# US 8,093,350 B2 · Coordination polymer crystal with porous metal-organic frameworks and preparation method thereof

> Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt

- Number: US 8,093,350 B2
- Document ID: US8093350B2
- Status: Granted
- Kind: B2
- Application number: 12/294,631
- Filed: 2007-11-30
- Published: 2010-07-08
- Granted: 2012-01-10
- Earliest claimed: 2007-01-03
- Assignees: Insilicotech Co., Ltd
- Inventors: Dong-Hyun Jung; Min-Kyoung Kim; Dae-Jin Kim; Tae-Bum Lee; Seung-Hoon Choi; Ji-Hye Yoon; Sang-Beom Choi; You-Jin Oh; Min-Jeong Seo; Ja-Heon Kim; Byoung-Ho Won; Ki-Hang Choi
- Web page: https://patentgrep.com/patent/US8093350B2

## CPC

- B01J 31/1691: {Coordination polymers, e.g. metal-organic frameworks [MOF] (preparation of metal complexes containing carboxylic acid moieties C07C51/418; MOF's per se C07F)}
- 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 31/2239: {Bridging ligands, e.g. OAc in Cr2(OAc)4, Pt4(OAc)8 or dicarboxylate ligands}
- C01B 3/001: characterised by the uptaking media; Treatment thereof
- C01B 13/02: Preparation of oxygen (by liquefying F25J)
- C07F 3/003: {without C-Metal linkages}
- B01J 2531/0216: Bi- or polynuclear complexes, i.e. comprising two or more metal coordination centres, without metal-metal bonds, e.g. Cp(Lx)Zr-imidazole-Zr(Lx)Cp
- B01J 2531/0222: Metal clusters, i.e. complexes comprising 3 to about 1000 metal atoms with metal-metal bonds to provide one or more all-metal (M)n rings, e.g. Rh4(CO)12
- B01J 2531/26: Zinc
- Y02E 60/32: Hydrogen storage
- Y02P 30/00: Technologies relating to oil refining and petrochemical industry
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- C01B: NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; {METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C}
- C07F: ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM (metal-containing porphyrins C07D487/22)
- Y02E: REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02P: CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS

## Abstract

Disclosed is a coordination polymer crystal with porous metal-organic frameworks (MOFs), in which, while a crystal state of the coordination polymer crystal is maintained, an additional material selected from the group consisting of an organic compound, a metal cluster, and an organometallic compound is chemically bonded to the coordination polymer crystal. Therefore it is possible easily adsorb and store more guest molecules regardless of a change in an ambient temperature or pressure due to the chemically bonded additional material.

## Claims

### Claim 1

A coordination polymer crystal with porous metal-organic frameworks, the polymer crystal comprising a metal and an organic ligand in which the metal is coordinated to the organic ligand,
wherein, while a crystal state of the coordination polymer crystal is maintained, at least one additional material selected from the group consisting of an organic compound, a metal cluster, and an organometallic compound is chemically bonded to the organic ligand and/or the metal of the coordination polymer crystal.

### Claim 2 (depends on 1)

The coordination polymer crystal as claimed in claim 1, wherein the chemical bond is a covalent bond, a coordinate bond, or chemical adsorption.

### Claim 3 (depends on 1)

The coordination polymer crystal as claimed in claim 1, wherein the additional material has at least one binding site for chemical bonding with the coordination polymer crystal, and is grafted to the coordination polymer crystal when only one binding site of the additional material is chemically bonded to the coordination polymer crystal.

### Claim 4 (depends on 1)

The coordination polymer crystal as claimed in claim 1, wherein the additional material has at least two binding sites for chemical bonding with the coordination polymer crystal, and forms a cross-linkage in the coordination polymer crystal when the binding sites of the additional material are chemically bonded to the coordination polymer crystal.

### Claim 5 (depends on 1)

The coordination polymer crystal as claimed in claim 1, wherein an average diameter of a pore is adjusted within a range of 3-5 Å by the additional material.

### Claim 6 (depends on 1)

The coordination polymer crystal as claimed in claim 1, wherein the organic compound as the additional material is selected from the group consisting of R—COOH, R—COX, R1—CO—O—OC—R2, R—NCY, R—CHO, R—O—COX, R—SO2X, R—X, R—OH, R—NH2, R—ONH2, R1—NR2NH2, R1—NH—R2, R1—O—R2, R1R2—C═R3R4, R1—C≡C—R2, and R—N3 (wherein each of R, R1, R2, R3, and R4 independently has C1-C50, and is selected from the group consisting of substituted/unsubstituted aromatic compounds, aliphatic compounds, and heterocyclic compounds; X comprises an element of group 17 of the Periodic Table; and Y comprises an element of group 16 of the Periodic Table).

### Claim 7 (depends on 1)

The coordination polymer crystal as claimed in claim 1, wherein the metal cluster as the additional material is a compound formed by bonding between metal atoms selected from the group consisting of group 1 to 16 metals of the Periodic Table.

### Claim 8 (depends on 7)

The coordination polymer crystal as claimed in claim 7, wherein the metal atoms of the metal cluster are selected from the group consisting of Li, Na, Mg, Ca, Sr, Ba, Sc, Y, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Hg, Al, Ga, In, Tl, Si, Ge, Sn, Pb, As, Sb, and Bi.

### Claim 9 (depends on 1)

The coordination polymer crystal as claimed in claim 1, wherein the organometallic compound as the additional material contains a metal ion and organic ligands with functional groups.

### Claim 10 (depends on 9)

The coordination polymer crystal as claimed in claim 9, wherein the metal ion of the organometallic compound is selected from the group consisting of Li+, Na+, Mg2+, Ca2+, Sr2+, Ba2+, Sc3+, Y3+, Ti4+, Zr4+, Hf4+, V4+, V3+, V2+, Nb3−, Ta3+, Cr3+, Mo3+, W3+, Mn3+, Mn2+, Re3+, Re2+, Fe3+, Fe2+, Ru3+, Ru 2+, Os3+, Os2+, Co3+, Co2+, Rh2+, Rh+, Ir3+, Ir2+, Ir+, Ni2+, Ni+, Pd2+, Pd+, Pt2+, Pt+, Cu2+, Cu+, Ag+, Au+, Zn2+, Cd2+, Hg2+, Al3+, Ga3+. In3+, Tl3+, Si4+, Si2+, Ge4+, Ge2+, Sn4+, Sn2+, Pb4+, Pb2+, As5+, As+, Sb5+, Sb3+, Sb+, Bi5+, Bi3+, and Bi+.

### Claim 11 (depends on 9)

The coordination polymer crystal as claimed in claim 9, wherein the functional group of the organometallic compound is selected from the group consisting of —COOH, —COX, —CO—O—OC—, —NCY, —CHO, —SO2X, —X, —OH, —OCOX, —NH2, —ONH2,
—NH—, —O—, —C≡C—, and —N3 (herein, X comprises an element of group 17 of the Periodic Table; and Y comprises an element of group 16 of the Periodic Table).

### Claim 12 (depends on 1)

The coordination polymer crystal as claimed in claim 1, wherein an organic ligand forming MOFs in the coordination polymer crystal is selected from the group consisting of R—NH2, R—OH, R—CHO, R—COX, R—COOH, R—NCY, R—N3, R1R2C═CR3R4, and R1-C≡C—R2 (wherein each of R, R1, R2, R3, and R4 independently has C1-C50, and is selected from the group including substituted/unsubstituted aromatic compounds, aliphatic compounds, and heterocyclic compounds; X comprises an element of group 17 of the Periodic Table; and Y comprises an element of group 16 of the Periodic Table).

### Claim 13 (depends on 1)

The coordination polymer crystal as claimed in claim 1, wherein a metal forming MOFs in the coordination polymer crystal is selected from the group consisting of group 3 to 16 metals, lanthanide metals and actinide metals of the Periodic Table, and alloys of at least two of these metals.

### Claim 14 (depends on 1)

The coordination polymer crystal as claimed in claim 1, which is represented by the following Formula 1:
[{(MaOb)(L)c}. . . (A)m]n (Formula 1)
(in formula 1, M is any one metal selected from the group consisting of group 3 to 16 metals, lanthanide metals and actinide metals of the Periodic Table, and alloys of at least two of these metals; L is selected from the group consisting of
A is at least one kind of additional material selected from the group consisting of an organic compound, a metal cluster, and an organometallic compound; n indicates an integer between 1 and ∞; m indicates a random real number, 0<m≦600; a indicates a random real number, 0<a≦100; b indicates a random real number, 0≦b≦100; c indicates a random real number, and 0<c≦300).

### Claim 15 (depends on 1)

The coordination polymer crystal as claimed in claim 1, which is used for adsorbents, molecular sieves, catalysts, catalyst carriers, sensors, desiccants, ion exchange materials, fluid adsorbents/separators, materials for chromatography, selective release and absorption of a molecule, molecular recognition, nanotubes, or nano reactors.

### Claim 16 (depends on 1)

The coordination polymer crystal as claimed in claim 1, which can adsorb or store water, ammonia, carbon dioxide, carbon monoxide, hydrogen, amine, methane, oxygen, argon, or nitrogen.

### Claim 17 (depends on 1)

A method of preparing a coordination polymer crystal as claimed in claim 1, the method comprising the steps of:
(i) preparing a coordination polymer crystal with porous metal-organic frameworks, the polymer crystal comprising a metal and an organic ligand in which the metal is coordinated to the organic ligand; and
(ii) chemically bonding at least one additional material selected from the group consisting of an organic compound, a metal cluster, and an organometallic compound, to the metal or the organic ligand of the coordination polymer crystal.

### Claim 18 (depends on 17)

The method as claimed in claim 17, wherein in step (ii), content of the additional material is about 10−23-1 times as many as a number of binding sites within the coordination polymer crystal, which can be chemically bonded with the additional material.

### Claim 19 (depends on 17)

The method as claimed in claim 17, wherein step (ii) is performed in a solvent, and the solvent is selected from the group consisting of 2,6-lutidine, dichloromethane, and a mixture thereof.

### Claim 20 (depends on 17)

The method as claimed in claim 17, wherein in step (ii), the additional material is heated at a temperature of 110-600° C., and thus is chemically bonded to the coordination polymer crystal as a gas phase.