# US 11,078,581 B2 · Catalyst composite and method for manufacturing the same

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- Number: US 11,078,581 B2
- Document ID: US11078581B2
- Status: Granted
- Kind: B2
- Application number: 15/769,658
- Filed: 2017-06-16
- Published: 2020-07-30
- Granted: 2021-08-03
- Earliest claimed: 2017-02-22
- Assignees: Unist (Ulsan National Institute of Science and Technology)
- Applicants: Ulsan National Institute of Science and Technology (UNIST)
- Inventors: Jong Beom Baek; Seok Jin Kim; Javeed Mahmood; Feng Li
- Web page: https://patentgrep.com/patent/US11078581B2

## CPC

- C25B 11/051: Electrodes formed of electrocatalysts on a substrate or carrier
- B01J 23/10: of rare earths
- B01J 23/46: Ruthenium, rhodium, osmium or iridium
- B01J 31/02: containing organic compounds or metal hydrides
- B01J 35/60: characterised by their surface properties or porosity
- B01J 37/00: Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J 37/02: Impregnation, coating or precipitation ({B01J37/0009 and B01J37/0018 take precedence } ; protection by coating B01J33/00)
- B01J 37/16: Reducing
- C08G 73/10: Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08L 79/08: Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C25B 1/04: by electrolysis of water
- C25B 11/057: consisting of a single element or compound
- C25B 11/075: consisting of a single catalytic element or catalytic compound
- Y02E 60/36: Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
- C25B: ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR (anodic or cathodic protection C23F13/00; single-crystal growth C30B)
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08L: COMPOSITIONS OF MACROMOLECULAR COMPOUNDS (compositions based on polymerisable monomers C08F, C08G; artificial filaments or fibres D01F; textile treating compositions D06)
- Y02E: REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION

## Abstract

Disclosed are a catalyst composite including a metal; and a nitrogen-containing porous 2D polymer carrier, and a method of manufacturing the catalyst composite. Accordingly, provided is a high-efficiency catalyst composite that does not depend on pH acid concentration using a nitrogen-containing porous two-dimensional (2D) polymer carrier and a low-cost metal.

## Claims

### Claim 1

A catalyst composite comprising:
(i)ruthenium (Ru);
(ii) at least one selected from the group consisting of cerium (Ce), iron (Fe), rhodium (Rh), palladium (Pd), cobalt (Co), nickel (Ni), gold (Au), silver (Ag), manganese (Mn), zinc (Zn), copper (Cu), and molybdenum (Mo); and
(iii) a nitrogen-containing porous two-dimensional (2D) polymer carrier;
wherein a ratio of the ruthenium to all other metal is a molar ratio of 1:0.01 to 1:0.5; and
wherein the nitrogen-containing porous two-dimensional (2D) polymer carrier comprises six aromatic rings arranged to form a hole and a diameter of the hole is 0.1 nm to 10 nm.

### Claim 2 (depends on 1)

The catalyst composite of claim 1, wherein the nitrogen-containing porous 2D polymer carrier is a 2D porous organic produced through a cyclization reaction of an amine-based compound; and at least one of a ketone-based compound, an aldehyde-based compound, and a carboxylic acid-based compound, 2D porous carbon nitride, or both thereof.

### Claim 3 (depends on 2)

The catalyst composite of claim 2, wherein the amine-based compound comprises at least one selected from the group consisting of hexaaminobenzene, hexaaminobenzene (HAB) trihydrochloride, triphenylene hexaamine triptycene hexamine, tetraaminobenzene, p-phenylenediamine, m-phenylenediamine, aromatic diamine, melamine, adamantanetetraamine, ethylenediamine, pyridinetetramine, 1,3,5-tris(4-aminophenyl)benzene, [1,1′-biphenyl]-3,3′,4,4′-tetraamine, naphthalene-tetraamine, 4,4′-oxydianiline, 4,4′-thiodianiline, 4,4′-thiobis(benzene-1,2-diamine), 4,4′-oxybis(benzene-1,2-diamine), pyrenediamine, pyrenetetramine, and 4,4′,4″,4′″-methanetetrayltetraaniline.

### Claim 4 (depends on 2)

The catalyst composite of claim 2, wherein the ketone-based compound comprises at least one of hexaketocyclohexane, hexaketocyclohexane (HKH) octa hydrate, tetraketone, and pyreneteteraketone,
the aldehyde-based compound comprises at least one of benzenedialdehyde and benzenetrialdehyde, and
the carboxylic acid-based compound comprises at least one of benzenedicarboxylic acid, benzenetricarboxylic acid, benzenetetracarboxylic acid, benzenehexacarboxylic acid, pyromellitic dianhydride, mellitic anhydride, cyclobutane-1,2,3,4-tetracarboxylic dianhydride, perylenetetracarboxylic dianhydride, naphthalenetetracarboxylic dianhydride, perylenetetracarboxylic acid, and naphthalenetetracarboxylic acid.

### Claim 5 (depends on 1)

The catalyst composite of claim 1, wherein the ruthenium comprises a metal particle having a particle size of 100 nm or less.

### Claim 6 (depends on 1)

The catalyst composite of claim 1, wherein the catalyst composite is a hydrogen evolution reaction (HER) catalyst.

### Claim 7 (depends on 1)

The catalyst composite of claim 1, wherein the catalyst composite has a catalytic activity for hydrogen evolution reaction in an area of pH 1 to 14.

### Claim 8

A method of manufacturing a catalyst composite, the method comprising:
obtaining a reaction mixture by mixing a precursor of porous two-dimensional (2D) polymer and a metal precursor in a solvent;
performing a primary reflux on the reaction mixture; and
performing a secondary reflux after adding a reducing agent,
wherein the catalyst composite comprises:
(i) ruthenium (Ru);
(ii) at least one selected from the group consisting of cerium (Ce), iron (Fe), rhodium (Rh), palladium (Pd), cobalt (Co), nickel (Ni), gold (Au), silver (Ag), manganese (Mn), zinc (Zn), copper (Cu), and molybdenum (Mo); and
(iii) a nitrogen-containing porous two-dimensional (2D) polymer carrier;
wherein a ratio of the ruthenium to all other metal is a molar ratio of 1:0.01 to 1:0.5; and
wherein the nitrogen-containing porous two-dimensional (2D) polymer carrier comprises six aromatic rings arranged to form a hole and a diameter of the hole is 0.1 nm to 10 nm.

### Claim 9 (depends on 8)

The method of claim 8, wherein the precursor of the porous 2D polymer comprises an amine-based compound; and at least one of a ketone-based compound, an aldehyde-based compound, and a carboxylic acid-based compound.

### Claim 10 (depends on 8)

The method of claim 8, wherein a mixture ratio of the amine-based compound to at least one of a ketone-based compound, an aldehyde-based compound, and a carboxylic acid-based compound is a molar ratio of 1:0.5 to 3.

### Claim 11 (depends on 8)

The method of claim 8, wherein the metal precursor comprises at least one selected from the group consisting of a halogen salt, a phosphate salt, a nitrate salt, a sulfate salt, an ammonium salt, an acetate salt, and a carbonate salt of a metal.

### Claim 12 (depends on 8)

The method of claim 8, wherein a mixture ratio of the precursor of the porous 2D polymer to the metal precursor is a molar ratio of 1:0.01 to 0.5.

### Claim 13 (depends on 8)

The method of claim 8, wherein the reducing agent comprises at least one selected from the group consisting of NaBH4, NaAlH4, LiBH4, LiAlH4, hydrazine, KBH4, and LiBH4.

### Claim 14 (depends on 8)

The method of claim 8, further comprising:
thermally treating a product obtained after performing the secondary reflux.

### Claim 15 (depends on 14)

The method of claim 14, wherein the thermally treating comprises thermally treating the product in an inert gas atmosphere and at the temperature of 400° C. or more.