Robust and versatile metal–organic frameworks (MOFs) have emerged as sophisticated scaffolds to meet the critical needs of the nuclear community, but their performance depends on their underexplored structural integrities in high- radiation fields. The contributions of selected metal nodes in the radiation stability of MOFs within the isostructural M-UiO-66 series (where M = Zr, Ce, Hf, Th, and Pu; Zr-UiO-66 experiments were executed in a previous work) have been determined. Ce-, Hf-, and Th-UiO-66 MOF samples were irradiated via gamma and He-ion methodologies to obtain doses up to 3 MGy and 85 MGy, respectively, the latter strikingly higher than that obtained in most other studies. Appreciable self-irradiation constituted the total absorbed doses, up to 31 MGy of the gamma-irradiated Pu-UiO-66 samples. Structural degradation was ascertained by powder X-ray diffraction, X-ray total scattering, vibrational spectroscopy, and, where possible, N2 physisorption isotherms. Diffuse reflectance infrared Fourier transform spectroscopy provided atomic-level mechanistic insights to reveal that the node-linker connection was most susceptible to radiation damage. Density functional theory calculations were performed on cluster models to evaluate the binding energy of the linkers to each metal node. Here, while the isostructures disclosed the same breakdown signatures, distinct radiation sensitivity as a function of metal selection was evident and followed the trend Hf-UiO-66 ~ Zr-UiO-66 > Th-UiO-66 > Pu-UiO-66 > Ce-UiO-66. We anticipate that these endeavors will contribute to the rational design of radiation-resistant materials for targeted applications.
Hastings, Ashley M., et al. "Role of Metal Selection in the Radiation Stability of Isostructural M-UiO-66 Metal–Organic Frameworks." Chemistry of Materials, vol. 34, no. 18, Sep. 2022. https://doi.org/10.1021/acs.chemmater.2c02170
Hastings, Ashley M., Fairley, Melissa, Wasson, Megan C., Campisi, Dario, Sarkar, Arup, Emory, Zoë C., Brunson, Kieran, Fast, Dylan B., Islamoglu, Timur, Nyman, May, Burns, Peter C., Gagliardi, Laura, Farha, Omar K., Hixon, Amy E., & LaVerne, Jay A. (2022). Role of Metal Selection in the Radiation Stability of Isostructural M-UiO-66 Metal–Organic Frameworks. Chemistry of Materials, 34(18). https://doi.org/10.1021/acs.chemmater.2c02170
Hastings, Ashley M., Fairley, Melissa, Wasson, Megan C., et al., "Role of Metal Selection in the Radiation Stability of Isostructural M-UiO-66 Metal–Organic Frameworks," Chemistry of Materials 34, no. 18 (2022), https://doi.org/10.1021/acs.chemmater.2c02170
@article{osti_1886847,
author = {Hastings, Ashley M. and Fairley, Melissa and Wasson, Megan C. and Campisi, Dario and Sarkar, Arup and Emory, Zoë C. and Brunson, Kieran and Fast, Dylan B. and Islamoglu, Timur and Nyman, May and others},
title = {Role of Metal Selection in the Radiation Stability of Isostructural M-UiO-66 Metal–Organic Frameworks},
annote = {Robust and versatile metal–organic frameworks (MOFs) have emerged as sophisticated scaffolds to meet the critical needs of the nuclear community, but their performance depends on their underexplored structural integrities in high- radiation fields. The contributions of selected metal nodes in the radiation stability of MOFs within the isostructural M-UiO-66 series (where M = Zr, Ce, Hf, Th, and Pu; Zr-UiO-66 experiments were executed in a previous work) have been determined. Ce-, Hf-, and Th-UiO-66 MOF samples were irradiated via gamma and He-ion methodologies to obtain doses up to 3 MGy and 85 MGy, respectively, the latter strikingly higher than that obtained in most other studies. Appreciable self-irradiation constituted the total absorbed doses, up to 31 MGy of the gamma-irradiated Pu-UiO-66 samples. Structural degradation was ascertained by powder X-ray diffraction, X-ray total scattering, vibrational spectroscopy, and, where possible, N2 physisorption isotherms. Diffuse reflectance infrared Fourier transform spectroscopy provided atomic-level mechanistic insights to reveal that the node-linker connection was most susceptible to radiation damage. Density functional theory calculations were performed on cluster models to evaluate the binding energy of the linkers to each metal node. Here, while the isostructures disclosed the same breakdown signatures, distinct radiation sensitivity as a function of metal selection was evident and followed the trend Hf-UiO-66 ~ Zr-UiO-66 > Th-UiO-66 > Pu-UiO-66 > Ce-UiO-66. We anticipate that these endeavors will contribute to the rational design of radiation-resistant materials for targeted applications.},
doi = {10.1021/acs.chemmater.2c02170},
url = {https://www.osti.gov/biblio/1886847},
journal = {Chemistry of Materials},
issn = {ISSN 0897-4756},
number = {18},
volume = {34},
place = {United States},
publisher = {American Chemical Society (ACS)},
year = {2022},
month = {09}}
Ziegler, James F.; Ziegler, M. D.; Biersack, J. P.
Nuclear Instruments and Methods in Physics Research Section B: Beam Interactions with Materials and Atoms, Vol. 268, Issue 11-12https://doi.org/10.1016/j.nimb.2010.02.091