Metal–organic frameworks—prospective industrial applications

The generation of metal–organic framework (MOF) coordination polymers enables the tailoring of novel solids with regular porosity from the micro to nanopore scale. Since the discovery of this new family of nanoporous materials and the concept of so called ‘reticular design’, nowadays several hundred different types of MOF are known. The self assembly of metal ions, which act as coordination centres, linked together with a variety of polyatomic organic bridging ligands, results in tailorable nanoporous host materials as robust solids with high thermal and mechanical stability. Describing examples of different zinc-containing structures, e.g. MOF-2, MOF-5 and IRMOF-8 verified synthesis methods will be given, as well as a totally novel electrochemical approach for transition metal based MOFs will be presented for the first time. With sufficient amounts of sample now being available, the testing of metal–organic frameworks in fields of catalysis and gas processing is exemplified. Report is given on the catalytic activation of alkynes (formation of methoxypropene from propyne, vinylester synthesis from acetylene). Removal of impurities in natural gas (traces of tetrahydrothiophene in methane), pressure swing separation of rare gases (krypton and xenon) and storage of hydrogen (3.3 wt% at 2.0 MPa/77 K on Cu-BTC-MOF) will underline the prospective future industrial use of metal–organic frameworks in gas processing. Whenever possible, comparison is made to state-of-art applications in order to outline possibilities which might be superior by using MOFs.

[1]  Chuan-De Wu,et al.  A homochiral porous metal-organic framework for highly enantioselective heterogeneous asymmetric catalysis. , 2005, Journal of the American Chemical Society.

[2]  W. Mori,et al.  Syntheses and Characterization of Microporous Coordination Polymers with Open Frameworks , 2002 .

[3]  B. Rieger,et al.  New Zinc Dicarboxylate Catalysts for the CO2/Propylene Oxide Copolymerization Reaction: Activity Enhancement Through Zn(II)-Ethylsulfinate Initiating Groups , 2004 .

[4]  M. P. Suh,et al.  Multifunctionality and crystal dynamics of a highly stable, porous metal-organic framework [Zn4O(NTB)2]. , 2005, Journal of the American Chemical Society.

[5]  M. O'keeffe,et al.  Design and synthesis of an exceptionally stable and highly porous metal-organic framework , 1999, Nature.

[6]  Michael O'Keeffe,et al.  Systematic Design of Pore Size and Functionality in Isoreticular MOFs and Their Application in Methane Storage , 2002, Science.

[7]  Y. Kawazoe,et al.  Highly controlled acetylene accommodation in a metal–organic microporous material , 2005, Nature.

[8]  Michael O'Keeffe,et al.  A route to high surface area, porosity and inclusion of large molecules in crystals , 2004, Nature.

[9]  S. Kaskel,et al.  Improved synthesis, thermal stability and catalytic properties of the metal-organic framework compound Cu3(BTC)2 , 2004 .

[10]  Omar M. Yaghi,et al.  Metal-organic frameworks: a new class of porous materials , 2004 .

[11]  Douglas A. Loy,et al.  Tailored Porous Materials , 1999 .

[12]  Ian D. Williams,et al.  A chemically functionalizable nanoporous material (Cu3(TMA)2(H2O)3)n , 1999 .

[13]  Susumu Kitagawa,et al.  Functional porous coordination polymers. , 2004, Angewandte Chemie.

[14]  Chongli Zhong,et al.  Molecular simulation of adsorption and diffusion of hydrogen in metal-organic frameworks. , 2005, The journal of physical chemistry. B.

[15]  Mohamed Eddaoudi,et al.  Highly Porous and Stable Metal−Organic Frameworks: Structure Design and Sorption Properties , 2000 .

[16]  Joanna Rowsell,et al.  Strategien für die Wasserstoffspeicherung in metall‐organischen Kompositgerüsten , 2005 .

[17]  E. Tomic Thermal stability of coordination polymers , 1965 .

[18]  C. Serre,et al.  Hydrogen adsorption in the nanoporous metal-benzenedicarboxylate M(OH)(O2C-C6H4-CO2) (M = Al3+, Cr3+), MIL-53. , 2003, Chemical communications.

[19]  Young Hee Lee,et al.  Benzene-templated hydrothermal synthesis of metal-organic frameworks with selective sorption properties. , 2004, Chemistry.

[20]  Jinho Oh,et al.  A homochiral metal–organic porous material for enantioselective separation and catalysis , 2000, Nature.

[21]  Kimoon Kim,et al.  Microporous manganese formate: a simple metal-organic porous material with high framework stability and highly selective gas sorption properties. , 2004, Journal of the American Chemical Society.