Process for preparing a zirconium-based metal organic framework

Patent metadata

Field	Value
Publication number	US-10450330-B2
Application number	US-201515512905-A
Country	US
Kind code	B2
Filing date	Sep 25, 2015
Priority date	Sep 26, 2014
Publication date	Oct 22, 2019
Grant date	Oct 22, 2019

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).

First claim

The invention claimed is:

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 (NH 2 ), 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 .

Assignees

• Univ Oslo
• Univ Kiel Christian Albrechts
• Univ Leuven Kath

Inventors

• Reinsch Helge
• Lillerud Karl Peter
• Chavan Sachin
• Olsbye Unni
• De Vos Dirk
• Stock Norbert

Classifications

• 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

• C07F7/003 Primary

  without C-Metal linkages · CPC title

• C01G25/06

  Sulfates · CPC title

• C01G25/04

  Halides · CPC title

• C07C63/26

  1,4 - Benzenedicarboxylic acid · CPC title