HIGHLY POROUS LAYERS MADE OF MOF MATERIALS AND METHOD FOR PRODUCING SUCH LAYERS

• US 20090169857A1
• Filed: 07/25/2006
• Published: 07/02/2009
• Est. Priority Date: 07/29/2005
• Status: Abandoned Application

• Current Assignee: Sud-Chemie AG (Clariant AG)
• Original Assignee: Sud-Chemie AG (Clariant AG)
• Inventors: Hermes, Stephan, Fischer, Roland, Woll, Christof, Schroder, Felicitas, Fischer, Richard
• Application Number:
  US11/995,241
• Publication Number:
  US 20090169857A1
• Time in Patent Office: Days
• US Class Current: 428/304.400
• 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: B01J 20/3265 with an organic functional group containing a metal, e.g. a metal affinity ligand
• CPC Class Codes: C23C 26/00 Coating not provided for in groups C23C2/00 - C23C24/00
• CPC Class Codes: Y10T 428/249953 Composite having voids in a component [e.g., porous, cellular, etc.]

Abstract

The invention relates to a process for producing highly porous layers, which comprises

• • making available a substrate having a substrate surface;
  • modifying at least sections of the substrate surface so as to produce surface-modified sections in which anchor groups for metal ions are provided;
  • applying at least one MOF to the surface-modified sections of the substrate so as to produce a layer of the MOF.

The invention further relates to a composite comprising a substrate and a porous layer of an MOF located on the substrate.

Claims

1. A process for producing highly porous layers, which comprises

making available a substrate having a substrate surface;

modifying at least sections of the substrate surface so as to produce surface-modified sections in which anchor groups for metal ions are provided, wherein the surface-modified sections are produced by applying a spacer molecule which has at least one anchor group for metal ions and at least one head group which can bond to the substrate surface to at least sections of the substrate surface, and;

applying at least one MOF to the surface-modified sections of the substrate so as to produce a layer of the MOF.

3. The process as claimed in claim 1, wherein the spacer molecule has the formula A-R¹—

K, where;

A;

an anchor group selected from the group consisting of —

OH, —

COOH, pyridyl, —

NR²₂, and —

SR⁴, where R², R⁴ are each hydrogen or an alkyl radical having from 1 to 6 carbon atoms and R⁴ may also may be —

SR²;

Z;

a head group selected from the group consisting of —

SR⁴, —

SiX₃, —

COOH, and —

C(O)NHOH, where X comprises halogen or an alkoxy group having from 1 to 6 carbon atoms and R⁴ is selected from the group consisting of hydrogen, an alkyl radical having from 1 to 6 carbon atoms and SR²; and

R¹;

a radical selected from the group consisting of an alkylene radical having from 1 to 6 carbon atoms, an arylene radical having from 6 to 18 carbon atoms and an aralkylene radical having from 7 to 30 carbon atoms, where the radicals may also be perfluorinated or partially fluorinated.

4. The process as claimed in claim 1, wherein at least the sections of the substrate surface are surface-treated so that groups for bonding of the head groups are provided.

5. The process as claimed in claim 1, wherein, to apply the MOF layer, a solution of at least one metal ion and at least one linker molecule that is at least bidentate is prepared and the solution is brought into contact with at least the sections of the substrate surface.

6. The process as claimed in claim 5, wherein the solution is prepared by dissolving the at least one metal ion and the at least one linker molecule that is at least bidentate in a concentration close to the saturation limit of the MOF at a first, relatively high temperature, at least the sections of the substrate surface are brought into contact with the solution and the solution is cooled to a second, lower temperature at which the MOF grows on at least the sections of the substrate surface.

7. The process as claimed in claim 5, wherein the solution of the at least one metal ion and the at least one linker molecule that is at least bidentate is prepared in the presence of the substrate surface.

8. The process as claimed in claim 5, wherein the layer of the MOF is produced by treating at least the sections of the substrate surface sequentially at least with a solution of the at least one metal ion and with a solution of the at least one linker molecule that is at least bidentate.

9. The process as claimed in claim 1, wherein the at least one metal ion of the MOF is selected from the group consisting of Zn, Sn, In, Ti, Cu, and Fe.

10. The process as claimed in claim 5, wherein the at least one linker molecule that is at least bidentate is selected from the group consisting of compounds of the formula Z-R⁵-Z, where:

Z;

a group selected from the group consisting of a carboxyl group, a carbamide group, a hydroxy group, a thiol group, an amino group and a pyridyl group;

R⁵;

an at least divalent hydrocarbon radical selected from the group consisting of

 

where n is an integer from 1 to 5 and A is selected from the group consisting of hydrogen, alkyl groups having 1-6 carbon atoms, alkenyl groups having 2-6 carbon atoms, alkoxy groups having 1-6 carbon atoms and from 1 to 3 oxygen atoms, halogen atoms or amino groups, with A being able to be identical or different on each occurrence and R⁵ also being able to be a single bond when Z is a pyridyl group.

11. The process as claimed in claim 1, wherein the substrate is comprises a silicon wafer.

12. The process as claimed in claim 1, wherein an active metal is incorporated into the layer of the MOF.

2. (canceled)

13. A composite comprising a substrate and a highly porous layer applied to at least sections of a substrate surface of the substrate, wherein the layer is made up of an MOF, which is bound to the substrate surface with a layer of spacer molecules, wherein the spacer molecules have at least one anchor group for metal ions and at least one head group which can bond to the substrate surface.

14. The composite as claimed in claim 13, wherein the MOF is made up of at least one metal ion and at least one linker molecule that is at least bidentate.

15. The composite as claimed in claim 13, wherein the metal ion is selected from the group consisting of Zn, Sn, In, Ti, Cu, and Fe.

16. The composite as claimed in claim 13, wherein the thickness of the highly porous layer is less than 100 μ

m.

17. The composite as claimed in claim 13, wherein an active metal has been incorporated into the highly porous layer.