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Title: Block co-polyMOFs: morphology control of polymer–MOF hybrid materials

Abstract

The hybridization of block copolymers and metal–organic frameworks (MOFs) to create novelmaterials (block co-polyMOFs, BCPMOFs) with controlled morphologies is reported. In this study, block copolymers containing poly(1,4-benzenedicarboxylic acid, H2bdc) and morphology directing poly(ethylene glycol) (PEG) or poly(cyclooctadiene) (poly(COD)) blocks were synthesized for the preparation of BCPMOFs. Block copolymer architecture and weight fractions were found to have a significant impact on the resulting morphology, mediated through the assembly of polymer precursors prior to MOF formation, as determined through dynamic light scattering. Simple modification of block copolymer weight fraction allowed for tuning of particle size and morphology with either faceted and spherical features. Modification of polymer block architecture represents a simple and powerful method to direct morphology in highly crystalline polyMOF materials. Furthermore, the BCPMOFs could be prepared from both Zr4+ and Zn2+ MOFs, yielding hybrid materials with appreciable surface areas and tuneable porosities. The resulting Zn2+ BCPMOF yielded materials with very narrow size distributions and uniform cubic morphologies. The use of topology in BCPMOFs to direct morphology in block copolymer assemblies may open new methodologies to access complex materials far from thermodynamic equilibrium.

Authors:
 [1]; ORCiD logo [1]; ORCiD logo [1]
  1. Department of Chemistry and Biochemistry, University of California, San Diego, La Jolla, USA
Publication Date:
Research Org.:
Univ. of California, San Diego, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Materials Sciences & Engineering Division; National Science Foundation (NSF); Inamori Foundation
OSTI Identifier:
1484919
Alternate Identifier(s):
OSTI ID: 1610002
Grant/Contract Number:  
FG02-08ER46519; ECCS-1542148
Resource Type:
Published Article
Journal Name:
Chemical Science
Additional Journal Information:
Journal Name: Chemical Science Journal Volume: 10 Journal Issue: 6; Journal ID: ISSN 2041-6520
Publisher:
Royal Society of Chemistry
Country of Publication:
United Kingdom
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Chemistry

Citation Formats

Ayala, Sergio, Bentz, Kyle C., and Cohen, Seth M. Block co-polyMOFs: morphology control of polymer–MOF hybrid materials. United Kingdom: N. p., 2018. Web. doi:10.1039/C8SC04250K.
Ayala, Sergio, Bentz, Kyle C., & Cohen, Seth M. Block co-polyMOFs: morphology control of polymer–MOF hybrid materials. United Kingdom. doi:10.1039/C8SC04250K.
Ayala, Sergio, Bentz, Kyle C., and Cohen, Seth M. Fri . "Block co-polyMOFs: morphology control of polymer–MOF hybrid materials". United Kingdom. doi:10.1039/C8SC04250K.
@article{osti_1484919,
title = {Block co-polyMOFs: morphology control of polymer–MOF hybrid materials},
author = {Ayala, Sergio and Bentz, Kyle C. and Cohen, Seth M.},
abstractNote = {The hybridization of block copolymers and metal–organic frameworks (MOFs) to create novelmaterials (block co-polyMOFs, BCPMOFs) with controlled morphologies is reported. In this study, block copolymers containing poly(1,4-benzenedicarboxylic acid, H2bdc) and morphology directing poly(ethylene glycol) (PEG) or poly(cyclooctadiene) (poly(COD)) blocks were synthesized for the preparation of BCPMOFs. Block copolymer architecture and weight fractions were found to have a significant impact on the resulting morphology, mediated through the assembly of polymer precursors prior to MOF formation, as determined through dynamic light scattering. Simple modification of block copolymer weight fraction allowed for tuning of particle size and morphology with either faceted and spherical features. Modification of polymer block architecture represents a simple and powerful method to direct morphology in highly crystalline polyMOF materials. Furthermore, the BCPMOFs could be prepared from both Zr4+ and Zn2+ MOFs, yielding hybrid materials with appreciable surface areas and tuneable porosities. The resulting Zn2+ BCPMOF yielded materials with very narrow size distributions and uniform cubic morphologies. The use of topology in BCPMOFs to direct morphology in block copolymer assemblies may open new methodologies to access complex materials far from thermodynamic equilibrium.},
doi = {10.1039/C8SC04250K},
journal = {Chemical Science},
number = 6,
volume = 10,
place = {United Kingdom},
year = {2018},
month = {11}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
DOI: 10.1039/C8SC04250K

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Cited by: 9 works
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