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Mixed matrix formulations with MOF molecular sieving for key energy-intensive separations

Nature Materials volume 17, pages 283–289 (2018)Cite this article

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A Publisher Correction to this article was published on 27 May 2021

A Publisher Correction to this article was published on 20 November 2018

This article has been updated

Abstract

Membrane-based separations can improve energy efficiency and reduce the environmental impacts associated with traditional approaches. Nevertheless, many challenges must be overcome to design membranes that can replace conventional gas separation processes. Here, we report on the incorporation of engineered submicrometre-sized metal-organic framework (MOF) crystals into polymers to form hybrid materials that successfully translate the excellent molecular sieving properties of face-centred cubic (fcu)-MOFs into the resultant membranes. We demonstrate, simultaneously, exceptionally enhanced separation performance in hybrid membranes for two challenging and economically important applications: the removal of CO2 and H2S from natural gas and the separation of butane isomers. Notably, the membrane molecular sieving properties demonstrate that the deliberately regulated and contracted MOF pore-aperture size can discriminate between molecular pairs. The improved performance results from precise control of the linkers delimiting the triangular window, which is the sole entrance to the fcu-MOF pore. This rational-design hybrid approach provides a general toolbox for enhancing the transport properties of advanced membranes bearing molecular sieve fillers with sub-nanometre-sized pore-apertures.

Gas separations are essential processes in the energy and chemical industries1,2, typified by natural gas purification and butane isomer separation. Raw natural gas typically contains acid gas components, and must be purified by amine scrubbing to meet pipeline specifications (< 2% CO2 and < 4 ppm H2S)3. Moreover, n-butane must be separated from iso-butane by distillation prior to the production of high-octane gasoline blending stock4. Gas separation membranes, although widely used for hydrogen recovery and air separation, face challenges for the abovementioned energy-intensive processes5. Existing high-performance membrane materials for CO2/CH4 separation show much lower efficiency in H2S removal due to the closer molecular kinetic diameter (dk) of H2S (3.6 Å) than CO2 (3.3 Å) to CH4 (3.8 Å), which hinders the attainment of an ultralow H2S concentration for pipeline transportation. For separating butane isomers with similar physicochemical properties, existing pure polymer membranes are economically unattractive due to their low permeability or selectivity6, whereas zeolite (for example, MFI, a type of aluminosilicate zeolite) membranes show high permeability and selectivity7 but face difficulties in economical and scalable fabrication.

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Fig. 1: Design and fabrication of RE-fcu-MOF/polymer hybrid membranes
Fig. 2: Gas permeation properties
Fig. 4: Mixed-gas separation performance
Fig. 3: Transport properties and RE-fcu-MOFs pore structure

Change history

  • 20 November 2018

    In the version of this Article originally published, the units of the y axis of Fig. 3b were incorrectly given as “106 cm2 s-1” they should have been “10-8 cm2 s-1”. This has been corrected in the online versions of the Article.

  • 27 May 2021

    A Correction to this paper has been published: https://doi.org/10.1038/s41563-021-01007-1

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Acknowledgements

The research reported in this publication was supported by KAUST CRG Research Grant URF/1/2222-01; Y.B., O.S. and M.E. acknowledge support from King Abdullah University of Science and Technology; G.L. acknowledges support from National Natural Science Foundation of China (Grant Nos.: 21490585, 21776125, 21406107).

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Authors and Affiliations

  1. School of Chemical & Biomolecular Engineering, Georgia Institute of Technology, Atlanta, GA, USA

    Gongping Liu, Yang Liu, Kuang Zhang, Chen Zhang, Shouliang Yi & William J. Koros

  2. State Key Laboratory of Materials-Oriented Chemical Engineering, Jiangsu National Synergetic Innovation Center for Advanced Materials, College of Chemical Engineering, Nanjing Tech University, Nanjing, China

    Gongping Liu

  3. Advanced Membranes & Porous Materials Center, Division of Physical Sciences and Engineering, Functional Materials Design, King Abdullah University of Science and Technology, Discovery and Development research group (FMD3), Thuwal, Saudi Arabia

    Valeriya Chernikova, Youssef Belmabkhout, Osama Shekhah & Mohamed Eddaoudi

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Contributions

G.L. fabricated the hybrid mixed-matrix membranes and performed the adsorption and permeation tests. V.C., O.S. and Y.B. carried out the synthesis and scale-up of the MOFs. G.L., W.J.K., M.E. and Y.B. interpreted the adsorption and permeation data. K.Z., G.L., O.S. and V.C. developed the cryo-grinding/sedimentation method. K.Z. and G.L. fabricated the hybrid hollow fibre composite membranes. C.Z. guided the Maxwell prediction and diffusivity calculations. S.Y. guided the H2S sorption and permeation. W.J.K. and M.E conceived, designed and guided the whole project. G.L., Y.L., W.J.K., Y.B. and M.E. discussed the findings in this paper. G.L., Y.B. M.E. and W.J.K. coordinated the writing of the paper, and all authors contributed to revising the paper.

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Correspondence to Mohamed Eddaoudi or William J. Koros.

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Supplementary Figures 1-29, Supplementary Schematic 1-4, Supplementary Tables 1-2, Supplementary References 1-7

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Liu, G., Chernikova, V., Liu, Y. et al. Mixed matrix formulations with MOF molecular sieving for key energy-intensive separations. Nature Mater 17, 283–289 (2018). https://doi.org/10.1038/s41563-017-0013-1

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