FABRICATION OF HIGHLY CO2 SELECTIVE METAL ORGANIC FRAMEWORK MEMBRANE USING LIQUID PHASE EPITAXY APPROACH

• US 20170203261A1
• Filed: 07/24/2015
• Published: 07/20/2017
• Est. Priority Date: 07/24/2014
• Status: Active Grant

• Current Assignee: King Abdullah University of Science and Technology
• Original Assignee: King Abdullah University of Science and Technology
• Inventors: SHEKHAH, Osama, EDDAOUDI, Mohamed, BELMABKHOUT, Youssef
• Granted Patent: US 10,441,924 B2
• Time in Patent Office: Days
• CPC Class Codes: B01D 2256/10 Nitrogen
• CPC Class Codes: B01D 2256/12 Oxygen
• CPC Class Codes: B01D 2256/16 Hydrogen
• CPC Class Codes: B01D 2256/245 Methane
• CPC Class Codes: B01D 2257/504 Carbon dioxide
• CPC Class Codes: B01D 2258/0283 Flue gases
• CPC Class Codes: B01D 2323/2189 Metal-organic compounds or complexes
• CPC Class Codes: B01D 2323/40 in-situ membrane formation
• CPC Class Codes: B01D 2325/20 Specific permeability or cut-off range
• CPC Class Codes: B01D 53/228 characterised by specific membranes
• CPC Class Codes: B01D 69/02 characterised by their properties
• CPC Class Codes: B01D 69/10 Supported membranes; Membrane supports
• CPC Class Codes: B01D 71/00 Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
• CPC Class Codes: B01D 71/02232 Nickel
• CPC Class Codes: B01D 71/06 Organic material
• CPC Class Codes: C07F 15/045 without a metal-carbon linkage
• CPC Class Codes: Y02C 20/40 of CO2
• CPC Class Codes: Y02P 20/151 Reduction of greenhouse gas [GHG] emissions, e.g. CO2

Abstract

Embodiments include a method of making a metal organic framework membrane comprising contacting a substrate with a solution including a metal ion and contacting the substrate with a solution including an organic ligand, sufficient to form one or more layers of a metal organic framework on a substrate. Embodiments further include a defect-free metal organic framework membrane comprising MSiF₆(pyz)₂, wherein M is a metal, wherein the thickness of the membrane is less than 1,000 μm, and wherein the metal organic has a growth orientation along the [110] plane relative to a substrate.

Claims

1. A method of making a CO₂ selective metal organic framework membrane based on hexafluorosilicate comprising:

contacting a substrate with a solution including a metal ion, the metal ion solution including MSiF₆, wherein M is a metal; and

contacting the substrate with a solution including an organic ligand;

wherein contacting the substrate with the metal ion solution and contacting the substrate with the organic ligand solution constitutes one growth cycle, and one growth cycle forms one or more layers of a metal organic framework on the substrate.

2. The method of claim 1, wherein contacting comprises immersing.

3. The method of claim 1, further comprising after contacting the substrate with the metal ion solution, the step of washing the substrate with a solvent.

4. The method of claim 1, further comprising after contacting the substrate with the organic ligand solution, the step of washing the substrate with a solvent.

5. The method of claim 1, wherein the metal comprises one or more of Ni, Cu, Zn, Fe, Al, Nb, Mn, and Co.

6. The method of claim 1, wherein the metal comprises Ni.

7. The method of claim 1, wherein the metal ion solution includes NiSiF₆.

8. The method of claim 1, wherein the organic ligand solution includes pyrazine.

9. The method of claim 1, wherein the substrate includes one or more of alumina, titanium oxide, polymer, copolymer, ceramic, glass, indium phosphide metal or metal oxide, combinations thereof and composites thereof.

10. The method of claim 1, wherein the metal organic framework is a defect-free NiSiF₆(pyz)₂ metal organic framework.

11. The method of claim 1, further comprising executing a plurality of growth cycles to grow a defect-free membrane.

12. A metal organic framework membrane comprising MSiF₆(Ligand)₂, wherein M is a metal, and wherein the thickness of the membrane is less than 1,000 μ

m.

13. The metal organic framework membrane of claim 12, wherein the metal comprises one or more of Ni, Cu, Zn, Fe, Al, Nb, Mn and Co.

14. The metal organic framework membrane of claim 12, wherein the ligand comprises pyridine, 4,4′

-Bipyridin, pyrazine, pyrimidine, pyridazine, triazine, thiazole, oxazole, pyrrole, imidazole, pyrazole, triazole, oxadiazole, thiadiazole, quinoline, benzoxazole, benzimidazole, 1,4-Diazabicyclo[2.2.2]octane (DABCO), or 1,2-bis(4-pyridyl)acetylene (dpa).

15. The metal organic framework membrane of claim 12, wherein the metal includes Ni and the ligand comprises pyrazine.

16. The metal organic framework membrane of claim 12, wherein the metal organic framework membrane is contiguous with a substrate, and the metal organic framework membrane has a growth orientation along the [110] plane relative to the substrate.

17. The metal organic framework of claim 16, wherein the substrate is alumina, titanium oxide, polymer, copolymer, glass, ceramic, indium phosphide, metal or metal oxide.

18. The metal organic framework of claim 16, wherein the substrate comprises one or more of —

OH nucleation sites and —

COOH nucleation sites.

19. The metal organic framework membrane of claim 12, wherein the membrane is CO₂ selective over one or more of O₂, H₂, N₂ and CH₄.