# US 2019/0168173 A1 · Nanocomposite membranes and methods of forming the same

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- Number: US 2019/0168173 A1
- Document ID: US20190168173A1
- Status: Published application
- Kind: A1
- Application number: 16/172,581
- Filed: 2018-10-26
- Published: 2019-06-06
- Earliest claimed: 2017-10-27
- Assignees: Michael Tsapatsis; Xiaoli Ma
- Applicants: Regents of the University of Minnesota
- Inventors: Michael Tsapatsis; Xiaoli Ma
- Web page: https://patentgrep.com/patent/US20190168173A1

## CPC

- B01D 69/148: {Organic/inorganic mixed matrix membranes}
- B01D 53/228: {characterised by specific membranes}
- B01D 67/0072: {by deposition from the gaseous phase, e.g. sputtering, CVD, PVD}
- B01D 67/00793: {Dispersing a component, e.g. as particles or powder, in another component}
- B01D 69/02: characterised by their properties
- B01D 69/10: Supported membranes; Membrane supports
- B01D 69/106: {Membranes in the pores of a support, e.g. polymerized in the pores or voids}
- B01D 71/0281: {Zeolites}
- B01D 71/06: Organic material
- C23C 16/045: {Coating cavities or hollow spaces, e.g. interior of tubes; Infiltration of porous substrates}
- C23C 16/40: Oxides
- C23C 16/407: {of zinc, germanium, cadmium, indium, tin, thallium or bismuth}
- C23C 16/45525: {Atomic layer deposition [ALD]}
- C23C 16/45555: {applied in non-semiconductor technology}
- C23C 16/56: After-treatment
- B01D 69/08: Hollow fibre membranes (manufacture of hollow fibres D01D5/24, D01F1/08)
- B01D 69/147: {containing embedded adsorbents}
- B01D 71/025: {Aluminium oxide}
- B01D 2256/24: Hydrocarbons
- B01D 2257/7022: Aliphatic hydrocarbons
- B01D 2325/20: Specific permeability or cut-off range
- 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)
- C23C: COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL (making metal-coated products by extrusion B21C23/22; covering with metal by connecting pre-existing layers to articles, see the relevant places, e.g. B21D39/00, B23K; metallising of glass C03C; metallising mortars, concrete, artificial stone, ceramics or natural stone C04B41/00; enamelling of, or applying a vitreous layer to, metals C23D; treating metal surfaces or coating of metals by electrolysis or electrophoresis C25D; single-crystal film growth C30B; by metallising textiles D06M11/83; decorating textiles by locally metallising D06Q1/04)

## Abstract

A nanocomposite including a mesoporous, macroporous, or a combination thereof oxide and a zeolitic imidazolate framework (ZIF) that is filling the pores of the oxide to form a ZIF phase embedded and at least substantially confined mostly within the oxide. Methods of making nanocomposites including the steps of depositing an oxide in the pores of a mesoporous oxide; and further treating the resulting material with vapor, liquid, or supercritical CO2 comprising an azole-based compound, a carboxylate based compound, or a combination thereof. Use of disclosed articles to separate propylene and propane in a mixture thereof.

## Claims

### Claim 1

A nanocomposite comprising a mesoporous, macroporous, or combination thereof oxide and a zeolitic imidazolate framework (ZIF) that is filling the pores of the mesoporous, macroporous, or combination thereof oxide to form a ZIF phase embedded and at least substantially confined mostly within the mesoporous, macroporous, or combination thereof oxide pores.

### Claim 2 (depends on 1)

The nanocomposite of claim 1 where the mesoporous, macroporous, or combination thereof oxide is γ-alumina

### Claim 3 (depends on 1)

The nanocomposite of claim 1 where the mesoporous, macroporous, or combination thereof oxide is any of or a mixture of γ-alumina, silica, titania, zirconia, tin oxide and zinc oxide.

### Claim 4 (depends on 1)

The nanocomposite of claim 1 where the ZIF is ZIF-8

### Claim 5 (depends on 1)

The nanocomposite of claim 1 where the ZIF is amorphous ZIF

### Claim 6 (depends on 1)

The nanocomposite of claim 1 where the ZIF is any of or a mixture of ZIF-1, ZIF-2, ZIF-3, ZIF-4, ZIF-5, ZIF-6, ZIF-7, ZIF-8, ZIF-9, ZIF-10, ZIF-11, ZIF-12, ZIF-67.

### Claim 7 (depends on 1)

The nanocomposite of claim 1 where the oxide is γ-alumina, silica, titania, zirconia, tin oxide, zinc oxide, or a combination thereof and the ZIF is amorphous ZIF, ZIF-1, ZIF-2, ZIF-3, ZIF-4, ZIF-5, ZIF-6, ZIF-7, ZIF-8, ZIF-9, ZIF-10, ZIF-11, ZIF-12, ZIF-67, or any of a mixture thereof.

### Claim 8 (depends on 1)

The nanocomposite of claim 1 where the oxide is γ-alumina and the ZIF is ZIF-8, or amorphous ZIF-8 or a combination of crystalline and amorphous ZIF-8.

### Claim 9 (depends on 8)

The nanocomposite of claim 8 further comprising ZnO.

### Claim 10 (depends on 1)

An article comprising the nanocomposite of claim 1 supported on a macroporous support

### Claim 11 (depends on 10)

The article of claim 10 where the macroporous support is α-alumina

### Claim 12 (depends on 10)

The article of claim 10, wherein the article exhibits a mixture separation factor for a propylene/propane mixture larger than 50 and propylene flux larger than 0.001 mol/m2-s or larger than 0.01 mol/m2-s

### Claim 13 (depends on 10)

The article of claim 10, wherein the article further exhibits selective permeation properties for a mixture of gases, vapors or liquids and can be used as a selective separation membrane

### Claim 14

A method for fabricating a nanocomposite comprising the steps of:
depositing an oxide in the pores of a mesoporous, macroporous, or combination thereof oxide; and
further treating the resulting material with vapor, liquid, or supercritical CO2 comprising an azole-based compound, a carboxylate based compound, or a combination thereof.

### Claim 15 (depends on 14)

The method of claim 14, wherein the oxide is deposited using atomic layer deposition (ALD).

### Claim 16 (depends on 15)

The method of claim 15, where the oxide deposited comprises Zn, Co, Fe, In, Cu, Mn, Li, B, Cd, Hg, Pr, Mg, Ni, Al, Zr, Si, Hf, Ti and Ta oxides or a mixture thereof.

### Claim 17 (depends on 14)

The method of claim 14, where the azole based compound comprises any of imidazole, methyl-imidazole, benzimidazole, nitroimidazole, 2-chloro-1H-imidazole, dichloroimidazole, imidazole-2-carboxylic acid, 5,6-dimethylbenzimidazole, imidazole-2-carboxaldehyde, 2-ethylimidazole, 4-bromoimidazolate, 4,5-dichloroimidazolate, dimethylimidazolate or a mixture thereof.

### Claim 18 (depends on 14)

The method of claim 14, where the resulting material is treated with vapor comprising an azole-based compound, a carboxylate based compound, or a combination thereof.

### Claim 19

An article comprising a macroporous α-alumina support and a gamma alumina layer on the alpha alumina support and a ZIF phase filling the pores of the gamma alumina sufficiently to create a selective membrane that can separate a mixture of gases, vapors or liquids

### Claim 20 (depends on 18)

An article according to claim 18, wherein the membrane is a selective membrane that exhibits a mixture separation factor for a propylene/propane mixture larger than 50 and propylene flux larger than 0.001 mol/m2-s or larger than 0.01 mol/m2-s.