# US 2014/0194639 A1 · Metal-organic framework with optimized open metal sites and pore spaces for high methane storage at room temperature

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- Number: US 2014/0194639 A1
- Document ID: US20140194639A1
- Status: Published application
- Kind: A1
- Application number: 13/984,724
- Filed: 2012-02-15
- Published: 2014-07-10
- Earliest claimed: 2011-02-15
- Assignees: Board of Regents, The University of Texas System
- Inventors: Banglin Chen; Zhiyong Guo
- Web page: https://patentgrep.com/patent/US20140194639A1

## CPC

- C10L 3/003: {Additives for gaseous fuels}
- 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)}
- C07C 63/331: with all carboxyl groups bound to non-condensed rings
- C07F 1/08: Copper compounds
- C10L 3/10: Working-up natural gas or synthetic natural gas
- F17C 11/005: {for hydrogen}
- F17C 11/007: {for hydrocarbon gases, such as methane or natural gas, propane, butane or mixtures thereof [LPG]}
- C10L: FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07F: ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM (metal-containing porphyrins C07D487/22)
- 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)

## Abstract

A 3D porous metal-organic framework and method of making are described. In some embodiments, a 3D porous metal-organic framework may be based on a trinodal (3,3,4) net of zyg topology by the self-assembly of the nonlinear hexacarboxylate (BHB) with the paddle-wheel Cu2(COO)4 cluster. Although its porosity and surface area are moderate, the open copper sites and optimal pore spaces enable the pore spaces to be fully utilized for methane storage, resulting in a high methane storage density and high absolute volumetric methane storage at room temperature and 35 bar. By the immobilization of high density open metal sites and the deliberate control of the pore space for their efficient methane storage, this porous MOF functions as an efficient media for methane and natural gas storage.

## Claims

### Claim 1

A process of preparing a metal-organic framework, comprising:
reacting 3,3′,3″,5,5′,5″-benzene-1,3,5-triyl-hexabenzoic acid and a copper salt and an acid in a polar solvent;
allowing the reaction to run at a temperature of at least 50° C. for at least one day; and
separating the metal-organic framework from the polar solvent.

### Claim 2 (depends on 1)

The method of claim 1, wherein the polar solvent comprises N,N-dimethylformamide.

### Claim 3 (depends on 1)

The method of claim 1, wherein the copper salt comprises Cu(NO3)2.

### Claim 4

(canceled)

### Claim 5

(canceled)

### Claim 6 (depends on 1)

The method of claim 1, further comprising allowing the reaction to run at a temperature of at least 50° C. for at least two days.

### Claim 7 (depends on 1)

The method of claim 1, further comprising activating the metal-organic framework by heating the metal-organic framework above 100° C. for about one day under vacuum.

### Claim at position 8

8-10. (canceled)

### Claim 11 (depends on 1)

A metal-organic framework made by the method of claim 1.

### Claim at position 10

12-17. (canceled)

### Claim 18 (depends on 11)

The metal-organic framework of claim 11, comprising a linker channel site comprising at least two organic linkers.

### Claim at position 12

19-20. (canceled)

### Claim 21

A method of storing gases in a metal-organic framework, comprising:
exposing the metal-organic framework to a gas, wherein the metal-organic framework comprises a 3,3′,3″,5,5′,5″-benzene-1,3,5-triyl-hexabenzoate or a derivative thereof and copper, wherein the 3,3′,3″,5,5′,5″-benzene-1,3,5-triyl-hexabenzoate or derivative thereof and the copper coordinate to one another to form a microporous framework comprising open copper sites and linker channel sites.

### Claim 22 (depends on 21)

The method of claim 21, wherein the gas is methane.

### Claim 23

(canceled)

### Claim 24

A metal-organic framework, comprising a 3,3′,3″,5,5′,5″-benzene-1,3,5-triyl-hexabenzoate or a derivative thereof and copper, wherein the 3,3′,3″,5,5′,5″-benzene-1,3,5-triyl-hexabenzoate or derivative thereof and the copper coordinate to one another to form a microporous framework comprising open copper sites and linker channel sites.

### Claim 25 (depends on 24)

The metal-organic framework of claim 24, wherein the metal-organic framework is configured to store methane.

### Claim 26

(canceled)

### Claim 27 (depends on 24)

The metal-organic framework of claim 24, wherein the metal-organic framework comprises a plurality of linker channel sites configured to bind to a gas with at least two organic linkers forming the metal-organic framework.

### Claim at position 20

28-29. (canceled)