Methods for making oxygen reduction reaction catalysts formed of platinum alloy nanoparticles embedded in porous carbon

Patent metadata

Field	Value
Publication number	US-10875015-B2
Application number	US-201816139936-A
Country	US
Kind code	B2
Filing date	Sep 24, 2018
Priority date	Sep 24, 2018
Publication date	Dec 29, 2020
Grant date	Dec 29, 2020

Abstract

Methods for making porous materials having metal alloy nanoparticles formed therein are described herein. By preparing a porous material and delivering the precursor solutions under vacuum, the metal precursors can be uniformly embedded within the pores of the porous material. Once absorption is complete, the porous material can be heated in the presence of one or more functional gases to reduce the metal precursors to metal alloy nanoparticles, and embed the metal alloy nanoparticles inside of the pores. As such, the metal alloy nanoparticles can be formed within the pores, while avoiding surface wetting and absorption problems which can occur with small pores.

First claim

What is claimed is:

1. A method for forming platinum alloy nanoparticles within pores of a porous carbon material, the method comprising:
heating a porous carbon material within a chamber;
applying a vacuum to the chamber to create evacuated pores in the porous carbon material;
impregnating the evacuated pores of the porous carbon material with a metal precursor solution comprising a platinum salt and at least one other metal salt; and
reducing metal ions from the platinum salt and the at least one other metal salt in the metal precursor solution to form platinum alloy nanoparticles within the pores of the porous carbon material.

2. The method of claim 1 , further comprising delivering a purge gas into the chamber prior to the step of reducing metal ions, the purge gas being a gas that is inert with respect to the metal precursor solution.

3. The method of claim 1 , wherein the at least one other metal salt comprises a salt of copper, nickel, or a combination thereof.

4. The method of claim 1 , wherein applying the vacuum creates a pressure within the chamber of less than 500 millibars.

5. The method of claim 1 , wherein the porous carbon material is a mesoporous carbon.

6. The method of claim 1 , wherein the step of reducing metal ions comprises delivering a functional gas into the chamber at a partial pressure ratio of from 1:100 to 1:1 of H 2 to CO, and a volumetric flow rate of from 10 sccm to 1000 sccm.

7. The method of claim 1 , wherein the step of reducing metal ions comprises heating the porous carbon material having metal ions from the platinum salt and the at least one other metal salt to a functional temperature of from 150° C. to 300° C.

8. The method of claim 7 , further comprising maintaining the functional temperature for a time period of from 1 hour to 5 hours in the presence of the functional gas a functional gas.

9. A method for forming platinum alloy particles within pores of a porous carbon material, the method comprising:
removing moisture from a porous carbon material within a chamber;
applying a vacuum to the chamber to create evacuated pores in the porous carbon material;
delivering one or more precursors to impregnate the evacuated pores in the porous carbon material, the one or more precursors comprising platinum, nickel, and copper;
purging the chamber using a purge gas;
heating the porous carbon material to a functional temperature; and
delivering a functional gas into the chamber and to the porous carbon material, the one or more precursors reacting with the functional gas to form platinum alloy particles within the pores of the porous carbon material.

10. The method of claim 9 , comprising delivering the one or more precursors with agitation.

11. The method of claim 9 , wherein removing moisture comprises heating the porous carbon material to a first temperature in a controlled atmosphere comprising air, Ar, N 2 , O 2 , or combinations thereof.

12. The method of claim 9 , wherein applying the vacuum creates a pressure within the chamber of less than 500 millibars.

13. The method of claim 9 , comprising maintaining the vacuum during the purging of the chamber.

14. The method of claim 9 , wherein the functional gas is a gas mixture comprising H 2 and CO.

15. The method of claim 14 , comprising delivering the functional gas at a partial pressure ratio of from 1:100 to 1:1 of H 2 to CO, and a volumetric flow rate of from 10 sccm to 1000 sccm.

16. The method of claim 9 , wherein the functional temperature is from 150° C. to 300° C.

17. The method of claim 16 , further comprising maintaining the functional temperature for a time period of from 1 hour to 5 hours in the presence of the functional gas.

18. A method for forming platinum alloy particles within pores of a porous carbon material, the method comprising:
heating a porous carbon material in a chamber to a temperature of from 150° C. to 300 ° C., for a time period of from 1 hour to 24 hours, in an atmosphere comprising air, Ar, N 2 , O 2 , or combinations thereof;
reducing pressure within the chamber to less than 500 millibars to create evacuated pores in the porous carbon material;
delivering one or more precursors to the evacuated pores in the porous carbon material, the one or more precursors comprising platinum(acac) 2 , copper(acac) 2 , and nickel(acac) 2 , the one or more precursors being dissolved in a volatile solvent;
purging the chamber using a purge gas;
heating the porous carbon material to a temperature from 150° C. to 300° C. for a period of from 1 hour to 5 hours; and
delivering a functional gas into the chamber and to the porous carbon material, the one or more precursors reacting with the functional gas to form platinum alloy within the pores of the porous carbon material.

19. The method of claim 18 , wherein the functional gas comprises H 2 and CO, delivered at a partial pressure ratio of from 1:100 to 1:1 of H 2 to CO, and a volumetric flow rate of from 10 sccm to 1000 sccm.

Assignees

• Toyota Eng & Mfg North America
• Toyota Motor Co Ltd
• Univ Akron

Inventors

• Zhou Li Qin
• Huang Kan
• Nagai Tomoyuki
• Jia Hongfei
• Kato Hisao
• Shen Xiaochen
• Peng Zhenmeng

Classifications

• B01J2235/30

  Scanning electron microscopy; Transmission electron microscopy · CPC title

• B01J35/70

  characterised by their crystalline properties, e.g. semi-crystalline (catalysts comprising carbon B01J21/18; molecular sieves B01J29/00) · CPC title

• B01J2235/15

  X-ray diffraction · CPC title

• B01J35/45

  Nanoparticles · CPC title

• B01J23/8926

  Copper and noble metals · CPC title