Pair your accounts.

Export articles to Mendeley

Get article recommendations from ACS based on references in your Mendeley library.

Pair your accounts.

Export articles to Mendeley

Get article recommendations from ACS based on references in your Mendeley library.

You’ve supercharged your research process with ACS and Mendeley!

Click to create an ACS ID

Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

Your Mendeley pairing has expired. Please reconnect
ACS Publications. Most Trusted. Most Cited. Most Read
My Activity

Role of Metal Selection in the Radiation Stability of Isostructural M-UiO-66 Metal–Organic Frameworks

Cite this: Chem. Mater. 2022, 34, 18, 8403–8417
Publication Date (Web):September 9, 2022
Copyright © 2022 American Chemical Society

    Article Views





    Other access options
    Supporting Info (3)»


    Abstract Image

    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. 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.

    Read this article

    To access this article, please review the available access options below.

    Get instant access

    Purchase Access

    Read this article for 48 hours. Check out below using your ACS ID or as a guest.


    Access through Your Institution

    You may have access to this article through your institution.

    Your institution does not have access to this content. You can change your affiliated institution below.

    Supporting Information

    Jump To

    The Supporting Information is available free of charge at

    • MOF irradiation literature, irradiation methodologies, dose calculations, plutonium experimental design, characterization by PXRD, DRIFTS, Raman spectroscopy, PDF, pore size distributions, computational data, and supporting content for the metal trend discussion (PDF)

    • Optimized structure package (ZIP)

    • Computational input/output files (ZIP)

    Terms & Conditions

    Most electronic Supporting Information files are available without a subscription to ACS Web Editions. Such files may be downloaded by article for research use (if there is a public use license linked to the relevant article, that license may permit other uses). Permission may be obtained from ACS for other uses through requests via the RightsLink permission system:

    Cited By

    This article is cited by 12 publications.

    1. Martin Glavinović, Nancy Chou, Fisher B. Hall, Kevin L. Lesage, Benjamin S. Gelfand, Denis M. Spasyuk, Jian-Bin Lin, Robert A. Marriott, George K. H. Shimizu. Measuring Diffusion Kinetics with Zero-Length Chromatography in Isomorphous and Ultramicroporous Phosphonate Metal–Organic Frameworks. Chemistry of Materials 2024, 36 (5) , 2269-2278.
    2. Xiaokang Wang, Hongyan Liu, Meng Sun, Haoyang Wang, Xueying Feng, Wenmiao Chen, Xiang Feng, Weidong Fan, Daofeng Sun. Thiadiazole-Functionalized Th/Zr-UiO-66 for Efficient C2H2/CO2 Separation. ACS Applied Materials & Interfaces 2024, 16 (6) , 7819-7825.
    3. Mohammad Shohel, A. Kirstin Sockwell, Amy E. Hixon, May Nyman. Plutonium and Cerium Perrhenate/Pertechnetate Coordination Polymers and Frameworks. Inorganic Chemistry 2024, 63 (4) , 2044-2052.
    4. Ana Arteaga, Aaron D. Nicholas, Michael A. Sinnwell, Bruce K. McNamara, Edgar C. Buck, Robert G. Surbella, III. Expanding the Transuranic Metal–Organic Framework Portfolio: The Optical Properties of Americium(III) MOF-76. Inorganic Chemistry 2023, 62 (51) , 21036-21043.
    5. Julie Nguyen-Sadassivame, Anaïs Massaloux, Jérémy Dhainaut, Riad Sarraf, Philippe Chantereau, Laurent Cantrel, Thierry Loiseau, Christophe Volkringer, Philippe Nérisson. Test Bench Development and Application to a Parametric Experimental Study on the Dynamic Adsorption Capacity of Noble Gases (Kr, Xe) in the Metal–Organic Framework HKUST-1. Industrial & Engineering Chemistry Research 2023, 62 (48) , 20727-20740.
    6. Sara E. Skrabalak, Ramanathan Vaidhyanathan. The Chemistry of Metal Organic Framework Materials. Chemistry of Materials 2023, 35 (15) , 5713-5722.
    7. Songzhu Qi, Shunshun Xiong, Liangping Xiong, Hao Li, Boyu Liu, Yi Liu, Ke Xiong, Heng Yan, Kai Lv, Hewen Liu, Sheng Hu. Crystalline versus Amorphous: High-Performance Hafnium Phosphonate Framework for the Separation of Uranium and Transuranium Elements. Inorganic Chemistry 2023, 62 (28) , 10881-10886.
    8. Yu Ju, Zi-Jian Li, Jie Qiu, Xiaoyun Li, Junpu Yang, Zhi-Hui Zhang, Ming-Yang He, Jian-Qiang Wang, Jian Lin. Adsorption and Detection of Iodine Species by a Thorium-Based Metal–Organic Framework. Inorganic Chemistry 2023, 62 (21) , 8158-8165.
    9. Xingzheng Chen, Gan Li, Songtao Xiao, Wenjuan Xue, Xudong Zhao, Qingyuan Yang. Efficient Capture of Th(IV) and U(VI) by Radiation-Resistant Oxygen-Rich Ion Traps Based on a Metal–Organic Framework. ACS Applied Materials & Interfaces 2023, 15 (20) , 25029-25040.
    10. Changjiang Hu, Liwei Cheng, Liheng Zhou, Zhiwen Jiang, Pingping Gan, Shuiyan Cao, Qiuhao Li, Chong Chen, Yunlong Wang, Mehran Mostafavi, Shuao Wang, Jun Ma. Radiolytic Water Splitting Sensitized by Nanoscale Metal–Organic Frameworks. Journal of the American Chemical Society 2023, 145 (9) , 5578-5588.
    11. Xiaofan Ding, Songtao Xiao, Ting Wang, Zucao Zeng, Xudong Zhao, Qingyuan Yang. Stability of metal-organic frameworks towards β-ray irradiation: Role of organic groups. Microporous and Mesoporous Materials 2023, 354 , 112533.
    12. Zhaofa Zheng, Huangjie Lu, Huiliang Hou, Yaoyao Bai, Jie Qiu, Xiaofeng Guo, Jian‐Qiang Wang, Jian Lin. Stepwise Crystallization of Millimeter Scale Thorium Cluster Single Crystals as a Bifunctional Platform for X‐ray Detection and Shielding. Small 2023, 19 (10) , 2206782.