# US 9,518,012 B2 · Method of preparing core-shell copper nanoparticles immobilized on activated carbon and method of preparing chalcogenide compound using nanoparticles as catalyst

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

- Number: US 9,518,012 B2
- Document ID: US9518012B2
- Status: Granted
- Kind: B2
- Application number: 14/862,632
- Filed: 2015-09-23
- Published: 2016-10-27
- Granted: 2016-12-13
- Earliest claimed: 2015-04-21
- Assignees: Pusan National University Industry-University Cooperation Foundation
- Applicants: Pusan National University Industry-University Cooperation Foundation
- Inventors: Kang Hyun Park; Sung Kyun Park; Bu Hyun Youn; Jin Kyoon Park; Jung Sub Lee; Balaji Mohan; Seong Wan Jang; Sang Geun Lee; Cho Hye Yoon
- Web page: https://patentgrep.com/patent/US9518012B2

## CPC

- C07C 391/02: having selenium atoms bound to carbon atoms of six-membered aromatic rings
- B01J 21/18: Carbon
- B01J 23/72: Copper
- B01J 35/393: {Metal or metal oxide crystallite size}
- B01J 35/45: Nanoparticles
- B01J 37/0211: {using a colloidal suspension}
- B01J 37/16: Reducing
- B01J 37/343: {of ultrasonic wave energy}
- C07B 47/00: Formation or introduction of functional groups not provided for in groups C07B39/00 - C07B45/00
- C07C 395/00: Compounds containing tellurium
- 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 31/2239: {Bridging ligands, e.g. OAc in Cr2(OAc)4, Pt4(OAc)8 or dicarboxylate ligands}
- B01J 35/397: {Egg shell like}
- B01J 37/031: {Precipitation}
- B01J 37/10: in the presence of water, e.g. steam
- B01J 2235/00: Indexing scheme associated with group B01J35/00, related to the analysis techniques used to determine the catalysts form or properties
- B01J 2235/15: X-ray diffraction
- B01J 2235/30: Scanning electron microscopy; Transmission electron microscopy
- B01J 2531/16: Copper
- C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- C07B: GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR (preparation of carboxylic acid esters by telomerisation C07C67/47; telomerisation C08F)

## Abstract

Disclosed herein is a method of preparing a Cu/Cu2O core-shell copper nanoparticle catalyst having high catalytic activity from [Cu3(BTC)2] and NaBH4 via a simple chemical reduction method. Also disclosed is a method of preparing a chalcogenide compound by using the nanoparticle catalyst as a heterogeneous catalyst in a cross-coupling reaction between a chalcogenide precursor compound and a boron-containing compound. The disclosed cross-coupling reaction is performed via a simple process, and the disclosed nanoparticle catalyst is compatible with various substrates under mild reaction conditions and exhibits excellent recyclability without a reduction in catalytic activity.

## Claims

### Claim 1

A method of preparing immobilized copper nanoparticles, the method comprising:
adding Cu(NO3)2.2.5H2O and H3BTC to an organic solvent, followed by stirring to prepare a mixture;
separating a solid product from the mixture, and drying the separated product in a vacuum to yield [Cu3(BTC)2];
adding an aqueous solution of NaBH4 dropwise to an aqueous solution of the [Cu3(BTC)2] in water to obtain reduced copper particles;
adding the reduced copper particles to a mixture of ethyl alcohol and activated carbon, followed by sonication at room temperature and refluxing to obtain a solution of copper nanoparticles immobilized on the activated carbon; and
cooling the solution of the copper nanoparticles immobilized on the activated carbon, and purifying a product resulting from the cooling of the solution.

### Claim 2 (depends on 1)

The method of claim 1, wherein the copper nanoparticles have a Cu/Cu2O core-shell structure with a core composed of zero-valent copper and a shell composed of monovalent copper.

### Claim 3 (depends on 1)

The method of claim 1, wherein the organic solvent is a mixed solvent obtained by mixing dimethylformamide, ethanol and water at a ratio of 1:1:1.

### Claim 4

A method of preparing a chalcogenide compound the method comprising:
adding Cu(NO)2.2.5H2O and HBTC to an organic solvent, followed by stirring to prepare a mixture;
separating a solid product from the mixture, and drying the separated product in a vacuum to yield [Cu3(BTC)2];
adding an aqueous solution of NaBH4 dropwise to an aqueous solution of the [Cu3(BTC)] in water to obtain reduced copper particles;
adding the reduced copper particles to a mixture of ethyl alcohol and activated carbon, followed by sonication at room temperature and refluxing to obtain a solution of copper nanoparticles immobilized on the activated carbon;
obtaining an immobilized copper nanoparticles by cooling the solution of the copper nanoparticles immobilized on the activated carbon, and purifying a product resulting from the cooling of the solution; and
performing a cross-coupling reaction between diphenyl dichalcogenide and phenylboronic acid in the presence of the immobilized copper nanoparticles as a catalyst.

### Claim 5

A method of preparing a chalcogenide compound, the method comprising:
adding Cu(NO3)2.2.5H2O and H3BTC to an organic solvent, followed by stirring to prepare a mixture;
separating a solid product from the mixture, and drying the separated product in a vacuum to yield [Cu3(BTC)2];
adding an aqueous solution of NaBH4 dropwise to an aqueous solution of the [Cu3(BTC)2] in water to obtain reduced copper particles;
adding the reduced copper particles to a mixture of ethyl alcohol and activated carbon, followed by sonication at room temperature and refluxing to obtain a solution of copper nanoparticles immobilized on the activated carbon;
obtaining an immobilized copper nanoparticles by cooling the solution of the copper nanoparticles immobilized on the activated carbon, and purifying a product resulting from the cooling of the solution; and
performing a cross-coupling reaction between dibenzyl dichalcogenide and phenylboronic acid in the presence of the immobilized copper nanoparticles as a catalyst.

### Claim 6 (depends on 4)

The method of claim 4, wherein the cross-coupling reaction comprises:
mixing diphenyl dichalcogenide or dibenzyl dichalcogenide with phenylboronic acid in an organic solvent to obtain a reaction solution, and sonicating the reaction solution at room temperature;
magnetically stirring the reaction solution in an oil bath preheated to 100° C.; and
purifying and drying a product resulting from the magnetic stirring.

### Claim 7 (depends on 4)

The method of claim 4, wherein the diphenyl dichalcogenide is diphenyl diselenide or diphenyl ditelluride.

### Claim 8 (depends on 5)

The method of claim 5, wherein the dibenzyl dichalcogenide is diphenyl diselenide or diphenyl ditelluride.

### Claim 9 (depends on 4)

The method of claim 4, wherein the phenylboronic acid is represented by the following formula 1:
where R1, R2 and R3 are identical or different and are selected from the group consisting of hydrogen, a C1-C3 alkyl group, a C1-C3 alkoxy group, an acetyl group, an ethoxycarbonyl group, a trifluoromethyl group, a cyano group, a biphenyl group, a formyl group, and a halogen group.

### Claim 10 (depends on 6)

The method of claim 6, wherein the organic solvent is at least one selected from the group consisting of dimethyl sulfoxide (DMSO), N,N′-dimethylformamide (DMF), N,N′-dimethylacetamide (DMA), N-methyl pyrrolidinone (NMP), and N,N′-dimethylpropylene urea (DMPU).

### Claim 11 (depends on 4)

The method of claim 4, wherein the cross-coupling reaction is performed using the catalyst in an amount of 4 mole % based on diphenyl diselenide, in DMSO as a solvent at a temperature of 100° C. for 3-9 hours.

### Claim 12 (depends on 7)

The method of claim 7, wherein the diphenyl dichalcogenide is diphenyl ditelluride, and the cross-coupling reaction is performed at room temperature.

### Claim 13

A method of preparing a dichalcogenide compound the method comprising:
adding Cu(NO3)2.2.5H2O and H1BTC to an organic solvent, followed by stirring to prepare a mixture;
separating a solid product from the mixture, and drying the separated product in a vacuum to yield [Cu3(BTC)2];
adding an aqueous solution of NaBH4 dropwise to an aqueous solution of the [Cu3(BTC)2] in water to obtain reduced copper particles;
adding the reduced copper particles to a mixture of ethyl alcohol and activated carbon, followed by sonication at room temperature and refluxing to obtain a solution of copper nanoparticles immobilized on the activated carbon;
obtaining an immobilized copper nanoparticles by cooling the solution of the copper nanoparticles immobilized on the activated carbon, and purifying product resulting from the cooling of the solution; and
performing a cross-coupling reaction between diphenyl dichalcogenide and heterocyclic aromatic boronic acid in the presence of the immobilized copper nanoparticles as a catalyst.

### Claim 14

A method of preparing a dichalcogenide compound the method comprising:
adding Cu(NO3)2.2.5H2O and HBTC to an organic solvent, followed by stirring to prepare a mixture;
separating a solid product from the mixture, and drying the separated product in a vacuum to yield [Cu3(BTC)2];
adding an aqueous solution of NaBH4 dropwise to an aqueous solution of the [Cu3(BTC)2] in water to obtain reduced copper particles;
adding the reduced copper particles to a mixture of ethyl alcohol and activated carbon, followed by sonication at room temperature and refluxing to obtain a solution of copper nanoparticles immobilized on the activated carbon;
obtaining an immobilized copper nanoparticles by cooling the solution of the copper nanoparticles immobilized on the activated carbon, and purifying a product resulting from the cooling of the solution; and
performing a cross-coupling reaction between dibenzyl dichalcogenide and heterocyclic aromatic boronic acid in the presence of the immobilized copper nanoparticles as a catalyst.

### Claim 15 (depends on 13)

The method of claim 13, wherein the heterocyclic aromatic boronic acid has a nitrogen or sulfur substituent in at least one CH unit in an aromatic ring thereof.

### Claim 16

A method of preparing styryl phenyl selenide, the method comprising:
adding Cu(NO3)2.2.5H2O and H3BTC to an organic solvent, followed by stirring to prepare a mixture;
separating a solid product from the mixture, and drying the separated product in a vacuum to yield [Cu3(BTC)2];
adding an aqueous solution of NaBH4 dropwise to an aqueous solution of the [Cu3(BTC)2] in water to obtain reduced copper particles;
adding the reduced copper particles to a mixture of ethyl alcohol and activated carbon, followed by sonication at room temperature and refluxing to obtain a solution of copper nanoparticles immobilized on the activated carbon;
obtaining an immobilized copper nanoparticles by cooling the solution of the copper nanoparticles immobilized on the activated carbon, and purifying a product resulting from the cooling of the solution; and
performing a cross-coupling reaction between diphenyl dichalcogenide and trans-2-phenylvinylboronic acid in the presence of the immobilized copper nanoparticles as a catalyst.

### Claim 17

A method of preparing phenyl(phenylethynyl)selane, the method comprising:
adding Cu(NO3)2.2.5H2O and HBTC to an organic solvent, followed by stirring to prepare a mixture;
separating a solid product from the mixture, and drying the separated product in a vacuum to yield [Cu3(BTC)2];
adding an aqueous solution of NaBH4 dropwise to an aqueous solution of the [Cu3(BTC)2] in water to obtain reduced copper particles;
adding the reduced copper particles to a mixture of ethyl alcohol and activated carbon, followed by sonication at room temperature and refluxing to obtain a solution of copper nanoparticles immobilized on the activated carbon;
obtaining an immobilized copper nanoparticles by cooling the solution of the copper nanoparticles immobilized on the activated carbon, and purifying a product resulting from the cooling of the solution; and
performing a cross-coupling reaction between diphenyl dichalcogenide and 2-phenyl-1-ethynylboronic acid pinacol ester in the presence of the immobilized copper nanoparticles as a catalyst.