# US 12,109,549 B2 · Method of making colloidal suspensions of metal organic frameworks in polymeric solutions and uses thereof

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- Number: US 12,109,549 B2
- Document ID: US12109549B2
- Status: Granted
- Kind: B2
- Application number: 17/054,590
- Filed: 2019-05-17
- Published: 2021-02-25
- Granted: 2024-10-08
- Earliest claimed: 2018-05-18
- Assignees: Research Triangle Institute
- Applicants: Research Triangle Institute
- Inventors: Ignacio Luz Minguez; Mustapha Soukri; Marty Lail; Lora Goon Toy
- Web page: https://patentgrep.com/patent/US12109549B2

## CPC

- B01J 20/226: {Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF] (preparation of metal complexes containing carboxylic acid moieties C07C51/418; MOF's per se C07F)}
- B01J 31/1691: {Coordination polymers, e.g. metal-organic frameworks [MOF] (preparation of metal complexes containing carboxylic acid moieties C07C51/418; MOF's per se C07F)}
- B01D 53/02: by adsorption, e.g. preparative gas chromatography {(solid sorbent compositions B01J20/00, preparation of inorganic compounds or elements C01)}
- B01D 53/228: {characterised by specific membranes}
- B01J 20/261: {obtained by reactions only involving carbon to carbon unsaturated bonds (macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds per se C08F)}
- B01J 20/262: {obtained otherwise than by reactions only involving carbon to carbon unsaturated bonds, e.g. obtained by polycondensation (macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds per se C08G)}
- B01J 20/28026: {Particles within, immobilised, dispersed, entrapped in or on a matrix, e.g. a resin}
- B01J 20/28033: {Membrane, sheet, cloth, pad, lamellar or mat}
- B01J 20/28057: {Surface area, e.g. B.E.T specific surface area}
- B01J 20/28059: {being less than 100 m2/g}
- B01J 20/28061: {being in the range 100-500 m2/g}
- B01J 20/28064: {being in the range 500-1000 m2/g}
- B01J 20/28066: {being more than 1000 m2/g}
- B01J 20/28078: {Pore diameter}
- B01J 20/28083: {being in the range 2-50 nm, i.e. mesopores}
- B01J 31/06: containing polymers {(organometallic polymers B01J31/123; polymer-bound organometallic complexes B01J31/165; coordination polymers B01J31/1691)}
- B01J 31/1815: {with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine}
- B01J 31/2239: {Bridging ligands, e.g. OAc in Cr2(OAc)4, Pt4(OAc)8 or dicarboxylate ligands}
- B01J 35/23: in a colloidal state
- B01J 35/27: in a liquid or molten state
- B01J 35/45: Nanoparticles
- B01J 35/59: Membranes
- B01J 37/04: Mixing {(B01J37/0009, B01J37/0018 take precedence)}
- B01D 2253/204: Metal organic frameworks (MOF's)
- B01J 31/069: {Hybrid organic-inorganic polymers, e.g. silica derivatized with organic groups (nitrogen containing groups on mineral substrates B01J31/0254; organometallic polymers B01J31/123; coordination complexes immobilised on an inorganic support B01J31/1616; coordination polymers, e.g. metal-organic frameworks B01J31/1691)}
- B01J 2531/0216: Bi- or polynuclear complexes, i.e. comprising two or more metal coordination centres, without metal-metal bonds, e.g. Cp(Lx)Zr-imidazole-Zr(Lx)Cp
- B01J 2531/26: Zinc
- B01J 2531/48: Zirconium
- B01J 2531/845: Cobalt
- Y02C 20/40: of CO2
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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)
- Y02C: CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]

## Abstract

A method for making a metal organic framework suspension is described herein. The method includes providing a hybrid material comprising a nano-crystalline metal organic framework comprising micropores and a mesoporous polymeric material comprising mesopores, wherein the nano-crystalline metal organic framework is homogeneously dispersed and substantially present only within the mesopores or void spaces of the mesoporous polymeric material; and wherein the hybrid material has a weight percentage of the metal organic framework in the range of 5-50% relative to the total weight of the hybrid material. The method includes contacting the hybrid material with a solvent in which the mesoporous polymeric material is soluble, thereby forming a polymeric solution in which the nano-crystalline metal organic framework is substantially homogeneously dispersed and suspended.

## Claims

### Claim 1

A method for making a metal organic framework suspension comprising
providing a hybrid material comprising a nano-crystalline metal organic framework comprising micropores and a mesoporous polymeric material comprising mesopores, wherein the nano-crystalline metal organic framework is homogeneously dispersed and substantially present only within the mesopores or void spaces of the mesoporous polymeric material; and wherein the hybrid material has a weight percentage of the metal organic framework in the range of 5-50% relative to the total weight of the hybrid material; and
contacting the hybrid material with a solvent in which the mesoporous polymeric material is soluble, thereby forming a polymeric solution in which the nano- crystalline metal organic framework is substantially homogeneously dispersed and suspended.

### Claim 2 (depends on 1)

The method of claim 1, further comprising
providing a solution of a second polymeric material; and
combining the metal organic framework suspension with the second polymer solution to form a second metal organic framework suspension.

### Claim 3 (depends on 1)

The method of claim 1, wherein the metal organic framework, comprises at least one metal selected from the group consisting of Mg, V, Cr, Mo, Zr, Hf, Mn, Fe, Co, Cu, Ni, Zn, Ru, Al, and Ga.

### Claim 4 (depends on 1)

The method of claim 1, wherein the metal organic framework is at least one selected from the group consisting of MIL-101, MIL -100, MIL-53, MOF-74, UiO-66, UiO-67, ZIF-8, ZIFs, HKUST-1, M2(dobpdc), NU -1000, PCN-222, PCN-224, and derivatives thereof.

### Claim 5 (depends on 1)

The method of claim 1, wherein the micropores have an average diameter in the range of 0.5-5.0 nm.

### Claim 6 (depends on 1)

The method of claim 1, wherein the hybrid material comprises mesopores with an average diameter in the range of 2-50 nm and micropores with an average diameter in the range of 0.5-5.0 nm.

### Claim 7 (depends on 1)

The method of claim 1, wherein the mesopores, the micropores, or both are monodisperse, having a coefficient of variation of less than 10%.

### Claim 8 (depends on 1)

The method of claim 1, wherein the nano- crystalline metal organic framework has an average longest linear dimension of less than 200 nm.

### Claim 9 (depends on 1)

The method of claim 1, wherein the hybrid material has a surface area in the range of 10-1200 m2/g.

### Claim 10 (depends on 1)

The method of claim 1, wherein the hybrid material has an average longest linear dimension of 100-500 μm.

### Claim 11 (depends on 1)

The method of claim 1, wherein the polymeric material comprises Tenax®, mesoporous polyacrylamides, or mesoporous polyacrylonitriles.

### Claim 12 (depends on 1)

The method of claim 1, wherein the solvent comprises an organic solvent.

### Claim 13 (depends on 1)

The method of claim 1, wherein the organic solvent comprises: acetone, methanol, ethanol, isopropanol, propanol, butanol, acetonitrile, THF, DMF, CHCl3, CH2Cl2, toluene, or dioxane.

### Claim 14 (depends on 1)

The method of claim 1, further comprising purifying the hybrid material prior to contacting it with the solvent.

### Claim 15 (depends on 14)

The method of claim 14, wherein purifying comprises
dissolving the hybrid material in a solvent;
filtering the resulting solution; and
precipitating a purified hybrid material from the filtered solution.