IP Library Granted Patent US 7,481,866
Granted Patent B2
US 7,481,866 · App. 10/465,535 · Granted Jan 27, 2009

Gas storage materials and devices

Assignee: University of Iowa Research Foundation
View Patent ↗
Loading inventors, assignments & file history…
Monitor This Case
Get email alerts when status or documents change.
Order Certified Copies
Most orders are placed with the USPTO same day — all within 24 business hours.
Order via The Patent Place →
Pre-filled with this patent's details
Quick Facts
Patent No.
US 7,481,866
App. No.
10/465,535
Granted
Jan 27, 2009
Kind
B2
Abstract

The invention provides a porous metal-organic framework that can be used to store gases, such as hydrogen. Also provided is metal-organic framework comprising bifunctional metallic bridging groups and organic nodes having three or more points of connection, wherein the framework has one or more cavities suitable for containing one or more storage gas molecules. The invention further provides a metal-organic framework comprising organic functional groups directed into the one or more cavities that are capable of reacting with a storage gas.

Claims (45)

1. A metal-organic framework comprising bifunctional metallic bridging groups and organic nodes having three or more points of connection, wherein the framework has one or more cavities suitable for containing one or more storage gas molecules.

2. The metal-organic framework of claim 1 wherein each metallic bridging group is linked to organic nodes at two cites.

3. The metal-organic framework of claim 1 wherein each metallic bridging group is linear.

4. The metal-organic framework of any one of claims 1 - 3 wherein each metallic bridging group comprises a first row transition metal.

5. The metal-organic framework of any one of claims 1 - 3 wherein each metallic bridging group comprises copper.

6. The metal-organic framework of claim 1 wherein each metallic bridging group is a paddle-wheel complex.

7. The metal-organic framework of claim 1 wherein each metallic bridging group is a compound of the formula [Cu(O 2 CR)(L) 2 ], wherein R is (C 1 -C 6 )alkyl, (C 2 -C 6 )alkenyl, (C 2 -C 6 )alkynyl, aryl, hydroxy, (C 1 -C 6 )alkanoyl, or amino; L is H 2 O, R a OH, amino, or pyridyl; and R a is hydrogen, (C 1 -C 6 )alkyl, (C 2 -C 6 )alkenyl, (C 2 -C 6 )alkynyl, aryl, or (C 1 -C 6 )alkanoyl.

8. The metal-organic framework of claim 1 wherein each metallic bridging group is independently selected from [Cu(O 2 CCH 3 ) 2 (H 2 O) 2 ], [Cu(O 2 CCH═CH 2 ) 2 (H 2 O) 2 ], [Cu(O 2 CC(CH 3 )═CH 2 ) 2 (H 2 O) 2 ] [Cu(O 2 CC≡CH) 2 (H 2 O) 2 ], and [Cu(O 2 CCH 2 C≡CH) 2 (H 2 O) 2 ].

9. The metal-organic framework of claim 1 wherein each organic node is not planar.

10. The metal-organic framework of claim 1 wherein each organic node has three points of connection.

11. The metal-organic framework of claim 1 wherein each organic node has at least four points of connection.

12. The metal-organic framework of claim 1 wherein each organic node has four points of connection.

13. The metal-organic framework of claim 1 wherein each organic node is 1,2,3-tris(4-pyridyl)cyclopropane, bis(4-pyridyl)cyclobutane, tetrakis(4-pyridyl)cyclobutane, pentakis(4-pyridyl)cyclopentane, hexakis(4-pyridyl)cyclohexane, or hexakis(4-pyridyl)benzene.

14. The metal-organic framework of claim 1 wherein each organic node is tetrakis(4-pyridyl)cyclobutane.

15. The metal-organic framework of claim 1 wherein the volume of each cavity is from about 20 cubic angstroms to about 2000 cubic angstroms.

16. The metal-organic framework of claim 1 wherein the volume of each cavity is from about 50 cubic angstroms to about 1000 cubic angstroms.

17. The metal-organic framework of claim 1 which includes organic functional groups directed into, or lining the cavities of the metal-organic framework.

18. The metal-organic framework of claim 17 wherein the organic groups comprise carbon-carbon double bonds or triple bonds.

19. The metal-organic framework of claim 17 wherein the organic groups are capable of reacting with the storage gas to fix the gas within the cavity temporarily.

20. The metal-organic framework of claim 17 wherein the organic groups are capable of reacting with the storage gas to fix the gas within the cavity permanently.

21. The metal-organic framework of claim 1 which includes a metal lining the cavities that is capable of reacting with the storage gas to fix the gas within the cavity.

22. The metal-organic framework of claim 1 which includes metal-organic groups and/or inorganic groups lining the cavities that are capable of reacting with the storage gas to fix the gas within the cavity permanently.

23. The metal-organic framework of claim 1 wherein each linear metallic bridging group is [Cu(O 2 CCH 3 ) 2 (H 2 O) 2 ]; and each organic node is tetrakis(4-pyridyl)cyclobutane.

24. The metal-organic framework of claim 1 wherein each linear metallic bridging groups is selected from [Cu(O 2 CCH═CH 2 ) 2 (H 2 O) 2 ], [Cu(O 2 CC(CH 3 )═CH 2 ) 2 (H 2 O) 2 ] [Cu(O 2 CC≡CH) 2 (H 2 O) 2 ], and [Cu(O 2 CCH 2 C≡CH) 2 (H 2 O) 2 ]; and each organic node is tetrakis(4-pyridyl)cyclobutane.

25. The metal-organic framework of claim 1 wherein each linear metallic bridging group is [Cu(O 2 CC(CH 3 )═CH 2 ) 2 (H 2 O) 2 ] and each organic node is tetrakis(4-pyridyl)cyclobutane.

26. The metal-organic framework of claim 1 wherein the storage gas is a mono-atomic gas.

27. The metal-organic framework of claim 1 wherein the storage gas is a di-atomic gas.

28. The metal-organic framework of claim 1 wherein the storage gas is a poly-atomic gas.

29. The metal-organic framework of claim 1 wherein the storage gas is helium, neon, argon, krypton, xenon, or radon.

30. The metal-organic framework of claim 1 wherein the storage gas is hydrogen, oxygen or nitrogen.

31. The metal-organic framework of claim 1 wherein the storage gas is hydrogen.

32. The metal-organic framework of claim 1 wherein the storage gas is methane ethane, propane, butane, or a related halocarbon.

33. The metal-organic framework of claim 1 wherein the storage gas is radioactive.

34. A gas storage cell comprising a metal-organic framework as described in claim 1 .

35. A fuel storage cell comprising a metal-organic framework as described in claim 1 .

36. A method for storing a gas comprising contacting the metal organic framework of claim 1 with the gas under conditions suitable for the gas to enter the cavities of the framework and be stored.

37. A method for storing a gas comprising contacting the metal organic framework of claim 17 , with the gas under conditions suitable for the gas to enter the cavities of the framework and react with the organic groups so as to become fixed to the organic groups.

38. A method for preparing a metal-organic framework as described in claim 1 comprising reacting metallic bridging groups and organic nodes having three or more possible points of connection in a suitable solvent to provide the metal-organic framework.

39. A metal-organic framework comprising bifunctional metallic bridging groups and organic nodes having three or more points of connection, wherein

the framework has one or more cavities suitable for containing one or more storage gas molecules; and

each metallic bridging group comprises copper; and

each organic node is 1,2,3-tris(4-pyridyl)cyclopropane, bis(4-pyridyl)cyclobutane, tetrakis(4-pyridyl)cyclobutane, pentakis(4-pyridyl)cyclopentane, hexakis(4-pyridyl)cyclohexane, or hexakis(4-pyridyl)benzene; and

the volume of each cavity is from about 20 cubic angstroms to about 2000 cubic angstroms.

40. The metal-organic framework of claim 39 which includes organic functional groups directed into, or lining the cavities of the metal-organic framework, wherein the organic groups are capable of reacting with the storage gas to fix the gas within the cavity permanently.

41. The metal-organic framework of claim 39 or 40 , wherein the storage gas is helium, neon, argon, krypton, xenon, or radon.

Assignments (3)
CONFIRMATORY LICENSE Recorded Jul 29, 2009
From: UNIVERSITY OF IOWA
To: NATIONAL SCIENCE FOUNDATION
Reel/Frame 023015/0508 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded May 21, 2008
From: PAPAFSTATHIOU, GIANNIS S.
To: UNIVERSITY OF IOWA RESEARCH FOUNDATION
Reel/Frame 020980/0887 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Nov 3, 2003
From: MACGILLIVRAY, LEONARD R.
To: UNIVERSITY OF IOWA RESEARCH FOUNDATION
Reel/Frame 014648/0468 →
Continuity (2)
Provisional Application 6038982800 · Jun 19, 2002
Related Publication 20090000474A1 · Jan 1, 2009