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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}
}

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

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