Metallated metal-organic frameworks

Patent metadata

Field	Value
Publication number	US-9738665-B2
Application number	US-201615374218-A
Country	US
Kind code	B2
Filing date	Dec 9, 2016
Priority date	Jul 23, 2013
Publication date	Aug 22, 2017
Grant date	Aug 22, 2017

Abstract

Porous metal-organic frameworks (MOFs) and metallated porous MOFs are provided. Also provided are methods of metallating porous MOFs using atomic layer deposition and methods of using the metallated MOFs as catalysts and in remediation applications.

First claim

What is claimed is:

1. A metal-organic framework comprising:
inorganic nodes that comprise an octahedral Zr 6 cluster capped by eight μ 3 -ligands and have twelve octahedral edges, wherein the the μ 3 -ligands are hydroxo ligands, oxo ligands, aquo ligands, or a combination thereof; and
organic linkers connecting the inorganic nodes, the inorganic linkers comprising 1,3,6,8-tetrakis(p-benzoic acid)pyrene units;
wherein eight of the twelve octahedral edges of the inorganic nodes are connected to the 1,3,6,8-tetrakis(p-benzoic acid)pyrene units.

2. The metal-organic framework of claim 1 , wherein the μ 3 -ligands comprise hydroxo ligands.

3. A metallated metal-organic framework comprising:
a porous metal-organic framework comprising:
inorganic nodes that comprise an octahedral Zr 6 cluster capped by eight μ 3 -ligands and have twelve octahedral edges, wherein the the μ 3 -ligands are hydroxo ligands, oxo ligands, aquo ligands, or a combination thereof; and
organic linkers connecting the inorganic nodes, the inorganic linkers comprising 1,3,6,8-tetrakis(p-benzoic acid)pyrene units;
wherein eight of the twelve octahedral edges of the inorganic nodes are connected to the 1,3,6,8-tetrakis(p-benzoic acid)pyrene units; and

a metal film on the surfaces within the pores of the porous metal-organic framework.

4. The metallated metal-organic framework of claim 3 , wherein the μ 3 -ligands comprise hydroxo ligands.

5. The metallated metal-organic framework of claim 3 , wherein the film comprises zinc.

6. The metallated metal-organic framework of claim 3 , wherein the film comprises aluminum.

7. A method of catalyzing a reaction, the method comprising exposing chemical reactants to the metallated metal-organic framework of claim 3 , whereby the metal film catalyzes a reaction between the chemical reactants.

8. The method of claim 7 , wherein the reaction is a condensation reaction catalyzed by Lewis acidic sites on the metal film.

9. The method of claim 8 , wherein the metal film comprises zinc and the Lewis acidic sties on the metal film are Zn II sites.

10. The method of claim 8 , wherein the metal film comprises aluminum and the Lewis acidic sties on the film are Al III sites.

11. A method of remediating species from a sample comprising the species, the method comprising:
exposing the sample to the metallated metal-organic framework of claim 3 , whereby the species in the sample are adsorbed or absorbed by the metallated metal-organic framework; and
removing the metallated metal-organic framework and the adsorbed or absorbed species from the sample.

12. The method of claim 11 , wherein the species comprise, metal elements, molecules, or ions.

13. The method of claim 11 , wherein species comprise heavy metals.

14. A metal-organic framework comprising:
a porous metal-organic framework comprising:
inorganic nodes that comprise an octahedral Zr 6 cluster capped by eight μ 3 -ligands and have twelve octahedral edges, wherein the the μ 3 -ligands are hydroxo ligands, oxo ligands, aquo ligands, or a combination thereof; and
organic linkers connecting the inorganic nodes, the inorganic linkers comprising 1,3,6,8-tetrakis(p-benzoic acid)pyrene units;
wherein eight of the twelve octahedral edges of the inorganic nodes are connected to the 1,3,6,8-tetrakis(p-benzoic acid)pyrene units; and

an oxide film on the surfaces within the pores of the porous metal-organic framework.

15. The metal-organic framework of claim 14 , wherein the oxide film comprises a metal oxide.

Assignees

• Univ Northwestern

Inventors

• Bury Wojciech
• Farha Omar K
• Hupp Joseph T
• Mondloch Joseph E

Classifications

• C02F1/288

  using composite sorbents, e.g. coated, impregnated, multi-layered · CPC title

• B01J2531/48

  Zirconium · CPC title

• C07C253/30 Primary

  by reactions not involving the formation of cyano groups · CPC title

• C07F7/006 Primary

  Chemistry & Metallurgy · mapped topic

• B01J31/1691

  Coordination polymers, e.g. metal-organic frameworks [MOF] (preparation of metal complexes containing carboxylic acid moieties C07C51/418; MOF's per se C07F) · CPC title