Abstract
Metal-organic frameworks (MOFs) NU-1000 and UiO-66 are herein exposed to two different gamma irradiation doses and dose rates and analyzed to determine the structural features that affect their stability in these environments. MOFs have shown promise for the capture and sensing of off-gases at civilian nuclear energy reprocessing sites, nuclear waste repositories, and nuclear accident locations. However, little is understood about the structural features of MOFs that contribute to their stability levels under the ionizing radiation conditions present at such sites. This study is the first of its kind to explore the structural features of MOFs that contribute to their radiolytic stability. Both NU-1000 and UiO-66 are MOFs that contain Zr metal-centers with the same metal absorption cross section. However, the two MOFs exhibit different linker connectivities, linker aromaticities, node densities, node connectivities, and interligand separations. In this study, NU-1000 and UiO-66 were exposed to high (423.3 Gy/min, 23 min, and 37 s) and low (0.78 Gy/min, 4320 min) dose rates of 60Co gamma irradiation. NU-1000 displayed insignificant radiation damage under both dose rates due to its high linker connectivity, low node density, and low node connectivity. However, low radiation dose rates caused considerable damage to UiO-66, a framework with lower aromaticity and smaller interligand separation. Results suggest that chronic, low-radiation environments are more detrimental to Zr MOF stability than acute, high-radiation conditions.
| Original language | English (US) |
|---|---|
| Pages (from-to) | 7520-7526 |
| Number of pages | 7 |
| Journal | Industrial and Engineering Chemistry Research |
| Volume | 59 |
| Issue number | 16 |
| DOIs | |
| State | Published - Apr 22 2020 |
Funding
O.K.F. and S.L.H. acknowledge support from the U.S. Department of Energy, National Nuclear Security Administration, under Award Number DE-NA0003763. S.L.H. gratefully acknowledges support from the International Institute for Nanotechnology (IIN) Ryan Fellowship and the U.S. Department of Energy National Nuclear Security Administration Stewardship Science Graduate Fellowship (DOE NNSA SSGF). Additionally, we thank the Integrated Molecular Structure Education and Research Center (IMSERC) and Electron Probe Instrumentation Center (EPIC) facilities at Northwestern University where PXRD, SEM, and NMR studies were performed. T.M.N., D.X.R., and D.J.H. acknowledge support from the Center for Understanding and Control of Acid Gas-Induced Evolution of Materials for Energy (UNCAGE-ME), an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences under Award Number DE-SC0012577. Sandia National Laboratories is a multi-mission laboratory managed and operated by National Technology & Engineering Solutions of Sandia, LLC, a wholly owned subsidiary of Honeywell International Inc., for the U.S. Department of Energy’s National Nuclear Security Administration under contract DE-NA0003525. The views expressed in the article do not necessarily represent the views of the U.S. Department of Energy or the United States Government. Department of Energy, National Nuclear Security Administration, under Award Number DE-NA0003763. S.L.H. gratefully acknowledges support from the International Institute for Nanotechnology (IIN) Ryan Fellowship and the U.S. Department of Energy National Nuclear Security Administration Stewardship Science Graduate Fellowship (DOE NNSA SSGF). Additionally, we thank the Integrated Molecular Structure Education and Research Center (IMSERC) and Electron Probe Instrumentation Center (EPIC) facilities at Northwestern University where PXRD, SEM, and NMR studies were performed. T.M.N., D.X.R., and D.J.H. acknowledge support from the Center for Understanding and Control of Acid Gas-Induced Evolution of Materials for Energy (UNCAGE-ME), an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences under Award Number DE-SC0012577. Sandia National Laboratories is a multi-mission laboratory managed and operated by National Technology & Engineering Solutions of Sandia, LLC, a wholly owned subsidiary of Honeywell International Inc., for the U.S. Department of Energy?s National Nuclear Security Administration under contract DE-NA0003525. The views expressed in the article do not necessarily represent the views of the U.S. Department of Energy or the United States Government.
ASJC Scopus subject areas
- General Chemistry
- General Chemical Engineering
- Industrial and Manufacturing Engineering
