Materials and methods for the electrochemical reduction of carbon dioxide

Patent metadata

Field	Value
Publication number	US-2018057950-A1
Application number	US-201515516495-A
Country	US
Kind code	A1
Filing date	Oct 1, 2015
Priority date	Oct 1, 2014
Publication date	Mar 1, 2018
Grant date	—

Abstract

Disclosed are methods for electrochemically reducing carbon dioxide to provide a product. The methods can comprise contacting the carbon dioxide with an electroreduction catalyst in an electrochemical cell, and applying a potential to the electrochemical ceil to form the product. The electroreduction catalyst can comprise a nanoporous Cu catalyst, a nanoporous Cu-M catalyst, or a combination thereof, where M is a metal chosen from Pt, Ir, Pd, Ag, Au, Rh, Ru, Zn, Sn, Ni, Fe, Re, Ga, In, Cd, Tl, and Ti. The product can comprise a C 2 -C 3 alkane, a C 2 -C 3 alkene, a C 2 -C 3 alcohol, a C 2 -C 3 carboxylic acid, a C 2 -C 3 aldehyde, or a combination thereof.

First claim

1 . A method for electrochemically reducing carbon dioxide to provide a product, the method comprising contacting the carbon dioxide with an electroreduction catalyst in an electrochemical cell, and applying a potential to the electrochemical cell to form the product,
wherein the electroreduction catalyst comprises a nanoporous Cu catalyst, a nanoporous Cu-M catalyst, or a combination thereof, where M is a metal chosen from Pt, Ir, Pd, Ag, Au, Rh, Ru, Zn, Sn, Ni, Fe, Re, Ga, In, Cd, Tl, and Ti; and wherein the product comprises a C 2 -C 3 alkane, a C 2 -C 3 alkene, a C 2 -C 3 alcohol, a C 2 -C 3 carboxylic acid, a C 2 -C 3 aldehyde, or a combination thereof.

2 . The method of claim 1 , wherein the electroreduction catalyst comprises nanoparticles having an average particle size of from 10 nm to 500 nm, as determined by scanning electron microscopy (SEM).

3 . The method of claim 2 , wherein the nanoparticles have a BET surface area of from 10 m 2 /g to 40 m 2 /g.

4 . The method of claim 1 , wherein the electroreduction catalyst comprises a nanoporous Cu-M catalyst where M is a metal chosen from Pt, Ir, Pd, Ag, Au, Rh, Ru, Zn, Sn, Ni, Fe, Re, Ga, In, Cd, Tl, and Ti.

5 . The method of claim 4 , wherein the electroreduction catalyst comprises a nanoporous Cu—Ru catalyst.

6 . The method of claim 1 , wherein the product comprises ethanol, propanol, or a combination thereof.

7 . The method of claim 6 , wherein the wherein the product comprises propanol.

8 . The method of claim 7 , wherein the propanol is formed at a Faradaic efficiency of from 0.5% to 15%.

9 . The method of claim 1 , wherein the method is selective for the formation of C 2 -C 3 alcohols over methanol, such that the C 2 -C 3 alcohols are formed with at least 10 times greater Faradaic efficiency than methanol.

10 . The method of claim 1 , wherein the product comprises ethane, ethylene, or a combination thereof.

11 . The method of claim 1 , wherein the method is selective for the formation of C 2 -C 3 alkanes over methane, such that the C 2 -C 3 alkanes are formed with at least 10 times greater Faradaic efficiency than methane.

12 . The method of claim 1 , wherein the electrochemical cell is a divided electrochemical cell comprising
a working electrode comprising the electroreduction catalyst in a first cell compartment, a counter electrode in a second cell compartment, and a solid electrolyte membrane interposed between the working electrode and the counter electrode, both the first cell compartment and the second cell compartment further comprising an aqueous solution of an electrolyte; wherein contacting the carbon dioxide with the electroreduction catalyst comprises introducing the carbon dioxide into the first cell compartment of the divided electrochemical cell; and wherein applying a potential to the electrochemical cell comprises applying a negative voltage and a positive voltage to the working electrode and the counter electrode, respectively, to reduce the carbon dioxide to form the product.

13 . The method of claim 12 , wherein the electrolyte comprises an alkali metal bicarbonate.

14 . The method of claim 13 , wherein the alkali metal bicarbonate is potassium bicarbonate.

15 . The method of claim 1 , wherein the applied potential is from −0.15 V to −1.8 V vs. a reversible hydrogen electrode.

16 . An electrochemical cell for electrochemically reducing carbon dioxide to provide a product, the electrochemical cell comprising
a working electrode comprising an electroreduction catalyst in a first cell compartment, wherein the electroreduction catalyst comprises a nanoporous Cu catalyst, a nanoporous Cu-M catalyst, or a combination thereof, where M is a metal chosen from Pt, Ir, Pd, Ag, Au, Rh, Ru, Zn, Sn, Ni, Fe, Re, Ga, In, Cd, Tl, and Ti; a counter electrode in a second cell compartment; and a solid electrolyte membrane interposed between the working electrode and the counter electrode; both the first cell compartment and the second cell compartment further comprising an aqueous solution of an electrolyte.

17 . The cell of claim 16 , wherein the electroreduction catalyst comprises a nanoporous Cu-M catalyst where M is a metal chosen from Pt, Ir, Pd, Ag, Au, Rh, Ru, Zn, Sn, Ni, Fe, Re, Ga, In, Cd, Tl, and Ti.

18 . The cell of claim 17 , wherein the electroreduction catalyst comprises a nanoporous Cu—Ru catalyst

19 . A method for preparing an organic compound defined by Formula II from a carboxylic acid defined by Formula I and a carboxylic acid defined by Formula I′ according to the equation below

where R and R′ interdependently represent hydrogen, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted alkylaryl group, or a substituted or unsubstituted alkylheteroaryl group, the method comprising contacting the carboxylic acid defined by Formula I and the carboxylic acid defined by Formula I′ with an electroreduction catalyst in an electrochemical cell, and applying a potential to the electrochemical cell to form the organic compound defined by Formula II,
wherein the electroreduction catalyst comprises a nanoporous Cu catalyst, a nanoporous Cu-M catalyst, or a combination thereof, where M is a metal chosen from Pt, Ir, Pd, Ag, Au, Rh, Ru, Zn, Sn, Ni, Fe, Re, Ga, In, Cd, Tl, and Ti.

Assignees

• Ohio State Innovation Foundation

Inventors

• Co Anne
• Billy Joshua
• Coleman Eric
• Walz Kendahl

Classifications

• C25B11/0473

  Chemistry & Metallurgy · mapped topic

• C25B3/04 Primary

  Chemistry & Metallurgy · mapped topic

• B01D2257/504

  Carbon dioxide · CPC title

• C25B11/04 Primary

  characterised by the material · CPC title

• C25B11/081

  the element being a noble metal · CPC title