microscope. The authors thank Prof. Michael Wiescher for making available the facilities of the Notre Dame Nuclear Science Laboratory, which is supported by the U.S. National Science Foundation through grant Phys-0758100, and Prof. Ian Carmichael for making available the facilities of the Notre Dame Radiation Laboratory, which is supported by DOE BES through grant DE-FC02-04ER15533. This contribution is NDRL-5329 from the Notre Dame Radiation Laboratory.

Funders	Funder number
DOE NNSA SSGF	DE-NA0003960
U.S. Department of Energy National Nuclear Security Administration
National Science Foundation	Phys-0758100
National Science Foundation
U.S. Department of Energy
Basic Energy Sciences	DE-FC02-04ER15533
Basic Energy Sciences
National Nuclear Security Administration	DE-NA0003763
National Nuclear Security Administration

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Fairley, M., Gilson, S. E., Hanna, S. L., Mishra, A., Knapp, J. G., Idrees, K. B., Chheda, S., Traustason, H., Islamoglu, T., Burns, P. C., Gagliardi, L., Farha, O. K., & Laverne, J. A. (2021). Linker Contribution toward Stability of Metal-Organic Frameworks under Ionizing Radiation. Chemistry of Materials, 33(23), 9285-9294. https://doi.org/10.1021/acs.chemmater.1c02999

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title = "Linker Contribution toward Stability of Metal-Organic Frameworks under Ionizing Radiation",

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.",

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

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AU - Fairley, Melissa

AU - Gilson, Sara E.

AU - Hanna, Sylvia L.

AU - Mishra, Anushrut

AU - Knapp, Julia G.

AU - Idrees, Karam B.

AU - Chheda, Saumil

AU - Traustason, Hrafn

AU - Islamoglu, Timur

AU - Burns, Peter C.

AU - Gagliardi, Laura

AU - Farha, Omar K.

AU - Laverne, Jay A.

PY - 2021/12/14

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N2 - 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.

AB - 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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VL - 33

SP - 9285

EP - 9294

JO - Chemistry of Materials

JF - Chemistry of Materials

IS - 23

ER -

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

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