# US 2008/0188677 A1 · Mesoporous Metal-Organic Framework

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- Number: US 2008/0188677 A1
- Document ID: US20080188677A1
- Status: Published application
- Kind: A1
- Application number: 11/996,976
- Filed: 2006-08-16
- Published: 2008-08-07
- Earliest claimed: 2005-08-22
- Assignees: BASF SE
- Inventors: Markus Schubert; Ulrich Muller; Hendrick Mattenheimer; Markus Tonigold
- Web page: https://patentgrep.com/patent/US20080188677A1

## CPC

- C07F 5/069: {without C-aluminium linkages}
- 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)}
- B01J 20/3085: {Chemical treatments not covered by groups B01J20/3007 - B01J20/3078}
- C01B 3/001: characterised by the uptaking media; Treatment thereof
- C01B 3/0015: Organic compounds, e.g. liquid organic hydrogen carriers [LOHC] or metalorganic compounds; Solutions thereof
- C01B 3/0026: Metals or metal hydrides
- C07C 51/418: {Preparation of metal complexes containing carboxylic acid moieties}
- Y02E 60/32: Hydrogen storage
- C07F: ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM (metal-containing porphyrins C07D487/22)
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- C01B: NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; {METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C}
- C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS
- Y02E: REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION

## Abstract

The present invention relates to a porous metal-organic framework comprising AlIII and at least one at least bidentate compound, wherein the at least one at least bidentate organic compound is a six-membered aromatic hydrocarbon ring A in which one or more ring carbons may be replaced by nitrogen and which has three substituents X and optionally one or more substituents selected from the group consisting of R, NRR′, OR, SR, F, Cl and Br, where R, R′ are each, independently of one another, hydrogen, methyl which may optionally be substituted by one or more fluorine atoms or ethyl which may optionally be substituted by one or more fluorine atoms and each X is, independently of the others, C(═O)O−, C(═S)O−, C(═O)S−, C(═S)S− or a protonated form thereof. The invention further provides a process for preparing it and provides for the use of the new porous metal-organic framework.

## Claims

### Claim 1

A porous metal-organic framework comprising at least one at least bidentate organic compound coordinated to at least one metal ion, wherein the at least one metal ion is AlIII and the at least one at least bidentate organic compound is a six-membered aromatic hydrocarbon ring A in which one or more ring carbons may be replaced by nitrogen and which has three substituents X and optionally one or more substituents selected from the group consisting of R, NRR′, OR, SR, F, Cl and Br, where R, R′ are each, independently of one another, hydrogen, methyl which may optionally be substituted by one or more fluorine atoms or ethyl which may optionally be substituted by one or more fluorine atoms and each X is, independently of the others, C(═O)O−, C(═S)O−, C(═O)S−, C(═S)S− or a protonated form thereof, characterized in that the metal-organic framework in powder has a specific surface area determined by the Langmuir method of at least 800 m2/g.

### Claim 2 (depends on 1)

The framework according to claim 1, wherein A is benzene, pyridine, pyridazine, pyrimidine, pyrazine or triazine.

### Claim 3 (depends on 1)

The framework according to claim 1, wherein the at least one at least bidentate organic compound is 1,3,5-, 1,2,3-, 1,2,4-benzenetricarboxylate or a protonated form thereof.

### Claim 4 (depends on 1)

The framework according to claim 1 which has a mole fraction of the at least one at least bidentate organic compound of at least 50% of the total amount of the organic compounds.

### Claim 5 (depends on 1)

The framework according to claim 1, wherein at least 50% of the pore volume is formed by pores having a pore diameter of from 2 to 10 nm and the most frequently occurring pore diameter is preferably in the range from 3 to 9 nm.

### Claim 6 (depends on 1)

The framework according to claim 1 whose pore volume is at least 0.8 mg/l.

### Claim 7 (depends on 1)

The framework according to claim 1 which in powder form has a specific surface area determined by the Langmuir method of at least 1000 m2/g.

### Claim 8 (depends on 1)

A process for preparing a framework according to claim 1, which comprises
reacting at least one metal compound with at least one at least bidentate organic compound which can coordinate to the metal ion, wherein the metal is AlIII and the at least one at least bidentate organic compound is a six-membered aromatic hydrocarbon ring A in which one or more ring carbons may be replaced by nitrogen and which has three substituents X and optionally one or more substituents selected from the group consisting of R, NRR′, OR, SR, F, Cl and Br, where R, R′ are each, independently of one another, hydrogen, methyl which may optionally be substituted by one or more fluorine atoms or ethyl which may optionally be substituted by one or more fluorine atoms and each X is, independently of the others, C(═O)O−, C(═S)O−, C(═O)S−, C(═S)S− or a protonated form thereof.

### Claim 9 (depends on 8)

The process according to claim 8, wherein the framework formed is after-treated with an organic solvent and/or calcined after the reaction.

### Claim 10 (depends on 8)

The process according to claim 8, wherein AlIII is made available for the reaction by means of anodic oxidation.

### Claim 11

(canceled)

### Claim 12 (depends on 14)

The method according to claim 14 for the storage of hydrogen.

### Claim 13 (depends on 14)

The method according to claim 14 for diffusion-limited reaction with large-volume reactants.

### Claim 14 (depends on 1)

A method of using the framework according to claim 1 comprising uptaking at least one substance and storing, separating, controlledly releasing or chemically reacting the at least one substrate.

### Claim 15 (depends on 1)

A support material comprising the framework according to claim 1.