Carbon-coated transition metal nanocomposite material, preparation and application thereof

Patent metadata

Field	Value
Publication number	US-11224859-B2
Application number	US-201816630906-A
Country	US
Kind code	B2
Filing date	Jul 27, 2018
Priority date	Jul 28, 2017
Publication date	Jan 18, 2022
Grant date	Jan 18, 2022

Abstract

A carbon-coated transition metal nanocomposite material includes carbon-coated transition metal particles having a core-shell structure. The shell layer of the core-shell structure is a graphitized carbon layer doped with oxygen and/or nitrogen, and the core of the core-shell structure is a transition metal nanoparticle. The nanocomposite material has a structure rich in mesopores, is an adsorption/catalyst material with excellent performance, can be used for catalyzing various hydrogenation reduction reactions, or used as a catalytic-oxidation catalyst useful for the treatment of volatile organic compounds in industrial exhaust gases.

First claim

The invention claimed is:

1. A nanocomposite material comprising carbon-coated transition metal particles, the carbon-coated transition metal particles having a core-shell structure, the shell layer being a graphitized carbon layer doped with oxygen and/or nitrogen, and the core being a transition metal nanoparticle, wherein the nanocomposite material is a porous material having at least one distribution peak of mesopores.

2. The nanocomposite material according to claim 1 , wherein the nanocomposite material has a loss on acid leaching of 40% or less.

3. The nanocomposite material according to claim 1 , further comprising an amorphous carbon matrix, the carbon-coated transition metal particles being dispersed in the amorphous carbon matrix.

4. The nanocomposite material according to claim 1 , wherein the nanocomposite material has a proportion of mesopore volume to total pore volume of greater than about 50%, and the mesopore volume of the nanocomposite material is between about 0.05 cm 3 /g and about 1.25 cm 3 /g.

5. The nanocomposite material according to claim 1 , wherein the nanocomposite material has a carbon content of about 10.0% to about 60.0% by mass and a transition metal content of about 30.0% to about 85.0% by mass.

6. The nanocomposite material according to claim 1 , wherein the shell layer of the carbon-coated transition metal particles is a graphitized carbon layer doped with oxygen, and the nanocomposite material has an oxygen content of less than about 15.0% by mass; or the shell layer of the carbon-coated transition metal particles is a graphitized carbon layer doped with oxygen and nitrogen, and the nanocomposite material has a total content of nitrogen and oxygen of less than about 15.0% by mass, wherein the nitrogen content is preferably about 0.1% to about 10% by mass.

7. The nanocomposite material according to claim 1 , wherein the nanocomposite material further has one or more of the following characteristics:
the graphitized carbon layer has a thickness of about 0.3 nm to about 6 nm;
the particle size of the core-shell structure is about 1 nm to about 200 nm; and
the transition metal is one or more selected from the group consisting of iron, cobalt, nickel, copper, and zinc.

8. The nanocomposite material according to claim 1 , wherein the shell layer of the carbon-coated transition metal particles is a graphitized carbon layer doped with oxygen and nitrogen, and the transition metal nanoparticles have a face-centered-cubic lattice structure and/or a hexagonal-close-packed lattice structure.

9. A method for the preparation of a nanocomposite material according to claim 1 , comprising the steps of:
i) mixing a mixture comprising a transition metal source and a polybasic organic carboxylic acid with a solvent to form a homogeneous solution;
ii) removing the solvent from the homogeneous solution to obtain a precursor;
iii) subjecting the precursor to high-temperature pyrolysis under an inert protective atmosphere or a reducing atmosphere; and
iv) optionally, subjecting the pyrolysis product obtained in step iii) to a treatment by a non-oxidizing strong acid.

10. The method according to claim 9 , wherein the mixture used in step i) further comprises a nitrogen-containing organic compound and/or an oxygen-containing organic compound that is different from the polybasic organic carboxylic acid, and optionally an additional organic compound.

11. The method according to claim 10 , wherein the nitrogen-containing organic compound is one or more selected from the group consisting of urea, melamine, dicyanodiamine, hexamethylenetetramine, and amino acids, and the oxygen-containing organic compound is selected from the group consisting of polyols and organic carboxylic acids.

12. The method according to claim 10 , wherein the mass ratio of the transition metal source, the polybasic organic carboxylic acid and the nitrogen-containing organic compound is about 1:0.1-100: 0.1-100.

13. The method according to claim 9 , wherein the transition metal is one or more selected from the group consisting of iron, cobalt, nickel, copper, and zinc.

14. The method according to claim 9 , wherein the transition metal source is one or more selected from the group consisting of organic acid salts, carbonates, basic carbonates, oxides, and hydroxides of transition metals.

15. The method according to claim 9 , wherein the polybasic organic carboxylic acid is one or more selected from the group consisting of citric acid, maleic acid, trimesic acid, terephthalic acid, malic acid, EDTA, and dipicolinic acid.

16. The method according to claim 14 , wherein the mass ratio of the transition metal source to the polybasic organic carboxylic acid is about 1:0.1 to about 1:10.

17. The method according to claim 14 , wherein:
the solvent used in step i) is selected from the group consisting of water, methanol, ethanol, n-propanol, isopropanol, and mixtures thereof;
in step iii), the inert protective atmosphere is nitrogen or argon, and the reducing atmosphere is a mixed gas of an inert gas and hydrogen; the high-temperature pyrolysis is carried out by heating up to the temperature of a temperature-sustaining stage at a heating rate of about 0.5° C/min to about 30° C/min, and then keeping the temperature constant at the temperature-sustaining stage for about 20 min to about 600 min, with the temperature employed at the temperature-sustaining stage being about 400° C. to about 800° C.; and/or the non-oxidizing strong acid used in step iv) is one or more selected from the group consisting of hydrofluoric acid, hydrochloric acid, nitric acid, and sulfuric acid.

18. A method for treating a volatile organic compound, comprising contacting the volatile organic compound with the nanocomposite material of claim 1 to conduct a catalytic oxidation reaction.

19. A method for hydrogenation reduction reaction, comprising contacting a reactant to be hydrogenated with the nanocomposite material of claim 1 in the presence of hydrogen to conduct a catalytic hydrogenation reaction, wherein the reactant is selected from the group consisting of p-chloronitrobenzene nitrobenzene, nitrophenol p-nitroanisole, phenol, olefins, aromatic hydrocarbons, aldehydes, and ketones.

20. The nanocomposite material according to claim 1 , wherein the nanocomposite material is a porous material having two or more distribution peaks of mesopores.

21. The nanocomposite material according to claim 1 , wherein the nanocomposite material has a loss on acid leaching of 10% or less.

Assignees

• China Petroleum & Chem Corp
• Sinopec Res Inst Petroleum

Inventors

• Rong Junfeng
• Wu Genghuang
• Xie Jingxin
• Zong Mingsheng
• Lin Weiguo
• Yu Peng
• Ji Hongbo

Classifications

• B82Y30/00

  Nanotechnology for materials or surface science, e.g. nanocomposites · CPC title

• B01J21/18 Primary

  Carbon · CPC title

• B01J37/04

  Mixing {(B01J37/0009, B01J37/0018 take precedence)} · CPC title

• B01J35/633

  less than 0.5 ml/g · CPC title

• B01J35/647

  2-50 nm · CPC title