HETEROCYCLE CATALYZED ELECTROCHEMICAL PROCESS

• US 20110226632A1
• Filed: 07/29/2010
• Published: 09/22/2011
• Est. Priority Date: 03/19/2010
• Status: Active Grant

• Current Assignee: Avantium Knowledge Centre B.V. (Avantium NV), Princeton University
• Original Assignee: Liquid Light, Inc. (Avantium NV), Princeton University
• Inventors: Bocarsly, Andrew, Cole, Emily Barton
• Granted Patent: US 8,845,877 B2
• Time in Patent Office: Days
• US Class Current: 205/446
• CPC Class Codes: C25B 1/55 Photoelectrolysis
• CPC Class Codes: C25B 3/25 Reduction
• CPC Class Codes: C25B 3/295 hydrodimerisation
• CPC Class Codes: Y02E 60/36 Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

Abstract

A method for heterocycle catalyzed electrochemical reduction of a carbonyl compound is disclosed. The method generally includes steps (A) to (C). Step (A) may introduce the carbonyl compound into a solution of an electrolyte and a heterocycle catalyst in a divided electrochemical cell. The divided electrochemical cell may include an anode in a first cell compartment and a cathode in a second cell compartment. The cathode generally reduces the carbonyl compound to at least one aldehyde compound. Step (B) may vary which of the aldehyde compounds is produced by adjusting one or more of (i) a cathode material, (ii) the electrolyte, (iii) the heterocycle catalyst, (iv) a pH level and (v) an electrical potential. Step (C) may separate the aldehyde compounds from the solution.

Claims

1. A method for heterocycle catalyzed electrochemical reduction of a carbonyl compound, comprising the steps of:

(A) introducing said carbonyl compound into a solution of an electrolyte and a heterocycle catalyst in a divided electrochemical cell, wherein (i) said divided electrochemical cell comprises an anode in a first cell compartment and a cathode in a second cell compartment, (ii) said cathode reducing said carbonyl compound to at least one aldehyde compound;

(B) varying which of said aldehyde compounds is produced by adjusting one or more of (i) a cathode material, (ii) said electrolyte, (iii) said heterocycle catalyst, (iv) a pH level and (v) an electrical potential; and

(C) separating said aldehyde compounds from said solution.

2. The method according to claim 1, wherein said cathode material is at least one of Al, Au, Ag, C, Cd, Co, Cr, Cu, Cu alloys, Ga, Hg, In, Mo, Nb, Ni, Ni alloys, Ni—

Fe alloys, Sn, Sn alloys, Ti, V, W, Zn, elgiloy, Nichrome, austenitic steel, duplex steel, ferritic steel, martensitic steel, stainless steel, degenerately doped p-Si, degenerately doped p-Si;

As and degenerately doped p-Si;

B.

3. The method according to claim 1, wherein said electrolyte is at least one of Na₂SO₄, KCl, NaNO₃, NaCl, NaF, NaClO₄, KClO₄, K₂SiO₂, CaCl₂, a H cation, a Li cation, a Na cation, a K cation, a Rb cation, a Cs cation, a Ca cation, an ammonium cation, an alkylammonium cation, a F anion, a Cl anion, a Br anion, an I anion, an At anion, an alkyl amine, borates, carbonates, nitrites, nitrates, phosphates, polyphosphates, perchlorates, silicates, sulfates, and a tetraalkyl ammonium salt.

4. The method according to claim 1, wherein said heterocycle catalyst is one or more of amino-thiazole, aromatic heterocyclic amines with an aromatic 5-member heterocyclic ring, aromatic heterocyclic amines with 6-member heterocyclic ring, azoles, benzimidazole, bipyridines, furan, imidazoles, imidazole related species with at least one five-member ring, indoles, pyridines, pyridine related species with at least one six-member ring, pyrrole, thiophene and thiazoles.

5. The method according to claim 1, wherein said pH level ranges from approximately 3 to approximately 8.

6. The method according to claim 1, wherein said electrical potential ranges from approximately −

1 volt to approximately −

2 volts.

7. The method according to claim 1, wherein said aldehyde compounds comprise one or more of acetaldehyde, benzaldehyde, butanal, formaldehyde and glyoxal.

8. A method for heterocycle catalyzed electrochemical reduction of an aldehyde compound, comprising the steps of:

(A) introducing said aldehyde compound into a solution of an electrolyte and a heterocycle catalyst in a divided electrochemical cell, wherein (i) said divided electrochemical cell comprises an anode in a first cell compartment and a cathode in a second cell compartment, (ii) said cathode reducing said aldehyde compound to at least one alcohol;

(B) varying which of said alcohols is produced by adjusting one or more of (i) a cathode material, (ii) said electrolyte, (iii) said heterocycle catalyst, (iv) a pH level and (v) an electrical potential; and

(C) separating said alcohol from said solution.

9. The method according to claim 8, wherein said cathode material is at least one of Al, Au, Ag, C, Cd, Co, Cr, Cu, Cu alloys, Ga, Hg, In, Mo, Nb, Ni, Ni alloys, Ni—

Fe alloys, Sn, Sn alloys, Ti, V, W, Zn, elgiloy, Nichrome, austenitic steel, duplex steel, ferritic steel, martensitic steel, stainless steel, degenerately doped p-Si, degenerately doped p-Si;

As and degenerately doped p-Si;

B.

10. The method according to claim 8, wherein said electrolyte is at least one of Na₂SO₄, KCl, NaNO₃, NaCl, NaF, NaClO, KClO₄, K₂SiO₃, CaCl₂, a H cation, a Li cation, a Na cation, a K cation, a Rb cation, a Cs cation, a Ca cation, an ammonium cation, an alkylammonium cation, a F anion, a Cl anion, a Br anion, an I anion, an At anion, an alkyl amine, borates, carbonates, nitrites, nitrates, phosphates, polyphosphates, perchlorates, silicates, sulfates, and a tetraalkyl ammonium salt.

11. The method according to claim 8, wherein said heterocycle catalyst is one or more of amino-thiazole, aromatic heterocyclic amines with an aromatic 5-member heterocyclic ring, aromatic heterocyclic amines with 6-member heterocyclic ring, azoles, benzimidazole, bipyridines, furan, imidazoles, imidazole related species with at least one five-member ring, indoles, pyridines, pyridine related species with at least one six-member ring, pyrrole, thiophene and thiazoles.

12. The method according to claim 8, wherein said alcohol comprises one or more of 2-butanol, n-butanol, ethanol, methanol, propanol and propioin.

13. The method according to claim 8, wherein said cathode further reduces a keto compound to at least one hydroxyl compound.

14. The method according to claim 8, wherein said reducing is performed at ambient temperature and ambient pressure.

15. The method according to claim 8, wherein a faradaic yield of said alcohol is at least 50 percent.

16. A method for heterocycle catalyzed hydrodimerization of carbonyl-containing molecules, comprising the steps of:

(A) introducing said carbonyl-containing molecules into a solution of an electrolyte and a heterocycle catalyst in a divided electrochemical cell, wherein (i) said divided electrochemical cell comprises an anode in a first cell compartment and a cathode in a second cell compartment, (ii) said cathode hydrodimerizing said carbonyl-containing molecules into at least one organic product;

(B) varying which of said organic products is produced by adjusting one or more of (i) a cathode material, (ii) said electrolyte, (iii) said heterocycle catalyst, (iv) a pH level and (v) an electrical potential; and

(C) separating said organic products from said solution.

17. The method according to claim 16, wherein said electrolyte is at least one of Na₂SO₄, KCl, NaNO₃, NaCl, NaF, NaClO₄, KClO₄, K₂SiO₃, CaCl₂, a H cation, a L1 cation, a Na cation, a K cation, a Rb cation, a Cs cation, a Ca cation, an ammonium cation, an alkylammonium cation, a F anion, a Cl anion, a Br anion, an I anion, an At anion, an alkyl amine, borates, carbonates, nitrites, nitrates, phosphates, polyphosphates, perchlorates, silicates, sulfates, and a tetraalkyl ammonium salt.

18. The method according to claim 16, wherein said heterocycle catalyst is one or more of amino-thiazole, aromatic heterocyclic amines with an aromatic 5-member heterocyclic ring, aromatic heterocyclic amines with 6-member heterocyclic ring, azoles, benzimidazole, bipyridines, furan, imidazoles, imidazole related species with at least one five-member ring, indoles, pyridines, pyridine related species with at least one six-member ring, pyrrole, thiophene and thiazoles.

19. The method according to claim 16, wherein said organic products comprise one or more of butanone, butanol, octanone and octanol.

20. The method according to claim 16, wherein said carbonyl-containing molecules comprise one or more of acetaldehyde, butyric acid and lactic acid.