skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Increasing the Stability of Metal-Organic Frameworks

Abstract

Metal-organic frameworks (MOFs) are a new category of advanced porous materials undergoing study by many researchers for their vast variety of both novel structures and potentially useful properties arising from them. Their high porosities, tunable structures, and convenient process of introducing both customizable functional groups and unsaturated metal centers have afforded excellent gas sorption and separation ability, catalytic activity, luminescent properties, and more. However, the robustness and reactivity of a given framework are largely dependent on its metal-ligand interactions, where the metal-containing clusters are often vulnerable to ligand substitution by water or other nucleophiles, meaning that the frameworks may collapse upon exposure even to moist air. Other frameworks may collapse upon thermal or vacuum treatment or simply over time. This instability limits the practical uses of many MOFs. In order to further enhance the stability of the framework, many different approaches, such as the utilization of high-valence metal ions or nitrogen-donor ligands, were recently investigated. This review details the efforts of both our research group and others to synthesize MOFs possessing drastically increased chemical and thermal stability, in addition to exemplary performance for catalysis, gas sorption, and separation.

Authors:
ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [2]
  1. Department of Chemistry, Texas A&M University, College Station, TX 77842, USA
  2. Department of Chemistry, Texas A&M University, College Station, TX 77842, USA, Department of Materials Science and Engineering, Texas A&M University, College Station, TX 77842, USA
Publication Date:
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1209730
Grant/Contract Number:  
SC0001015; FC36-07G017033
Resource Type:
Published Article
Journal Name:
Advances in Chemistry
Additional Journal Information:
Journal Name: Advances in Chemistry Journal Volume: 2014; Journal ID: ISSN 2356-6612
Publisher:
Hindawi Publishing Corporation
Country of Publication:
Country unknown/Code not available
Language:
English

Citation Formats

Bosch, Mathieu, Zhang, Muwei, and Zhou, Hong-Cai. Increasing the Stability of Metal-Organic Frameworks. Country unknown/Code not available: N. p., 2014. Web. doi:10.1155/2014/182327.
Bosch, Mathieu, Zhang, Muwei, & Zhou, Hong-Cai. Increasing the Stability of Metal-Organic Frameworks. Country unknown/Code not available. doi:10.1155/2014/182327.
Bosch, Mathieu, Zhang, Muwei, and Zhou, Hong-Cai. Thu . "Increasing the Stability of Metal-Organic Frameworks". Country unknown/Code not available. doi:10.1155/2014/182327.
@article{osti_1209730,
title = {Increasing the Stability of Metal-Organic Frameworks},
author = {Bosch, Mathieu and Zhang, Muwei and Zhou, Hong-Cai},
abstractNote = {Metal-organic frameworks (MOFs) are a new category of advanced porous materials undergoing study by many researchers for their vast variety of both novel structures and potentially useful properties arising from them. Their high porosities, tunable structures, and convenient process of introducing both customizable functional groups and unsaturated metal centers have afforded excellent gas sorption and separation ability, catalytic activity, luminescent properties, and more. However, the robustness and reactivity of a given framework are largely dependent on its metal-ligand interactions, where the metal-containing clusters are often vulnerable to ligand substitution by water or other nucleophiles, meaning that the frameworks may collapse upon exposure even to moist air. Other frameworks may collapse upon thermal or vacuum treatment or simply over time. This instability limits the practical uses of many MOFs. In order to further enhance the stability of the framework, many different approaches, such as the utilization of high-valence metal ions or nitrogen-donor ligands, were recently investigated. This review details the efforts of both our research group and others to synthesize MOFs possessing drastically increased chemical and thermal stability, in addition to exemplary performance for catalysis, gas sorption, and separation.},
doi = {10.1155/2014/182327},
journal = {Advances in Chemistry},
number = ,
volume = 2014,
place = {Country unknown/Code not available},
year = {2014},
month = {9}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
DOI: 10.1155/2014/182327

Save / Share:

Works referenced in this record:

A Chemically Functionalizable Nanoporous Material [Cu3(TMA)2(H2O)3]n
journal, February 1999


Stability and degradation mechanisms of metal–organic frameworks containing the Zr6O4(OH)4 secondary building unit
journal, January 2013

  • DeCoste, Jared B.; Peterson, Gregory W.; Jasuja, Himanshu
  • Journal of Materials Chemistry A, Vol. 1, Issue 18
  • DOI: 10.1039/c3ta10662d

Synthesis Modulation as a Tool To Increase the Catalytic Activity of Metal–Organic Frameworks: The Unique Case of UiO-66(Zr)
journal, July 2013

  • Vermoortele, Frederik; Bueken, Bart; Le Bars, Gaëlle
  • Journal of the American Chemical Society, Vol. 135, Issue 31
  • DOI: 10.1021/ja405078u

Ligand-Directed Strategy for Zeolite-Type Metal–Organic Frameworks: Zinc(II) Imidazolates with Unusual Zeolitic Topologies
journal, February 2006

  • Huang, Xiao-Chun; Lin, Yan-Yong; Zhang, Jie-Peng
  • Angewandte Chemie International Edition, Vol. 45, Issue 10, p. 1557-1559
  • DOI: 10.1002/anie.200503778

Metal-Ion Metathesis in Metal-Organic Frameworks: A Synthetic Route to New Metal-Organic Frameworks
journal, November 2012

  • Kim, Yonghwi; Das, Sunirban; Bhattacharya, Saurav
  • Chemistry - A European Journal, Vol. 18, Issue 52
  • DOI: 10.1002/chem.201202899

Enhanced Hydrostability in Ni-Doped MOF-5
journal, August 2012

  • Li, Huanhuan; Shi, Wei; Zhao, Kaina
  • Inorganic Chemistry, Vol. 51, Issue 17
  • DOI: 10.1021/ic3002898

Modulated Synthesis of Zr-Based Metal-Organic Frameworks: From Nano to Single Crystals
journal, May 2011

  • Schaate, Andreas; Roy, Pascal; Godt, Adelheid
  • Chemistry - A European Journal, Vol. 17, Issue 24
  • DOI: 10.1002/chem.201003211

Cation-Triggered Drug Release from a Porous Zinc−Adeninate Metal−Organic Framework
journal, June 2009

  • An, Jihyun; Geib, Steven J.; Rosi, Nathaniel L.
  • Journal of the American Chemical Society, Vol. 131, Issue 24
  • DOI: 10.1021/ja902972w

Metal-adeninate vertices for the construction of an exceptionally porous metal-organic framework
journal, January 2012

  • An, Jihyun; Farha, Omar K.; Hupp, Joseph T.
  • Nature Communications, Vol. 3, Issue 1
  • DOI: 10.1038/ncomms1618

Disclosing the Complex Structure of UiO-66 Metal Organic Framework: A Synergic Combination of Experiment and Theory
journal, April 2011

  • Valenzano, Loredana; Civalleri, Bartolomeo; Chavan, Sachin
  • Chemistry of Materials, Vol. 23, Issue 7, p. 1700-1718
  • DOI: 10.1021/cm1022882

Characterization of metal-organic frameworks by water adsorption
journal, April 2009


An Isoreticular Series of Metal-Organic Frameworks with Dendritic Hexacarboxylate Ligands and Exceptionally High Gas-Uptake Capacity
journal, June 2010

  • Yuan, Daqiang; Zhao, Dan; Sun, Daofeng
  • Angewandte Chemie International Edition, Vol. 49, Issue 31, p. 5357-5361
  • DOI: 10.1002/anie.201001009

Stability improvement of Cu3(BTC)2 metal–organic frameworks under steaming conditions by encapsulation of a Keggin polyoxometalate
journal, January 2011

  • Mustafa, Danilo; Breynaert, Eric; Bajpe, Sneha R.
  • Chemical Communications, Vol. 47, Issue 28
  • DOI: 10.1039/c1cc12341f

Construction of Ultrastable Porphyrin Zr Metal–Organic Frameworks through Linker Elimination
journal, October 2013

  • Feng, Dawei; Chung, Wan-Chun; Wei, Zhangwen
  • Journal of the American Chemical Society, Vol. 135, Issue 45
  • DOI: 10.1021/ja408084j

Hydrogen Storage in a Microporous Metal−Organic Framework with Exposed Mn 2+ Coordination Sites
journal, December 2006

  • Dincǎ, Mircea; Dailly, Anne; Liu, Yun
  • Journal of the American Chemical Society, Vol. 128, Issue 51
  • DOI: 10.1021/ja0656853

Jahn-Teller distortions in octahedral copper(II) complexes
journal, March 1969

  • Veidis, M. V.; Schreiber, G. H.; Gough, T. E.
  • Journal of the American Chemical Society, Vol. 91, Issue 7
  • DOI: 10.1021/ja01035a051

Tuning the Moisture and Thermal Stability of Metal–Organic Frameworks through Incorporation of Pendant Hydrophobic Groups
journal, September 2013

  • Makal, Trevor A.; Wang, Xuan; Zhou, Hong-Cai
  • Crystal Growth & Design, Vol. 13, Issue 11, p. 4760-4768
  • DOI: 10.1021/cg4009224

Porous Metal-Organic Frameworks Based on an Anthracene Derivative: Syntheses, Structure Analysis, and Hydrogen Sorption Studies
journal, June 2009

  • Ma, Shengqian; Simmons, Jason M.; Sun, Daofeng
  • Inorganic Chemistry, Vol. 48, Issue 12
  • DOI: 10.1021/ic900217t

Introduction to Metal–Organic Frameworks
journal, September 2011

  • Zhou, Hong-Cai; Long, Jeffrey R.; Yaghi, Omar M.
  • Chemical Reviews, Vol. 112, Issue 2, p. 673-674
  • DOI: 10.1021/cr300014x

CHEMISTRY: Enhanced: Better Living Through Nanopore Chemistry
journal, September 2005


Nanoporous Nanorods Fabricated by Coordination Modulation and Oriented Attachment Growth
journal, June 2009

  • Tsuruoka, Takaaki; Furukawa, Shuhei; Takashima, Yohei
  • Angewandte Chemie International Edition, Vol. 48, Issue 26
  • DOI: 10.1002/anie.200901177

An Exceptionally Stable, Porphyrinic Zr Metal–Organic Framework Exhibiting pH-Dependent Fluorescence
journal, September 2013

  • Jiang, Hai-Long; Feng, Dawei; Wang, Kecheng
  • Journal of the American Chemical Society, Vol. 135, Issue 37
  • DOI: 10.1021/ja406844r

Separation of Hexane Isomers in a Metal-Organic Framework with Triangular Channels
journal, May 2013


Unusual and Highly Tunable Missing-Linker Defects in Zirconium Metal–Organic Framework UiO-66 and Their Important Effects on Gas Adsorption
journal, May 2013

  • Wu, Hui; Chua, Yong Shen; Krungleviciute, Vaiva
  • Journal of the American Chemical Society, Vol. 135, Issue 28
  • DOI: 10.1021/ja404514r

Symmetry-Guided Synthesis of Highly Porous Metal-Organic Frameworks with Fluorite Topology
journal, November 2013

  • Zhang, Muwei; Chen, Ying-Pin; Bosch, Mathieu
  • Angewandte Chemie International Edition, Vol. 53, Issue 3
  • DOI: 10.1002/anie.201307340

OLEX2 : a complete structure solution, refinement and analysis program
journal, January 2009

  • Dolomanov, Oleg V.; Bourhis, Luc J.; Gildea, Richard J.
  • Journal of Applied Crystallography, Vol. 42, Issue 2
  • DOI: 10.1107/S0021889808042726

Establishing Microporosity in Open Metal−Organic Frameworks:  Gas Sorption Isotherms for Zn(BDC) (BDC = 1,4-Benzenedicarboxylate)
journal, August 1998

  • Li, Hailian; Eddaoudi, Mohamed; Groy, Thomas L.
  • Journal of the American Chemical Society, Vol. 120, Issue 33, p. 8571-8572
  • DOI: 10.1021/ja981669x

A Series of Isoreticular, Highly Stable, Porous Zirconium Oxide Based Metal-Organic Frameworks
journal, August 2012

  • Guillerm, V.; Ragon, F.; Dan-Hardi, M.
  • Angewandte Chemie International Edition, Vol. 51, Issue 37
  • DOI: 10.1002/anie.201204806

Stability and Hydrolyzation of Metal Organic Frameworks with Paddle-Wheel SBUs upon Hydration
journal, August 2012

  • Tan, Kui; Nijem, Nour; Canepa, Pieremanuele
  • Chemistry of Materials, Vol. 24, Issue 16
  • DOI: 10.1021/cm301427w

A Route to Metal–Organic Frameworks through Framework Templating
journal, January 2013

  • Wei, Zhangwen; Lu, Weigang; Jiang, Hai-Long
  • Inorganic Chemistry, Vol. 52, Issue 3
  • DOI: 10.1021/ic3019937

Structural design of porous coordination networks from tetrahedral building units
journal, January 2013

  • Zhang, Muwei; Chen, Ying-Pin; Zhou, Hong-Cai
  • CrystEngComm, Vol. 15, Issue 45
  • DOI: 10.1039/c3ce41105b

How Linker’s Modification Controls Swelling Properties of Highly Flexible Iron(III) Dicarboxylates MIL-88
journal, November 2011

  • Horcajada, Patricia; Salles, Fabrice; Wuttke, Stefan
  • Journal of the American Chemical Society, Vol. 133, Issue 44
  • DOI: 10.1021/ja206936e

Metal–Organic Frameworks in Biomedicine
journal, September 2011

  • Horcajada, Patricia; Gref, Ruxandra; Baati, Tarek
  • Chemical Reviews, Vol. 112, Issue 2, p. 1232-1268
  • DOI: 10.1021/cr200256v

Stabilization of Metal−Organic Frameworks with High Surface Areas by the Incorporation of Mesocavities with Microwindows
journal, July 2009

  • Zhao, Dan; Yuan, Daqiang; Sun, Daofeng
  • Journal of the American Chemical Society, Vol. 131, Issue 26
  • DOI: 10.1021/ja901109t

High-Throughput Synthesis of Zeolitic Imidazolate Frameworks and Application to CO2 Capture
journal, February 2008


Topological Analysis of Metal–Organic Frameworks with Polytopic Linkers and/or Multiple Building Units and the Minimal Transitivity Principle
journal, November 2013

  • Li, Mian; Li, Dan; O’Keeffe, Michael
  • Chemical Reviews, Vol. 114, Issue 2
  • DOI: 10.1021/cr400392k

Mapping of Functional Groups in Metal-Organic Frameworks
journal, July 2013


Thermochemistry of Paddle Wheel MOFs: Cu-HKUST-1 and Zn-HKUST-1
journal, June 2013

  • Bhunia, Manas K.; Hughes, James T.; Fettinger, James C.
  • Langmuir, Vol. 29, Issue 25
  • DOI: 10.1021/la4012839

A Chromium Terephthalate-Based Solid with Unusually Large Pore Volumes and Surface Area
journal, September 2005

  • Ferey, G.; Mellot-Draznieks, C.; Serre, C.
  • Science, Vol. 309, Issue 5743, p. 2040-2042
  • DOI: 10.1126/science.1116275

Design and synthesis of nucleobase-incorporated metal–organic materials
journal, January 2014

  • Zhang, Muwei; Lu, Weigang; Li, Jian-Rong
  • Inorganic Chemistry Frontiers, Vol. 1, Issue 2
  • DOI: 10.1039/c3qi00042g

Metal Azolate Frameworks: From Crystal Engineering to Functional Materials
journal, September 2011

  • Zhang, Jie-Peng; Zhang, Yue-Biao; Lin, Jian-Bin
  • Chemical Reviews, Vol. 112, Issue 2
  • DOI: 10.1021/cr200139g

Porous Interpenetrated Zirconium-Organic Frameworks (PIZOFs): A Chemically Versatile Family of Metal-Organic Frameworks
journal, July 2011

  • Schaate, Andreas; Roy, Pascal; Preuße, Thomas
  • Chemistry - A European Journal, Vol. 17, Issue 34
  • DOI: 10.1002/chem.201101015

Zr(iv) and Hf(iv) based metal–organic frameworks with reo-topology
journal, January 2012

  • Bon, Volodymyr; Senkovskyy, Volodymyr; Senkovska, Irena
  • Chemical Communications, Vol. 48, Issue 67
  • DOI: 10.1039/c2cc34246d

Highly Hydrophobic Isoreticular Porous Metal-Organic Frameworks for the Capture of Harmful Volatile Organic Compounds
journal, June 2013

  • Padial, Natalia M.; Quartapelle Procopio, Elsa; Montoro, Carmen
  • Angewandte Chemie International Edition, Vol. 52, Issue 32
  • DOI: 10.1002/anie.201303484

A New Zirconium Inorganic Building Brick Forming Metal Organic Frameworks with Exceptional Stability
journal, October 2008

  • Cavka, Jasmina Hafizovic; Jakobsen, Søren; Olsbye, Unni
  • Journal of the American Chemical Society, Vol. 130, Issue 42, p. 13850-13851
  • DOI: 10.1021/ja8057953

Mixed-Linker Hybrid Superpolyhedra for the Production of a Series of Large-Pore Iron(III) Carboxylate Metal-Organic Frameworks
journal, April 2013

  • Chevreau, Hubert; Devic, Thomas; Salles, Fabrice
  • Angewandte Chemie International Edition, Vol. 52, Issue 19
  • DOI: 10.1002/anie.201300057

Homochiral Metal–Organic Frameworks for Asymmetric Heterogeneous Catalysis
journal, September 2011

  • Yoon, Minyoung; Srirambalaji, Renganathan; Kim, Kimoon
  • Chemical Reviews, Vol. 112, Issue 2, p. 1196-1231
  • DOI: 10.1021/cr2003147

Fluorous Metal–Organic Frameworks with Superior Adsorption and Hydrophobic Properties toward Oil Spill Cleanup and Hydrocarbon Storage
journal, November 2011

  • Yang, Chi; Kaipa, Ushasree; Mather, Qian Zhang
  • Journal of the American Chemical Society, Vol. 133, Issue 45, p. 18094-18097
  • DOI: 10.1021/ja208408n

Synthesis and Stability of Tagged UiO-66 Zr-MOFs
journal, December 2010

  • Kandiah, Mathivathani; Nilsen, Merete Hellner; Usseglio, Sandro
  • Chemistry of Materials, Vol. 22, Issue 24
  • DOI: 10.1021/cm102601v

Molecular building blocks approach to the assembly of zeolite-like metal–organic frameworks (ZMOFs) with extra-large cavities
journal, January 2006

  • Liu, Yunling; Kravtsov, Victor Ch.; Larsen, Randy
  • Chemical Communications, Issue 14
  • DOI: 10.1039/b600188m

Design and synthesis of an exceptionally stable and highly porous metal-organic framework
journal, November 1999

  • Li, Hailian; Eddaoudi, Mohamed; M., O'Keeffe
  • Nature, Vol. 402, Issue 6759, p. 276-279
  • DOI: 10.1038/46248

Single-Crystal Structure of a Covalent Organic Framework
journal, October 2013

  • Zhang, Yue-Biao; Su, Jie; Furukawa, Hiroyasu
  • Journal of the American Chemical Society, Vol. 135, Issue 44
  • DOI: 10.1021/ja409033p

Zirconium-Metalloporphyrin PCN-222: Mesoporous Metal-Organic Frameworks with Ultrahigh Stability as Biomimetic Catalysts
journal, August 2012

  • Feng, Dawei; Gu, Zhi-Yuan; Li, Jian-Rong
  • Angewandte Chemie International Edition, Vol. 51, Issue 41
  • DOI: 10.1002/anie.201204475