Hybrid zeolitic imidazolate frameworks: controlling framework porosity and functionality by a mixed-ligand synthetic approach

Patent metadata

Field	Value
Publication number	US-9527872-B2
Application number	US-201313754430-A
Country	US
Kind code	B2
Filing date	Jan 30, 2013
Priority date	Jan 30, 2012
Publication date	Dec 27, 2016
Grant date	Dec 27, 2016

Abstract

Metal-organic frameworks, in particular hybrid zeolitic imidazolate frameworks (ZIFs), devices having hybrid ZIFs, and methods for preparing hybrid ZIFs are disclosed herein. In some embodiments, the method includes preparing a first solution comprising a first imidazolate and a second imidazolate, preparing a second solution comprising a metal ion, and combining the first solution and the second solution to form the hybrid ZIF.

First claim

The invention claimed is:

1. A metal-organic framework (MOF) comprising:
a hybrid zeolitic imidazolate framework comprising:
a first imidazolate;
a second imidazolate; and
a metal ion;

wherein the first imidazolate comprises 2-methylimidazolate and the second imidazolate comprises carboxaldehyde-2-imidazolate, or the first imidazolate comprises benzimidazolate and the second imidazolate comprises 2-aminobenzimidazolate, or the first imidazolate comprises 2-methylimidazolate and the second imidazolate comprises imidazolate.

2. The MOF of claim 1 , wherein the first imidazolate comprises benzimidazolate and the second imidazolate comprises 2-aminobenzimidazolate.

3. The MOF of claim 1 , wherein the first imidazolate comprises 2-methylimidazolate and the second imidazolate comprises imidazolate.

4. The MOF of claim 1 , wherein the metal ion is a transition metal.

5. The MOF of claim 1 , wherein the metal ion is zinc.

6. The MOF of claim 1 , wherein the metal ion is cobalt.

7. The MOF of claim 1 , wherein the hybrid ZIF has CO 2 /CH 4 selectivity of at least 1.2 times greater than a non-hybrid ZIF.

8. The MOF of claim 1 , wherein the hybrid ZIF has CO 2 /CH 4 adsorption selectivity from about 2.5 to about 13.1.

9. The MOF of claim 1 , wherein the hybrid ZIF has a pore size from about 0.25 to about 0.40 nm.

10. The MOF of claim 1 , wherein the hybrid ZIF has a continuous crystal structure.

11. A metal-organic framework (MOF) comprising:
a hybrid zeolitic imidazolate framework comprising:
a first imidazolate;
a second imidazolate; and
a metal ion;

the MOF further comprising a functionalized hybrid ZIF.

12. The MOF of claim 11 , wherein the functionalized hybrid ZIF comprises an aldehyde.

13. The MOF of claim 11 , wherein the functionalized hybrid ZIF comprises an amine.

14. A molecular sieve device comprising a metal-organic framework (MOF) comprising:
a hybrid zeolitic imidazolate framework comprising:
a first imidazolate;
a second imidazolate; and
a metal ion;
wherein the hybrid ZIF has a pore size from about 0.25 to about 0.40 nm.

15. The device of claim 14 , wherein the hybrid ZIF has CO 2 /CH 4 selectivity of at least 1.2 times greater than a non-hybrid ZIF.

16. The device of claim 14 , wherein the hybrid ZIF has CO 2 /CH 4 adsorption selectivity from about 2.5 to about 13.1.

17. The MOF of claim 1 , wherein the first imidazolate comprises 2-methylimidazolate and the second imidazolate comprises carboxaldehyde-2-imidazolate.

Assignees

• Georgia Tech Res Inst

Inventors

• Thompson Joshua Allen
• Blad Catherine Rose
• Jones Christopher W
• Nair Sankar

Classifications

• C01B39/00

  Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination (treatment to modify the sorption properties, e.g. shaping using a binder, B01J20/10; treatment to modify the catalytic properties, e.g. combination of treatments to make the zeolites appropriate to their use as a catalyst, B01J29/04; treatment to improve the ion-exchange properties B01J39/14) · CPC title

• B01D2253/204

  Metal organic frameworks (MOF's) · CPC title

• C07F3/06 Primary

  Zinc compounds · CPC title

• B01J20/226

  Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF] (preparation of metal complexes containing carboxylic acid moieties C07C51/418; MOF's per se C07F) · CPC title

• B01D2257/504

  Carbon dioxide · CPC title