# US 11,077,398 B2 · Compositions comprising metal organic frameworks for the uptake of compounds and related methods

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- Number: US 11,077,398 B2
- Document ID: US11077398B2
- Status: Granted
- Kind: B2
- Application number: 16/866,218
- Filed: 2020-05-04
- Published: 2020-10-22
- Granted: 2021-08-03
- Earliest claimed: 2016-05-27
- Assignees: Massachusetts Institute of Technology
- Applicants: Massachusetts Institute of Technology
- Inventors: Mircea Dinca; Adam J. Rieth; Yuri Tulchinsky
- Web page: https://patentgrep.com/patent/US11077398B2

## CPC

- B01D 53/04: with stationary adsorbents {(B01D53/025 takes precedence)}
- B01D 53/02: by adsorption, e.g. preparative gas chromatography {(solid sorbent compositions B01J20/00, preparation of inorganic compounds or elements C01)}
- 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 20/3425: {of sorbents or filter aids comprising organic materials}
- C07F 13/00: Compounds containing elements of Groups 7 or 17 of the Periodic Table
- C07F 15/065: {without a metal-carbon linkage}
- B01D 2253/204: Metal organic frameworks (MOF's)
- B01D 2257/202: Single element halogens
- B01D 2257/2022: Bromine
- B01D 2257/406: Ammonia
- B01D 2257/80: Water
- B01D 2258/06: Polluted air
- B01D 2259/4525: for storage and dispensing systems
- B01D 2259/4541: for portable use, e.g. gas masks
- Y02C 20/40: of CO2
- 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)
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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]

## Abstract

Compositions and methods for adsorption of a species (e.g., ammonia, water, a halogen) comprising metal organic frameworks (MOFs) are generally provided. In some embodiments, a MOF comprises a plurality of metal ions, each coordinated with at least one ligand comprising at least two unsaturated N-heterocyclic aromatic groups arranged about an organic core.

## Claims

### Claim 1

A method, comprising:
exposing a metal organic framework (MOF) to a compound, wherein the MOF adsorbs at least a portion of the compound,
wherein the compound is ammonia,
wherein the MOF comprises a plurality of metal ions, each metal ion coordinated with at least one ligand, and
wherein the at least one ligand comprises two unsaturated N-heterocyclic aromatic groups.

### Claim 2 (depends on 1)

The method of claim 1, wherein the MOF adsorbs greater than or equal to about 8.6 mmol ammonia per gram of adsorbent and less than or equal to about 17.9 mmol ammonia per gram of adsorbent after exposure to one bar of at least 99% ammonia gas.

### Claim 3

A method, comprising:
exposing a metal organic framework (MOF) to a compound, wherein the MOF adsorbs at least a portion of the compound,
wherein the compound is a halogen,
wherein the MOF comprises a plurality of metal ions, each metal ion coordinated with at least one ligand, and
wherein the at least one ligand comprises two unsaturated N-heterocyclic aromatic groups.

### Claim 4 (depends on 3)

The method of claim 3, wherein the halogen is Br2.

### Claim 5

A method, comprising:
exposing a metal organic framework (MOF) to a compound, wherein the MOF adsorbs at least a portion of the compound,
wherein the compound is selected from the group consisting of ammonia, water, or a halogen,
wherein the MOF comprises a plurality of metal ions, each metal ion coordinated with at least one ligand,
wherein the at least one ligand comprises two unsaturated N-heterocyclic aromatic groups, and
wherein the MOF retains greater than or equal to 96.5% of its initial adsorption capacity on a third adsorption cycle.

### Claim 6

A method, comprising:
exposing a metal organic framework (MOF) to a compound, wherein the MOF adsorbs at least a portion of the compound,
wherein the compound is selected from the group consisting of ammonia, water, or a halogen,
wherein the MOF comprises a plurality of metal ions, each metal ion coordinated with at least one ligand,
wherein the at least one ligand is selected from the group consisting of bis(1H-1,2,3-triazolo[4,5-b],[4′,5′-i])dibenzo[1,4]dioxin, benzo(1,2-d:4,5-d′)bistriazole, 6,6,14,14-tetramethyl-6,14-dihydroquinoxalino[2,3-b]phenazinebistriazole, and 5,5′-bibenzotriazole.

### Claim 7

A method, comprising:
exposing a metal organic framework (MOF) to a compound, wherein the MOF adsorbs at least a portion of the compound,
wherein the compound is selected from the group consisting of ammonia, water, or a halogen,
wherein the MOF comprises a plurality of metal ions, each metal ion coordinated with at least one ligand, wherein the metal ions are arranged in the form of a helix, and
wherein the at least one ligand comprises two unsaturated N-heterocyclic aromatic groups.

### Claim 8 (depends on 7)

The method of claim 7, further comprising desorbing at least a portion of the compound.

### Claim 9 (depends on 7)

The method of claim 7, wherein the metal ions comprise one or more of Mg2+, Mn2+, Mn3+, Fe2+, Fe3+, Co2+, Co3+, Ni2+, Cu2+, Cd2+, Cr2+, Cr3+, V2+, V3+, Ca2+, Be2+, Mo2+, Mo3+, W2+, and W3+.

### Claim 10 (depends on 7)

The method of claim 7, wherein the MOF has a crystalline structure with tetragonal symmetry.

### Claim 11 (depends on 7)

The method of claim 7, wherein the metal ions are associated with at least one auxiliary ligand.

### Claim 12 (depends on 7)

The method of claim 7, wherein the MOF comprises pores.

### Claim 13 (depends on 7)

The method of claim 7, wherein the metal ions are further coordinated by two auxiliary ligands.

### Claim 14 (depends on 7)

The method of claim 7, wherein the metal ions are coordinated by one solvent molecule.

### Claim 15 (depends on 7)

The method of claim 7, wherein at least a portion of the metal ions comprise an open coordination site.

### Claim 16 (depends on 7)

The method of claim 7, wherein the MOF is a component of a filter, gas mask, adsorption heat pump device, atmospheric water generator, or thermal battery.

### Claim 17 (depends on 7)

The method of claim 7, wherein the MOF is incorporated into an article comprising a binder and/or an additive.

### Claim 18 (depends on 17)

The method of claim 17, wherein the binder and/or additive is one or more of polyvinylidene difluoride (PVDF), other polymers, thermal conductivity enhancers, and activated carbons.

### Claim 19

A method, comprising:
exposing a metal organic framework (MOF) to a compound, wherein the MOF adsorbs at least a portion of the compound,
wherein the compound is selected from the group consisting of ammonia, water, or a halogen,
wherein the MOF comprises a plurality of metal ions, each metal ion coordinated with at least one ligand,
wherein the at least one ligand comprises two unsaturated N-heterocyclic aromatic groups, and
wherein the MOF comprises pores having an average pore diameter of greater than or equal to 20 Angstroms.

### Claim 20

A method, comprising:
exposing a metal organic framework (MOF) to a compound, wherein the MOF adsorbs at least a portion of the compound,
wherein the compound is selected from the group consisting of ammonia, water, or a halogen,
wherein the MOF comprises a plurality of metal ions, each metal ion coordinated with at least one ligand,
wherein the at least one ligand comprises two unsaturated N-heterocyclic aromatic groups, and
wherein the MOF comprises pores comprising hexagonal symmetry.