Title: Isoreticular metal-organic frameworks, process for forming the same, and systematic design of pore size and functionality therein, with application for gas storage

Abstract

The ability to design and construct solid-state materials with pre-determined structures is a grand challenge in chemistry. An inventive strategy based on reticulating metal ions and organic carboxylate links into extended networks has been advanced to a point that has allowed the design of porous structures in which pore size and functionality can be varied systematically. MOF-5, a prototype of a new class of porous materials and one that is constructed from octahedral Zn--O--C clusters and benzene links, was used to demonstrate that its 3-D porous system can be functionalized with the organic groups, --Br, --NH2, --OC₃H₇, --OC₅H₁₁, --H₄C₂, and --H₄C₄, and its pore size expanded with the long molecular struts biphenyl, tetrahydropyrene, pyrene, and terphenyl. The ability to direct the formation of the octahedral clusters in the presence of a desired carboxylate link is an essential feature of this strategy, which resulted in the design of an isoreticular (having the same framework topology) series of sixteen well-defined materials whose crystals have open space representing up to 91.1% of the crystal volume, and homogeneous periodic pores that can be incrementally varied from 3.8 to 28.8 angstroms. Unlike the unpredictable nature of zeolite and other molecular sieve syntheses, the deliberate controlmore » exercised at the molecular level in the design of these crystals is expected to have tremendous implications on materials properties and future technologies. Indeed, data indicate that members of this series represent the first monocrystalline mesoporous organic/inorganic frameworks, and exhibit the highest capacity for methane storage (155 cm³/cm³ at 36 atm) and the lowest densities (0.41 to 0.21 g/cm³) attained to date for any crystalline material at room temperature. « less

Inventors:

Yaghi, Omar M.; Eddaoudi, Mohamed; Li, Hailian; Kim, Jaheon; Rosi, Nathaniel

Issue Date:

Tue Mar 27 00:00:00 EDT 2007

Research Org.:

Univ. of Michigan, Ann Arbor, MI (United States)

Sponsoring Org.:

USDOE

OSTI Identifier:

1176167

Patent Number(s):

7196210

Application Number:

11/119,563

Assignee:

The Regents of the University of Michigan (Ann Arbor, MI)

Patent Classifications (CPCs):

B - PERFORMING OPERATIONS B01 - PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL B01J - CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY

C - CHEMISTRY C07 - ORGANIC CHEMISTRY C07F - ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM

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B - PERFORMING OPERATIONS B01 - PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL B01J - CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY

B01J20/226 - {Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
B01J20/28011 - {Other properties, e.g. density, crush strength}
B01J20/28014 - {characterised by their form}
B01J20/28069 - {Pore volume, e.g. total pore volume, mesopore volume, micropore volume}
B01J20/28078 - {Pore diameter}
B01J20/2808 - {being less than 2 nm, i.e. micropores or nanopores}
B01J20/30 - Processes for preparing, regenerating, or reactivating
B01J2531/26 - Zinc
B01J31/1691 - {Coordination polymers, e.g. metal-organic frameworks [MOF]

C - CHEMISTRY C07 - ORGANIC CHEMISTRY C07F - ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM

C07F3/003 - {without C-Metal linkages}

F - MECHANICAL ENGINEERING F17 - STORING OR DISTRIBUTING GASES OR LIQUIDS F17C - VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES

F17C11/007 - {for hydrocarbon gases, such as methane or natural gas, propane, butane or mixtures thereof [LPG]}

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DOE Contract Number:  

FG02-99ER15000; FG03-98ER14903

Resource Type:

Patent

Resource Relation:

Patent File Date: 2005 May 02

Country of Publication:

United States

Language:

English

Subject:

36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY