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Solution processable metal–organic frameworks for mixed matrix membranes using porous liquids

Nature Materials volume 19, pages 1346–1353 (2020)Cite this article

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Abstract

The combination of well-defined molecular cavities and chemical functionality makes crystalline porous solids attractive for a great number of technological applications, from catalysis to gas separation. However, in contrast to other widely applied synthetic solids such as polymers, the lack of processability of crystalline extended solids hampers their application. In this work, we demonstrate that metal–organic frameworks, a type of highly crystalline porous solid, can be made solution processable via outer surface functionalization using N-heterocyclic carbene ligands. Selective outer surface functionalization of relatively large nanoparticles (250 nm) of the well-known zeolitic imidazolate framework ZIF-67 allows for the stabilization of processable dispersions exhibiting permanent porosity. The resulting type III porous liquids can either be directly deployed as liquid adsorbents or be co-processed with state-of-the-art polymers to yield highly loaded mixed matrix membranes with excellent mechanical properties and an outstanding performance in the challenging separation of propylene from propane. We anticipate that this approach can be extended to other metal–organic frameworks and other applications.

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Fig. 1: Comparison between pristine and modified ZIF-67.
Fig. 2: Linker substitution energies.
Fig. 3: Gas adsorption and breakthrough curves of propylene/methane mixture on porous liquid.
Fig. 4: Physical characterization of membranes.
Fig. 5: Gas permeation properties.

Data availability

All data generated and/or analysed in this study are included in this published article and its supplementary information file and are also available from the corresponding author (Jorge Gascon) on reasonable request.

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Acknowledgements

L.S., A.K. and J.C. acknowledge support by the Deutsche Forschungsgemeinschaft in the priority program SPP 1928 COORNETs (Coordination Networks: Building Block for Functional Systems), grant no. CA 147/20-1 (J.C.). R.A., S.K and L.C. acknowledge the Supercomputing Laboratory at KAUST for computational resources (Cray XC40, ShaheenII). We thank P. M. Bhatt for helping with the propylene/propane adsorption kinetic study. King Abdullah University of Science and Technology is acknowledged for financial support.

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Author notes

  1. These authors contributed equally: Alexander Knebel, Anastasiya Bavykina, Shuvo Jit Datta, Lion Sundermann.

Authors and Affiliations

  1. Institute of Physical Chemistry and Electrochemistry, Leibniz University Hannover, Hannover, Germany

    Alexander Knebel, Lion Sundermann & Jürgen Caro

  2. Advanced Catalytic Materials, KAUST Catalysis Center, King Abdullah University of Science and Technology, Thuwal, Saudi Arabia

    Alexander Knebel, Anastasiya Bavykina, Luis Garzon-Tovar, Yury Lebedev, Sara Durini, Genrikh Shterk & Jorge Gascon

  3. Functional Materials Design, Discovery and Development, Advanced Membranes & Porous Materials Center, King Abdullah University of Science and Technology, Thuwal, Saudi Arabia

    Shuvo Jit Datta, Madhavan Karunakaran, Ionela Daniela Carja & Mohamed Eddaoudi

  4. Computational Chemistry Laboratory, KAUST Catalysis Center, King Abdullah University of Science and Technology, Thuwal, Saudi Arabia

    Rafia Ahmad, Sergey M. Kozlov, Luigi Cavallo & Magnus Rueping

  5. Deutsches Institut für Kautschuktechnologie e. V., Hannover, Germany

    Dino Simic, Irina Weilert, Manfred Klüppel & Ulrich Giese

  6. School of Chemistry and Chemical Engineering, South China University of Technology, Guangzhou, China

    Jürgen Caro

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  1. Alexander Knebel
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Contributions

J.G. and A.K. conceived and designed the project and managed cooperation between KAUST, LUH and DIK. A.K., L.S., L.G.-T. and A.B. were responsible for the synthesis and functionalization of the particles. A.K. and L.S. performed the X-ray dispersion, SEM and ATR-FTIR measurements. A.B. and S.J.D. were responsible for the adsorption measurements. A.B., L.G.-T. and S.D. performed the breakthrough measurements. D.S. and I.W. performed and helped with interpretation of the dynamic viscosity measurements. G.S. performed the X-ray photoelectron spectroscopy measurements. L.G.-T. performed NMR measurements. Y.L. proposed the use of and synthesized the carbenes. S.D. obtained adsorption isotherms on the liquid samples. S.J.D. and M.E. designed MMMs. S.J.D. fabricated and analysed MMMs and measured propylene and propane sorption isotherms on MOFs powder, MMMs and polymers. S.J.D. calculated solubility and diffusivity and described the MMM findings in the manuscript. M.K. performed membrane permeation tests. I.D.C. synthesized 6FDA-DHTM-Durene polymer. I.D.C. and S.J.D. characterized MMMs using SEM, X-ray diffraction, thermal gravimetric analysis and ATR-FTIR. R.A., S.K. and L.C. performed density functional theory simulations. A.K., L.S., A.B., J.C., S.J.D., R.A., S.K., L.C. and J.G. drafted the paper. All authors contributed to the writing of the manuscript.

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Correspondence to Alexander Knebel, Anastasiya Bavykina, Yury Lebedev or Jorge Gascon.

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Supplementary information

Supplementary Information

Supplementary discussion, Figs. 1–54 and Tables 1–14.

Supplementary Video 1

Focused ion beam SEM reconstruction of a ZIF-67-IDip/6FDA-DAM MMM.

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Knebel, A., Bavykina, A., Datta, S.J. et al. Solution processable metal–organic frameworks for mixed matrix membranes using porous liquids. Nat. Mater. 19, 1346–1353 (2020). https://doi.org/10.1038/s41563-020-0764-y

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