Copper-palladium-loaded mesoporous silicon carbide-based catalyst, preparation method and application thereof

Patent metadata

Field	Value
Publication number	US-11306403-B2
Application number	US-202017126052-A
Country	US
Kind code	B2
Filing date	Dec 18, 2020
Priority date	Jun 30, 2020
Publication date	Apr 19, 2022
Grant date	Apr 19, 2022

Abstract

A copper-palladium-loaded mesoporous silicon carbide-based catalyst, a preparation method, and an application thereof are provided. First, a mesoporous silicon carbide material is prepared by using mesoporous silica as a hard template; subsequently, the mesoporous silicon carbide material is mixed with a copper-palladium precursor mixed solution, and dried after the solvent is completely volatilized. The dried powder is successively subjected to calcination with N2 and reduction with H2 to finally obtain the copper-palladium-loaded mesoporous silicon carbide-based catalyst. The catalyst is made into an electrode, and the nitrate in water body is catalytically reduced by electrochemical method. The preparation method of the catalyst of the present invention is simple. The catalyst can realize high-efficiency catalytic denitrification at a low metal loading amount, with high selectivity of nitrogen. Moreover, the catalyst has the advantages of high activity, good stability, wide application range and low cost.

First claim

What is claimed is:

1. A method for preparing a copper-palladium-loaded mesoporous silicon carbide-based catalyst, comprising the following steps:
S1. mixing and stirring P123, water, hydrochloric acid, and tetraethyl orthosilicate to obtain a homogeneous solution; stirring the homogeneous solution in a water bath for crystallization to obtain a crystallized solution, then performing a first treatment of cooling, filtering, drying and calcination on the crystallized solution to obtain mesoporous silica;
S2. dissolving polycarbosilane in xylene to obtain a polycarbosilane solution, wherein a number-average molecular weight of the polycarbosilane is 1500-2500; mixing and stirring the mesoporous silica and the polycarbosilane solution to obtain a first mixture, drying the first mixture after the xylene is completely volatilized to obtain a first dried powder, and then subjecting the first dried powder to a second treatment of calcination, etching, washing and drying to obtain mesoporous silicon carbide;
S3. mixing PdCl 2 and Cu(NO 3 ) 2 .3H 2 O to obtain a copper-palladium precursor mixed solution; and
S4. adding the mesoporous silicon carbide to the copper-palladium precursor mixed solution to obtain a second mixture, drying the second mixture after a solvent of the second mixture is completely volatilized to obtain a second dried powder, and then subjecting the second dried powder to a third treatment of calcination in a nitrogen atmosphere and reduction in a hydrogen atmosphere to obtain the copper-palladium-loaded mesoporous silicon carbide-based catalyst.

2. The method according to claim 1 , wherein in step S1, 2 g of the P123, 63.95 mL, of the water, and 10 mL of the hydrochloric acid are mixed and stirred to obtain a first mixed solution, and 4.25 g of the tetraethyl orthosilicate is added dropwise to the first mixed solution to obtain the homogeneous solution.

3. The method according to claim 2 , wherein in step S1,
the crystallization is performed at a temperature of 130° C. for 72 hours; and
the calcination of the first treatment is performed for 6 hours under conditions of an air atmosphere, a required temperature of 550° C., and a heating rate of 1° C./min.

4. The method according to claim 1 , wherein in step S1,
the crystallization is performed at a temperature of 130° C. for 72 hours; and
the calcination of the first treatment is performed for 6 hours under conditions of an air atmosphere, a required temperature of 550° C., and a heating rate of 1° C./min.

5. The method according to claim 1 , wherein a concentration of the polycarbosilane in the polycarbosilane solution is 10 wt %, and the mesoporous silica and the polycarbosilane solution are mixed in a mass ratio of 1:(1-1.2).

6. The method according to claim 5 , wherein in step S2:
a drying temperature is 80° C., and a drying time is 12 hours; and
the etching is to mix and stir the first dried powder with an excess of 4 wt % HF aqueous solution for 24 hours.

7. The method according to claim 1 , wherein in step S2:
a drying temperature is 80° C., and a drying time is 12 hours; and
the etching is to mix and stir the first dried powder with an excess of 4 wt % HF aqueous solution for 24 hours.

8. The method according to claim 1 , wherein, the calcination in step S2 is as follows: in a nitrogen atmosphere, first, raising a temperature of the first dried powder to 350° C. at a rate of 2° C./min, and keeping the temperature at 350° C. for 5 hours; then raising the temperature to 700° C. at a rate of 0.5° C./min; and then raising the temperature to 1200° C.-1400° C. at the rate of 2° C./min, and keeping the temperature at 1200° C.-1400° C. for 2 hours; finally, naturally cooling the first dried powder to room temperature under a protection of nitrogen.

9. The method according to claim 1 , wherein in the copper-palladium precursor mixed solution: a mass concentration of palladium is 0.1-5 g/L; a mass concentration of copper is 0.05-2.5 g/L; and a mass ratio of the palladium to the copper is 2:1.

10. The method according to claim 1 , wherein in step S4:
a mass concentration of the mesoporous silicon carbide in the copper-palladium precursor mixed solution is 100 g/L;
a drying temperature is 80° C., and a drying time is 12 hours; and
conditions for the calcination and the reduction of the third treatment are as follows: a required temperature is 400° C., and a heating rate is 1° C./min; a time for the calcination in the nitrogen atmosphere is 3 hours, and a time for the reduction in the hydrogen atmosphere is 1 hour.

Assignees

• Univ Tongji

Inventors

• Fan Jianwei
• Wang Yue
• Zhang Weixian
• Teng Wei
• Ran Xianqiang
• Yu Bei
• Chen Xiaoqian

Classifications

• C25B11/054

  Electrodes comprising electrocatalysts supported on a carrier · CPC title

• C25B1/01

  Products · CPC title

• C25B11/061

  Metal or alloy · CPC title

• C25B11/091

  consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds · CPC title

• C02F1/46109

  Electrodes · CPC title