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Title: MOF‐5‐Polystyrene: Direct Production from Monomer, Improved Hydrolytic Stability, and Unique Guest Adsorption

Abstract

Abstract An unprecedented mode of reactivity of Zn 4 O‐based metal–organic frameworks (MOFs) offers a straightforward and powerful approach to polymer‐hybridized porous solids. The concept is illustrated with the production of MOF‐5‐polystyrene wherein polystyrene is grafted and uniformly distributed throughout MOF‐5 crystals after heating in pure styrene for 4–24 h. The surface area and polystyrene content of the material can be fine‐tuned by controlling the duration of heating styrene in the presence of MOF‐5. Polystyrene grafting significantly alters the physical and chemical properties of pristine MOF‐5, which is evident from the unique guest adsorption properties (solvatochromic dye uptake and improved CO 2 capacity) as well as the dramatically improved hydrolytic stability of composite. Based on the fact that MOF‐5 is the best studied member of the structure class, and has been produced at scale by industry, these findings can be directly leveraged for a range of current applications.

Authors:
 [1];  [1]; ORCiD logo [2]
+ Show Author Affiliations
  1. University of Michigan Department of Chemistry 930 N. University Ave Ann Arbor MI 48109 USA
  2. University of Michigan Department of Chemistry 930 N. University Ave Ann Arbor MI 48109 USA, Department of Macromolecular Science and Engineering University of Michigan Ann Arbor MI 48109 USA
Publication Date:
Sponsoring Org.:
USDOE
OSTI Identifier:
1400788
Grant/Contract Number:  
SC0004888
Resource Type:
Publisher's Accepted Manuscript
Journal Name:
Angewandte Chemie (International Edition)
Additional Journal Information:
Journal Name: Angewandte Chemie (International Edition) Journal Volume: 55 Journal Issue: 39; Journal ID: ISSN 1433-7851
Publisher:
Wiley Blackwell (John Wiley & Sons)
Country of Publication:
Germany
Language:
English

Citation Formats

Gamage, Nipuni‐Dhanesha H., McDonald, Kyle A., and Matzger, Adam J. MOF‐5‐Polystyrene: Direct Production from Monomer, Improved Hydrolytic Stability, and Unique Guest Adsorption. Germany: N. p., 2016. Web. doi:10.1002/anie.201606926.
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Gamage, Nipuni‐Dhanesha H., McDonald, Kyle A., & Matzger, Adam J. MOF‐5‐Polystyrene: Direct Production from Monomer, Improved Hydrolytic Stability, and Unique Guest Adsorption. Germany. https://doi.org/10.1002/anie.201606926
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Gamage, Nipuni‐Dhanesha H., McDonald, Kyle A., and Matzger, Adam J. Wed . "MOF‐5‐Polystyrene: Direct Production from Monomer, Improved Hydrolytic Stability, and Unique Guest Adsorption". Germany. https://doi.org/10.1002/anie.201606926.
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@article{osti_1400788,
title = {MOF‐5‐Polystyrene: Direct Production from Monomer, Improved Hydrolytic Stability, and Unique Guest Adsorption},
author = {Gamage, Nipuni‐Dhanesha H. and McDonald, Kyle A. and Matzger, Adam J.},
abstractNote = {Abstract An unprecedented mode of reactivity of Zn 4 O‐based metal–organic frameworks (MOFs) offers a straightforward and powerful approach to polymer‐hybridized porous solids. The concept is illustrated with the production of MOF‐5‐polystyrene wherein polystyrene is grafted and uniformly distributed throughout MOF‐5 crystals after heating in pure styrene for 4–24 h. The surface area and polystyrene content of the material can be fine‐tuned by controlling the duration of heating styrene in the presence of MOF‐5. Polystyrene grafting significantly alters the physical and chemical properties of pristine MOF‐5, which is evident from the unique guest adsorption properties (solvatochromic dye uptake and improved CO 2 capacity) as well as the dramatically improved hydrolytic stability of composite. Based on the fact that MOF‐5 is the best studied member of the structure class, and has been produced at scale by industry, these findings can be directly leveraged for a range of current applications.},
doi = {10.1002/anie.201606926},
journal = {Angewandte Chemie (International Edition)},
number = 39,
volume = 55,
place = {Germany},
year = {Wed Aug 24 00:00:00 EDT 2016},
month = {Wed Aug 24 00:00:00 EDT 2016}
}
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https://doi.org/10.1002/anie.201606926
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Works referenced in this record:

Water Sensitivity in Zn 4 O-Based MOFs is Structure and History Dependent
journal, February 2015

  • Guo, Ping; Dutta, Dhanadeep; Wong-Foy, Antek G.
  • Journal of the American Chemical Society, Vol. 137, Issue 7
  • DOI: 10.1021/ja512382f

polyMOFs: A Class of Interconvertible Polymer-Metal-Organic-Framework Hybrid Materials
journal, April 2015

  • Zhang, Zhenjie; Nguyen, Ha Thi Hoang; Miller, Stephen A.
  • Angewandte Chemie International Edition, Vol. 54, Issue 21
  • DOI: 10.1002/anie.201502733

Computational screening of metal organic frameworks for mixed matrix membrane applications
journal, July 2012

Macro-/microporous MOF composite beads
journal, January 2010

  • O'Neill, Laura D.; Zhang, Haifei; Bradshaw, Darren
  • Journal of Materials Chemistry, Vol. 20, Issue 27
  • DOI: 10.1039/c0jm00515k

Evolution of Nanoscale Pore Structure in Coordination Polymers During Thermal and Chemical Exposure Revealed by Positron Annihilation
journal, January 2010

  • Liu, Ming; Wong-Foy, Antek G.; Vallery, Richard S.
  • Advanced Materials, Vol. 22, Issue 14
  • DOI: 10.1002/adma.200903618

Coordination-Driven In Situ Self-Assembly Strategy for the Preparation of Metal-Organic Framework Hybrid Membranes
journal, July 2014

  • Zhang, Rong; Ji, Shulan; Wang, Naixin
  • Angewandte Chemie International Edition, Vol. 53, Issue 37
  • DOI: 10.1002/anie.201403978

Spontaneous polymerization of styrene in the presence of acid: further confirmation of the Mayo mechanism
journal, January 1992

The Mechanism of the Self-Initiated Thermal Polymerization of Styrene. Theoretical Solution of a Classic Problem
journal, February 2005

  • Khuong, Kelli S.; Jones, Walter H.; Pryor, William A.
  • Journal of the American Chemical Society, Vol. 127, Issue 4
  • DOI: 10.1021/ja0448667

Metal based gels as versatile precursors to synthesize stiff and integrated MOF/polymer composite membranes
journal, January 2015

  • Su, Pengcheng; Li, Wanbin; Zhang, Congyang
  • Journal of Materials Chemistry A, Vol. 3, Issue 40
  • DOI: 10.1039/C5TA04400F

In Situ Modification of Metal-Organic Frameworks in Mixed-Matrix Membranes
journal, June 2015

Polymer functionalization to enhance interface quality of mixed matrix membranes for high CO 2 /CH 4 gas separation
journal, January 2015

  • Tien-Binh, Nguyen; Vinh-Thang, Hoang; Chen, Xiao Yuan
  • Journal of Materials Chemistry A, Vol. 3, Issue 29
  • DOI: 10.1039/C5TA01597A

Improving Gas Separation Performance of Poly(vinylidene fluoride) Based Mixed Matrix Membranes Containing Metal–Organic Frameworks by Chemical Modification
journal, November 2015

  • Ahmadi Feijani, Elahe; Tavasoli, Ahmad; Mahdavi, Hossein
  • Industrial & Engineering Chemistry Research, Vol. 54, Issue 48
  • DOI: 10.1021/acs.iecr.5b02549

Filling Pore Space in a Microporous Coordination Polymer to Improve Methane Storage Performance
journal, February 2015

  • Tran, Ly D.; Feldblyum, Jeremy I.; Wong-Foy, Antek G.
  • Langmuir, Vol. 31, Issue 7
  • DOI: 10.1021/la504607c

From metal–organic framework (MOF) to MOF–polymer composite membrane: enhancement of low-humidity proton conductivity
journal, January 2013

  • Liang, Xiaoqiang; Zhang, Feng; Feng, Wei
  • Chem. Sci., Vol. 4, Issue 3
  • DOI: 10.1039/C2SC21927A

Carbon dioxide (CO2) absorption behavior of mixed matrix polymer composites containing a flexible coordination polymer
journal, March 2013

Photoinduced Postsynthetic Polymerization of a Metal-Organic Framework toward a Flexible Stand-Alone Membrane
journal, March 2015

  • Zhang, Yuanyuan; Feng, Xiao; Li, Haiwei
  • Angewandte Chemie International Edition, Vol. 54, Issue 14
  • DOI: 10.1002/anie.201500207

Practical Approach to Zeolitic Membranes and Coatings: State of the Art, Opportunities, Barriers, and Future Perspectives
journal, July 2012

  • Gascon, Jorge; Kapteijn, Freek; Zornoza, Beatriz
  • Chemistry of Materials, Vol. 24, Issue 15
  • DOI: 10.1021/cm301435j

Metal-organic frameworks
journal, January 2003

  • James, Stuart L.
  • Chemical Society Reviews, Vol. 32, Issue 5
  • DOI: 10.1039/b200393g

The Thermal Reaction of Styrene with Ethyl Thioglycolate; Evidence for the Termolecular Thermal Initiation of Styrene Polymerization
journal, March 1959

  • Hiatt, Richard R.; Bartlett, Paul D.
  • Journal of the American Chemical Society, Vol. 81, Issue 5
  • DOI: 10.1021/ja01514a033

Metal–Organic Framework/Polymer Mixed-Matrix Membranes for H 2 /CO 2 Separation: A Fully Atomistic Simulation Study
journal, August 2012

  • Zhang, Liling; Hu, Zhongqiao; Jiang, Jianwen
  • The Journal of Physical Chemistry C, Vol. 116, Issue 36
  • DOI: 10.1021/jp3067124

Nonlinear Properties in Coordination Copolymers Derived from Randomly Mixed Ligands
journal, June 2011

  • Park, Tae-Hong; Koh, Kyoungmoo; Wong-Foy, Antek G.
  • Crystal Growth & Design, Vol. 11, Issue 6
  • DOI: 10.1021/cg200271e

The dimerization of styrene
journal, February 1968

  • Mayo, Frank R.
  • Journal of the American Chemical Society, Vol. 90, Issue 5
  • DOI: 10.1021/ja01007a032

Characterization of Micro- and Mesoporosity in SBA-15 Materials from Adsorption Data by the NLDFT Method
journal, July 2001

  • Ravikovitch, Peter I.; Neimark, Alexander V.
  • The Journal of Physical Chemistry B, Vol. 105, Issue 29
  • DOI: 10.1021/jp010621u

Surface Functionalization of Porous Coordination Nanocages Via Click Chemistry and Their Application in Drug Delivery
journal, October 2010

Raman Spectroscopic Investigation of CH4 and N2 Adsorption in Metal−Organic Frameworks
journal, July 2007

  • Siberio-Pérez, Diana Y.; Wong-Foy, Antek G.; Yaghi, Omar M.
  • Chemistry of Materials, Vol. 19, Issue 15, p. 3681-3685
  • DOI: 10.1021/cm070542g

Polymer@MOF@MOF: “grafting from” atom transfer radical polymerization for the synthesis of hybrid porous solids
journal, January 2015

  • McDonald, Kyle A.; Feldblyum, Jeremy I.; Koh, Kyoungmoo
  • Chemical Communications, Vol. 51, Issue 60
  • DOI: 10.1039/C5CC03027G

Chain Transfer in the Polymerization of Styrene. VIII. Chain Transfer with Bromobenzene and Mechanism of Thermal Initiation 1
journal, December 1953

  • Mayo, Frank R.
  • Journal of the American Chemical Society, Vol. 75, Issue 24
  • DOI: 10.1021/ja01120a010

One step synthesis of MOF–polymer composites
journal, January 2016

  • Calvez, C. Le; Zouboulaki, M.; Petit, C.
  • RSC Advances, Vol. 6, Issue 21
  • DOI: 10.1039/C5RA25238E

Density functional theory model for calculating pore size distributions: pore structure of nanoporous catalysts
journal, July 1998

  • Ravikovitch, Peter I.; Haller, Gary L.; Neimark, Alexander V.
  • Advances in Colloid and Interface Science, Vol. 76-77
  • DOI: 10.1016/S0001-8686(98)00047-5

A Facile and General Coating Approach to Moisture/Water-Resistant Metal–Organic Frameworks with Intact Porosity
journal, November 2014

  • Zhang, Wang; Hu, Yingli; Ge, Jin
  • Journal of the American Chemical Society, Vol. 136, Issue 49
  • DOI: 10.1021/ja509960n

Mixed Matrix Membranes with Strengthened MOFs/Polymer Interfacial Interaction and Improved Membrane Performance
journal, April 2014

  • Lin, Rijia; Ge, Lei; Hou, Lei
  • ACS Applied Materials & Interfaces, Vol. 6, Issue 8
  • DOI: 10.1021/am500081e

Postsynthetic tuning of hydrophilicity in pyrazolate MOFs to modulate water adsorption properties
journal, January 2013

  • Wade, Casey R.; Corrales-Sanchez, Tachmajal; Narayan, Tarun C.
  • Energy & Environmental Science, Vol. 6, Issue 7
  • DOI: 10.1039/c3ee40876k

Thermal Self-Initiation in Stable Free-Radical Polymerization of Styrene
journal, January 2009

Recent Advances in Metal-Organic Framework-Based Mixed Matrix Membranes
journal, March 2013

  • Erucar, Ilknur; Yilmaz, Gamze; Keskin, Seda
  • Chemistry - An Asian Journal, Vol. 8, Issue 8
  • DOI: 10.1002/asia.201300084

Functional Networks of Organic and Coordination Polymers: Catalysis of Fructose Conversion
journal, October 2014

  • Bromberg, Lev; Su, Xiao; Hatton, T. Alan
  • Chemistry of Materials, Vol. 26, Issue 21
  • DOI: 10.1021/cm503098p

Selective formation of rectangular grid coordination polymers with grid dimensions 10 × 15, 10 × 20 and 15 × 20 Å
journal, January 2001

  • Biradha, Kumar; Fujita, Makoto
  • Chemical Communications, Issue 1
  • DOI: 10.1039/b007014i

Challenges and opportunities for mixed-matrix membranes for gas separation
journal, January 2013

  • Dong, Guangxi; Li, Hongyu; Chen, Vicki
  • Journal of Materials Chemistry A, Vol. 1, Issue 15
  • DOI: 10.1039/c3ta00927k

Metal−organic framework composite membranes: Synthesis and separation applications
journal, October 2015

Systematic Design of Pore Size and Functionality in Isoreticular MOFs and Their Application in Methane Storage
journal, January 2002

  • Eddaoudi, Mohamed; Kim, Jaheon; Rosi, Nathaniel
  • Science, Vol. 295, Issue 5554, p. 469-472
  • DOI: 10.1126/science.1067208

Recent advances of inorganic fillers in mixed matrix membrane for gas separation
journal, October 2011

Coordination copolymerization of three carboxylate linkers into a pillared layer framework
journal, January 2014

  • Dutta, Ananya; Wong-Foy, Antek G.; Matzger, Adam J.
  • Chemical Science, Vol. 5, Issue 10
  • DOI: 10.1039/C3SC53549E

polyMOFs: A Class of Interconvertible Polymer-Metal-Organic-Framework Hybrid Materials
journal, April 2015

  • Zhang, Zhenjie; Nguyen, Ha Thi Hoang; Miller, Stephen A.
  • Angewandte Chemie, Vol. 127, Issue 21
  • DOI: 10.1002/ange.201502733

Metal–organic framework nanosheets in polymer composite materials for gas separation
journal, November 2014

  • Rodenas, Tania; Luz, Ignacio; Prieto, Gonzalo
  • Nature Materials, Vol. 14, Issue 1
  • DOI: 10.1038/nmat4113

MOF-Polymer Composite Microcapsules Derived from Pickering Emulsions
journal, April 2013

Coordination-Driven In Situ Self-Assembly Strategy for the Preparation of Metal-Organic Framework Hybrid Membranes
journal, July 2014

Polymer–Metal–Organic Frameworks (polyMOFs) as Water Tolerant Materials for Selective Carbon Dioxide Separations
journal, January 2016

  • Zhang, Zhenjie; Nguyen, Ha Thi Hoang; Miller, Stephen A.
  • Journal of the American Chemical Society, Vol. 138, Issue 3
  • DOI: 10.1021/jacs.5b11034

Metal–organic framework based mixed matrix membranes: a solution for highly efficient CO 2 capture?
journal, January 2015

  • Seoane, Beatriz; Coronas, Joaquin; Gascon, Ignacio
  • Chemical Society Reviews, Vol. 44, Issue 8
  • DOI: 10.1039/C4CS00437J

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

Adsorption of Gases in Multimolecular Layers
journal, February 1938

  • Brunauer, Stephen; Emmett, P. H.; Teller, Edward
  • Journal of the American Chemical Society, Vol. 60, Issue 2, p. 309-319
  • DOI: 10.1021/ja01269a023

Metal organic framework mixed matrix membranes for gas separations
journal, June 2010

In Situ Modification of Metal-Organic Frameworks in Mixed-Matrix Membranes
journal, June 2015

  • Denny, Michael S.; Cohen, Seth M.
  • Angewandte Chemie International Edition, Vol. 54, Issue 31
  • DOI: 10.1002/anie.201504077

Photoinduced Postsynthetic Polymerization of a Metal-Organic Framework toward a Flexible Stand-Alone Membrane
journal, March 2015

Nile Red as a solvatochromic dye for measuring solvent strength in normal liquids and mixtures of normal liquids with supercritical and near critical fluids
journal, March 1990

  • Deye, Jerry F.; Berger, T. A.; Anderson, Albert G.
  • Analytical Chemistry, Vol. 62, Issue 6
  • DOI: 10.1021/ac00205a015

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
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