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Dual Modification of MOFs Improves Dispersion and Ionic Conductivity of Mixed Matrix Membranes

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    Dual Modification of MOFs Improves Dispersion and Ionic Conductivity of Mixed Matrix Membranes
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    ACS Materials Letters

    Cite this: ACS Materials Lett. 2024, 6, 1, 159–164
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    https://doi.org/10.1021/acsmaterialslett.3c01304
    Published December 11, 2023
    Copyright © 2023 American Chemical Society
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    Abstract

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    Nonaqueous redox flow batteries (NARFBs) are a promising class of energy storage devices, but the lack of a chemically stable, conductive membrane that exhibits size-selectivity over redox-active species prevents their broader implementation. Recently, metal–organic frameworks (MOFs) have been implemented into mixed-matrix membranes (MMMs) for NARFBs, but the effects of the MOF linker functionality on membrane properties are not well-understood. In this work, we develop a series of MOF-based MMMs by blending postsynthetically modified variants of UiO-66-NH2 with poly(ethylene-co-vinyl acetate). The modification of UiO-66-NH2 with sulfate groups initially resulted in poor dispersion throughout the MMMs, but when dual-modified with poly(N-isopropylacrylamide), MOF dispersion throughout the MMM was improved, and ionic conductivity was significantly higher than the UiO-66-NH2 MMMs. Furthermore, the dual-modified MMMs demonstrated excellent size-selectivity by blocking redox active species transport. This work demonstrates a synergy between the MOF functional groups to improve MMM properties critical for the development of practical NARFBs.

    Copyright © 2023 American Chemical Society

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    • Experimental details, synthesis, and relevant characterization by FTIR, 1H NMR, EDX, and Raman Spectroscopy, in addition to PXRD, N2 sorption, GPC, SEM, and calibration curve for diffusion studies (PDF)

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    This article is cited by 6 publications.

    1. Qi-Jun Sun, Wen-Tao Guo, Shu-Zheng Liu, Xin-Gui Tang, Vellaisamy AL Roy, Xin-Hua Zhao. Rise of Metal–Organic Frameworks: From Synthesis to E-Skin and Artificial Intelligence. ACS Applied Materials & Interfaces 2024, 16 (35) , 45830-45860. https://doi.org/10.1021/acsami.4c07732
    2. Ashley N. Mapile, Michael A. LeRoy, Kevin Fabrizio, Lawrence F. Scatena, Carl K. Brozek. The Surface of Colloidal Metal–Organic Framework Nanoparticles Revealed by Vibrational Sum Frequency Scattering Spectroscopy. ACS Nano 2024, 18 (20) , 13406-13414. https://doi.org/10.1021/acsnano.4c03758
    3. Michael A. LeRoy, Anton S. Perera, Shasanka Lamichhane, Ashley N. Mapile, Faiqa Khaliq, Kentaro Kadota, Xianghui Zhang, Su Ha, Racheal Fisher, Di Wu, Chad Risko, Carl K. Brozek. Colloidal Stability and Solubility of Metal–Organic Framework Particles. Chemistry of Materials 2024, 36 (8) , 3673-3682. https://doi.org/10.1021/acs.chemmater.3c03191
    4. Tianxing Yuan, Shaotian Qi, Lingzhi Ye, Yanqin Zhao, Yingqiao Jiang, Zemin Feng, Jing Zhu, Lei Dai, Ling Wang, Zhangxing He. Metal-organic frameworks-based materials: A feasible path for redox flow battery. Coordination Chemistry Reviews 2025, 531 , 216503. https://doi.org/10.1016/j.ccr.2025.216503
    5. Chuanqi Shen, Jin Liu, Dong-Hai Zhang, Qing Li, Hui Zhang, Zhu Zhuo, Wei Wang, Zi-Ang Nan, Luyao Liu, You-Gui Huang. Heterometallic metal-organic cage doped PEO composite electrolyte for solid lithium ion battery. Journal of Molecular Structure 2025, 1321 , 140063. https://doi.org/10.1016/j.molstruc.2024.140063
    6. Ruibi Zhao, Zhixian Wang, Wenjing Li, Zhigang Zhang, Hongyan Xu, Huaiqing Zhao. Cu active centers anchored on Ce-MOFs as an efficient heterogenous catalyst for the selective oxidation of alcohols to acids. Journal of Materials Science 2025, 60 (2) , 861-880. https://doi.org/10.1007/s10853-024-10537-3
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    ACS Materials Letters

    Cite this: ACS Materials Lett. 2024, 6, 1, 159–164
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acsmaterialslett.3c01304
    Published December 11, 2023
    Copyright © 2023 American Chemical Society
    Request reuse permissions

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