Electrochemical and photoelectrochemical oxidation of 5-hydroxymethylfurfural to 2,5-furandicarboxylic acid and 2,5-diformylfuran

Patent metadata

Field	Value
Publication number	US-2016201204-A1
Application number	US-201514592031-A
Country	US
Kind code	A1
Filing date	Jan 8, 2015
Priority date	Jan 8, 2015
Publication date	Jul 14, 2016
Grant date	—

Abstract

Electrochemical and photoelectrochemical cells for the oxidation of 5-hydroxymethylfurfural to 2,5-furandicarboxylic acid and/or 2,5-diformylfuran are provided. Also provided are methods of using the cells to carry out the electrochemical and photoelectrochemical oxidation of 5-hydroxymethylfurfural to 2,5-furandicarboxylic acid and/or 2,5-diformylfuran.

First claim

What is claimed is:

1 . A method for the TEMPO-mediated electrochemical oxidation of 5-hydroxymethylfurfural in an electrochemical cell comprising: an anode in an anode electrolyte solution comprising 5-hydroxymethylfurfural; a TEMPO mediator immobilized on the anode or dissolved in the anode electrolyte solution; and a cathode in a cathode electrolyte solution, the method comprising: applying an anode potential to the anode, the anode potential being more positive than the onset potential for the oxidation of the TEMPO mediator, to induce the TEMPO-mediated oxidation of the 5-hydroxymethylfurfural to form 2,5-furandicarboxylic acid, 2,5-diformylfuran or both.

2 . The method of claim 1 , wherein the anode electrolyte solution serves as an oxygen donor and the TEMPO-mediated oxidation of the 5-hydroxymethylfurfural forms 2,5-furandicarboxylic acid at a yield of at least 90%.

3 . The method of claim 1 , wherein the anode electrolyte solution is an aqueous electrolyte solution and the TEMPO-mediated oxidation of the 5-hydroxymethylfurfural forms 2,5-furandicarboxylic acid at a yield of at least 99%.

4 . The method of claim 1 , wherein the anode electrolyte solution is an aqueous solution having a pH of less than 12 and the TEMPO-mediated oxidation of the 5-hydroxymethylfurfural forms 2,5-furandicarboxylic acid at a yield of at least 90%.

5 . The method of claim 1 , wherein the anode electrolyte solution does not serve as an oxygen donor and the TEMPO-mediated oxidation of the 5-hydroxymethylfurfural forms 2,5-diformylfuran at a yield of at least 94%.

6 . The method of claim 1 , wherein the anode does not comprise platinum, palladium or gold.

7 . An electrochemical cell comprising:
an anode in an anode electrolyte solution comprising 5-hydroxymethylfurfural; a TEMPO mediator immobilized on the anode or dissolved in the anode electrolyte solution; and a cathode in a cathode electrolyte solution, wherein the cathode is in electrical communication with the anode.

8 . The cell of claim 7 , wherein the anode electrolyte solution is an aqueous electrolyte solution having a pH of less than 12.

9 . The cell of claim 7 , wherein the anode does not comprise platinum, palladium or gold.

10 . The cell of claim 7 , wherein the anode electrolyte solution does not serve as an oxygen donor.

11 . A method for the photoelectrochemical oxidation of 5-hydroxymethylfurfural in a photoelectrochemical cell comprising: an anode in an anode electrolyte solution comprising 5-hydroxymethylfurfural; and a cathode in a cathode electrolyte solution, wherein at least one of the anode and the cathode is a photoelectrode comprising a semiconductor, the method comprising: exposing the at least one photoelectrode to radiation that is absorbed to produce electron-hole pairs, wherein holes are transported to the electrolyte-anode interface where they induce the oxidation of the 5-hydroxymethylfurfural to form 2,5-furandicarboxylic acid, 2,5-diformylfuran or both, and electrons are transported to the electrolyte-cathode interface where they induce a reduction reaction.

12 . The method of claim 11 , wherein the photoelectrochemical cell further comprises a TEMPO mediator immobilized on the anode or dissolved in the anode electrolyte solution, and further wherein oxidation of the 5-hydroxymethylfurfural to form 2,5-furandicarboxylic acid, 2,5-diformylfuran or both is mediated by the TEMPO mediator.

13 . The method of claim 12 , wherein the anode electrolyte solution serves as an oxygen donor and the TEMPO-mediated oxidation of the 5-hydroxymethylfurfural forms 2,5-furandicarboxylic acid at a yield of at least 90%.

14 . The method of claim 12 , wherein the anode electrolyte solution is an aqueous electrolyte solution and the TEMPO-mediated oxidation of the 5-hydroxymethylfurfural forms 2,5-furandicarboxylic acid at a yield of at least 99%.

15 . The method of claim 12 , wherein the anode electrolyte solution is an aqueous solution having a pH of less than 12 and the TEMPO-mediated oxidation of the 5-hydroxymethylfurfural forms 2,5-furandicarboxylic acid at a yield of at least 90%.

16 . The method of claim 12 , wherein the anode electrolyte solution does not serve as an oxygen donor and the TEMPO-mediated oxidation of the 5-hydroxymethylfurfural forms 2,5-diformylfuran at a yield of at least 94%.

17 . The method of claim 12 , wherein the anode is a photoanode comprising n-type BiVO 4 .

18 . A photoelectrochemical cell comprising:
an anode comprising in an anode electrolyte solution comprising 5-hydroxymethylfurfural; and a cathode in a cathode electrolyte solution; wherein at least one of the anode and the cathode is a photoelectrode comprising a semiconductor.

19 . The cell of claim 18 , further comprising a TEMPO mediator immobilized on the anode or dissolved in the anode electrolyte solution.

20 . The cell of claim 18 , wherein the anode electrolyte solution is an aqueous electrolyte solution having a pH of less than 12.

21 . The cell of claim 19 , wherein the anode anode does not comprise platinum, palladium or gold.

22 . The cell of claim 18 , wherein the anode is a photoanode comprising n-type BiVO 4 .

Assignees

• Wisconsin Alumni Res Found

Inventors

• Choi Kyoung-Shin
• Cha Hyun Gil

Classifications

• H01G9/2027

  comprising an oxide semiconductor electrode · CPC title

• H01G9/2004

  characterised by the electrolyte, e.g. comprising an organic electrolyte · CPC title

• C25B9/00

  Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features · CPC title

• C25B3/02 Primary

  Chemistry & Metallurgy · mapped topic

• C25B11/12

  Chemistry & Metallurgy · mapped topic