Conversion of carbon dioxide to organic products

• US 8,313,634 B2
• Filed: 01/29/2010
• Issued: 11/20/2012
• Est. Priority Date: 01/29/2009
• Status: Active Grant

• Current Assignee: Princeton University
• Original Assignee: Princeton University
• Inventors: Bocarsly, Andrew B., Cole, Emily Barton
• Primary Examiner(s): Hendricks, Keith
• Assistant Examiner(s): Jain, Salil
• Application Number:
  US12/696,840
• Publication Number:
  US 20100187123A1
• Time in Patent Office: 1,026 Days
• Field of Search: 205/355, 205/413, 205/440, 205/446, 205/448, 205/450, 205/455
• US Class Current: 205/440
• CPC Class Codes: C25B 1/55 Photoelectrolysis
• CPC Class Codes: C25B 3/25 Reduction
• CPC Class Codes: C25B 9/19 with diaphragms
• CPC Class Codes: Y02P 20/133 Renewable energy sources, e.g. sunlight

Abstract

The invention relates to various embodiments of an environmentally beneficial method for reducing carbon dioxide. The methods in accordance with the invention include electrochemically or photoelectrochemically reducing the carbon dioxide in a divided electrochemical cell that includes an anode, e.g., an inert metal counterelectrode, in one cell compartment and a metal or p-type semiconductor cathode electrode in another cell compartment that also contains an aqueous solution of an electrolyte and a catalyst of one or more substituted or unsubstituted aromatic amines to produce therein a reduced organic product.

Claims

1. A method of converting carbon dioxide to provide at least one product selected from the group consisting of glyoxal, isopropanol, ethanol, 2-propanol, acetone, acetaldehyde and mixtures thereof, comprising reducing the carbon dioxide electrochemically in a divided electrochemical cell comprising an anode in one cell compartment and a cathode in another cell compartment, the cathode selected from the group consisting of Au, Ag, Zn, Ga, Hg, In, Cd, Ti, Pt and hydrogenated Pd, the cell compartment including the cathode including one or more substituted or unsubstituted aromatic heterocyclic amines, each compartment containing an aqueous solution of an electrolyte,

wherein said at least one product selected from the group consisting of glyoxal, isopropanol, ethanol, 2-propanol, acetone, acetaldehyde and mixtures thereof is generated in the electrolyte by reduction of carbon dioxide and the aromatic heterocyclic amine is selected from the group consisting of lutidines and bipyridines, and mixtures thereof.

2. The method of claim 1 wherein the cathode is selected from the group consisting of Pt and hydrogenated Pd.

3. The method of claim 1, wherein the lutidines and bipyridines are selected from the group consisting of 2,6 lutidine and 4,4′

bypryridine.

8. The method of claim 1, which further comprises obtaining the carbon dioxide from an exhaust stream from a fossil fuel burning power or industrial plant, from a source accompanying natural gas or from a geothermal well.

9. The method of claim 1, wherein electrical energy for the electrochemical reduction of carbon dioxide is provided from an energy source based on nuclear, hydroelectric, wind, geothermal or solar power.

4. A method of converting carbon dioxide to provide at least one product selected from the group consisting of formic acid, glyoxal, isopropanol, ethanol, 2-propanol, acetone, acetaldehyde and mixtures thereof, comprising reducing the carbon dioxide electrochemically in a divided electrochemical cell comprising an anode in one cell compartment and a cathode in another cell compartment, the cathode selected from the group consisting of Au, Ag, Zn, Ga, Hg, In, Cd, Ti, Pt and hydrogenated Pd, the cell compartment including the cathode including one or more substituted or unsubstituted aromatic heterocyclic amines, each compartment containing an aqueous solution of an electrolyte,

wherein the aromatic heterocyclic amine is a lower alkyl substituted pyridine, a lower alkyl amino substituted pyridine, an unsubstituted bipyridine, a lower alkyl substituted bipyridine, hydroxy-pyridine, hydroxy-bipyridine, or lower alkyl amino substituted bipyridine.

5. A method of converting carbon dioxide to provide at least one product selected from the group consisting of formic acid, glyoxal, isopropanol, ethanol, 2-propanol, acetone, acetaldehyde and mixtures thereof, comprising reducing the carbon dioxide electrochemically in a divided electrochemical cell comprising an anode in one cell compartment and a cathode in another cell compartment, the cathode selected from the group consisting of Au, Ag, Zn, Ga, Hg, In, Cd, Ti, Pt and hydrogenated Pd, the cell compartment including the cathode including one or more substituted or unsubstituted aromatic heterocyclic amines, each compartment containing an aqueous solution of an electrolyte,

wherein the aromatic heterocyclic amine is a pyrazine, a pyridazine or a pyrimidine represented by formula 3:

6. A method of converting carbon dioxide to provide at least one product selected from the group consisting of formic acid, glyoxal, isopropanol, ethanol, 2-propanol, acetone, acetaldehyde and mixtures thereof, comprising reducing the carbon dioxide electrochemically in a divided electrochemical cell comprising an anode in one cell compartment and a cathode in another cell compartment, the cathode selected from the group consisting of Au, Ag, Zn, Ga, Hg, In, Cd, Ti, Pt and hydrogenated Pd, the cell compartment including the cathode including one or more substituted or unsubstituted aromatic heterocyclic amines, each compartment containing an aqueous solution of an electrolyte, wherein the aromatic heterocyclic amine is represented by formula 4:

7. The method of claim 6, wherein the aromatic heterocyclic amine is an imidazole or a pyrrole.

10. A method of converting carbon dioxide to provide at least one product selected from the group consisting of formic acid, formaldehyde, glyoxal, methanol, isopropanol, ethanol, 2-propanol, acetone, acetaldehyde and mixtures thereof, comprising reducing the carbon dioxide electrochemically in a divided electrochemical cell comprising an anode in one cell compartment and a cathode in another cell compartment, the cathode selected from the group consisting of Au, Ag, Zn, Ga, Hg, In, Cd, Ti, Pt and hydrogenated Pd, the cell compartment including the cathode including one or more substituted or unsubstituted aromatic heterocyclic amines except pyridine, p-aminopyridine, p-ethylpyridine and 4-methyl quinoline, each compartment containing an aqueous solution of an electrolyte,

wherein the aromatic heterocyclic amine is a pyrazine, a pyridazine or a pyrimidine represented by formula 3: