# US 9,751,074 B2 · Metal organic frameworks for electronic gas storage

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- Number: US 9,751,074 B2
- Document ID: US9751074B2
- Status: Granted
- Kind: B2
- Application number: 14/828,097
- Filed: 2015-08-17
- Published: 2015-12-10
- Granted: 2017-09-05
- Earliest claimed: 2013-08-05
- Assignees: NuMat Technologies, Inc.
- Applicants: Numat Technologies, Inc.
- Inventors: Han Sung Kim; Mitchell Hugh Weston; Patrick Fuller; Paul Wai-Man Siu
- Web page: https://patentgrep.com/patent/US9751074B2

## 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 20/28011: {Other properties, e.g. density, crush strength}
- B01J 20/28016: {Particle form}
- B01J 20/28019: {Spherical, ellipsoidal or cylindrical}
- B01J 20/28042: {Shaped bodies; Monolithic structures}
- B01J 20/28066: {being more than 1000 m2/g}
- B01J 20/28071: {being less than 0.5 ml/g}
- B01J 20/28073: {being in the range 0.5-1.0 ml/g}
- B01J 20/28076: {being more than 1.0 ml/g}
- B01J 20/2808: {being less than 2 nm, i.e. micropores or nanopores}
- B01J 20/28083: {being in the range 2-50 nm, i.e. mesopores}
- B01J 20/3085: {Chemical treatments not covered by groups B01J20/3007 - B01J20/3078}
- F17C 11/00: Use of gas-solvents or gas-sorbents in vessels {(absorbing compositions for acetylene C10L3/04; absorbing compositions for hydrogen C01B3/0005)}
- Y02C 20/40: of CO2
- Y02E 60/32: Hydrogen storage
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- F17C: VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES (storing fluids in natural or artificial cavities or chambers in the earth B65G5/00; construction or assembling of bulk storage containers employing civil-engineering techniques E04H7/00; variable-capacity gas-holders F17B; liquefaction or refrigeration machines, plants, or systems F25)
- Y02C: CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02E: REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION

## Abstract

A metal organic framework (MOF) includes a coordination product of a metal ion and an at least bidentate organic ligand, where the metal ion and the organic ligand are selected to provide a deliverable adsorption capacity of at least 70 g/l for an electronic gas. A porous organic polymer (POP) includes polymerization product from at least a plurality of organic monomers, where the organic monomers are selected to provide a deliverable adsorption capacity of at least 70 g/l for an electronic gas.

## Claims

### Claim 1

A method of making a metal organic framework (MOF) comprising reacting a metal ion and an at least bidentate organic ligand, wherein the metal ion and the organic ligand are selected to provide a deliverable adsorption capacity of at least 70 g/l for an electronic gas;
wherein the electronic gas is selected from a group consisting of hydride gases, halide gases, and organometallic Group V gaseous compounds.

### Claim 2 (depends on 1)

The method of claim 1, wherein the deliverable adsorption capacity is 70 to 840 g/l for the electronic gas.

### Claim 3 (depends on 1)

The method of claim 1, wherein the electronic gas is selected from a group consisting of ammonia, arsine, boron trichloride, boron trifluoride, diborane, dichlorosilane, dichlorosilane, difluoromethane, disilane, fluorine, germane, germanium tetrafluoride, hexafluoroethane, hydrogen bromide, hydrogen chloride, hydrogen fluoride, hydrogen selenide, hydrogen telluride, hydrogen sulfide, methyl fluoride, methyl silane, nitrogen trifluoride, perfluoropropane, phosphine, silane, silicon tetrachloride, tetrafluoromethane, tetramethylsilane, silicon tetrafluoride, stibine, sulfur hexafluoride, trichlorosilane, trifluoromethane, trimethylsilane, tungsten hexafluoride and acetylene.

### Claim 4

A method of making a metal organic framework (MOF) comprising reacting a metal ion and an at least bidentate organic ligand, wherein the metal ion and the organic ligand are selected to provide a deliverable adsorption capacity of at least 70 g/l for an electronic gas, wherein the metal ion is selected from Li+, Na+, K+, Rb+, Be2+, Mg2+, Ca2+, Sr2+, Ba2+, Sc3+, Y3+, Ti4+, Zr4+, Hf4+, V5+, V4+, V3+, Nb3+, Ta3+, Cr3+, Cr2+, Mo3+, W3+, Mn3+, Fe3+, Fe2+, Ru3+, Ru2+, Os3+, Os2+, Co3+, Co2+, Ni2+, Ni+, Pd2+, Pd+, Pt2+, Pt+, Cu2+, Cu+, Ag+, Au+, Zn2+, Al3+, Ga3+, In3+, Si4+, Si2+, Ge4+, Ge2+, Sn4+, Sn2+, Bi5+, Bi3+, Cd2+, Mn2+, Tb3+, Gd3+, Ce3+, La3+ and Cr4+, and combinations thereof.

### Claim 5 (depends on 1)

The method of claim 1, wherein the electronic gas comprises arsine and the at least bidentate organic ligand is selected from terephthalic acid and/or 1,4-diazabicyclo[2.2.2]octane (DABCO).

### Claim 6

A method of making a metal organic framework (MOF) comprising reacting a metal ion and an at least bidentate organic ligand, wherein the metal ion and the organic ligand are selected to provide a deliverable adsorption capacity of at least 70 g/l for an electronic gas, wherein:
the MOF comprises a gravimetric surface area between 1,000 and 14,500 m2/g, a pore volume between 1 and 3 cm2/g, and an average pore size between 3 Å and 32 Å; and
the electronic gas comprises boron trifluoride; and
the at least bidentate organic ligand comprises trimesic acid.

### Claim 7

A method of making a metal organic framework (MOF) comprising reacting a metal ion and an at least bidentate organic ligand, wherein the metal ion and the organic ligand are selected to provide a deliverable adsorption capacity of at least 70 g/l for an electronic gas, wherein the MOF is formed into pellets, disks or a monolithic body.

### Claim 8

A metal organic framework (MOF) comprising the coordination product of a metal ion and an at least bidentate organic ligand, wherein the metal ion and the organic ligand are selected to store an electronic gas other than arsine, phosphine, boron trifluoride, or germanium tetrafluoride, wherein the electronic gas is selected from a group consisting of hydride gases, halide gases, and organometallic Group V gaseous compounds.

### Claim 9 (depends on 8)

The MOF of claim 8, wherein the electronic gas is selected from a group consisting of ammonia, boron trichloride, diborane, dichlorosilane, dichlorosilane, difluoromethane, disilane, fluorine, germane, hexafluoroethane, hydrogen bromide, hydrogen chloride, hydrogen fluoride, hydrogen selenide, hydrogen telluride, hydrogen sulfide, methyl fluoride, methyl silane,-nitrogen trifluoride, perfluoropropane, silane, silicon tetrachloride, tetrafluoromethane, tetramethylsilane, silicon tetrafluoride, stibine, sulfur hexafluoride, trichlorosilane, trifluoromethane, trimethylsilane, tungsten hexafluoride and acetylene.

### Claim 10 (depends on 8)

A gas storage and dispensing apparatus comprising a tank filled with the MOF of claim 8.

### Claim 11 (depends on 10)

The apparatus of claim 10, wherein the apparatus comprises a MOF pellet filled tank.

### Claim 12 (depends on 10)

The apparatus of claim 10, wherein the apparatus comprises a MOF disk filled tank.

### Claim 13 (depends on 10)

The apparatus of claim 10, wherein the apparatus comprises a monolithic MOF filled tank.

### Claim 14 (depends on 4)

The method of claim 4, wherein the deliverable adsorption capacity is 70 to 840 g/l for the electronic gas.

### Claim 15 (depends on 4)

The method of claim 4, wherein the electronic gas is selected from a group consisting of ammonia, arsine, boron trichloride, boron trifluoride, carbonyl sulfide, chlorine, deuterium, diborane, dichlorosilane, dichlorosilane, difluoromethane, disilane, fluorine, germane, germanium tetrafluoride, hexafluoroethane, hydrogen bromide, hydrogen chloride, hydrogen fluoride, hydrogen selenide, hydrogen telluride, hydrogen sulfide, methyl fluoride, methyl silane, neon, nitric organic, nitrogen trifluoride, perfluoropropane, phosphine, silane, silicon tetrachloride, tetrafluoromethane, tetramethylsilane, silicon tetrafluoride, stibine, sulfur hexafluoride, trichlorosilane, trifluoromethane, trimethylsilane, tungsten hexafluoride, acetylene, and organometallic gaseous reagents.

### Claim 16 (depends on 4)

The method of claim 4, wherein the electronic gas comprises arsine and the at least bidentate organic ligand is selected from terephthalic acid and/or 1,4-diazabicyclo[2.2.2]octane (DABCO).

### Claim 17 (depends on 6)

The method of claim 6, wherein the deliverable adsorption capacity is 70 to 840 g/l for the electronic gas.

### Claim 18 (depends on 6)

The method of claim 6, wherein the electronic gas is selected from a group consisting of ammonia, arsine, boron trichloride, boron trifluoride, carbonyl sulfide, chlorine, deuterium, diborane, dichlorosilane, dichlorosilane, difluoromethane, disilane, fluorine, germane, germanium tetrafluoride, hexafluoroethane, hydrogen bromide, hydrogen chloride, hydrogen fluoride, hydrogen selenide, hydrogen telluride, hydrogen sulfide, methyl fluoride, methyl silane, neon, nitric organic, nitrogen trifluoride, perfluoropropane, phosphine, silane, silicon tetrachloride, tetrafluoromethane, tetramethylsilane, silicon tetrafluoride, stibine, sulfur hexafluoride, trichlorosilane, trifluoromethane, trimethylsilane, tungsten hexafluoride, acetylene, and organometallic gaseous reagents.

### Claim 19 (depends on 6)

The method of claim 6, wherein the electronic gas comprises arsine and the at least bidentate organic ligand is selected from terephthalic acid and/or 1,4-diazabicyclo[2.2.2]octane (DABCO).

### Claim 20 (depends on 7)

The method of claim 7, wherein the deliverable adsorption capacity is 70 to 840 g/l for the electronic gas.

### Claim 21 (depends on 7)

The method of claim 7, wherein the electronic gas is selected from a group consisting of ammonia, arsine, boron trichloride, boron trifluoride, carbonyl sulfide, chlorine, deuterium, diborane, dichlorosilane, dichlorosilane, difluoromethane, disilane, fluorine, germane, germanium tetrafluoride, hexafluoroethane, hydrogen bromide, hydrogen chloride, hydrogen fluoride, hydrogen selenide, hydrogen telluride, hydrogen sulfide, methyl fluoride, methyl silane, neon, nitric organic, nitrogen trifluoride, perfluoropropane, phosphine, silane, silicon tetrachloride, tetrafluoromethane, tetramethylsilane, silicon tetrafluoride, stibine, sulfur hexafluoride, trichlorosilane, trifluoromethane, trimethylsilane, tungsten hexafluoride, acetylene, and organometallic gaseous reagents.

### Claim 22 (depends on 7)

The method of claim 7, wherein the electronic gas comprises arsine and the at least bidentate organic ligand is selected from terephthalic acid and/or 1,4-diazabicyclo[2.2.2]octane (DABCO).