skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Increasing M2(dobdc) Loading in Selective Mixed-Matrix Membranes: A Rubber Toughening Approach

Abstract

Mixed-matrix membranes (MMMs) were formed by incorporating M2(dobdc) (M = Mg, Ni; dobdc4– = 2,5-dioxido-1,4-benzenedicarboxylate) metal–organic framework (MOF) nanoparticles in a series of poly(ether-imide) copolymers. Addition of the MOF nanoparticles improved the permeability of H2, N2, CH4, and CO2 relative to the pure copolymer by increasing gas solubility and, in most cases, diffusivity. More limited improvements in diffusivity were observed for the more strongly adsorbing gases. Because of such transport considerations, improvements in permeability and selectivity were most pronounced for H2/CH4 and H2/N2 separations. Incorporation of a greater ether content within the copolymers led to the formation of defect-free MMMs by physically sealing polymer–MOF interfacial defects, allowing higher MOF loadings to be achieved. For Mg2(dobdc), selective, defect-free films could be formed with loadings of up to 51 wt %. However, at these high loadings, films became weak and brittle. The mechanical properties of the composite materials were therefore quantified by tensile tests and compared to those of the neat polymers used commercially for membrane film formation. High contents of flexible ether units and small MOF nanoparticle sizes were found to be necessary to form strong and ductile MMMs, although clear trade-offs exist between transport performance, MOF loading, and mechanical properties.more » In conclusion, these trade-offs are critically examined to evaluate the current limitations and potential benefits to forming M2(dobdc) MMMs using this rubber toughening approach.« less

Authors:
 [1]; ORCiD logo [2];  [3];  [4]; ORCiD logo [5]; ORCiD logo [6];  [5]; ORCiD logo [7]; ORCiD logo [8]
  1. Univ. of California, Berkeley, CA (United States). Dept. of Chemistry; Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States). Dept. of Chemical Engineering
  2. Univ. of California, Berkeley, CA (United States). Dept. of Chemical and Biomolecular Engineering
  3. Univ. of California, Berkeley, CA (United States). Dept. of Materials Science and Engineering; ShanghaiTech Univ., Shanghai (China). School of Physical Science and Technology
  4. Univ. of New South Wales, Sydney, NSW (Australia). School of Mechanical and Manufacturing Engineering
  5. National Energy Technology Lab. (NETL), Pittsburgh, PA (United States)
  6. Univ. of California, Berkeley, CA (United States). Dept. of Chemistry; Univ. of California, Berkeley, CA (United States). Dept. of Materials Science and Engineering
  7. Univ. of California, Berkeley, CA (United States). Dept. of Materials Science and Engineering; Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Materials Sciences Division
  8. Univ. of California, Berkeley, CA (United States). Dept. of Chemistry; Univ. of California, Berkeley, CA (United States). Dept. of Chemical and Biomolecular Engineering
Publication Date:
Research Org.:
National Energy Technology Laboratory (NETL), Pittsburgh, PA, Morgantown, WV (United States); Energy Frontier Research Centers (EFRC) (United States). Center for Gas Separations Relevant to Clean Energy Technologies (CGS)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1455423
Grant/Contract Number:  
SC0001015; FE0004000
Resource Type:
Accepted Manuscript
Journal Name:
Chemistry of Materials
Additional Journal Information:
Journal Volume: 30; Journal Issue: 5; Journal ID: ISSN 0897-4756
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Smith, Zachary P., Bachman, Jonathan E., Li, Tao, Gludovatz, Bernd, Kusuma, Victor A., Xu, Ting, Hopkinson, David P., Ritchie, Robert O., and Long, Jeffrey R.. Increasing M2(dobdc) Loading in Selective Mixed-Matrix Membranes: A Rubber Toughening Approach. United States: N. p., 2018. Web. https://doi.org/10.1021/acs.chemmater.7b02908.
Smith, Zachary P., Bachman, Jonathan E., Li, Tao, Gludovatz, Bernd, Kusuma, Victor A., Xu, Ting, Hopkinson, David P., Ritchie, Robert O., & Long, Jeffrey R.. Increasing M2(dobdc) Loading in Selective Mixed-Matrix Membranes: A Rubber Toughening Approach. United States. https://doi.org/10.1021/acs.chemmater.7b02908
Smith, Zachary P., Bachman, Jonathan E., Li, Tao, Gludovatz, Bernd, Kusuma, Victor A., Xu, Ting, Hopkinson, David P., Ritchie, Robert O., and Long, Jeffrey R.. Tue . "Increasing M2(dobdc) Loading in Selective Mixed-Matrix Membranes: A Rubber Toughening Approach". United States. https://doi.org/10.1021/acs.chemmater.7b02908. https://www.osti.gov/servlets/purl/1455423.
@article{osti_1455423,
title = {Increasing M2(dobdc) Loading in Selective Mixed-Matrix Membranes: A Rubber Toughening Approach},
author = {Smith, Zachary P. and Bachman, Jonathan E. and Li, Tao and Gludovatz, Bernd and Kusuma, Victor A. and Xu, Ting and Hopkinson, David P. and Ritchie, Robert O. and Long, Jeffrey R.},
abstractNote = {Mixed-matrix membranes (MMMs) were formed by incorporating M2(dobdc) (M = Mg, Ni; dobdc4– = 2,5-dioxido-1,4-benzenedicarboxylate) metal–organic framework (MOF) nanoparticles in a series of poly(ether-imide) copolymers. Addition of the MOF nanoparticles improved the permeability of H2, N2, CH4, and CO2 relative to the pure copolymer by increasing gas solubility and, in most cases, diffusivity. More limited improvements in diffusivity were observed for the more strongly adsorbing gases. Because of such transport considerations, improvements in permeability and selectivity were most pronounced for H2/CH4 and H2/N2 separations. Incorporation of a greater ether content within the copolymers led to the formation of defect-free MMMs by physically sealing polymer–MOF interfacial defects, allowing higher MOF loadings to be achieved. For Mg2(dobdc), selective, defect-free films could be formed with loadings of up to 51 wt %. However, at these high loadings, films became weak and brittle. The mechanical properties of the composite materials were therefore quantified by tensile tests and compared to those of the neat polymers used commercially for membrane film formation. High contents of flexible ether units and small MOF nanoparticle sizes were found to be necessary to form strong and ductile MMMs, although clear trade-offs exist between transport performance, MOF loading, and mechanical properties. In conclusion, these trade-offs are critically examined to evaluate the current limitations and potential benefits to forming M2(dobdc) MMMs using this rubber toughening approach.},
doi = {10.1021/acs.chemmater.7b02908},
journal = {Chemistry of Materials},
number = 5,
volume = 30,
place = {United States},
year = {2018},
month = {1}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 3 works
Citation information provided by
Web of Science

Figures / Tables:

Figure 1 Figure 1: Synthesis of poly(ether-imide) copolymers.

Save / Share:

Works referenced in this record:

Gas Separation Membrane Materials: A Perspective
journal, September 2014

  • Baker, Richard W.; Low, Bee Ting
  • Macromolecules, Vol. 47, Issue 20
  • DOI: 10.1021/ma501488s

Natural Gas Processing with Membranes:  An Overview
journal, April 2008

  • Baker, Richard W.; Lokhandwala, Kaaeid
  • Industrial & Engineering Chemistry Research, Vol. 47, Issue 7
  • DOI: 10.1021/ie071083w

The solution-diffusion model: a review
journal, November 1995


The upper bound revisited
journal, July 2008


Mixed matrix membranes (MMMs) comprising organic polymers with dispersed inorganic fillers for gas separation
journal, April 2007


Metal organic framework based mixed matrix membranes: An increasingly important field of research with a large application potential
journal, January 2013


Mixed matrix membranes using carbon molecular sieves
journal, January 2003


Mixed matrix membranes using carbon molecular sieves
journal, January 2003


Membrane Gas Separation: A Review/State of the Art
journal, May 2009

  • Bernardo, P.; Drioli, E.; Golemme, G.
  • Industrial & Engineering Chemistry Research, Vol. 48, Issue 10
  • DOI: 10.1021/ie8019032

High performance ZIF-8/6FDA-DAM mixed matrix membrane for propylene/propane separations
journal, February 2012


Unexpected Molecular Sieving Properties of Zeolitic Imidazolate Framework-8
journal, July 2012

  • Zhang, Chen; Lively, Ryan P.; Zhang, Ke
  • The Journal of Physical Chemistry Letters, Vol. 3, Issue 16
  • DOI: 10.1021/jz300855a

In Situ Synthesis of Thin Zeolitic–Imidazolate Framework ZIF-8 Membranes Exhibiting Exceptionally High Propylene/Propane Separation
journal, July 2013

  • Kwon, Hyuk Taek; Jeong, Hae-Kwon
  • Journal of the American Chemical Society, Vol. 135, Issue 29
  • DOI: 10.1021/ja403849c

Sharp separation of C2/C3 hydrocarbon mixtures by zeolitic imidazolate framework-8 (ZIF-8) membranes synthesized in aqueous solutions
journal, January 2011

  • Pan, Yichang; Lai, Zhiping
  • Chemical Communications, Vol. 47, Issue 37
  • DOI: 10.1039/c1cc14051e

Comprehensive study of carbon dioxide adsorption in the metal–organic frameworks M 2 (dobdc) (M = Mg, Mn, Fe, Co, Ni, Cu, Zn)
journal, January 2014

  • Queen, Wendy L.; Hudson, Matthew R.; Bloch, Eric D.
  • Chem. Sci., Vol. 5, Issue 12
  • DOI: 10.1039/C4SC02064B

Selective adsorption of ethylene over ethane and propylene over propane in the metal–organic frameworks M2(dobdc) (M = Mg, Mn, Fe, Co, Ni, Zn)
journal, January 2013

  • Geier, Stephen J.; Mason, Jarad A.; Bloch, Eric D.
  • Chemical Science, Vol. 4, Issue 5
  • DOI: 10.1039/c3sc00032j

Dramatic Tuning of Carbon Dioxide Uptake via Metal Substitution in a Coordination Polymer with Cylindrical Pores
journal, August 2008

  • Caskey, Stephen R.; Wong-Foy, Antek G.; Matzger, Adam J.
  • Journal of the American Chemical Society, Vol. 130, Issue 33, p. 10870-10871
  • DOI: 10.1021/ja8036096

CO2/N2 separations with mixed-matrix membranes containing Mg2(dobdc) nanocrystals
journal, January 2013

  • Bae, Tae-Hyun; Long, Jeffrey R.
  • Energy & Environmental Science, Vol. 6, Issue 12
  • DOI: 10.1039/c3ee42394h

Enhanced ethylene separation and plasticization resistance in polymer membranes incorporating metal–organic framework nanocrystals
journal, April 2016

  • Bachman, Jonathan E.; Smith, Zachary P.; Li, Tao
  • Nature Materials, Vol. 15, Issue 8
  • DOI: 10.1038/nmat4621

Plasticization-resistant Ni 2 (dobdc)/polyimide composite membranes for the removal of CO 2 from natural gas
journal, January 2016

  • Bachman, Jonathan E.; Long, Jeffrey R.
  • Energy & Environmental Science, Vol. 9, Issue 6
  • DOI: 10.1039/C6EE00865H

Molecular sieving realized with ZIF-8/Matrimid® mixed-matrix membranes
journal, September 2010

  • Ordoñez, Ma. Josephine C.; Balkus, Kenneth J.; Ferraris, John P.
  • Journal of Membrane Science, Vol. 361, Issue 1-2, p. 28-37
  • DOI: 10.1016/j.memsci.2010.06.017

Physical aging in glassy mixed matrix membranes; tuning particle interaction for mechanically robust nanocomposite films
journal, January 2016

  • Smith, Stefan J. D.; Lau, Cher Hon; Mardel, James I.
  • Journal of Materials Chemistry A, Vol. 4, Issue 27
  • DOI: 10.1039/C6TA02603F

Effect of methyl substituents on permeability and permselectivity of gases in polyimides prepared from methyl-substituted phenylenediamines
journal, July 1992

  • Tanaka, Kazuhiro; Okano, Masaaki; Toshino, Hiroyuki
  • Journal of Polymer Science Part B: Polymer Physics, Vol. 30, Issue 8
  • DOI: 10.1002/polb.1992.090300813

Influence of Diffusivity and Sorption on Helium and Hydrogen Separations in Hydrocarbon, Silicon, and Fluorocarbon-Based Polymers
journal, April 2014

  • Smith, Zachary P.; Tiwari, Rajkiran R.; Dose, Michelle E.
  • Macromolecules, Vol. 47, Issue 9
  • DOI: 10.1021/ma402521h

The Time Lag in Diffusion
journal, January 1957


Relationship between gas transport properties and fractional free volume determined from dielectric constant in polyimide films containing the hexafluoroisopropylidene group
journal, January 2007

  • Miyata, Sou; Sato, Shuichi; Nagai, Kazukiyo
  • Journal of Applied Polymer Science, Vol. 107, Issue 6
  • DOI: 10.1002/app.27496

Performance studies of mixed matrix membranes for gas separation: A review
journal, November 2010


Poly(imide siloxane) and carbon nanotube mixed matrix membranes for gas separation
journal, May 2006


Gas solubility, diffusivity and permeability in poly(ethylene oxide)
journal, August 2004


Thermal transitions in α,ω-diamino terminated poly(oxypropylene)-block-poly(oxyethylene)-block-poly(oxypropylene) aqueous solutions and their epoxy networks
journal, May 2005

  • Gómez Ribelles, Jose Luis; Salmerón Sanchez, Manuel; de la Osa, Luis Torres
  • Journal of Non-Crystalline Solids, Vol. 351, Issue 14-15
  • DOI: 10.1016/j.jnoncrysol.2005.02.015

Fluorinated polycarbonates for gas separation applications
journal, September 1989


Predictive Models for Mixed-Matrix Membrane Performance: A Review
journal, March 2013

  • Vinh-Thang, Hoang; Kaliaguine, Serge
  • Chemical Reviews, Vol. 113, Issue 7
  • DOI: 10.1021/cr3003888

637. The stability of transition-metal complexes
journal, January 1953

  • Irving, H.; Williams, R. J. P.
  • Journal of the Chemical Society (Resumed), Vol. 0, Issue 0, p. 3192-3210
  • DOI: 10.1039/jr9530003192

Hybrid membrane materials comprising organic polymers with rigid dispersed phases
journal, January 2004

  • Moore, Theodore T.; Mahajan, Rajiv; Vu, De Q.
  • AIChE Journal, Vol. 50, Issue 2
  • DOI: 10.1002/aic.10029

Characterization of permeability and sorption in Matrimid/C60 mixed matrix membranes
journal, January 2003


Basis of Permeability/Selectivity Tradeoff Relations in Polymeric Gas Separation Membranes
journal, January 1999


Water Reaction Mechanism in Metal Organic Frameworks with Coordinatively Unsaturated Metal Ions: MOF-74
journal, November 2014

  • Tan, Kui; Zuluaga, Sebastian; Gong, Qihan
  • Chemistry of Materials, Vol. 26, Issue 23
  • DOI: 10.1021/cm5038183

The diffusion time lag in polymer membranes containing adsorptive fillers
journal, January 1973

  • Paul, D. R.; Kemp, D. R.
  • Journal of Polymer Science: Polymer Symposia, Vol. 41, Issue 1
  • DOI: 10.1002/polc.5070410109

Enhanced H2 Adsorption in Isostructural Metal−Organic Frameworks with Open Metal Sites: Strong Dependence of the Binding Strength on Metal Ions
journal, November 2008

  • Zhou, Wei; Wu, Hui; Yildirim, Taner
  • Journal of the American Chemical Society, Vol. 130, Issue 46, p. 15268-15269
  • DOI: 10.1021/ja807023q

Computational and Experimental Studies on the Adsorption of CO, N 2 , and CO 2 on Mg-MOF-74
journal, June 2010

  • Valenzano, L.; Civalleri, B.; Chavan, S.
  • The Journal of Physical Chemistry C, Vol. 114, Issue 25
  • DOI: 10.1021/jp102574f

Evaluating metal–organic frameworks for natural gas storage
journal, January 2014

  • Mason, Jarad A.; Veenstra, Mike; Long, Jeffrey R.
  • Chemical Science, Vol. 5, Issue 1, p. 32-51
  • DOI: 10.1039/C3SC52633J

Evaluating metal–organic frameworks for post-combustion carbon dioxide capture via temperature swing adsorption
journal, January 2011

  • Mason, Jarad A.; Sumida, Kenji; Herm, Zoey R.
  • Energy & Environmental Science, Vol. 4, Issue 8, p. 3030-3040
  • DOI: 10.1039/c1ee01720a

CO2/CH4, CH4/H2 and CO2/CH4/H2 separations at high pressures using Mg2(dobdc)
journal, March 2012


    Works referencing / citing this record:

    High gas permselectivity in ZIF‐302/polyimide self‐consistent mixed‐matrix membrane
    journal, September 2019

    • Ghanem, Akram S.; Ba‐Shammakh, Mohamed; Usman, Muhammad
    • Journal of Applied Polymer Science, Vol. 137, Issue 13
    • DOI: 10.1002/app.48513

    2D molecular crystal lattices: advances in their synthesis, characterization, and application
    journal, January 2019

    • Solomos, Marina A.; Claire, F. James; Kempa, Thomas J.
    • Journal of Materials Chemistry A, Vol. 7, Issue 41
    • DOI: 10.1039/c9ta06534b

    Engineering of the Filler/Polymer Interface in Metal–Organic Framework‐Based Mixed‐Matrix Membranes to Enhance Gas Separation
    journal, July 2019

    • Ma, Liang; Svec, Frantisek; Lv, Yongqin
    • Chemistry – An Asian Journal, Vol. 14, Issue 20
    • DOI: 10.1002/asia.201900843