Carbon supported single atom carbon dioxide reduction electro catalysts

Patent metadata

Field	Value
Publication number	US-10844501-B2
Application number	US-201815915259-A
Country	US
Kind code	B2
Filing date	Mar 8, 2018
Priority date	Mar 8, 2018
Publication date	Nov 24, 2020
Grant date	Nov 24, 2020

Abstract

Electrocatalysts composed of single atoms dispersed over porous carbon support were prepared by a lithium-melt method. The new catalysts demonstrated high selectivity, high Faradic efficiency and low overpotential toward to the electrocatalytic reduction of carbon dioxide to fuels.

First claim

The invention claimed is:

1. A method of synthesizing a catalyst comprising:
adding a catalytic metal in its metallic form to molten alkaline metal;
atomically dispersing the catalytic metal in the molten alkaline metal;
forming an alkaline metal-catalytic metal solid;
converting a portion of alkaline metal in the alkaline metal-catalytic metal solid to alkaline metal hydroxide forming a metal-alkaline metal hydroxide solid;
mixing said metal-alkaline metal hydroxide solid with a conductive support material to form a mixture, the conductive support material being carbonaceous with a porous network and having catalytic metal decorated throughout the porous network;
removing alkaline metal hydroxide from the mixture leaving a mixture of metal in the conductive support material; and
drying the mixture of metal and the conductive support material to produce the catalyst containing the catalytic metal atomically dispersed over the conductive support material.

2. The method of claim 1 , wherein the molten alkaline metal is lithium.

3. The method of claim 2 , wherein converting the portion of the lithium-catalytic metal to metal-lithium hydroxide solid comprises reacting lithium in the metal-lithium solid with moist air.

4. The method of claim 2 , further comprising mixing the metal-lithium hydroxide solid with the conductive support material using a mechanical method.

5. The method of claim 2 , wherein the catalytic metal before adding to molten lithium is in metallic state and in the form of powder, ingot, wire and shredded pieces.

6. The method of claim 2 , wherein the catalytic metal is a transition metal.

7. The method of claim 2 , wherein the catalytic metal is a platinum group metal.

8. The method of claim 2 , wherein the catalytic metal is dispersed in a single atom form.

9. The method of claim 1 , wherein removing the metal hydroxide comprises washing the alkaline metal hydroxide with water thereby removing lithium.

10. The method of claim 9 , wherein the washing comprises forming an alkaline water solution and modifying the carbonaceous support with oxygenated species serving as anchoring sites for the catalytic metal.

11. The method of claim 1 having a catalytic selectivity of at least 95% and Faradaic efficiency of at least 93% in converting of carbon dioxide to ethanol.

12. The method of claim 1 having a catalytic selectivity of about 100% and Faradaic efficiency of higher than 97% in converting carbon dioxide to acetone.

13. The method of claim 1 , wherein the catalytic metal is a bimetallic compound.

14. The method of claim 1 , wherein the catalytic metal is selected from the group consisting of copper and rhenium.

15. A method of synthesizing a catalyst comprising:
forming an dispersion of multiple metals in a molten alkaline metal;
forming an alkaline metal-multiple metal solid;
converting a portion of alkaline metal in the alkaline metal-first catalytic metal-second catalytic metal solid to an alkaline metal hydroxide forming an alkaline metal hydroxide-multiple metal solid;
mixing said alkaline metal hydroxide-multiple metal solid with a conductive support material;
removing alkaline metal hydroxide from the mixture of the alkaline metal hydroxide-multiple metal solid and a conductive support material; and
drying the multiple metal and conductive support mixture to produce the catalyst containing the multiple metals atomically dispersed over the conductive support.

16. The method of claim 15 , wherein forming the dispersion of multiple metals comprises:
adding a first catalytic metal in its metallic form to the molten alkaline metal; and
adding a second catalytic metal in its metallic form to the molten alkaline metal.

17. The method of claim 15 , wherein forming the dispersion of multiple metals comprises adding a multi-metallic catalytic compound to the molten alkaline metal.

18. The method of claim 15 , wherein the conductive support material is a carbonaceous material having porous network and further catalytic metal is decorated through the porous network of carbonaceous material.

19. The method of claim 15 , wherein removing the metal hydroxide comprises forming an alkaline water solution and modifying the conductive support material with oxygenated species serving as anchoring sites for the catalytic metal.

20. A method of synthesizing a catalyst comprising:
adding a catalytic metal in its metallic form to molten alkaline metal;
atomically dispersing the catalytic metal in the molten alkaline metal;
forming an alkaline metal-catalytic metal solid;
converting a portion of alkaline metal in the alkaline metal-catalytic metal solid to alkaline metal hydroxide forming a metal-alkaline metal hydroxide solid;
mixing said metal-alkaline metal hydroxide solid with a carbonaceous conductive support material to form a mixture;
removing alkaline metal hydroxide from the mixture leaving a mixture of metal in the conductive support material; and
drying the mixture of metal and the conductive support material to produce the catalyst containing the catalytic metal atomically dispersed over the conductive support material.

Assignees

• Uchicago Argonne Llc
• Univ Northern Illinois Board Of Trustees

Inventors

• Liu Di-Jia
• Xu Tao
• Rebollar Dominic
• Xu Haiping

Classifications

• C25B11/054

  Electrodes comprising electrocatalysts supported on a carrier · CPC title

• C25B3/01

  Products · CPC title

• C25B3/07

  Oxygen containing compounds · CPC title

• C25B11/073

  characterised by the electrocatalyst material · CPC title

• C25B11/069

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