Highly stable [MaMbF6-n(O/H2O)n(ligand)2(solvent)x]n metal organic frameworks

Patent metadata

Field	Value
Publication number	US-10328414-B2
Application number	US-201615564909-A
Country	US
Kind code	B2
Filing date	Apr 7, 2016
Priority date	Apr 7, 2015
Publication date	Jun 25, 2019
Grant date	Jun 25, 2019

Abstract

Provided herein are metal organic frameworks having high selectivity and stability in the present of gases and vapors including H2S, H2O, and CO2. Metal organic frameworks can comprise metal nodes and N-donor organic ligands. Further provided are methods of making metal organic frameworks.

First claim

What is claimed is:

1. A metal organic framework, comprising:
a pillar characterized by the formula (M b F 5 (O/H 2 O)), where M b is an element from periodic groups IIIA, IIIB, IVB, VB, VIB, and VIII; and
a square grid characterized by the formula (M a (ligand) x ), where M a is Ni 2+ , ligand is pyrazine, and x is 2;
wherein pillaring of the square grids with the pillars forms a metal-organic framework.

2. The metal organic framework of claim 1 , wherein M b comprises Al +3 , Ga 3+ , Fe +2 , Fe +3 , Cr 2+ , Cr 3+ , Ti 3+ , V 3+ , V 5+ , Sc 3+ , In 3+ , Nb 5+ , or Y 3+ .

3. The metal organic framework of claim 1 , wherein the pillar is (NbOF 5 ) 2− , (AlF 5 (H 2 O)) 2− , or (FeF 5 (H 2 O)) 2− .

4. The metal organic framework of claim 1 , wherein the pillar is (NbOF 5 ) 2− , wherein the metal organic framework includes a double-bonded oxygen in a confined space.

5. The metal organic framework of claim 1 , wherein the metal organic framework includes open metal sites in a confined space.

6. The metal organic framework of claim 1 , wherein the metal organic framework is stable in the presence of water and H 2 S.

7. The metal organic framework of claim 1 , wherein the metal organic framework includes one or more open metal sites.

8. The metal organic framework of claim 1 , wherein a pore size of the metal organic framework ranges from about 2.8 Å to about 4.8 Å.

9. The metal organic framework of claim 1 , wherein a specific surface area of the metal organic framework ranges from about 250 m 2 /g to about 500 m 2 /g.

10. The metal organic framework of claim 1 , wherein a pore volume of the metal organic framework ranges from about 0.1 cm 3 /g to about 0.25 cm 3 /g.

11. A method of fabricating a metal organic framework, the method comprising:
combining a fluorhydric acid solution, a Ni 2+ source, a second metal source, and a solvent, sufficient to form a mixture;
reacting the mixture over a period of time sufficient to form a reacted mixture;
processing the reacted mixture to provide a metal organic framework via pillaring of square grids with a pillar,
wherein the pillar is characterized by the formula (M b F 5 (O/H 2 O)), where M b is an element from periodic groups IIIA, IIIB, IVB, VB, VIB, and VIII, and the square grids are characterized by the formula (M a (ligand) x ), where M a is Ni 2+ ; ligand is pyrazine, and x is 2.

12. The method of claim 11 , wherein the second metal source comprises an Al +3 source, an Fe +2 source, an Fe +3 source, a Cr 2+ source, a Cr 3+ source, a Ti 3+ source, a V 3+ source, a V 5+ source, a Sc 3+ source, an In 3+ source, a Nb 5+ source, or a Y 3+ source.

13. The method of claim 11 , wherein the solvent comprises one or more of water, ethanol, methanol, dimethylformamide, and diethylformamide.

14. The method of claim 11 , wherein reacting the mixture comprises heating the mixture to a temperature between about 80° C. to about 200° C.

15. The method of claim 11 , wherein processing the reacted mixture comprises one or more of filtering, rinsing with water, and removing excess reactants.

16. The method of claim 11 , further comprising evacuating guest molecules from the metal organic framework to create open metal sites.

17. The method of claim 11 , wherein the Ni 2+ source is nickel nitrate, hydrated nickel nitrate, nickel chloride, hydrated nickel chloride, nickel fluoride, hydrated nickel fluoride, nickel oxide, or hydrated nickel oxide.

18. The method of claim 11 , wherein the pillar is (NbOF 5 ) 2− , (AlF 5 (H 2 O)) 2− , or (FeF 5 (H 2 O)) 2− .

19. The method of claim 11 , wherein the pillar is (NbOF 5 ) 2− , wherein the metal organic framework includes a double-bonded oxygen in a confined space.

20. The method of claim 11 , wherein M b comprises Al +3 , Ga 3+ , Fe +2 , Fe +3 , Cr 2+ , Cr 3+ , Ti 3+ , V 3+ , V 5+ , Sc 3+ , In 3+ , Nb 5+ , or Y 3+ .

Assignees

• Univ King Abdullah Sci & Tech

Inventors

• Eddaoudi Mohamed
• Adil Karim
• Belmabkhout Youssef
• Shekhah Osama
• Bhatt Prashant M
• Cadiau Amandine

Classifications

• B01J20/2808

  being less than 2 nm, i.e. micropores or nanopores · CPC title

• B01D53/02

  by adsorption, e.g. preparative gas chromatography {(solid sorbent compositions B01J20/00, preparation of inorganic compounds or elements C01)} · CPC title

• B01D2256/245

  Methane · CPC title

• B01J20/28071

  being less than 0.5 ml/g · CPC title

• B01J20/3085

  Chemical treatments not covered by groups B01J20/3007 - B01J20/3078 · CPC title