# US 10,441,924 B2 · Fabrication of highly CO2 selective metal-organic framework membrane using liquid phase epitaxy approach

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- Number: US 10,441,924 B2
- Document ID: US10441924B2
- Status: Granted
- Kind: B2
- Application number: 15/328,186
- Filed: 2015-07-24
- Published: 2017-07-20
- Granted: 2019-10-15
- Earliest claimed: 2014-07-24
- Assignees: King Abdullah University of Science and Technology
- Applicants: King Abdullah University of Science and Technology
- Inventors: Mohamed Eddaoudi; Osama Shekhah; Youssef Belmabkhout
- Web page: https://patentgrep.com/patent/US10441924B2

## CPC

- B01D 71/06: Organic material
- B01D 53/228: {characterised by specific membranes}
- B01D 69/02: characterised by their properties
- B01D 69/10: Supported membranes; Membrane supports
- B01D 71/00: Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D 71/02232: {Nickel}
- C07F 15/045: {without a metal-carbon linkage}
- B01D 2256/10: Nitrogen
- B01D 2256/12: Oxygen
- B01D 2256/16: Hydrogen
- B01D 2256/245: Methane
- B01D 2257/504: Carbon dioxide
- B01D 2258/0283: Flue gases
- B01D 2323/2189: Metal-organic compounds or complexes
- B01D 2323/40: in-situ membrane formation
- B01D 2325/20: Specific permeability or cut-off range
- Y02C 20/40: of CO2
- Y02P 20/151: Reduction of greenhouse gas [GHG] emissions, e.g. CO2
- B01D: SEPARATION (separating solids from solids by wet methods B03B, B03D; by pneumatic jigs or tables B03B; by other dry methods B07; magnetic or electrostatic separation of solid materials from solid materials or fluids, separation by high-voltage electric fields B03C; centrifuges, vortex apparatus B04; presses per se for squeezing-out liquid from liquid-containing material B30B9/02; treatment of water C02F, e.g. softening by ion-exchange C02F1/42; {arrangements of air intake cleaners in gas turbine plants F02C7/05} ; arrangements or mounting of filters in air-conditioning, air-humidification or ventilation F24F13/28)
- C07F: ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM (metal-containing porphyrins C07D487/22)
- Y02C: CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02P: CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS

## 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

### Claim 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.

### Claim 2 (depends on 1)

The method of claim 1, wherein contacting comprises immersing.

### Claim 3 (depends on 1)

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

### Claim 4 (depends on 1)

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.

### Claim 5 (depends on 1)

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

### Claim 6 (depends on 1)

The method of claim 1, wherein the metal is Ni.

### Claim 7 (depends on 1)

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

### Claim 8 (depends on 1)

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

### Claim 9 (depends on 1)

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.

### Claim 10 (depends on 1)

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

### Claim 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 μm, 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.

### Claim 12 (depends on 11)

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).

### Claim 13 (depends on 11)

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

### Claim 14 (depends on 11)

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

### Claim 15 (depends on 11)

The metal-organic framework of claim 11, wherein the substrate comprises one or more of —OH nucleation sites and —COOH nucleation sites.

### Claim 16 (depends on 1)

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

### Claim 17 (depends on 2)

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

### Claim 18 (depends on 17)

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

### Claim 19 (depends on 9)

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