Fabrication of highly CO2 selective metal-organic framework membrane using liquid phase epitaxy approach

• US 10,441,924 B2
• Filed: 07/24/2015
• Issued: 10/15/2019
• 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: Eddaoudi, Mohamed, Shekhah, Osama, Belmabkhout, Youssef
• Primary Examiner(s): Shumate, Anthony R
• Application Number:
  US15/328,186
• Publication Number:
  US 20170203261A1
• Time in Patent Office: 1,544 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 framework 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, for a period of less than about 60 minutes to fabricate a MSiF₆ thin film on the substrate; and

contacting the MSiF₆ thin film on the substrate with a solution including an organic ligand for a period of less than about 60 minutes;

wherein contacting the substrate with the metal ion solution and contacting the MSiF₆ thin film on 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 washing the substrate with a solvent after contacting the substrate with the metal ion solution.

4. The method of claim 1, further comprising washing the substrate with a solvent after contacting the MSiF₆ thin film on the substrate with the organic ligand solution.

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 is 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, further comprising executing a plurality of growth cycles to grow a defect-free membrane.

16. The method of claim 1, further comprising performing 5 to 50 growth cycles.

17. The method of claim 2, wherein the substrate is immersed in the metal ion solution for up to about 10 minutes.

18. The method of claim 17, wherein the substrate is immersed in the organic ligand solution for up to about 10 minutes.

19. The method of claim 9, wherein the substrate is porous alumina.

11. A metal-organic framework membrane comprising MSiF₆(Ligand)₂, wherein M is a metal selected from the group consisting of Ni, Fe, Al, Nb, Mn and Co, the thickness of the membrane is less than 1,000 μ

m, the membrane is contiguous with a substrate, the membrane has a growth orientation along the [110] plane relative to the substrate, and the membrane is CO₂ selective over each of H₂, N₂ and CH₄.

12. The metal-organic framework membrane of claim 11, 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).

13. The metal-organic framework membrane of claim 11, wherein the metal is Ni and the ligand comprises pyrazine.

14. The metal-organic framework of claim 11, wherein the substrate is alumina, titanium oxide, polymer, copolymer, glass, ceramic, indium phosphide, metal or metal oxide.

15. The metal-organic framework of claim 11, wherein the substrate comprises one or more of —

OH nucleation sites and —

COOH nucleation sites.