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Electrochemical synthesis of continuous metal–organic framework membranes for separation of hydrocarbons

Abstract

Membrane-based approaches can offer energy-efficient and cost-effective methods for various separation processes. Practical membranes must have high permselectivity at industrially relevant high pressures and under aggressive conditions, and be manufacturable in a scalable and robust fashion. We report a versatile electrochemical directed-assembly strategy to fabricate polycrystalline metal–organic framework membranes for separation of hydrocarbons. We fabricate a series of face-centred cubic metal–organic framework membranes based on 12-connected rare-earth or zirconium hexanuclear clusters with distinct ligands. In particular, the resultant fumarate-based membranes containing contracted triangular apertures as sole entrances to the pore system enable molecular-sieving separation of propylene/propane and butane/isobutane mixtures. Prominently, increasing the feed pressure to the industrially practical value of 7 atm promoted a desired enhancement in both the total flux and separation selectivity. Process design analysis demonstrates that, for propylene/propane separation, the deployment of such face-centred cubic Zr-fumarate-based metal–organic framework membranes in a hybrid membrane–distillation system offers the potential to decrease the energy input by nearly 90% relative to a conventional single distillation process.

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Fig. 1: Isoreticulation of fcu-MOFs and designed synthesis of fcu-MOF membranes.
Fig. 2: SEM images and XRD patterns of the explored fcu-MOF membranes.
Fig. 3: Gas separation performance of fcu-MOF membranes.
Fig. 4: C3H6/C3H8 separation performance of Zr-fum-fcu-MOF membranes at practical conditions.
Fig. 5: Summary of techno-economic analysis comparison of distillation and hybrid membrane–distillation systems.

Data availability

The datasets analysed and generated during the current study are included in the paper and its Supplementary Information (Source data) are provided with this paper.

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Acknowledgements

The authors thank King Abdullah University of Science and Technology (KAUST) for financial support.

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Affiliations

Authors

Contributions

M.E. conceived, designed and guided the whole project. S.Z. fabricated the polycrystalline membranes and performed the permeation tests. S.Z. and J.J. proposed the membrane synthesis routes. S.Z. calculated the two guidelines for membrane preparations. O.S., J.C.-J. and P.M.B. assisted with instrument development. S.Z., O.S., J.J. and M.E. discussed the presented findings. A.R., P.M.B. and J.G. contributed to the process simulations. S.Z., O.S. and M.E. coordinated the writing of the paper, and all authors contributed to revising the paper.

Corresponding author

Correspondence to Mohamed Eddaoudi.

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The authors declare no competing interests.

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Peer review information Nature Energy thanks Simon Smart, Michael Tsapatsis and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Supplementary information

Supplementary information

Materials and instruments information. Supplementary Figs. 1–48, Tables 1–11, Notes 1–3 and Refs. 1–16.

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Source Data Fig. 3

Statistical source data.

Source Data Fig. 4

Statistical source data.

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Zhou, S., Shekhah, O., Jia, J. et al. Electrochemical synthesis of continuous metal–organic framework membranes for separation of hydrocarbons. Nat Energy 6, 882–891 (2021). https://doi.org/10.1038/s41560-021-00881-y

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