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

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. Access through your institution Buy or subscribe This is a preview of subscription content, access via your institution ACCESS OPTIONS Access through your institution Access

Nature and 54 other Nature Portfolio journals Get Nature+, our best-value online-access subscription $29.99 / 30 days cancel any time Learn more Subscribe to this journal Receive 12 print

issues and online access $259.00 per year only $21.58 per issue Learn more Buy this article * Purchase on SpringerLink * Instant access to full article PDF Buy now Prices may be subject to

local taxes which are calculated during checkout ADDITIONAL ACCESS OPTIONS: * Log in * Learn about institutional subscriptions * Read our FAQs * Contact customer support SIMILAR CONTENT

BEING VIEWED BY OTHERS METAL–ORGANIC FRAMEWORKS AND COVALENT ORGANIC FRAMEWORKS AS DISRUPTIVE MEMBRANE MATERIALS FOR ENERGY-EFFICIENT GAS SEPARATION Article 22 August 2022 MOF-IN-COF

MOLECULAR SIEVING MEMBRANE FOR SELECTIVE HYDROGEN SEPARATION Article Open access 04 January 2021 REVERSE FILLING APPROACH TO MIXED MATRIX COVALENT ORGANIC FRAMEWORK MEMBRANES FOR GAS

SEPARATION Article Open access 16 April 2025 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 _ REFERENCES * Koros, W. J. & Lively, R. P. Water and beyond: Expanding the spectrum of large-scale energy efficient separation processes.

_AIChE J._ 58, 2624-2633 (2012). CAS  Google Scholar  * Koros, W. J. & Zhang, C. Materials for next-generation molecularly selective synthetic membranes. _Nat. Mater._ 16, 289-297

(2017). CAS  Google Scholar  * Baker, R. W. & Lokhandwala, K. Natural gas processing with membranes:-An overview. _Ind. Eng. Chem. Res._ 47, 2109-2121 (2008). CAS  Google Scholar  *

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). CAS  Google Scholar  *

Baker, R. W. & Low, B. T. Gas separation membrane materials: A perspective. _Macromolecules_ 47, 6999-7013 (2014). CAS  Google Scholar  * Liu, J. et al. Butane isomer transport

properties of 6FDA-DAM and MFI-6FDA-DAM mixed matrix membranes. _J. Memb. Sci._ 343, 157-163 (2009). CAS  Google Scholar  * Agrawal, K. V. et al. Oriented MFI membranes by gel-less secondary

growth of sub-100 nm MFI-nanosheet seed layers. _Adv. Mater._ 27, 3243-3249 (2015). CAS  Google Scholar  * Park, H. B., Kamcev, J., Robeson, L. M., Elimelech, M. & Freeman, B. D.

Maximizing the right stuff: The trade-off between membrane permeability and selectivity. _Science_ 356, eaab0530 (2017). Google Scholar  * Bae, T.-H. et al. Facile high-yield solvothermal

deposition of inorganic nanostructures on zeolite crystals for mixed matrix membrane fabrication. _J. Am. Chem. Soc._ 131, 14662-14663 (2009). CAS  Google Scholar  * Chung, T.-S., Jiang, L.

Y., Li, Y. & Kulprathipanja, S. Mixed matrix membranes (MMMs) comprising organic polymers with dispersed inorganic fillers for gas separation. _Prog. Polym. Sci._ 32, 483-507 (2007). CAS

  Google Scholar  * Liu, G., Xiangli, F., Wei, W., Liu, S. & Jin, W. Improved performance of PDMS/ceramic composite pervaporation membranes by ZSM-5 homogeneously dispersed in PDMS via a

surface graft/coating approach. _Chem. Eng. J._ 174, 495-503 (2011). CAS  Google Scholar  * Nugent, P. et al. Porous materials with optimal adsorption thermodynamics and kinetics for CO2

separation. _Nature_ 495, 80-84 (2013). CAS  Google Scholar  * Cadiau, A., Adil, K., Bhatt, P. M., Belmabkhout, Y. & Eddaoudi, M. A metal-organic framework-based splitter for separating

propylene from propane. _Science_ 353, 137-140 (2016). CAS  Google Scholar  * Cui, X. et al. Pore chemistry and size control in hybrid porous materials for acetylene capture from ethylene.

_Science_ 353, 141-144 (2016). CAS  Google Scholar  * Cadiau, A. et al. Hydrolytically stable fluorinated metal-organic frameworks for energy-efficient dehydration. _Science_ 356, 731-735

(2017). CAS  Google Scholar  * O'Keeffe, M. & Yaghi, O. M. Deconstructing the crystal structures of metal-organic frameworks and related materials into their underlying nets. _Chem.

Rev._ 112, 675-702 (2012). CAS  Google Scholar  * Eddaoudi, M. et al. Systematic design of pore size and functionality in isoreticular MOFs and their application in methane storage.

_Science_ 295, 469-472 (2002). CAS  Google Scholar  * Peng, Y. et al. Metal-organic framework nanosheets as building blocks for molecular sieving membranes. _Science_ 346, 1356-1359 (2014).

CAS  Google Scholar  * Bae, T.-H. et al. A high-performance gas-separation membrane containing submicrometer-sized metal-organic framework crystals. _Angew. Chem. Int. Ed._ 49, 9863-9866

(2010). CAS  Google Scholar  * Rodenas, T. et al. Metal-organic framework nanosheets in polymer composite materials for gas separation. _Nat. Mater._ 14, 48-55 (2015). CAS  Google Scholar  *

Al-Maythalony, B. A. et al. Quest for anionic MOF membranes: Continuous sod-ZMOF membrane with CO2 adsorptio_n_-driven selectivity. _J. Am. Chem. Soc._ 137, 1754-1757 (2015). CAS  Google

Scholar  * Shen, J. et al. UiO-66-polyether block amide mixed matrix membranes for CO2 separation. _J. Memb. Sci._ 513, 155-165 (2016). CAS  Google Scholar  * Zhang, C., Dai, Y., Johnson, J.

R., Karvan, O. & Koros, W. J. High performance ZIF-8/6FDA-DAM mixed matrix membrane for propylene/propane separations. _J. Memb. Sci._ 389, 34-42 (2012). CAS  Google Scholar  * Brown,

A. J. et al. Interfacial microfluidic processing of metal-organic framework hollow fiber membranes. _Science_ 345, 72-75 (2014). CAS  Google Scholar  * 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).

CAS  Google Scholar  * Knebel, A. et al. Defibrillation of soft porous metal-organic frameworks with electric fields. _Science_ 358, 347-351 (2017). CAS  Google Scholar  * Adil, K. et al.

Gas/vapour separation using ultra-microporous metal-organic frameworks: insights into the structure/separation relationship. _Chem. Soc. Rev._ 46, 3402-3430 (2017). CAS  Google Scholar  *

Belmabkhout, Y. et al. Metal-organic frameworks to satisfy gas upgrading demands: fine-tuning the soc-MOF platform for the operative removal of H2S. _J. Mater. Chem. A_ 5, 3293-3303 (2017).

CAS  Google Scholar  * 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). CAS  Google Scholar  * Qiu, S., Xue, M. & Zhu, G. Metal-organic framework membranes: from synthesis to separation application. _Chem. Soc. Rev._ 43, 6116-6140 (2014).

CAS  Google Scholar  * Park, K. S. et al. Exceptional chemical and thermal stability of zeolitic imidazolate frameworks. _Proc. Natl Acad. Sci. USA_ 103, 10186-10191 (2006). CAS  Google

Scholar  * Chui, S. S.-Y., Lo, S. M.-F., Charmant, J. P. H., Orpen, A. G. & Williams, I. D. A chemically functionalizable nanoporous material [Cu3(TMA)2(H2O)3]n. _Science_ 283, 1148-1150

(1999). CAS  Google Scholar  * Loiseau, T. et al. A rationale for the large breathing of the porous aluminum terephthalate (MIL-53) upon hydration. _Chem. Eur. J._ 10, 1373-1382 (2004). CAS

  Google Scholar  * Rosi, N. L. et al. Hydrogen storage in microporous metal-organic frameworks. _Science_ 300, 1127-1129 (2003). CAS  Google Scholar  * Rosi, N. L. et al. Rod packings and

metal-organic frameworks constructed from rod-shaped secondary building units. _J. Am. Chem. Soc._ 127, 1504-1518 (2005). CAS  Google Scholar  * Xue, D.-X. et al. Tunable rare-earth

fcu-MOFs: A platform for systematic enhancement of CO2 adsorption energetics and uptake. _J. Am. Chem. Soc._ 135, 7660-7667 (2013). CAS  Google Scholar  * Xue, D.-X. et al. Tunable rare

earth fcu-MOF platform: access to adsorption kinetics driven gas/vapor separations via pore size contraction. _J. Am. Chem. Soc._ 137, 5034-5040 (2015). CAS  Google Scholar  * Zhang, C. et

al. Highly scalable ZIF-based mixed-matrix hollow fiber membranes for advanced hydrocarbon separations. _AIChE J._ 60, 2625-2635 (2014). CAS  Google Scholar  * Moore, T. T. & Koros, W.

J. No_n_-ideal effects in organic-inorganic materials for gas separation membranes. _J. Mol. Struct._ 739, 87-98 (2005). CAS  Google Scholar  * Jia, M., Peinemann, K.-V. & Behling, R.-D.

Molecular sieving effect of the zeolite-filled silicone rubber membranes in gas permeation. _J. Memb. Sci._ 57, 289-292 (1991). CAS  Google Scholar  * Woo, M., Choi, J. & Tsapatsis, M.

Poly(1-trimethylsilyl-1-propyne)/MFI composite membranes for butane separations. _Microporous Mesoporous Mater._ 110, 330-338 (2008). CAS  Google Scholar  * Kraftschik, B., Koros, W. J.,

Johnson, J. R. & Karvan, O. Dense film polyimide membranes for aggressive sour gas feed separations. _J. Memb. Sci._ 428, 608-619 (2013). CAS  Google Scholar  * Chatterjee, G., Houde, A.

A. & Stern, S. A. Poly(ether urethane) and poly(ether urethane urea) membranes with high H2S/CH4 selectivity. _J. Memb. Sci._ 135, 99-106 (1997). CAS  Google Scholar  * Rangnekar, N.,

Mittal, N., Elyassi, B., Caro, J. & Tsapatsis, M. Zeolite membranes -a review and comparison with MOFs. _Chem. Soc. Rev._ 44, 7128-7154 (2015). CAS  Google Scholar  * Wijmans, J. G.

& Baker, R. W. The solutio_n_-diffusion model: a review. _J. Memb. Sci._ 107, 1-21 (1995). CAS  Google Scholar  * Merkel, T. C. et al. Ultrapermeable, reverse-selective nanocomposite

membranes. _Science_ 296, 519-522 (2002). CAS  Google Scholar  * Zhang, C. et al. Unexpected molecular sieving properties of zeolitic imidazolate framework-8. _J. Phys. Chem. Lett._ 3,

2130-2134 (2012). CAS  Google Scholar  * Rungta, M. et al. Carbon molecular sieve structure development and membrane performance relationships. _Carbon_ 115, 237-248 (2017). CAS  Google

Scholar  * Wind, J. D. et al. Relaxation dynamics of CO2 diffusion, sorption, and polymer swelling for plasticized polyimide pembranes. _Macromolecules_ 36, 6442-6448 (2003). CAS  Google

Scholar  * Liu, G. et al. Molecularly designed stabilized asymmetric hollow fiber membranes for aggressive natural gas separation. _Angew. Chem. Int.l Ed._ 55, 13754-13758 (2016). CAS 

Google Scholar  * Robeson, L. M. The upper bound revisited. _J. Memb. Sci._ 320, 390-400 (2008). CAS  Google Scholar  * Koros, W. J. & Paul, D. R. Design considerations for measurement

of gas sorption in polymers by pressure decay. _J. Polym. Sci. Polym. Phys. Ed._ 14, 1903-1907 (1976). CAS  Google Scholar  * Ruthven, D. M. Sorption kinetics for diffusio_n_-controlled

systems with a strongly concentratio_n_-dependent diffusivity. _Chem. Eng. Sci._ 59, 4531-4545 (2004). CAS  Google Scholar  * Crank, J. _The Mathematics of Diffusion_ (Oxford Univ. Press,

Oxford, 1979). Download references 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). AUTHOR

INFORMATION AUTHORS AND AFFILIATIONS * 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 * 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 * 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 Authors * Gongping Liu View author publications You can also search for this author inPubMed Google Scholar * Valeriya Chernikova View author publications You

can also search for this author inPubMed Google Scholar * Yang Liu View author publications You can also search for this author inPubMed Google Scholar * Kuang Zhang View author publications

You can also search for this author inPubMed Google Scholar * Youssef Belmabkhout View author publications You can also search for this author inPubMed Google Scholar * Osama Shekhah View

author publications You can also search for this author inPubMed Google Scholar * Chen Zhang View author publications You can also search for this author inPubMed Google Scholar * Shouliang

Yi View author publications You can also search for this author inPubMed Google Scholar * Mohamed Eddaoudi View author publications You can also search for this author inPubMed Google

Scholar * William J. Koros View author publications You can also search for this author inPubMed Google Scholar 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. CORRESPONDING AUTHORS Correspondence to Mohamed

Eddaoudi or William J. Koros. ETHICS DECLARATIONS COMPETING INTERESTS The authors declare no competing financial interests. ADDITIONAL INFORMATION PUBLISHER'S NOTE: Springer Nature

remains neutral with regard to jurisdictional claims in published maps and institutional affiliations. SUPPLEMENTARY INFORMATION SUPPLEMENTARY INFORMATION Supplementary Figures 1-29,

Supplementary Schematic 1-4, Supplementary Tables 1-2, Supplementary References 1-7 RIGHTS AND PERMISSIONS Reprints and permissions ABOUT THIS ARTICLE CITE THIS ARTICLE 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

Download citation * Received: 18 September 2017 * Accepted: 14 December 2017 * Published: 12 February 2018 * Issue Date: March 2018 * DOI: https://doi.org/10.1038/s41563-017-0013-1 SHARE

THIS ARTICLE Anyone you share the following link with will be able to read this content: Get shareable link Sorry, a shareable link is not currently available for this article. Copy to

clipboard Provided by the Springer Nature SharedIt content-sharing initiative