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.
This is a preview of subscription content, access via your institution
Open Access articles citing this article.
Nature Communications Open Access 10 November 2022
Subscribe to Journal
Get full journal access for 1 year
only $9.92 per issue
All prices are NET prices.
VAT will be added later in the checkout.
Tax calculation will be finalised during checkout.
Get time limited or full article access on ReadCube.
All prices are NET prices.
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.
Sholl, D. S. & Lively, R. P. Seven chemical separations to change the world. Nature 532, 435–437 (2016).
Cadiau, A., Adil, K., Bhatt, P., Belmabkhout, Y. & Eddaoudi, M. A metal-organic framework–based splitter for separating propylene from propane. Science 353, 137–140 (2016).
Assen, A. H. et al. Ultra-tuning of the rare-earth fcu-MOF aperture size for selective molecular exclusion of branched paraffins. Angew. Chem. Int. Ed. 54, 14353–14358 (2015).
Koros, W. J. & Zhang, C. Materials for next-generation molecularly selective synthetic membranes. Nat. Mater. 16, 289–297 (2017).
Bachman, J. E., Smith, Z. P., Li, T., Xu, T. & Long, J. R. Enhanced ethylene separation and plasticization resistance in polymer membranes incorporating metal–organic framework nanocrystals. Nat. Mater. 15, 845–849 (2016).
Gokhale, V., Hurowitz, S. & Riggs, J. B. A comparison of advanced distillation control techniques for a propylene/propane splitter. Ind. Eng. Chem. Res. 34, 4413–4419 (1995).
Klemola, K. T. & Ilme, J. K. Distillation efficiencies of an industrial-scale i-butane/n-butane fractionator. Ind. Eng. Chem. Res. 35, 4579–4586 (1996).
Ma, X. et al. Zeolitic imidazolate framework membranes made by ligand-induced permselectivation. Science 361, 1008–1011 (2018).
Joseph, J. Purification of hydrocarbon feedstocks. US patent 3,816,975 (1974).
Belmabkhout, Y. et al. Natural gas upgrading using a fluorinated MOF with tuned H2S and CO2 adsorption selectivity. Nat. Energy 3, 1059–1066 (2018).
Freeman, B. D. & Pinnau, I. Gas and liquid separations using membranes: an overview. ACS Symp. Ser.: Adv. Mater. Membr. Sep. 876, 1–23 (2004).
Liu, Y. et al. Conformation-controlled molecular sieving effects for membrane-based propylene/propane separation. Adv. Mater. 31, 1807513 (2019).
Qian, Q. et al. MOF-based membranes for gas separations. Chem. Rev. 120, 8161–8266 (2020).
Caro, J. Are MOF membranes better in gas separation than those made of zeolites? Curr. Opin. Chem. Eng. 1, 77–83 (2011).
Shekhah, O., Chernikova, V., Belmabkhout, Y. & Eddaoudi, M. Metal–organic framework membranes: from fabrication to gas separation. Crystals 8, 412 (2018).
Hou, Q., Zhou, S., Wei, Y., Caro, J. & Wang, H. Balancing the grain boundary structure and the framework flexibility through bimetallic metal–organic framework (MOF) membranes for gas separation. J. Am. Chem. Soc. 142, 9582–9586 (2020).
Zhou, S. et al. Paralyzed membrane: current-driven synthesis of a metal-organic framework with sharpened propene/propane separation. Sci. Adv. 4, eaau1393 (2018).
Dutta, A. et al. Influence of hydrogen sulfide exposure on the transport and structural properties of the metal–organic framework ZIF-8. J. Phys. Chem. C 122, 7278–7287 (2018).
Park, K. S. et al. Exceptional chemical and thermal stability of zeolitic imidazolate frameworks. Proc. Natl Acad. Sci. USA 103, 10186–10191 (2006).
Kolokolov, D. I., Stepanov, A. G. & Jobic, H. Mobility of the 2-methylimidazolate linkers in ZIF-8 probed by 2H NMR: saloon doors for the guests. J. Phys. Chem. C 119, 27512–27520 (2015).
Knebel, A. et al. Defibrillation of soft porous metal-organic frameworks with electric fields. Science 358, 347–351 (2017).
Yassine, O. et al. H2S sensors: fumarate-based fcu-MOF thin film grown on a capacitive interdigitated electrode. Angew. Chem. Int. Ed. 55, 15879–15883 (2016).
Furukawa, H. et al. Water adsorption in porous metal–organic frameworks and related materials. J. Am. Chem. Soc. 136, 4369–4381 (2014).
Chen, Z. et al. Enhanced separation of butane isomers via defect control in a fumarate/zirconium-based metal organic framework. Langmuir 34, 14546–14551 (2018).
Liu, X., Demir, N. K., Wu, Z. & Li, K. Highly water-stable zirconium metal–organic framework UiO-66 membranes supported on alumina hollow fibers for desalination. J. Am. Chem. Soc. 137, 6999–7002 (2015).
Ghalei, B. et al. Rational tuning of zirconium metal–organic framework membranes for hydrogen purification. Angew. Chem. Int. Ed. 58, 19034–19040 (2019).
Ghalei, B. et al. Enhanced selectivity in mixed matrix membranes for CO2 capture through efficient dispersion of amine-functionalized MOF nanoparticles. Nat. Energy 2, 17086 (2017).
Liu, G. et al. Mixed matrix formulations with MOF molecular sieving for key energy-intensive separations. Nat. Mater. 17, 283–289 (2018).
Yu, J., Pan, Y., Wang, C. & Lai, Z. ZIF-8 membranes with improved reproducibility fabricated from sputter-coated ZnO/alumina supports. Chem. Eng. Sci. 141, 119–124 (2016).
Sheng, L. et al. Enhanced C3H6/C3H8 separation performance on MOF membranes through blocking defects and hindering framework flexibility by silicone rubber coating. Chem. Commun. 53, 7760–7763 (2017).
Guillerm, V. et al. Discovery and introduction of a (3,18)-connected net as an ideal blueprint for the design of metal–organic frameworks. Nat. Chem. 6, 673 (2014).
Hou, Q. et al. Ultra-tuning of the aperture size in stiffened ZIF-8_Cm frameworks with mixed-linker strategy for enhanced CO2/CH4 separation. Angew. Chem. Int. Ed. 58, 327–331 (2019).
Diestel, L. et al. MOF based MMMs with enhanced selectivity due to hindered linker distortion. J. Membr. Sci. 492, 181–186 (2015).
Knebel, A. et al. Solution processable metal–organic frameworks for mixed matrix membranes using porous liquids. Nat. Mater. 19, 1346–1353 (2020).
Friebe, S., Geppert, B., Steinbach, F. & Caro, J. Metal–organic framework UiO-66 layer: a highly oriented membrane with good selectivity and hydrogen permeance. ACS Appl. Mater. Interfaces 9, 12878–12885 (2017).
Friebe, S., Mundstock, A., Volgmann, K. & Caro, J. On the better understanding of the surprisingly high performance of metal−organic framework-based mixed-matrix membranes using the example of UiO-66 and Matrimid. ACS Appl. Mater. Interfaces 9, 41553–41558 (2017).
Bux, H., Chmelik, C., Krishna, R. & Caro, J. Ethene/ethane separation by the MOF membrane ZIF-8: molecular correlation of permeation, adsorption, diffusion. J. Membr. Sci. 369, 284–289 (2011).
Olujic, Z., Fakhri, F., De Rijke, A., De Graauw, J. & Jansens, P. J. Internal heat integration-the key to an energy-conserving distillation column. J. Chem. Technol. Biotechnol. 78, 241–248 (2003).
Eldridge, R. B. Olefin/paraffin separation technology: a review. Ind. Eng. Chem. Res. 32, 2208–2212 (1993).
Lee, U., Kim, J., Chae, I. S. & Han, C. Techno-economic feasibility study of membrane based propane/propylene separation process. Chem. Eng. Process. 119, 62–72 (2017).
Umo, A. M. & Bassey, E. N. Simulation and performance analysis of propylene–propane splitter in petroleum refinery case study. Int. J. Chem. Eng. 8, 1 (2017).
Olujić, Ž., Sun, L., De Rijke, A. & Jansens, P. Conceptual design of an internally heat integrated propylene–propane splitter. Energy 31, 3083–3096 (2006).
Alcántara-Avila, J. R., Gómez-Castro, F. I., Segovia-Hernández, J. G., Sotowa, K.-I. & Horikawa, T. Optimal design of cryogenic distillation columns with side heat pumps for the propylene/propane separation. Chem. Eng. Process. 82, 112–122 (2014).
TI, F. First-principles inference model improves deisobutanizer column control. Hydrocarb. Process. 1, 43 (2003).
Hommeltoft, S. I. Isobutane alkylation: recent developments and future perspectives. Appl. Catal. A 221, 421–428 (2001).
Mittal, N. et al. A mathematical model for zeolite membrane module performance and its use for techno-economic evaluation of improved energy efficiency hybrid membrane–distillation processes for butane isomer separations. J. Membr. Sci. 520, 434–449 (2016).
The authors thank King Abdullah University of Science and Technology (KAUST) for financial support.
The authors declare no competing interests.
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.
Publisher’s note Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
About this article
Cite this article
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
This article is cited by
Metal–organic frameworks and covalent organic frameworks as disruptive membrane materials for energy-efficient gas separation
Nature Nanotechnology (2022)
Nature Communications (2022)
Science China Chemistry (2022)