Modified metal-organic framework and catalyst for hydrogenation reaction including same

Patent metadata

Field	Value
Publication number	US-12226760-B2
Application number	US-202117341474-A
Country	US
Kind code	B2
Filing date	Jun 8, 2021
Priority date	Jun 9, 2020
Publication date	Feb 18, 2025
Grant date	Feb 18, 2025

Abstract

The present disclosure relates to a metal-organic framework modified using a compound having a hydroxyl group (—OH), a catalyst for a hydrogenation reaction including the same, and a method of manufacturing the same. The catalyst according to the present disclosure has high activity to the hydrogenation reaction even at a low temperature of 30 to 40° C., thus making low-grade waste heat usable.

First claim

What is claimed is:

1. A catalyst for a transfer hydrogenation reaction, comprising:
a metal-organic framework modified with one or more selected from among methanol, ethanol, and propanol,
wherein the metal-organic framework has a metal node coordination number 8 or less, and
wherein the catalyst is modified by a method comprising:
immersing the metal-organic framework in one or more alcohols selected from among methanol, ethanol, and propanol to manufacture a mixture;
performing refluxing while heating the mixture to or above a boiling point of the one or more alcohols selected from among methanol, ethanol, and propanol; and
filtering, washing, and drying the modified metal-organic framework after the refluxing.

2. The catalyst for a transfer hydrogenation reaction of claim 1 , wherein the metal-organic framework has a metal node coordination number of 10 or less.

3. The catalyst for a transfer hydrogenation reaction of claim 1 , wherein the metal-organic framework is represented by Chemical Formula 1 or Chemical Formula 2 below:
M 6 O 4+x (OH) m (BTC) 2 (OR) n   [Chemical Formula 1]

M is a Group 4A or 4B element on a periodic table or a lanthanide-based metal having an oxidation state of 4 + , x is greater than 0, a sum of m and n is 10 or less, m is greater than n, and R is an alkyl group having 1 to 10 carbon atoms
M 6 (μ 3 -O) 4 (μ 3 -OH) 4 (OH) x (H 2 O) 6 (BTC) 2 (OR) y   [Chemical Formula 2]

x is any number greater than 0 and less than or equal to 12, y is any number from 0 to 6, M is a Group 4A or 4B element or a lanthanide-based metal having an oxidation state of 4 + , and R is an alkyl group having 1 to 10 carbon atoms.

4. A method of producing a reduced organic compound, the method comprising:
performing a transfer hydrogenation reaction between an organic compound substrate and a hydrogen donor using the catalyst according to claim 1 ,
wherein the organic compound substrate possesses functional group which is selected from among aldehyde and ketone.

5. A method of producing a reduced organic compound, the method comprising:
performing a transfer hydrogenation reaction between an organic compound substrate and a hydrogen donor using the catalyst according to claim 2 ,
wherein the organic compound substrate possesses functional group which is selected from among aldehyde and ketone.

6. A method of producing a reduced organic compound, the method comprising:
performing a transfer hydrogenation reaction between an organic compound substrate and a hydrogen donor using the catalyst according to claim 1 ,
wherein the organic compound substrate possesses functional group which is selected from among aldehyde and ketone.

7. A method of producing a reduced organic compound, the method comprising:
performing a transfer hydrogenation reaction between an organic compound substrate and a hydrogen donor using the catalyst according to claim 3 ,
wherein the organic compound substrate possesses functional group which is selected from among aldehyde and ketone.

8. The method of claim 4 , wherein the organic compound substrate is a compound represented by Chemical Formula 3 below:

in Chemical Formula 3, R 1 and R 2 are the same or different, and are each independently an alkyl group having 1 to 10 carbon atoms substituted or unsubstituted by at least one substituent group selected from the group consisting of a hydroxy group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a heterocyclic group having 2 to 10 carbon atoms, a carbonyl group having 1 to 10 carbon atoms, and a carboalkoxy group having 1 to 10 carbon atoms; an alkenyl group having 2 to 10 carbon atoms substituted or unsubstituted by at least one substituent group selected from the group consisting of a hydroxy group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a heterocyclic group having 2 to 10 carbon atoms, a carbonyl group having 1 to 10 carbon atoms, and a carboalkoxy group having 1 to 10 carbon atoms; an aryl group having 6 to 20 carbon atoms substituted or unsubstituted by at least one substituent group selected from the group consisting of a halogen group, a hydroxy group, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, and an alkoxy group having 1 to 10 carbon atoms; a heterocyclic group having 2 to 20 carbon atoms, which has at least one heteroatom selected from the group consisting of N, O, and S groups and which is substituted or unsubstituted by at least one substituent group selected from the group consisting of an alkyl group having 1 to 10 carbon atoms and an alkoxy group having 1 to 10 carbon atoms; hydrogen; a halogen group; or a hydroxy group, R 1 and R 2 are connected to each other to form a ring, and n and m are each independently an integer of 0 to 5.

9. The method of claim 4 , wherein the organic compound substrate is at least one selected from among furfural, levulinic acid, 5-hydroxymethylfurfural (HMF), glycerol, fructose, glucose, 5-methyl furfural, butyl levulinate (BL), 1-(hydroxyethyl)benzene (1-HB), 7-keto-LCA (7-ketone-lithocholic acid), vanillin, citral, cinnamic aldehyde, carvone, ethyl levulinate, benzaldehyde, 4-chlorobenzaldehyde, acetophenone, and levulinic acid (LA).

10. The method of claim 4 , wherein the hydrogen donor is petroleum-based alcohol or biomass-based alcohol.

Assignees

• Korea Res Inst Chemical Tech

Inventors

• Hwang Young Kyu
• Valekar Anil Haribhau
• Lee Ma Eum
• Oh Kyung Ryul
• Hong Do Young

Classifications

• C07D307/58

  One oxygen atom, e.g. butenolide · CPC title

• C07D307/44 Primary

  Furfuryl alcohol · CPC title

• C07C37/055

  the substituted group being bound to oxygen, e.g. ether group · CPC title

• C07C29/145

  with hydrogen or hydrogen-containing gases · CPC title

• C07C29/141

  with hydrogen or hydrogen-containing gases · CPC title