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

Journal Article · · Chemistry of Materials
 [1];  [2];  [3];  [4];  [3];  [3];  [4];  [2];  [3];  [2];  [5];  [3];  [2]
  1. Univ. of Notre Dame, IN (United States); University of Notre Dame
  2. Univ. of Notre Dame, IN (United States)
  3. Northwestern Univ., Evanston, IL (United States)
  4. Univ. of Minnesota, Minneapolis, MN (United States)
  5. Univ. of Chicago, IL (United States)
+ Show Author Affiliations
Here, 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.
Research Organization:
Los Alamos National Laboratory (LANL), Los Alamos, NM (United States); Univ. of Notre Dame, IN (United States)
Sponsoring Organization:
USDOE National Nuclear Security Administration (NNSA); USDOE Office of Science (SC)
Grant/Contract Number:
89233218CNA000001; NA0003763
OSTI ID:
1832116
Alternate ID(s):
OSTI ID: 1885743
Report Number(s):
LA-UR-21-27690
Journal Information:
Chemistry of Materials, Journal Name: Chemistry of Materials Journal Issue: 23 Vol. 33; ISSN 0897-4756
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English

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Related Subjects

36 MATERIALS SCIENCE
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY
Irradiation
Metal organic frameworks
Radiation
Raman spectroscopy
Stability