# US 11,077,423 B2 · Highly stable [MaMbF6-n(O/H2O)n(Ligand)2(solvent)x]n metal organic frameworks

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- Number: US 11,077,423 B2
- Document ID: US11077423B2
- Status: Granted
- Kind: B2
- Application number: 16/943,998
- Filed: 2020-07-30
- Published: 2020-11-12
- Granted: 2021-08-03
- Earliest claimed: 2015-04-07
- Assignees: King Abdullah University of Science and Technology
- Applicants: King Abdullah University of Science and Technology
- Inventors: Mohamed Eddaoudi; Karim Adil; Youssef Belmabkhout; Osama Shekhah; Prashant M. Bhatt; Amandine Cadiau
- Web page: https://patentgrep.com/patent/US11077423B2

## 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)}
- B01D 53/02: by adsorption, e.g. preparative gas chromatography {(solid sorbent compositions B01J20/00, preparation of inorganic compounds or elements C01)}
- B01J 20/28061: {being in the range 100-500 m2/g}
- B01J 20/28071: {being less than 0.5 ml/g}
- B01J 20/2808: {being less than 2 nm, i.e. micropores or nanopores}
- B01J 20/3078: {Thermal treatment, e.g. calcining or pyrolizing}
- B01J 20/3085: {Chemical treatments not covered by groups B01J20/3007 - B01J20/3078}
- C07D 241/10: having three double bonds between ring members or between ring members and non-ring members
- C07F 19/005: {without metal-C linkages}
- B01D 2253/204: Metal organic frameworks (MOF's)
- B01D 2256/245: Methane
- B01D 2257/304: Hydrogen sulfide
- B01D 2257/504: Carbon dioxide
- B01D 2258/05: Biogas
- Y02C 20/40: of CO2
- Y02P 20/151: Reduction of greenhouse gas [GHG] emissions, e.g. 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)
- C07D: HETEROCYCLIC COMPOUNDS (macromolecular compounds C08)
- 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 of the present disclosure describe metal-organic framework compositions comprising a pillar characterized by the formula (MbF5(O/H2O)), where Mb is selected from periodic groups IIIA, IIIB, IVB, VB, VIB, and VIII; and a square grid characterized by the formula (Ma(ligand)x), where Ma is selected from periodic groups IB, IIA, IIB, IIIA, IVA, IVB, VIB, VIIB, and VIII, ligand is a polyfunctional organic ligand, and x is 1 or more; wherein the pillaring of the square grid with the pillars forms the metal-organic framework.

## Claims

### Claim 1

A metal-organic framework, comprising:
a pillar characterized by the formula (MbF5(O/H2O)), where Mb is selected from the group consisting of Al+3, Ga3+, Fe+2, Fe+3, Cr2+, Cr3+, Ti3+, V3+, V5+, Sc3+, In3+, and Y3+; and
a square grid characterized by the formula (Ma(ligand)x), where Ma is selected from periodic groups IB, IIA, IIB, IIIA, IVA, IVB, VIB, VIIB, and VIII, where the ligand is a polyfunctional organic ligand, and x is 1 or more;
wherein the square grid and pillar associate to form the metal-organic framework.

### Claim 2 (depends on 1)

The metal-organic framework of claim 1, wherein Ma is selected from Cu2+, Zn2+, Co2+, Ni2+, Mn2+, Zr2+, Ca2+, Ba2+, Pb2+, Pt2+, Pd2+, Ru2+, Rh2+, Cd2+, Mg2+, Al+3, Fe2+, Fe+3, Cr2+, Cr3+, Ru3+, and Co3+.

### Claim 3 (depends on 1)

The metal-organic framework of claim 1, wherein Ma is selected from Cu2+, Zn2+, Co2+, Ni2+, Mn2+, Zr2+, Fe2+, Ca2+, Ba2+, Pb2+, Pt2+, Pd2+, Rh2+, Cd2+, Mg2+, Cr2+, and Ru2+.

### Claim 4 (depends on 1)

The metal-organic framework of claim 1, wherein the ligand is a bifunctional N-donor ligand.

### Claim 5 (depends on 1)

The metal-organic framework of claim 1, wherein the ligand includes a monocyclic group structure or a polycyclic group structure.

### Claim 6 (depends on 1)

The metal-organic framework of claim 1, wherein the ligand is selected from pyridine, pyrazine, pyrimidine, pyridazine, triazine, thiazole, oxazole, pyrrole, imidazole, pyrazole, triazole, oxadiazole, thiadiazole, quinoline, benzoxazole, and benzimidazole.

### Claim 7 (depends on 1)

The metal-organic framework of claim 1, wherein the ligand includes one or more of pyrazine, pyridazine, oxazole, imidazole, pyrazole, and benzimidazole.

### Claim 8 (depends on 1)

The metal-organic framework of claim 1, wherein the ligand includes one or more of thiazole, oxadiazole, thiadiazole, and benzoxazole.

### Claim 9 (depends on 1)

The metal-organic framework of claim 1, wherein the ligand includes one or more of triazine and triazole.

### Claim 10 (depends on 1)

The metal-organic framework of claim 1, wherein the square grid is (Ma(pyrazine)2).

### Claim 11 (depends on 10)

The metal-organic framework of claim 10, wherein Ma is Ni.

### Claim 12 (depends on 10)

The metal-organic framework of claim 10, wherein the metal-organic framework exhibits a primitive cubic (pcu) topology.

### Claim 13 (depends on 1)

The metal-organic framework of claim 1, wherein Mb is Al+3, V3+, V5+, Fe+2, or Fe+3.

### Claim 14 (depends on 1)

The metal-organic framework of claim 1, wherein the pillar is (AlF5(H2O))2−.

### Claim 15 (depends on 1)

The metal-organic framework of claim 1, wherein the pillar is (FeF5(H2O))2−.

### Claim 16 (depends on 1)

The metal organic framework of claim 1, wherein a pore size of the metal-organic framework ranges from about 2.8 Å to about 4.8 Å.

### Claim 17 (depends on 1)

The metal organic framework of claim 1, wherein a pore size of the metal-organic framework ranges from about 3.3 Å to about 3.8 Å.

### Claim 18 (depends on 1)

The metal organic framework of claim 1, wherein a specific surface area of the metal-organic framework ranges from about 250 m2/g to about 500 m2/g.

### Claim 19 (depends on 1)

The metal organic framework of claim 1, wherein a pore volume of the metal-organic framework ranges from about 0.1 cm3/g to about 0.25 cm3/g.

### Claim 20

A metal-organic framework, comprising:
a pillar characterized by the formula (MbF5(O/H2O)), where Mb is selected from Al+3, Ga3+, Fe+2, Fe+3, Cr2+, Cr3+, Ti3+, V3+, V5+, Sc3+, In3+, and Y3+; and
a square grid characterized by the formula (Ma(ligand)x), wherein Ma is selected from Al+3, Fe+3, Cr3+, Ru3+, and Co3+, where the ligand is a polyfunctional organic ligand, and x is 1 or more;
wherein the square grid and pillar associate to form the metal-organic framework.