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

Journal Article · · Chemical Science
DOI:https://doi.org/10.1039/C8SC04250K· OSTI ID:1484919

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.

Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Materials Sciences & Engineering Division
Grant/Contract Number:
FG02-08ER46519
OSTI ID:
1484919
Alternate ID(s):
OSTI ID: 1610002
OSTI ID: 1779878
Journal Information:
Chemical Science, Journal Name: Chemical Science Journal Issue: 6 Vol. 10; ISSN 2041-6520; ISSN CSHCBM
Publisher:
Royal Society of ChemistryCopyright Statement
Country of Publication:
United Kingdom
Language:
English

References (55)

Double-Hydrophilic Block Copolymers: Synthesis and Application as Novel Surfactants and Crystal Growth Modifiers journal February 2001
Metallopolymers: New Multifunctional Materials journal November 2007
Higher-Order Organization by Mesoscale Self-Assembly and Transformation of Hybrid Nanostructures journal May 2003
polyMOFs: A Class of Interconvertible Polymer-Metal-Organic-Framework Hybrid Materials journal April 2015
Definitive Molecular Level Characterization of Defects in UiO-66 Crystals journal August 2015
Supramolecular Metallopolymers: From Linear Materials to Infinite Networks journal October 2018
Controlled Synthesis of Porous Coordination-Polymer Microcrystals with Definite Morphologies and Sizes under Mild Conditions journal September 2014
Synthesis of Coordination Polymer Nanoparticles using Self-Assembled Block Copolymers as Template journal November 2017
Polymer-assisted synthesis of nanocrystalline copper-based metal–organic framework for amine oxidation journal March 2011
Effects of polyvinylidene fluoride content in the synthesis of novel zinc-based metal-organic frameworks polymer composite crystals journal June 2018
Modulated synthesis of monodisperse MOF-5 crystals with tunable sizes and shapes journal July 2018
Acyclic diene metathesis polymerization: History, methods and applications journal June 2017
Tuning Dynamic Mechanical Response in Metallopolymer Networks through Simultaneous Control of Structural and Temporal Properties of the Networks journal August 2016
50th Anniversary Perspective : Block Polymers—Pure Potential journal December 2016
A Method for the Preparation of Highly Porous, Nanosized Crystals of Isoreticular Metal−Organic Frameworks journal January 2011
Effect of Organic Polymer Additive on Crystallization of Porous Coordination Polymer journal February 2006
Synthesis of Metal-Organic Frameworks (MOFs): Routes to Various MOF Topologies, Morphologies, and Composites journal September 2011
Controlling Mineral Morphologies and Structures in Biological and Synthetic Systems journal November 2008
Transformation of Metal–Organic Framework to Polymer Gel by Cross-Linking the Organic Ligands Preorganized in Metal–Organic Framework journal March 2013
Synthesis and Integration of Fe-soc-MOF Cubes into Colloidosomes via a Single-Step Emulsion-Based Approach journal May 2013
Growth-Controlled Formation of Porous Coordination Polymer Particles journal December 2008
Polymer–Metal–Organic Frameworks (polyMOFs) as Water Tolerant Materials for Selective Carbon Dioxide Separations journal January 2016
Metal–Organic Polyhedral Core as a Versatile Scaffold for Divergent and Convergent Star Polymer Synthesis journal May 2016
Poly(isophthalic acid)(ethylene oxide) as a Macromolecular Modulator for Metal–Organic Polyhedra journal July 2016
Block Co-PolyMOCs by Stepwise Self-Assembly journal August 2016
Morphogenesis of Metal–Organic Mesocrystals Mediated by Double Hydrophilic Block Copolymers journal February 2018
Precisely Defined Amphiphilic Graft Copolymers journal November 2007
Conductive Block Copolymers Integrated into Polynorbornene-Derived Scaffolds journal August 2008
Metal–organic frameworks for membrane-based separations journal November 2016
Colloidal inverse bicontinuous cubic membranes of block copolymers with tunable surface functional groups journal May 2014
A new method to position and functionalize metal-organic framework crystals journal March 2011
Cubosomes from hierarchical self-assembly of poly(ionic liquid) block copolymers journal January 2017
Correlated defect nanoregions in a metal–organic framework journal June 2014
Mixing of immiscible polymers using nanoporous coordination templates journal July 2015
A dynamic and multi-responsive porous flexible metal–organic material journal August 2018
Discovery, development, and functionalization of Zr( iv )-based metal–organic frameworks journal January 2012
Structuring of metal–organic frameworks at the mesoscopic/macroscopic scale journal January 2014
Solvent determines the formation and properties of metal–organic frameworks journal January 2015
Synthesis of highly monodispersed Ga- soc -MOF hollow cubes, colloidosomes and nanocomposites journal January 2016
Hierarchical structure and porosity in UiO-66 polyMOFs journal January 2017
Synthesis and characterization of metallo-supramolecular polymers journal January 2016
Hypercrosslinked porous polymer materials: design, synthesis, and applications journal January 2017
Metal–organic frameworks: functional luminescent and photonic materials for sensing applications journal January 2017
Isoreticular expansion of polyMOFs achieves high surface area materials journal January 2017
A general and efficient approach for tuning the crystal morphology of classical MOFs journal January 2018
Hybridization of MOFs and polymers journal January 2017
Metal–organic frameworks for the removal of toxic industrial chemicals and chemical warfare agents journal January 2017
Block co-polyMOFs: assembly of polymer–polyMOF hybrids via iterative exponential growth and “click” chemistry journal January 2017
High-throughput screening of solid-state catalysts for nerve agent degradation journal January 2018
Polymerization reactions in porous coordination polymers journal January 2009
Secondary building units, nets and bonding in the chemistry of metal–organic frameworks
  • Tranchemontagne, David J.; Mendoza-Cortés, José L.; O’Keeffe, Michael
  • Chemical Society Reviews, Vol. 38, Issue 5, p. 1257-1283 https://doi.org/10.1039/b817735j
journal January 2009
Self-assembly of block copolymers journal January 2012
Size- and morphology-controlled NH2-MIL-53(Al) prepared in DMF–water mixed solvents journal January 2013
Practical water production from desert air journal June 2018
On the Origins of Morphological Complexity in Block Copolymer Surfactants journal April 2003

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