Alloy based electrochemical catalyst for conversion of carbon dioxide to hydrocarbons

Patent metadata

Field	Value
Publication number	US-11519087-B2
Application number	US-202117488884-A
Country	US
Kind code	B2
Filing date	Sep 29, 2021
Priority date	Sep 30, 2020
Publication date	Dec 6, 2022
Grant date	Dec 6, 2022

Abstract

An electrocatalyst comprising (i) carbon nanospikes and (ii) copper alloy nanoparticles containing copper and at least one noble metal and residing on and/or between the carbon nanospikes. Also disclosed herein is a method of producing the electrocatalyst. Also described herein is a method for converting carbon dioxide into hydrocarbons by use of the above-described electrocatalyst. The method for producing hydrocarbons more specifically involves contacting the electrocatalyst with an aqueous solution of a bicarbonate salt while the aqueous solution is in contact with a source of carbon dioxide, and electrically powering the electrocatalyst as a cathode at negative potential condition while the cathode is in electrical communication with a counter electrode electrically powered as an anode, to convert the carbon dioxide into hydrocarbons containing at least four carbon atoms and composed of only carbon and hydrogen.

First claim

What is claimed is:

1. A method of converting carbon dioxide to hydrocarbons, the method comprising contacting an electrocatalyst with an aqueous solution of a bicarbonate salt while said aqueous solution is in contact with a source of carbon dioxide, which replenishes said bicarbonate salt as said bicarbonate salt decomposes to carbon dioxide and a hydroxide salt at a surface of said electrocatalyst, and said electrocatalyst is electrically powered as a cathode operated at negative potential condition and is in electrical communication with a counter electrode electrically powered as an anode, to convert said carbon dioxide into said hydrocarbons, wherein said hydrocarbons contain at least four carbon atoms and are composed of only carbon and hydrogen;
wherein said electrocatalyst comprises (i) carbon nanospikes, with each nanospike containing a tip, and (ii) metal nanoparticles residing on and/or between said carbon nanospikes, wherein said metal nanoparticles have an alloy composition comprising copper and at least one noble metal.

2. The method of claim 1 , wherein said carbon nanospikes are doped with a dopant selected from the group consisting of nitrogen, boron, and phosphorous.

3. The method of claim 1 , wherein said noble metal is selected from the group consisting of palladium, platinum, rhodium, iridium, silver, and gold.

4. The method of claim 1 , wherein said noble metal is palladium or platinum.

5. The method of claim 1 wherein at least a portion of the tips are curled.

6. The method of claim 1 , wherein said tip has a width within a range of 0.5 nm to 3 nm.

7. The method of claim 1 , wherein said carbon nanospikes have a length within a range of 20 nm to 100 nm.

8. The method of claim 1 , wherein said electrocatalyst is disposed on a semiconductive substrate or a conductive substrate.

9. The method of claim 1 , wherein said metal nanoparticles have a size within a range of 1 nm to 500 nm.

10. The method of claim 1 , wherein said hydrocarbons are produced along with any one or more of carbon monoxide, methane, or ethane, provided that carbon monoxide, methane, and ethane are produced in a sum total amount of no more than 20 wt %.

11. The method of claim 10 , wherein carbon monoxide, methane, and ethane are produced in a sum total amount of no more than 10 wt %.

12. The method of claim 10 , wherein carbon monoxide, methane, and ethane are produced in a sum total amount of no more than 5 wt %.

13. The method of claim 10 , wherein carbon monoxide, methane, and ethane are produced in a sum total amount of no more than 1 wt %.

14. The method of claim 1 , wherein said hydrocarbons are produced in the absence of producing carbon monoxide, methane, and ethane.

15. The method of claim 1 , wherein said hydrocarbons are produced in the absence of methanol or ethanol being produced.

16. The method of claim 1 , wherein said hydrocarbons containing at least four carbon atoms are produced along with molecules containing less than four carbon atoms, provided that molecules containing less than four carbon atoms are produced in a sum total amount of no more than 20 wt %.

17. The method of claim 1 , wherein said hydrocarbons containing at least four carbon atoms are produced along with molecules containing less than four carbon atoms, provided that molecules containing less than four carbon atoms are produced in a sum total amount of no more than 10 wt %.

18. The method of claim 1 , wherein said hydrocarbons containing at least four carbon atoms are produced along with molecules containing less than four carbon atoms, provided that molecules containing less than four carbon atoms are produced in a sum total amount of no more than 5 wt %.

19. The method of claim 1 , wherein said hydrocarbons containing at least four carbon atoms are produced in the absence of molecules containing less than four carbon atoms.

20. The method of claim 1 , wherein said copper and at least one noble metal are present in the metal nanoparticles in a noble metal to copper molar ratio of 1:1 to 20:1 or a copper to noble metal molar ratio of 1:1 to 20:1.

21. The method of claim 1 , wherein at least 40 wt % of said hydrocarbons contain at least four carbon atoms.

22. The method of claim 1 , wherein at least 50 wt % of said hydrocarbons contain at least four carbon atoms.

23. The method of claim 1 , wherein at least 40 wt % of said hydrocarbons contain at least five carbon atoms.

24. The method of claim 1 , wherein at least 50 wt % of said hydrocarbons contain at least five carbon atoms.

25. The method of claim 1 , wherein said electrocatalyst is housed in a first compartment of an electrochemical cell, wherein said first compartment contains said aqueous solution in contact with said electrocatalyst; said counter electrode is housed in a second compartment of said electrochemical cell, wherein said second compartment also contains said aqueous solution, and said first compartment and second compartment are separated by a solid electrolyte membrane.

Assignees

• Ut Battelle Llc

Inventors

• Rondinone Adam J
• Hensley Dale K
• Jin Seonah

Classifications

• C25B9/19

  with diaphragms · CPC title

• C25B11/065

  Carbon · CPC title

• C25B11/059

  Silicon · CPC title

• C25B11/054

  Electrodes comprising electrocatalysts supported on a carrier · CPC title

• C25B11/052

  Electrodes comprising one or more electrocatalytic coatings on a substrate · CPC title