# US 11,298,677 B2 · Lithiated cyclodextrin metal organic frameworks and methods of making and using the same

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- Number: US 11,298,677 B2
- Document ID: US11298677B2
- Status: Granted
- Kind: B2
- Application number: 16/632,653
- Filed: 2018-07-23
- Published: 2020-05-28
- Granted: 2022-04-12
- Earliest claimed: 2017-07-21
- Assignees: Northwestern University; King Abdulaziz City for Science and Technology
- Applicants: Northwestern University; King Abdulaziz City for Science and Technology
- Inventors: James Fraser Stoddart; Hasmukh A. Patel; Zhichang Liu; Siva Krishna Mohan Nalluri
- Web page: https://patentgrep.com/patent/US11298677B2

## 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 20/28011: {Other properties, e.g. density, crush strength}
- B01J 20/28057: {Surface area, e.g. B.E.T specific surface area}
- C08B 37/0015: {Inclusion compounds, i.e. host-guest compounds, e.g. polyrotaxanes}
- B01D 2253/204: Metal organic frameworks (MOF's)
- B01D 2257/102: Nitrogen
- B01D 2257/108: Hydrogen
- B01D 2257/504: Carbon dioxide
- 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)
- C08B: POLYSACCHARIDES; DERIVATIVES THEREOF (polysaccharides containing less than six saccharide radicals attached to each other by glycosidic linkages C07H; fermentation or enzyme-using processes C12P19/00; sugar industry C13; production of cellulose D21)
- Y02C: CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]

## Abstract

Disclosed herein are lithiated cyclodextrin metal organic frameworks and method of making and using the same. A metal organic framework comprising a coordinated network of repeating units extending in three dimensions, wherein the repeating unit comprises a cyclodextrin, a first coordinating metal cation, and a second coordinating metal cation.

## Claims

### Claim 1

A metal organic framework comprising a coordinated network of repeating units extending in three dimensions, wherein the repeating unit comprises a cyclodextrin and a metal salt component,
wherein the metal salt component comprises a first coordinating metal cation and a second coordinating metal cation and
wherein the first coordinating metal cation and the second coordinating metal cation are different.

### Claim 2 (depends on 1)

The metal organic framework of claim 1, wherein the first coordinating metal cation and the second coordinating metal cation are Group I metal cations.

### Claim 3 (depends on 2)

The metal organic framework of claim 2, wherein the first coordinating metal cation is Li+.

### Claim 4 (depends on 1)

The metal organic framework of claim 1, wherein the framework has one or more of the following properties:
(a) a Brunauer-Emmett-Teller (BET) surface area of at least 600 m2 g−1;
(b) a CO2 absorption capacity of at least 2.0 mmol g−1 at 298 K and 1 bar;
(c) a CO2 absorption capacity of at least 3.0 mmol g−1 at 273 K and 1 bar;
(d) a H2 absorption capacity of at least 80 cm3 g−1 at 77 K and 1 bar;
(e) a pore maxima centered between about 8.0 Å and about 20.0 Å; or
(f) any combination thereof.

### Claim 5 (depends on 2)

The metal organic framework of claim 2, wherein the second coordinating metal cation is K+.

### Claim 6 (depends on 1)

The metal organic framework of claim 1, wherein the cyclodextrin is a γ-cyclodextrin.

### Claim 7 (depends on 1)

The metal organic framework of claim 1, wherein the molar ratio of the first coordinating metal cation to the second coordinating metal cation is between about 1:99 to about 35:65.

### Claim 8 (depends on 7)

The metal organic framework of claim 7, wherein the molar ratio of the first coordinating metal cation to the second coordinating metal cation is between about 20:85 to about 35:65.

### Claim 9 (depends on 1)

The metal organic framework of claim 1, wherein the first coordinating metal cation and the second coordinating metal cation are coordinated to six of the eight α-D-glucopyranosyl residues in an alternating 1°/2° face fashion.

### Claim 10 (depends on 1)

The metal organic framework of claim 1, wherein the repeating unit comprises twisted (CD)6 repeating cubes.

### Claim 11 (depends on 1)

The metal organic framework of claim 1, wherein the metal organic framework has spherical cavities.

### Claim 12 (depends on 1)

The metal organic framework of claim 1, wherein the metal organic framework further comprises an adsorbed gas.

### Claim 13 (depends on 1)

A crystalline composition comprising the framework of claim 1 and having a molecular packing arrangement belonging to the R 3 2 space group.

### Claim 14 (depends on 13)

The composition of claim 13, wherein the metal organic framework has lattice parameters of a=43.1±1.0 Å, b=43.1±1.0 Å, c=28.0±1.0 Å, α=90°, β=90°, and γ=120°.

### Claim 15

A method for preparing a metal organic framework, the method comprising:
(a) providing a solution comprising a cyclodextrin, a metal salt component, and a first solvent and
(b) adding a second solvent to the solution to prepare the metal organic framework, wherein the metal salt component comprises a first coordinating metal cation and a second coordinating metal cation and
wherein the cyclodextrin, the first coordinating metal cation, or the second coordinating metal cation have a lower solubility in the second solvent than the first solvent.

### Claim 16 (depends on 15)

The method of claim 15, wherein the first coordinating metal atom and the second coordinating metal cation are Group I metal cations.

### Claim 17 (depends on 15)

The method of claim 15, wherein the first coordinating metal cation is Li+ and/or wherein the second coordinating metal cation is K+.

### Claim 18 (depends on 15)

The method of claim 15, wherein the cyclodextrin is a γ-cyclodextrin.

### Claim 19 (depends on 15)

The method of claim 15 further comprising isolating crystals comprising the metal organic framework.

### Claim 20 (depends on 1)

A method for the adsorption of a gas, the method comprising providing the metal organic framework of claim 1 or a composition comprising the metal organic framework and a gas to be adsorbed under conditions sufficient for the adsorption of the gas within the metal organic framework or the composition.