IP Library Granted Patent US 8,841,471
Granted Patent B2
US 8,841,471 · App. 13/496,019 · Granted Sep 23, 2014

Open metal organic frameworks with exceptional surface area and high gas storage capacity

Inventors: Omar M. Yaghi (Los Angeles, CA); Jaheon Kim (Seong-Nam, KR); Nakeun Ko (Incheon, KR); Sang Beom Choi (Daejeon, KR); Hiroyasu Furukawa (Los Angeles, CA)
Assignees: The Regents of the University of California; Foundation of Soongsil University-Industry Cooperation
C07F3/003C07C63/38C07C63/66C07C63/331
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 8,841,471
App. No.
13/496,019
Granted
Sep 23, 2014
Kind
B2
Abstract

The disclosure provides metal organic frameworks comprising exception porosity.

Claims (35)

1. A metal-organic framework (MOF) comprising:

a plurality of metal clusters, wherein each metal cluster comprises one or more metal ions; and

a plurality of at least one first-multidentate aromatic tritopic linking ligands comprising at least one first linking ligand and at least one second linking ligand which is different from the first linking ligand, wherein the linking ligands connect adjacent metal clusters, and wherein the plurality of linking ligands having a sufficient number of accessible sites for atomic or molecular adsorption such that the surface area of the metal-organic framework is greater than about 5500 m 2 /g.

2. The MOF of claim 1 , wherein each metal cluster comprises 3 or more metal ions.

3. The MOF of claim 1 , wherein the plurality of-linking ligands have a sufficient number of accessible sites for atomic or molecular adsorption that the surface area is greater than 6,000 m 2 /g.

4. The MOF of claim 1 , wherein the plurality of linking ligands have a sufficient number of accessible sites for atomic or molecular adsorption that the surface area is greater than about 6,500 m 2 /g.

5. The MOF of claim 1 , wherein the plurality of linking ligands have a sufficient number of accessible sites for atomic or molecular adsorption that the surface area is greater than about 10,000 m 2 /g.

6. The MOF of claim 1 , wherein the metal ion is selected from the group consisting of Li + , Na + , Rb + , Mg 2+ , Ca 2+ , Sr 2+ , Ba 2+ , Sc 3+ , Ti 4+ , Zr 4+ , Ta 3+ , Cr 3+ , Mo 3+ , W 3+ , Mn 3+ , Fe 3+ , Fe 2+ , Ru 3+ , Ru 2+ , Os 3+ , Os 2+ , Co 3+ , Co 2+ , Ni 2+ , Ni+, Pd 2+ , Pd+, Pt 2+ , Pt+, Cu 2+ , Cu+, Au+, Zn 2 + , Al 3+ , Ga 3+ , In 3+ , Si 4+ , Si 2+ , Ge 4 + , Ge 2+ , Sn 4+ , Sn 2+ , Bi 5+ , Bi 3+ , Cd 2+ , Mn 2+ , Tb 3+ , Gd 3+ , Ce 3+ , La 3+ , Cr 4+ and combinations thereof.

7. The MOF of claim 1 , wherein the plurality of linking ligands is comprised of two or more linking ligands comprised of at least two general structural formulas selected from Formula I, II, IV, VI, or VII:

wherein,

R1-R15 are each individually selected from: alkyl, aryl, alkoxy, akenes, alkynes, phenyl, substitutions of the foregoing, sulfur-containing groups, silicon-containing groups, nitrogen-containing groups, oxygen-containing groups, halogen, nitro, amino, cyano, boron-containing groups, phosphorous-containing groups, carboxylic acids, or esters, H, NH 2 , CN, OH, ═O, ═S, CI, I, F,

wherein X=1, 2, or 3;

wherein R16, R17 and R18 may or may not be present, if present R16, R17 and R18 are selected from an alkyl or cycloalkyl group, comprising 1 to 20 carbon atoms, an aryl group comprising 1 to 5 phenyl rings, an alkyl or aryl amine comprising alkyl or cycloalkyl groups having from 1 to 20 carbon atoms or aryl groups comprising 1 to 5 phenyl rings, or —C≡C—.

8. The MOF of claim 1 , wherein the plurality of linking ligands is comprised of two or more linking ligands comprised of at least two general structural formulas selected from Formula III, V, VIII, or IX:

9. The MOF of claim 1 , wherein the at least one first linking ligand has a general formula selected from the group comprising Formula VI, VII, VIII, and IX:

and wherein the at least one second linking ligand has a general formula selected from the group comprising Formula I, II, Ill, IV, and V:

10. The MOF of claim 1 , wherein the at least one first linking ligand has a general formula selected from the group comprising Formula VI, VII, VIII, and IX:

and wherein the at least one second linking ligand is selected from the group consisting of Formula I and II:

wherein the structure of Formula I lacks R 16 , R 17 and R 18 .

11. The MOF of claim 1 , wherein the plurality of multidentate aromatic tritopic linking ligands is comprised of a first linking ligand having structural Formula VIII:

and a second linking ligand having structural Formula I:

wherein the structure of Formula I lacks R 16 , R 17 and R 18 .

12. The MOF of claim 11 , wherein the metal-organic framework has the structure and chemical properties of MOF-205.

13. The MOF of claim 1 , wherein the plurality of multidentate aromatic tritopic linking ligands is comprised of at least one first linking ligand having structural Formula IX:

and at least one second linking ligand having structural Formula I

wherein the structure of Formula I lacks R 16 , R 17 and R 18 .

14. The MOF of claim 13 , wherein the metal-organic framework has the structure and chemical properties of MOF-210.

15. The MOF of claim 6 , wherein the metal ion is a metal ion selected from the group consisting of Mg 2+ , Ca 2+ , Sr 2+ , Ba 2+ , Fe 2+ , Ru 2+ , Os 2+ , Co 2+ , Ni 2+ , Pd 2+ , Pt 2+ , Cu 2+ , Zn 2+ , Si 2+ , Ge 2+ , Sn 2+ , Cd 2+ , and combinations thereof.

16. The MOF of claim 6 , wherein the metal ion is Zn 2+ .

17. The MOF of claim 1 , wherein the plurality of linking ligands comprise at least one linking cluster selected from the group consisting of carboxylate, CO 2 H, CS 2 H, NO 2 , SO 3 H, Si(OH) 3 , Ge(OH) 3 , Sn(OH) 3 , Si(SH) 4 , Ge(SH) 4 , Sn(SH) 4 , PO 3 H, AsO 3 H, AsO 4H , P(SH) 3 , As(SH) 3 , CH(RSH) 2 , C(RSH) 3 , CH(RNH 2 ) 2 , C(RNH 2 ) 3 , CH(ROH) 2 , C(ROH) 3 , CH(RCN) 2 , C(RCN) 3 , CH(SH) 2 , C(SH) 3 , CH(NH 2 ) 2 , C(NH 2 ) 3 , CH(OH) 2 , C(OH) 3 , CH(CN) 2 , and C(CN) 3 , wherein R is an alkyl group having from 1 to 5 carbon atoms, or an aryl group comprising 1 to 2 phenyl rings.

18. The MOF of claim 17 , wherein the plurality of linking ligands comprise carboxylate linking clusters.

19. A method for gas storage and separation comprising contacting the MOF of claim 1 with a fluid wherein an analyte in the fluid interacts and is absorbed by the MOF.

20. A method of forming a MOF, the method comprising: combining a solution comprising a solvent and metal ions selected from the group consisting Group 1 through 16 metals including actinides, and lanthanides, and combinations thereof with at least one first linking ligand comprising the general formula of I-V:

and with at least one second linking ligand comprising the general formula VI-IX:

such that the surface area of the metal-organic framework is greater than 5500 m 2 /g.

Assignments (4)
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Aug 8, 2014
From: KIM, JAHEON; KO, NAKEUN; CHOI, SANG BEOM
To: FOUNDATION OF SOONGSIL UNIVERSITY-INDUSTRY COOPERATION (FSUIC)
Reel/Frame 033495/0814 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Aug 8, 2014
From: YAGHI, OMAR; FURUKAWA, HIROYASU
To: THE REGENTS OF THE UNIVERSITY OF CALIFORNIA
Reel/Frame 033496/0103 →
CONFIRMATORY LICENSE Recorded Jan 3, 2013
From: UNIVERSITY OF CALIFORNIA LOS ANGELES
To: DEFENSE THREAT REDUCTION AGENCY; DEPT. OF DEFENSE; UNITED STATES GOVERNMENT
Reel/Frame 029568/0052 →
CONFIRMATORY LICENSE Recorded Jun 20, 2012
From: UNIVERSITY OF CALIFORNIA LOS ANGELES
To: DEFENSE THREAT REDUCTION AGENCY; DEPT. OF DEFENSE; UNITED STATES GOVERNMENT
Reel/Frame 028414/0918 →
Continuity (2)
Provisional Application 61246065 · Sep 25, 2009
Related Publication 20120172612A1 · Jul 5, 2012