@article{27ed2f1ab04249f8825acd297a58d729,
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.}",
note = "Funding Information: 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. Funding Information: 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. Publisher Copyright: {\textcopyright} ",
year = "2021",
month = dec,
day = "14",
doi = "10.1021/acs.chemmater.1c02999",
language = "English (US)",
volume = "33",
pages = "9285--9294",
journal = "Chemistry of Materials",
issn = "0897-4756",
publisher = "American Chemical Society",
number = "23",
}