SYSTEMS, METHODS, AND MATERIALS FOR PRODUCING HYDROCARBONS FROM CARBON DIOXIDE

• US 20150345034A1
• Filed: 03/18/2015
• Published: 12/03/2015
• Est. Priority Date: 03/18/2014
• Status: Abandoned Application

• Current Assignee: Indian Institute of Technology Madras
• Original Assignee: Indian Institute of Technology Madras
• Inventors: SUNDARA, Ramaprabhu, PALANISAMY, Tamilarasan
• Application Number:
  US14/661,764
• Publication Number:
  US 20150345034A1
• Time in Patent Office: Days
• US Class Current: 1/1
• CPC Class Codes: C25B 1/55 Photoelectrolysis
• CPC Class Codes: C25B 11/043 Carbon, e.g. diamond or graphene
• CPC Class Codes: C25B 11/051 Electrodes formed of electrocatalysts on a substrate or carrier
• CPC Class Codes: C25B 11/095 at least one of the compounds being organic
• CPC Class Codes: C25B 3/25 Reduction
• CPC Class Codes: C25B 9/19 with diaphragms
• CPC Class Codes: C25B 9/23 comprising ion-exchange membranes in or on which electrode material is embedded
• CPC Class Codes: Y02P 20/133 Renewable energy sources, e.g. sunlight

Abstract

Disclosed herein are systems and methods to effectively convert carbon dioxide to hydrocarbons by electrochemical and/or photoelectrochemical methods. In one embodiment, a photoelectro-chemical cell may include an anode, a cathode comprising a carbon material, wherein the carbon material is surface functionalized with at least one poly(ionic) liquid, and wherein at least one metallic nanoparticle is disposed on the functionalized carbon material surface, and an energy source configured to irradiate the anode.

Claims

1. A photoelectrochemical cell comprising:

an anode;

a cathode comprising a carbon material, wherein the carbon material is surface functionalized with at least one poly(ionic) liquid, and wherein at least one metallic nanoparticle is disposed on the functionalized carbon material surface; and

an energy source configured to irradiate the anode.

3. The photoelectrochemical cell of claim 1, wherein the anode is in contact with water in a first compartment of the photoelectrochemical cell.

4. The photoelectrochemical cell of claim 3, wherein the anode is configured to oxidize water molecules.

6. The photoelectrochemical cell of claim 1, wherein the cathode is in contact with carbon dioxide dissolved in water in a second compartment of the photoelectrochemical cell.

7. The photoelectrochemical cell of claim 6, wherein the cathode is configured to reduce carbon dioxide to at least one hydrocarbon selected from the group consisting of methanol, methane, isopropanol, formic acid, formaldehyde, glyoxal, ethanol, butanol, and any combination thereof.

9. The photoelectrochemical cell of claim 1, wherein the at least one metallic nanoparticle comprises Au, Ag, Pd, Co, Cu, Pt, Ni, Fe, Mn, Cr, V, Ti, Sc, Ce, or any combination thereof.

10. The photoelectrochemical cell of claim 1, wherein the at least one poly(ionic) liquid comprises 3-ethyl-1-vinylimidazolium tetrafluoroborate, 1-methyl-3-vinylimidazolium tetrafluoroborate, 1-butyl-3-methylimidazolium tetrafluoroborate, 1-vinyl-3-methylimidazolium tetrafluoroborate, 1-isobutenyl-3-methylimidazolium tetrafluoroborate, 1-allyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, 1-allyl-3-methylimidazolium bromide, 1,3-bis(cyanomethyl)imidazolium bis(trifluoromethylsulfonyl)imide, or any combination thereof.

11. The photoelectrochemical cell of claim 1, wherein the carbon material comprises a carbon nanotube, graphene, graphene oxide, or any combination thereof.

14. The photoelectrochemical cell of claim 1, wherein the anode comprises a metal or a semiconductor.

18. The photoelectrochemical cell of claim 1, further comprising an electrolyte in contact with the first compartment and the second compartment, wherein the electrolyte allows movement of protons from the first compartment to the second compartment through a proton exchange membrane.

20. The photoelectrochemical cell of claim 1, wherein the energy source comprises UV light, visible light, sunlight, or any combination thereof.

2. (canceled)

5. (canceled)

8. (canceled)

12-13. -13. (canceled)

15-17. -17. (canceled)

19. (canceled)

21. A method of reducing carbon dioxide to one or more hydrocarbons, the method comprising:

introducing water to a first compartment of an electrochemical cell, wherein the first compartment includes an anode;

introducing carbon dioxide dissolved in water to a second compartment of the electrochemical cell, wherein the second compartment includes a cathode, wherein the cathode comprises a carbon material that is surface functionalized with at least one poly(ionic) liquid and at least one metallic nanoparticle disposed on the functionalized carbon material surface; and

applying an electrical potential between the anode and the cathode sufficient to reduce carbon dioxide to one or more hydrocarbons.

22. The method of claim 21, wherein applying the electrical potential comprises applying the electrical potential by an external electrical power, irradiation, or any combination thereof.

23. The method of claim 21, wherein introducing water comprises introducing water to the first compartment of the electrochemical cell, wherein the first compartment includes a metal anode or a semiconductor anode.

25. The method of claim 21, wherein introducing carbon dioxide dissolved in water comprises introducing carbon dioxide dissolved in water to the second compartment of the electrochemical cell, wherein the second compartment includes the cathode, wherein the cathode is a carbon nanotube, graphene, graphene oxide, or any combination thereof that is surface functionalized with at least one poly(ionic) liquid and at least one metallic nanoparticle disposed on the functionalized surface, and wherein the metallic nanoparticle is selected from Au, Ag, Pd, Co, Cu, Pt, Ni, Fe, Mn, Cr, V, Ti, Sc, Ce, and any combination thereof.

29. The method of claim 21, wherein applying the electrical potential comprises applying the electrical potential between the anode and the cathode sufficient to reduce carbon dioxide to the one or more hydrocarbons selected from the group consisting of methanol, isopropanol, formic acid, formaldehyde, glyoxal, ethanol, butanol, and any combination thereof.

32. The method of claim 21, further comprising isolating the one or more hydrocarbons from the second compartment of the electrochemical cell.

24. (canceled)

26-28. -28. (canceled)

30-31. -31. (canceled)

33. A catalyst comprising an exfoliated graphene, wherein the exfoliated graphene is surface functionalized with at least one poly(ionic liquid), and wherein at least one metallic nanoparticle is disposed on the functionalized graphene surface.

34. The catalyst of claim 33, wherein the at least one poly(ionic) liquid comprises 3-ethyl-1-vinylimidazolium tetrafluoroborate, 1-methyl-3-vinylimidazolium tetrafluoroborate, 1-butyl-3-methylimidazolium tetrafluoroborate, 1-vinyl-3-methylimidazolium tetrafluoroborate, 1-isobutenyl-3-methylimidazolium tetrafluoroborate, 1-allyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, 1-allyl-3-methylimidazolium bromide, 1,3-bis(cyanomethyl)imidazolium bis(trifluoromethylsulfonyl)imide, or any combination thereof.

37. The catalyst of claim 33, wherein the at least one metallic nanoparticle comprises Au, Ag, Pd, Co, Cu, Pt, Ni, Fe, Mn, Cr, V, Ti, Sc, Ce, or any combination thereof.

39. The catalyst of claim 33, wherein the catalyst is an electrode in a photoelectrochemical cell, electrochemical cell, or a fuel cell.

35-36. -36. (canceled)

38. (canceled)

40. A method of preparing a catalyst, the method comprising:

oxidizing graphite to form graphite oxide;

exfoliating graphite oxide to form one or more graphene nanosheets;

contacting the one or more graphene nanosheets with a poly(ionic) liquid to form one or more coated graphene nanosheets; and

contacting a metal compound with the one or more coated graphene nanosheets.

41. The method of claim 40, wherein oxidizing the graphite comprises heating a powdered graphite with a mixture of an acid, sodium nitrate, and an oxidizing agent to a temperature of about 0°

C. to about 90°

C. for about 30 minutes to about 6 hours.

46. The method of claim 40, wherein exfoliating the graphite oxide comprises heating the graphite oxide to a temperature of about 150°

C. to about 400°

C. in the presence of hydrogen (H₂).

48. The method of claim 40, wherein contacting the one or more graphene nanosheets with the poly(ionic) liquid comprises refluxing the one or more graphene nanosheets with the poly(ionic) liquid and an initiator at a temperature of about 60°

C. to about 90°

C. for about 10 hours to about 24 hours.

49. The method of claim 48, wherein refluxing comprises refluxing the one or more graphene nanosheets with the poly(ionic) liquid selected from the group consisting of 3-ethyl-1-vinylimidazolium tetrafluoroborate, 1-methyl-3-vinylimidazolium tetrafluoroborate, 1-butyl-3-methylimidazolium tetrafluoroborate, 1-vinyl-3-methylimidazolium tetrafluoroborate, 1-isobutenyl-3-methylimidazolium tetrafluoroborate, 1-allyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, 1-allyl-3-methylimidazolium bromide, 1,3-bis(cyanomethyl)imidazolium bis(trifluoromethylsulfonyl)imide, and any combination thereof and the initiator.

54. The method of claim 40, wherein contacting the metal compound with the one or more coated graphene nanosheets comprises:

mixing the one or more coated graphene nanosheets with the metal compound in a solvent to form a solution; and

dielectrically heating the solution.

55. The method of claim 54, wherein mixing comprises mixing the one or more coated graphene nanosheets with the metal compound selected from the group consisting of a Au compound, a Ag compound, a Pd compound, a Co compound, a Cu compound, a Pt compound, a Ni compound, a Fe compound, a Mn compound, a Cr compound, a V compound, a Ti compound, a Sc compound, a Ce compound, and any combination thereof.

58. The method of claim 54, wherein the dielectrically heating the solution comprises heating by a radio frequency energy having a frequency of about 300 MHz to about 300 GHz for about 10 seconds to about 60 minutes.

42-45. -45. (canceled)

47. (canceled)

50-53. -53. (canceled)

56-57. -57. (canceled)

59-60. -60. (canceled)