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Stable Metal–Organic Frameworks: Design, Synthesis, and Applications

Journal Article · · Advanced Materials
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  1. Department of Chemistry Texas A&,M University College Station TX 77843‐3255 USA
  2. Department of Chemistry Texas A&,M University College Station TX 77843‐3255 USA, Department of Materials Science and Engineering Texas A&,M University College Station TX 77843‐3003 USA
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Abstract

Metal–organic frameworks (MOFs) are an emerging class of porous materials with potential applications in gas storage, separations, catalysis, and chemical sensing. Despite numerous advantages, applications of many MOFs are ultimately limited by their stability under harsh conditions. Herein, the recent advances in the field of stable MOFs, covering the fundamental mechanisms of MOF stability, design, and synthesis of stable MOF architectures, and their latest applications are reviewed. First, key factors that affect MOF stability under certain chemical environments are introduced to guide the design of robust structures. This is followed by a short review of synthetic strategies of stable MOFs including modulated synthesis and postsynthetic modifications. Based on the fundamentals of MOF stability, stable MOFs are classified into two categories: high‐valency metal–carboxylate frameworks and low‐valency metal–azolate frameworks. Along this line, some representative stable MOFs are introduced, their structures are described, and their properties are briefly discussed. The expanded applications of stable MOFs in Lewis/Brønsted acid catalysis, redox catalysis, photocatalysis, electrocatalysis, gas storage, and sensing are highlighted. Overall, this review is expected to guide the design of stable MOFs by providing insights into existing structures, which could lead to the discovery and development of more advanced functional materials.

Sponsoring Organization:
USDOE
Grant/Contract Number:
FE0026472; SC0001015
OSTI ID:
1420186
Alternate ID(s):
OSTI ID: 1537364
Journal Information:
Advanced Materials, Journal Name: Advanced Materials Journal Issue: 37 Vol. 30; ISSN 0935-9648
Publisher:
Wiley Blackwell (John Wiley & Sons)Copyright Statement
Country of Publication:
Germany
Language:
English

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Metal–organic frameworks as selectivity regulators for hydrogenation reactions journal October 2016
Selectivity and direct visualization of carbon dioxide and sulfur dioxide in a decorated porous host journal September 2012
Highly ordered alignment of a vinyl polymer by host–guest cross-polymerization journal February 2013
Discovery and introduction of a (3,18)-connected net as an ideal blueprint for the design of metal–organic frameworks journal June 2014
Made-to-order metal-organic frameworks for trace carbon dioxide removal and air capture journal June 2014
Kinetically tuned dimensional augmentation as a versatile synthetic route towards robust metal–organic frameworks journal December 2014
Stable metal-organic frameworks containing single-molecule traps for enzyme encapsulation journal January 2015
A microdiffraction set-up for nanoporous metal–organic-framework-type solids journal September 2007
Porous metal–organic-framework nanoscale carriers as a potential platform for drug delivery and imaging journal December 2009
Destruction of chemical warfare agents using metal–organic frameworks journal March 2015
Scalable synthesis and post-modification of a mesoporous metal-organic framework called NU-1000 journal December 2015
Hydrothermal synthesis, thermal behaviour and structure determination from powder data of a porous three-dimensional europium trimesate: Eu 3 (H 2 O)(OH) 6 [C 6 H 3 (CO 2 ) 3 ]·3H 2 O or MIL-63 journal January 2002
Synthesis, structure and properties of a three-dimensional porous rare-earth carboxylate MIL-83(Eu): Eu 2 (O 2 C-C 10 H 14 -CO 2 ) 3 journal January 2004
A new isoreticular class of metal-organic-frameworks with the MIL-88 topology journal January 2006
Synthesis and catalytic properties of MIL-100(Fe), an iron( iii ) carboxylate with large pores journal January 2007
A zirconium methacrylate oxocluster as precursor for the low-temperature synthesis of porous zirconium( iv ) dicarboxylates journal January 2010
Hydrogenstorage in water-stable metal–organic frameworks incorporating 1,3- and 1,4-benzenedipyrazolate journal January 2010
An amino-modified Zr-terephthalate metal–organic framework as an acid–base catalyst for cross-aldol condensation journal January 2011
Iron( iii ) metal–organic frameworks as solid Lewis acids for the isomerization of α-pinene oxide journal January 2012
A mesoporous aluminium metal–organic framework with 3 nm open pores journal January 2013
A p-type Ti( iv )-based metal–organic framework with visible-light photo-response journal January 2014
Metal–organic framework composites journal January 2014
Toxic gas removal – metal–organic frameworks for the capture and degradation of toxic gases and vapours journal January 2014
The surface chemistry of metal–organic frameworks journal January 2015
Synthesis of a mixed valence state Ce-MOF as an oxidase mimetic for the colorimetric detection of biothiols journal January 2015
Tuning the structure and function of metal–organic frameworks via linker design journal January 2014
Water adsorption in MOFs: fundamentals and applications journal January 2014
High valence 3p and transition metal based MOFs journal January 2014
A supermolecular building approach for the design and construction of metal–organic frameworks journal January 2014
Co@NH 2 -MIL-125(Ti): cobaloxime-derived metal–organic framework-based composite for light-driven H 2 production journal January 2015
Merging of the photocatalysis and copper catalysis in metal–organic frameworks for oxidative C–C bond formation journal January 2015
Exploiting parameter space in MOFs: a 20-fold enhancement of phosphate-ester hydrolysis with UiO-66-NH 2 journal January 2015
Cerium-based metal organic frameworks with UiO-66 architecture: synthesis, properties and redox catalytic activity journal January 2015
Synthesis of nanocrystals of Zr-based metal–organic frameworks with csq-net: significant enhancement in the degradation of a nerve agent simulant journal January 2015
A visually detectable pH responsive zirconium metal–organic framework journal January 2016
Nickel( ii ) and copper( i , ii )-based metal-organic frameworks incorporating an extended tris-pyrazolate linker journal January 2015
Zr-based metal–organic frameworks: design, synthesis, structure, and applications journal January 2016
Comparative study of titanium-functionalized UiO-66: support effect on the oxidation of cyclohexene using hydrogen peroxide journal January 2015
Controlled synthesis of highly stable zeolitic imidazolate framework-67 dodecahedra and their use towards the templated formation of a hollow Co 3 O 4 catalyst for CO oxidation journal January 2016
A single crystalline porphyrinic titanium metal–organic framework journal January 2015
The preparation of an ultrastable mesoporous Cr( iii )-MOF via reductive labilization journal January 2015
AIE-active tetraphenylethene functionalized metal–organic framework for selective detection of nitroaromatic explosives and organic photocatalysis journal January 2016
A highly stable dimethyl-functionalized Ce( iv )-based UiO-66 metal–organic framework material for gas sorption and redox catalysis journal January 2016
Applications of water stable metal–organic frameworks journal January 2016
Synthesis and structure of Zr( iv )- and Ce( iv )-based CAU-24 with 1,2,4,5-tetrakis(4-carboxyphenyl)benzene journal January 2016
Coupling two enzymes into a tandem nanoreactor utilizing a hierarchically structured MOF journal January 2016
Rationally tuning host–guest interactions to free hydroxide ions within intertrimerically cuprophilic metal–organic frameworks for high OH − conductivity journal January 2017
Titanium coordination compounds: from discrete metal complexes to metal–organic frameworks journal January 2017
Hybridization of MOFs and polymers journal January 2017
Enzyme–MOF (metal–organic framework) composites journal January 2017
Catalytic properties of MIL-101 journal January 2008
Selective gas adsorption and separation in metal–organic frameworks journal January 2009
Metal–organic framework materials as catalysts journal January 2009
Enantioselective catalysis with homochiral metal–organic frameworks journal January 2009
Isoreticular synthesis and modification of frameworks with the UiO-66 topology journal January 2010
Rapid synthesis of zeolitic imidazolate framework-8 (ZIF-8) nanocrystals in an aqueous system journal January 2011
Titanium oxo-clusters: precursors for a Lego-like construction of nanostructured hybrid materials journal January 2011
High thermal and chemical stability in pyrazolate-bridged metal–organic frameworks with exposed metal sites journal January 2011
Enhanced carbon dioxide capture upon incorporation of N,N′-dimethylethylenediamine in the metal–organic framework CuBTTri journal January 2011
Zr(iv) and Hf(iv) based metal–organic frameworks with reo-topology journal January 2012
Amine-functionalized zirconium metal–organic framework as efficient visible-light photocatalyst for aerobic organic transformations journal January 2012
CAU-3: A new family of porous MOFs with a novel Al-based brick: [Al2(OCH3)4(O2C-X-CO2)] (X = aryl) journal January 2012
Probing the adsorption performance of the hybrid porous MIL-68(Al): a synergic combination of experimental and modelling tools journal January 2012
Tuning the catalytic performance of metal–organic frameworks in fine chemistry by active site engineering journal January 2012
Versatile functionalization of the NU-1000 platform by solvent-assisted ligand incorporation journal January 2014
Tailoring of network dimensionality and porosity adjustment in Zr- and Hf-based MOFs journal January 2013
Bifunctional pyrazolate–carboxylate ligands for isoreticular cobalt and zinc MOF-5 analogs with magnetic analysis of the {Co4(μ4-O)} node journal January 2013
CFA-2 and CFA-3 (Coordination Framework Augsburg University-2 and -3); novel MOFs assembled from trinuclear Cu(i)/Ag(i) secondary building units and 3,3′,5,5′-tetraphenyl-bipyrazolate ligands journal January 2013
Postsynthetic tuning of hydrophilicity in pyrazolate MOFs to modulate water adsorption properties journal January 2013
Stability and degradation mechanisms of metal–organic frameworks containing the Zr6O4(OH)4 secondary building unit journal January 2013
Extended and functionalized porous iron(iii) tri- or dicarboxylates with MIL-100/101 topologies journal January 2014
Exceptional chemical and thermal stability of zeolitic imidazolate frameworks journal June 2006
Systematic Design of Pore Size and Functionality in Isoreticular MOFs and Their Application in Methane Storage journal January 2002
A Chromium Terephthalate-Based Solid with Unusually Large Pore Volumes and Surface Area journal September 2005
Role of Solvent-Host Interactions That Lead to Very Large Swelling of Hybrid Frameworks journal March 2007
High-Throughput Synthesis of Zeolitic Imidazolate Frameworks and Application to CO2 Capture journal February 2008
Ultrahigh Porosity in Metal-Organic Frameworks journal July 2010
A Chemically Functionalizable Nanoporous Material [Cu3(TMA)2(H2O)3]n journal February 1999
A metal-organic framework-based splitter for separating propylene from propane journal July 2016
Hydrolytically stable fluorinated metal-organic frameworks for energy-efficient dehydration journal May 2017
Water harvesting from air with metal-organic frameworks powered by natural sunlight journal April 2017

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