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Flexibility of a Metal–Organic Framework Enhances Gas Separation and Enables Quantum Sieving
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    Flexibility of a Metal–Organic Framework Enhances Gas Separation and Enables Quantum Sieving
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    • Omid T. Qazvini
      Omid T. Qazvini
      MacDiarmid Institute for Advanced Materials and Nanotechnology, School of Fundamental Sciences, Massey University, Palmerston North 4410, New Zealand
      Department of Chemical Engineering and Analytical Science, University of Manchester, Oxford Road, Manchester M13 9PL, U.K.
    • Victoria-Jayne Scott
      Victoria-Jayne Scott
      MacDiarmid Institute for Advanced Materials and Nanotechnology, School of Fundamental Sciences, Massey University, Palmerston North 4410, New Zealand
    • Linda Bondorf
      Linda Bondorf
      Max Planck Institute for Intelligent Systems, Heisenbergstraße 3, 70569 Stuttgart, Germany
    • Maxime Ducamp
      Maxime Ducamp
      Chimie ParisTech, PSL Research University, CNRS, Institut de Recherche de Chimie Paris, 75005 Paris, France
    • Michael Hirscher
      Michael Hirscher
      Max Planck Institute for Intelligent Systems, Heisenbergstraße 3, 70569 Stuttgart, Germany
    • François-Xavier Coudert
      François-Xavier Coudert
      Chimie ParisTech, PSL Research University, CNRS, Institut de Recherche de Chimie Paris, 75005 Paris, France
    • Shane G. Telfer*
      Shane G. Telfer
      MacDiarmid Institute for Advanced Materials and Nanotechnology, School of Fundamental Sciences, Massey University, Palmerston North 4410, New Zealand
      *Email: [email protected]
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    Chemistry of Materials

    Cite this: Chem. Mater. 2021, 33, 22, 8886–8894
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    https://doi.org/10.1021/acs.chemmater.1c03170
    Published November 2, 2021
    Copyright © 2021 American Chemical Society

    Abstract

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    Flexible metal–organic frameworks (MOFs) undergo reversible structural transformations triggered by external stimuli. An interesting feature of some MOFs is their ability to flex in response to specific guests, which can enable selective separation. Here, we introduce MUF-15-OMe ([Co63-OH)2(ipa-OMe)5(H2O)4]), a variant of MUF-15 that comprises hexanuclear cobalt(II) clusters connected by 5-methoxyisophthalate (ipa-OMe) ligands. MUF-15 itself has isophthalate linkers and is inflexible upon uptake of common gases. On the other hand, MUF-15-OMe flexes upon the uptake of gases such as CO2 and C2 hydrocarbons at pressures less than 1 bar, as revealed by distinct steps in its gas adsorption isotherms. Computational analysis showed that the underlying mechanism involves partial detachment of one of the carboxyl groups of the framework linkers. The gas pressure required to induce framework dynamics can be tuned by replacing some of the ipa-OMe by isophthalate ligands in multivariate frameworks. The flexing of MUF-15-OMe opens up space for the adsorption of specific additional gas molecules. This enhances the separation of CO2 and N2 and enables the differentiation of H2 and D2 by quantum sieving. By providing a clear illustration of how flexibility allows the discrimination of gas mixtures, this study underpins the use of dynamic MOFs for challenging separations.

    Copyright © 2021 American Chemical Society

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    Supporting Information

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    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.chemmater.1c03170.

    • TG curves, PXRD patterns, additional isotherm data, dual-site Langmuir–Freundlich isotherm model fitting, isosteric heat of adsorption calculation, BET surface area calculations, simulated and experimental breakthrough curves, calculation details, and additional isotope adsorption plots (PDF)

    • Crystallographic data for MUF-15-OMe (CCDC 2055679) (CIF)

    • Calculation files (ZIP)

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    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: http://pubs.acs.org/page/copyright/permissions.html.

    Cited By

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    This article is cited by 14 publications.

    1. Hilal Daglar, Seda Keskin, Randall Q. Snurr. Exploring the Effect of Framework Flexibility on Water Adsorption in the Metal–Organic Framework NbOFFIVE-1-Ni Using Molecular Modeling. The Journal of Physical Chemistry C 2024, 128 (44) , 18913-18922. https://doi.org/10.1021/acs.jpcc.4c04486
    2. Christopher Bachetzky, Jhonatan Luiz Fiorio, Mariia Maliuta, Tobias Bode, Jan-Ole Joswig, Irena Senkovska, Thomas Heine, Stefan Kaskel, Eike Brunner. Adsorption of Xenon, Krypton, and Their Mixture on the Flexible Metal–Organic Framework DUT-8(Ni). The Journal of Physical Chemistry C 2024, 128 (16) , 6997-7006. https://doi.org/10.1021/acs.jpcc.4c01796
    3. Niyaz Cakan, Abduselam Abubeker Issa, Hamza Alsalman, Emin Aliyev, Enes Ibrahim Duden, Kubra Gurcan Bayrak, Mujdat Caglar, Servet Turan, Mustafa Erkartal, Unal Sen. Enhancing the Properties of Yttria-Stabilized Zirconia Composites with Zeolitic Imidazolate Framework-Derived Nanocarbons. ACS Applied Materials & Interfaces 2023, 15 (50) , 58931-58939. https://doi.org/10.1021/acsami.3c15359
    4. Filip Formalik, Michael Fischer, Bogdan Kuchta. Correlating Phonons and Deformations: A Method for Structural Phase Transformation Analysis in Metal–Organic Frameworks. Crystal Growth & Design 2023, 23 (12) , 8962-8971. https://doi.org/10.1021/acs.cgd.3c01013
    5. Arijit Halder, Ryan A. Klein, Sarah Shulda, Gavin A. McCarver, Philip A. Parilla, Hiroyasu Furukawa, Craig M. Brown, C. Michael McGuirk. Multivariate Flexible Framework with High Usable Hydrogen Capacity in a Reduced Pressure Swing Process. Journal of the American Chemical Society 2023, 145 (14) , 8033-8042. https://doi.org/10.1021/jacs.3c00344
    6. Benjamin A. Trump, Omid T. Qazvini, Seok J. Lee, Elnaz Jangodaz, Wei Zhou, Craig M. Brown, Shane G. Telfer. Flexing of a Metal–Organic Framework upon Hydrocarbon Adsorption: Atomic Level Insights from Neutron Scattering. Chemistry of Materials 2023, 35 (3) , 1387-1394. https://doi.org/10.1021/acs.chemmater.2c03450
    7. Jan Berger, Andreas Schneemann, Inke Hante, Yuan Jing, Jack D. Evans, Yuh Hijikata, Jenny Pirillo, Takashi Toyao, Ken-ichi Shimizu, Shin-ichiro Noro, Gregor Kieslich, Roland A. Fischer. Designing Adsorptive Gating via Linker Side-Chain Functionalization in a Honeycomb-MOF. The Journal of Physical Chemistry C 2022, 126 (30) , 12755-12764. https://doi.org/10.1021/acs.jpcc.2c01979
    8. Li-Na Ma, Gang-Ding Wang, Lei Hou, Zhonghua Zhu, Yao-Yu Wang. Efficient One-Step Purification of C1 and C2 Hydrocarbons over CO2 in a New CO2-Selective MOF with a Gate-Opening Effect. ACS Applied Materials & Interfaces 2022, 14 (23) , 26858-26865. https://doi.org/10.1021/acsami.2c06744
    9. H.J. Xu, P.Y. Hu. Progress on fundamentals of adsorption transport of metal-organic frameworks materials and sustainable applications for water harvesting and carbon capture. Journal of Cleaner Production 2023, 393 , 136253. https://doi.org/10.1016/j.jclepro.2023.136253
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    11. Wei Gao, Cui‐Li Wang, Le Chen, Cai‐Yong Zhu, Peng Li, Ji‐Yang Li, Jie‐Ping Liu, Xiu‐Mei Zhang. Bifunctional metal–organic frameworks afforded by postsynthetic modification for efficient cycloaddition of CO 2 and epoxides. Applied Organometallic Chemistry 2022, 36 (9) https://doi.org/10.1002/aoc.6810
    12. Qiang Zhang, Lei Zhou, Puxu Liu, Libo Li, Shan-Qing Yang, Zhuo-Fei Li, Tong-Liang Hu. Integrating tri-mural nanotraps into a microporous metal-organic framework for C2H2/CO2 and C2H2/C2H4 separation. Separation and Purification Technology 2022, 296 , 121404. https://doi.org/10.1016/j.seppur.2022.121404
    13. Pietro Rassu, Xiaojie Ma, Bo Wang. Engineering of catalytically active sites in photoactive metal–organic frameworks. Coordination Chemistry Reviews 2022, 465 , 214561. https://doi.org/10.1016/j.ccr.2022.214561
    14. Linda Bondorf, Jhonatan Luiz Fiorio, Volodymyr Bon, Linda Zhang, Mariia Maliuta, Sebastian Ehrling, Irena Senkovska, Jack D. Evans, Jan-Ole Joswig, Stefan Kaskel, Thomas Heine, Michael Hirscher. Isotope-selective pore opening in a flexible metal-organic framework. Science Advances 2022, 8 (15) https://doi.org/10.1126/sciadv.abn7035

    Chemistry of Materials

    Cite this: Chem. Mater. 2021, 33, 22, 8886–8894
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acs.chemmater.1c03170
    Published November 2, 2021
    Copyright © 2021 American Chemical Society

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