Process for preparing a zirconium-based metal organic framework

• US 10,450,330 B2
• Filed: 09/25/2015
• Issued: 10/22/2019
• Est. Priority Date: 09/26/2014
• Status: Active Grant

• Current Assignee: Christian-Albrechts-Universität zu Kiel, Katholieke Universiteit Leuven, Universitetet I Oslo (Kunnskapsdepartementet)
• Original Assignee: Christian-Albrechts-Universität zu Kiel
• Inventors: Reinsch, Helge, Lillerud, Karl Peter, Chavan, Sachin, Olsbye, Unni, De Vos, Dirk, Stock, Norbert
• Primary Examiner(s): Brooks, Clinton A
• Application Number:
  US15/512,905
• Publication Number:
  US 20170291912A1
• Time in Patent Office: 1,488 Days
• Field of Search: None
• 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: C01G 25/04 Halides
• CPC Class Codes: C01G 25/06 Sulfates
• CPC Class Codes: C07C 63/26 1,4 - Benzenedicarboxylic acid
• CPC Class Codes: C07F 7/00 Compounds containing elements of Groups 4 or 14 of the Periodic Table
• CPC Class Codes: C07F 7/003 without C-Metal linkages

Abstract

There is provided a process for preparing a zirconium-based metal organic framework (Zr-MOF), the process comprising the steps (i) preparing a reaction mixture comprising zirconium ions, sulfate ions and at least one organic linker compound in an aqueous solvent; and (ii) heating the reaction mixture from step (i).

Claims

1. A process for preparing a zirconium-based metal organic framework (Zr-MOF), comprising the steps:

(i) preparing a reaction mixture comprising zirconium ions, sulfate ions and at least one organic linker compound in an aqueous solvent; and

(ii) heating the reaction mixture from step (i),

wherein said Zr-MOF comprises pores and wherein said aqueous solvent consists of water and wherein the process is carried out in the absence of a base.

2. A process as claimed in claim 1, further comprising step (iii) isolating the Zr-MOF, wherein step (iii) is carried out by filtration.

3. A process as claimed in claim 1, wherein the zirconium ions are provided in the form of at least one zirconium salt.

4. A process as claimed in claim 3, wherein said zirconium salt(s) is selected from the group consisting of zirconium acetate, zirconium acrylate, zirconium carboxylate, zirconium sulfate, zirconium hydroxide, zirconium nitrate, zirconium oxynitrate, zirconium oxide, zirconium oxychloride and zirconium chloride, or mixtures thereof.

5. A process as claimed in claim 3, wherein said zirconium salt(s) is selected from the group consisting of zirconium sulfate and zirconium hydroxide, or mixtures thereof.

6. A process as claimed in claim 1, wherein the sulfate ions are provided in the form of sulfuric acid or at least one sulfate salt (e.g. zirconium sulfate).

7. A process as claimed in claim 1, wherein both the zirconium and sulfate ions are provided in the form of zirconium sulfate.

8. A process as claimed in claim 1, wherein the at least one organic linker compound comprises at least two functional groups selected from the group consisting of carboxylate (COOH), amine (NH₂), anhydride and hydroxyl (OH) or a mixture thereof.

9. A process as claimed in claim 1, wherein the at least one organic linker compound comprises a linear or branched C_1-20 alkyl group, a C_3-12 cycloalkyl group and/or an aromatic moiety, preferably an aromatic moiety such as benzene, naphthalene, biphenyl, bipyridyl or pyridyl.

10. A process as claimed in claim 1, wherein the organic linker compound is selected from the group consisting of 1,4-benzene dicarboxylic acid (BDC), 2-amino-1,4-benzene dicarboxylic acid, 1,2,4-benzene tricarboxylic acid, 2-nitro-1,4-benzene dicarboxylic acid and 1,2,4,5-benzene tetracarboxylic acid, or mixtures thereof.

11. A process as claimed in claim 1, wherein in step (ii) of the process, the reaction mixture from step (i) is heated to a temperature in the range 50-120°

C.

12. A process as claimed in claim 1, wherein step (ii) is performed for a time period of at least 20 minutes.

13. A process as claimed in claim 1, wherein the Zr-MOF is produced as a crystalline powder.

14. A zirconium-based metal organic framework (Zr-MOF) produced by the process as defined in claim 1.