Process for preparing and organometallic framework material

• US 7,411,081 B2
• Filed: 01/13/2004
• Issued: 08/12/2008
• Est. Priority Date: 01/13/2004
• Status: Active Grant

• Current Assignee: BASF AG (BASF SE), University of Michigan
• Original Assignee: BASF AG (BASF SE), Board of Regents of the University of Michigan (University of Michigan)
• Inventors: Schubert, Olga, Hesse, Michael, Hess, Reinhard, Mueller, Ulrich, Stoesser, Michael, Yaghi, Omar M., Lippert, Gerald
• Primary Examiner(s): Keys; Rosalynd
• Application Number:
  US10/755,231
• Publication Number:
  US 20050154222A1
• Time in Patent Office: 1,673 Days
• Field of Search: 556/46, 556/118, 556/131, 556/136, 556/138
• US Class Current: 556/118
• CPC Class Codes: B01J 20/226 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 Class Codes: C07F 3/003 without C-Metal linkages

Abstract

A process for preparing an organometallic framework material comprising reacting at least one metal salt with at least one at least bidentate compound capable of coordination to the metal ion of said metal salt, in the presence of an aqueous solvent system and at least one base wherein at least one bidentate compound comprises at least carboxy group and at least one further group which is not a carboxy group and which is capable of forming a hydrogen bridge linkage.

Claims

1. A process for preparing an organometallic framework material comprising reacting at least one metal salt with at least one at least bidentate compound capable of coordinating to the metal ion of said metal salt, in the presence of an aqueous solvent system and at least one base wherein at least one bidentate compound comprises at least two carboxy groups and at least one hydroxy group which is capable of forming a hydrogen bridge linkage.

2. A process as claimed in claim 1 wherein the at least one at least bidentate compound comprises two carboxy groups.

3. A process as claimed in claim 1 wherein the at least one at least bidentate compound comprises two hydroxy groups.

4. A process as claimed in claim 1 wherein the at least one bidentate compound is dihydroxy terephthalic acid.

5. A process as claimed in claim 1 wherein the aqueous solvent system comprises water and at least one compound comprising at least one hydroxy group.

6. A process as claimed in claim 1 wherein the aqueous solvent system comprises at least one alcohol selected from the group consisting of methanol, ethanol, n-propanol, and isopropanol.

7. A process as claimed in claim 1 wherein the at least one base is an alkali metal hydroxide, an alkaline earth metal hydroxide and/or a basic metal hydroxide which is at least partially soluble or miscible in the aqueous solvent system.

8. A process as claimed in claim 1 wherein the at least one base is sodium hydroxide or potassium hydroxide or a mixture of sodium hydroxide and potassium hydroxide.

9. A process as claimed in claim 1 wherein the reaction of the at least one metal salt with the at least one bidentate compound is carried out at a pH in the range of from 3 to 9.

10. A process as claimed in claim 1 wherein the reaction of the at least one metal salt with the at least one bidentate compound is carried out at a pH in the range of from 7.3 to 7.6.

11. A process as claimed in claim 1 wherein the at least one metal salt is a salt of Zn, Cu, Co, Ni, Pd, Pt, Ru, Rh, Fe and mixtures of two or more thereof.

12. A process as claimed in claim 1 wherein the metal salt is a salt of Zn, Co, Cu and/or Fe.

21. A process as claimed in claim 1 wherein the reaction of the at least one metal salt with the at least one bidentate compound is carried out at a pH in the range of from 7.0 to 8.0.

13. A process for preparing an organometallic framework material comprising reacting at least one metal salt with at least one at least bidentate compound capable of co-ordination to the metal ion of said metal salt, in the presence of an aqueous solvent and at least one alkali metal hydroxide or alkaline earth metal hydroxide wherein the at least one bidentate compound comprises two hydroxy groups and two carboxy groups.

14. A process as claimed in claim 13 wherein the at least one bidentate compound is dihydroxy terephthalic acid.

15. A process as claimed in claim 13 wherein the at least hydroxide is sodium hydroxide.

16. A process as claimed in claim 13 wherein the at least one metal salt is a zinc salt.

17. A process as claimed in claim 13 wherein the aqueous solvent is water.

18. A process as claimed in claim 13 wherein the reaction of the at least one metal salt with the at least one bidentate compound is carried out at a pH in the range of from 3 to 9.

20. A process as claimed in claim 18 wherein the aqueous solvent is water.

19. A process for preparing an organometallic framework material comprising reacting a zinc salt with a bidentate compound in the presence of an aqueous solvent and sodium hydroxide wherein the bidentate compound is dihydroxy terephthalic acid.

22. A process for preparing an organometallic framework material comprising reacting a zinc salt with dihydroxy terephthalic acid in the presence of water as solvent and sodium hydroxide wherein the reaction is carried out at a pH in the range of from 7.3 to 7.6.

23. A method of using an organometallic framework material, comprising at least one metal ion and at least one at least bidentate organic compound coordinately bound to said at least one metal ion, said organometallic framework material being obtainable by a process comprising reacting at least one metal salt with at least one at least bidentate compound capable of coordination to the metal ion of said metal salt, in the presence of an aqueous solvent system and at least one base wherein at least one bidentate compound comprises at least carboxy group and at least one hydroxy group comprising the step of catalyzing, adsorbing, desiccating, flame retarding, storing or depositing active substances, sensor material, pigment, or electronic component.

24. A method of catalyzing a reaction of an organic compound comprising the step of reacting an organic compound catalyzed by a catalyst wherein the catalyst is an organometallic framework material comprising at least one metal ion and at least one at least bidentate organic compound coordinately bound to said at least one metal ion, obtainable by a process comprising reacting at least one metal salt with at least one at least bidentate compound capable of coordination to the metal ion of said metal salt, in the presence of an aqueous solvent system and at least one base wherein at least one bidentate compound comprises at least carboxy group and at least one hydroxy group.

25. A method as claimed in claim 24 wherein the reacting of the organic compound is selected from the group consisting of oxidizing, reducing, ring opening, C—

C coupling, epoxidizing, adding, aminating, hydrating, etherificating, alkoxylating, decarbonylating, decarboxylating, dehydrating, dehydrogenating, hydrogenating, isomerizing, C—

C bond cleaving, reforming, oligomerizing, polymerizing, catalytic purifying of waste gas and wastewater, and photocatalysing.