# US 2019/0169036 A1 · Solid-state crystallization of metal organic frameworks within mesoporous materials methods and hybrid materials thereof

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- Number: US 2019/0169036 A1
- Document ID: US20190169036A1
- Status: Published application
- Kind: A1
- Application number: 16/324,296
- Filed: 2017-08-10
- Published: 2019-06-06
- Earliest claimed: 2016-08-10
- Assignees: Research Triangle Institute
- Applicants: Research Triangle Institute
- Inventors: Ignacio Luz Minguez; Mustapha Soukri; Marty Lail
- Web page: https://patentgrep.com/patent/US20190169036A1

## CPC

- C01B 39/026: {After-treatment}
- B01J 20/103: {comprising silica}
- 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 20/3236: {containing metal, other than zeolites, e.g. oxides, hydroxides, sulphides or salts}
- B01J 20/3265: {with an organic functional group containing a metal, e.g. a metal affinity ligand}
- B01J 29/06: Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- 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)}
- B01J 31/2239: {Bridging ligands, e.g. OAc in Cr2(OAc)4, Pt4(OAc)8 or dicarboxylate ligands}
- C01B 39/00: Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination (treatment to modify the sorption properties, e.g. shaping using a binder, B01J20/10; treatment to modify the catalytic properties, e.g. combination of treatments to make the zeolites appropriate to their use as a catalyst, B01J29/04; treatment to improve the ion-exchange properties B01J39/14)
- C01B 39/02: Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B 39/48: using at least one organic template directing agent
- B01D 2253/108: Zeolites
- B01D 2253/204: Metal organic frameworks (MOF's)
- B01D 2259/4583: for removing chemical, biological and nuclear warfare agents
- B01J 2531/26: Zinc
- B01J 2531/31: Aluminium
- B01J 2531/48: Zirconium
- B01J 2531/64: Molybdenum
- B01J 2531/821: Ruthenium
- B01J 2531/845: Cobalt
- B01J 2531/847: Nickel
- C01B: NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; {METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C}
- 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)

## Abstract

A method, comprising i) contacting an aqueous solution of an organic ligand salt of the formula AX(L−X) with a mesoporous material (MPM) to form an impregnated mesoporous salt material of the formula AX(L−X)/MPM, ii) treating the impregnated mesoporous salt material with an aqueous acidic solution to form an impregnated mesoporous acid material of the formula HX(L−X)/MPM, iii) contacting an aqueous solution of a metal precursor of the formula M+y(B)y with the impregnated mesoporous acid material to form an impregnated mesoporous metal organic framework precursor of the formula [M+y(B)y][Hx(L−x)]/MPM, and iv) at least one of 1) heating the impregnated mesoporous metal organic framework precursor in the absence of a solvent or 2) exposing the impregnated mesoporous metal organic framework precursor to a volatile vapor in the absence of a solvent such that the heating or the exposing forms a hybrid material of the formula (M+yL−x)/MPM, wherein the hybrid material comprises a nano-crystalline metal organic framework (MOF) embedded within the mesoporous material.

## Claims

### Claim 1

A method, comprising:
contacting an aqueous solution of an organic ligand salt of the formula Ax(L−x) with a mesoporous material (MPM) to form an impregnated mesoporous salt material of the formula Ax(L−x)/MPM where A is a counter ion, each x is independently a whole number, and L is an organic ligand;
treating the impregnated mesoporous salt material with an aqueous acidic solution to form an impregnated mesoporous acid material of the formula Hx(L−x)/MPM where H is hydrogen;
contacting an aqueous solution of a metal precursor of the formula M+y(B)y with the impregnated mesoporous acid material to form an impregnated mesoporous metal organic framework precursor of the formula [M+y(B)y][Hx(L−x)]/MPM where M is a metal, each y is independently a whole number, and B is an anion; and
at least one of 1) heating the impregnated mesoporous metal organic framework precursor in the absence of a solvent or 2) exposing the impregnated mesoporous metal organic framework precursor to a volatile vapor in the absence of a solvent such that the heating or the exposing forms a hybrid material of the formula (M+yL−x)-MPM;
wherein the hybrid material comprises a nano-crystalline metal organic framework (MOF) embedded within the mesoporous material.

### Claim 2

(canceled)

### Claim 3

(canceled)

### Claim 4 (depends on 1)

The method of claim 1, wherein the nano-crystalline metal organic framework is present only within the mesopores or void spaces of the mesoporous material and homogeneously dispersed within the mesopores or void spaces of the mesoporous material.

### Claim 5 (depends on 1)

The method claim 1, further comprising drying at least one selected from the group consisting of the impregnated mesoporous salt material, the impregnated mesoporous acid material, the impregnated mesoporous metal organic framework precursor, and the hybrid material at a temperature in the range of 25-160° C. under a vacuum.

### Claim 6 (depends on 1)

The method claim 1, further comprising:
washing the hybrid material with distilled water; and
extracting water from the hybrid material in a Soxhlet system recycling methanol.

### Claim 7 (depends on 1)

The method claim 1, wherein the mesoporous material is at least one selected from the group consisting of a mesoporous metal oxide (aluminum oxide, cerium oxide, titanium oxide, zirconium oxide, magnesium oxide, etc.), a mesoporous silica, a mesoporous carbon, a mesoporous polymer, a mesoporous silicoalumina (zeolite), a mesoporous organosilica, and a mesoporous aluminophosphate.

### Claim 8 (depends on 1)

The method claim 1, wherein the organic ligand (L−x) of the organic ligand salt is at least one selected from the group consisting of polycarboxylate ligands, azaheterocyclic ligands, and derivatives thereof.

### Claim 9 (depends on 8)

The method of claim 8, wherein the organic ligand (L−x) of the organic ligand salt is at least one selected from the group consisting of, terephthalate, benzene-1,3,5-tricarboxylate, 2,5-dioxibenzene dicarboxylate, biphenyl-4,4′-dicarboxylate and derivatives thereof.

### Claim 10 (depends on 1)

The method claim 1, wherein the organic ligand (L−x) of the organic ligand salt is at least one selected from the group consisting of imidazolate, pyrimidinazolate, triazolate, and derivatives thereof.

### Claim 11 (depends on 1)

The method claim 1, wherein the metal (M+y) of the metal precursor is at least one transition metal selected from the group consisting of Mg, V, Cr, Mo, Zr, Hf, Mn, Fe, Co, Cu, Ni, Zn, Ru, Al, and Ga.

### Claim 12 (depends on 1)

The method 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 13 (depends on 1)

The method claim 1, 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.

### Claim 14 (depends on 1)

The method 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 15 (depends on 14)

The method of claim 14, wherein the mesopores, the micropores, or both are monodisperse having a coefficient of variation of less than 10%.

### Claim 16 (depends on 1)

The method claim 1, wherein the nano-crystalline metal organic framework has an average longest linear dimension of less than 40 nm.

### Claim 17 (depends on 1)

The method claim 1, wherein the hybrid material has a surface area in the range of 200-1200 m2/g.

### Claim 18 (depends on 1)

The method of claim 1, wherein the hybrid material has a surface area in the range of 105-500% that of the surface area of the impregnated mesoporous salt material.

### Claim 19 (depends on 1)

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

### Claim 20

A hybrid material, comprising:
a mesoporous material comprising mesopores; and
a nano-crystalline metal organic framework comprising micropores;
wherein the nano-crystalline metal organic framework is homogeneously dispersed and substantially present only within the mesopores or void spaces of the mesoporous 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.

### Claim at position 21

-25. (canceled)

### Claim 26 (depends on 20)

The hybrid material of claim 20, wherein the mesoporous material is at least one selected from the group consisting of a mesoporous metal oxide (aluminum oxide, cerium oxide, titanium oxide, zirconium oxide, magnesium oxide, etc.), a mesoporous silica, a mesoporous carbon, a mesoporous polymer, a mesoporous silicoalumina (zeolite), a mesoporous organosilica, and a mesoporous aluminophosphate.

### Claim at position 23

-28. (canceled)

### Claim 29 (depends on 20)

The hybrid material of claim 20, 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 30

(canceled)

### Claim 31 (depends on 20)

A gas adsorbent comprising the hybrid material of claim 20.

### Claim 32 (depends on 20)

A method of adsorbing, separating, storing or sequestering at least one gas, comprising:
contacting the gas adsorbent of claim 20 with the at least one gas;
wherein the at least one gas is selected from the group consisting of hydrogen (H2), hydrogen sulfide (H2S), sulfur dioxide (SO2), methane (CH4) and carbon dioxide (CO2).

### Claim 33 (depends on 20)

A catalyst comprising the hybrid material of claim 20.

### Claim 34 (depends on 31)

A method of catalyzing a reaction, comprising:
reacting a substrate in the presence of the catalyst of claim 31.

### Claim 35 (depends on 20)

A device or material comprising the hybrid material of claim 20, wherein the device or material is at least one selected from the group consisting of a drug delivery carrier, a proton conductive material, a sensor and an optoelectronic device.

### Claim 36

A method, comprising:
contacting an aqueous solution of an organic ligand salt of the formula Ax(L−x) with a mesoporous material (MPM) to form an impregnated mesoporous salt material of the formula Ax(L−x)/MPM where A is a counter ion, x is a whole number, and L is an organic ligand;
treating the impregnated mesoporous salt material with an aqueous acidic solution to form an impregnated mesoporous acid material of the formula Hx(L−x)/MPM where H is hydrogen;
contacting an aqueous solution of a metal precursor of the formula M+y(B)y with the impregnated mesoporous acid material to form an impregnated mesoporous metal organic framework precursor of the formula [M+y(B)y][Hx(L−x)]/MPM where M is a metal, y is a whole number, and B is an anion; and
at least one of 1) heating the impregnated mesoporous metal organic framework precursor in the presence of a catalytic amount of a solvent or 2) exposing the impregnated mesoporous metal organic framework precursor to a volatile vapor in the presence of a catalytic amount of a solvent such that the heating or the exposing forms a hybrid material of the formula (M+yL−x)/MPM;
wherein the hybrid material comprises a nano-crystalline metal organic framework (MOF) embedded within the mesoporous material;
wherein the nano-crystalline metal organic framework is homogeneously dispersed and substantially present only within the mesopores or void spaces of the mesoporous material; and
wherein the solvent is at least one selected from the group consisting of water, ethanol, methanol, tetrahydrofuran, and N,N-dimethylformamide and is present in a weight amount of less than 75% of the weight amount of the hybrid material formed.