Iron metal organic framework materials

Patent metadata

Field	Value
Publication number	US-9724668-B2
Application number	US-201615165247-A
Country	US
Kind code	B2
Filing date	May 26, 2016
Priority date	Nov 26, 2013
Publication date	Aug 8, 2017
Grant date	Aug 8, 2017

Abstract

The invention relates to an improved process for preparing metal-organic framework materials, metal-organic frameworks obtainable by such processes, methods using the same, and the use thereof. The process of the invention provides an improved process for preparing metal-organic frameworks in particular monocrystalline metal-organic frameworks having large crystal sizes. The invention also relates to metal organic frameworks comprising iron or titanium, and their uses.

First claim

The invention claimed is:

1. A single crystal iron metal-organic framework, the metal organic framework comprising at least one metal-ligand cluster comprising a metal cluster and one or more ligands having two or more carboxylate groups;
wherein the metal cluster has the formula Fe 2 XO, where X is a metal ion selected from the group consisting of Fe, Co, Mn, Zn, Ni, Mg, Cu, and Ca;
wherein the single crystal has a size greater than or equal to 10 μm; the metal organic framework comprises cavities having a free diameter of about 4 to about 40 Å; and the metal organic framework comprises pores having a pore volume of from about 0.1 cm 3 /g to about 4 cm 3 /g.

2. The single crystal iron metal-organic framework of claim 1 , wherein the crystal is monocrystalline or polycrystalline.

3. The single crystal metal-organic framework according to claim 1 , having a Brunauer-Emmett-Teller (BET) specific surface area of at least 200 m 2 /g.

4. The single crystal metal-organic framework according to claim 1 , having a surface area of less than or equal to 8000 m 2 /g.

5. The single crystal metal-organic framework according to claim 1 , the metal-organic framework comprising cavities having a free diameter of from about 5 Å to about 25 Å.

6. The single crystal metal-organic framework according to claim 1 , the metal-organic framework comprising pores having a pore volume from about 0.2 cm 3 /g to about 3 cm 3 /g.

7. The single crystal metal-organic framework according to claim 1 , having a size greater than or equal to 20 μm.

8. The single crystal metal-organic framework according to claim 1 , having a crystal size from 10 μm to about 2000 μm.

9. The single crystal metal-organic framework according to claim 1 , wherein the one or more ligands are derived from a dicarboxylic acid, a tricarboxylic acid, a tetracarboxylic acid, a hexacarboxylic acid, or a octacarboxylic acid.

10. The single crystal metal-organic framework according to claim 1 , wherein each metal cluster is coordinated with 4, 5, or 6 ligands.

11. The single crystal of a metal-organic framework according to claim 1 , wherein the at least one metal ion is Fe(II) or Fe(III).

12. The single crystal of a metal-organic framework according to claim 1 , wherein the metal cluster has a formula Fe 3 O.

13. A process for preparing the single crystal iron metal-organic framework of claim 1 , the process comprising:
reacting a starting compound of formula M 3 O(CH 3 COO) 6 with a ligand precursor having at least two carboxylic acid groups in the presence of acetic acid to provide a metal-organic framework comprising a M 3 O cluster where at least one (CH 3 COO) ligand is replaced by at least one ligand having at least two carboxylate groups; wherein M 3 has the formula Fe 2 X, where X is a metal ion selected from the group consisting of Fe, Co, Mn, Zn, Ni, Mg, Cu, and Ca.

14. The process according to claim 13 , wherein the starting compound has a formula Fe 2 MO(CH 3 COO) 6 or Fe 3 O(CH 3 COO) 6 , where M is Co, Mn, Zn, or Ni.

Assignees

• Texas A & M Univ Sys

Inventors

• Zhou Hong-Cai
• Feng Dawei
• Wang Kecheng

Classifications

• B01J20/28057

  Surface area, e.g. B.E.T specific surface area · CPC title

• C01B31/20

  Chemistry & Metallurgy · mapped topic

• C07F15/02

  Iron compounds · CPC title

• C07F15/025

  without a metal-carbon linkage · CPC title

• C07F7/28

  Titanium compounds · CPC title