Electrochemical sensor having a mediator compound with a solid

• US 8,268,161 B2
• Filed: 02/22/2007
• Issued: 09/18/2012
• Est. Priority Date: 03/30/2006
• Status: Active Grant

• Current Assignee: Dragerwerk AG & Company KGaA (FPS Vermögensverwaltung GmbH)
• Original Assignee: Dragerwerk AG & Company KGaA (FPS Vermögensverwaltung GmbH)
• Inventors: Sommer, Sabrina, Kiesele, Herbert, Mett, Frank
• Primary Examiner(s): Olsen, Kaj K
• Assistant Examiner(s): LEONG, SUSAN DANG
• Application Number:
  US11/677,782
• Publication Number:
  US 20080035493A1
• Time in Patent Office: 2,035 Days
• Field of Search: 204/400, 204/403.06, 204/431, 205/793, 205/794.5, 205/786.5
• US Class Current: 205/786.5
• CPC Class Codes: G01N 27/404 Cells with anode, cathode and cell electrolyte on the same side of a permeable membrane which separates them from the sample fluid , e.g. Clark-type oxygen sensors

Abstract

An electrochemical sensor is provided especially for gases. The electrochemical sensor has a mediator compound, which is both dissolved in an electrolyte (9) in a saturated form and is present as an excess solid (10) in the electrolyte (9).

Claims

1. An electrochemical gas sensor for detecting an analyte, the electrochemical gas sensor comprising:

a housing defining an electrolyte space;

a measuring electrode comprising a carbon-containing material, said measuring electrode being disposed in said electrolyte space;

an auxiliary electrode disposed in said electrolyte space;

a liquid electrolyte disposed in said electrolyte space; and

an analyte-selective mediator, said analyte-selective mediator being provided in a saturated form in said electrolyte and being present as an excess solid in the electrolyte space, said measuring electrode detecting a concentration of one of H₂S and SO₂ in a gas.

2. An electrochemical gas sensor in accordance with claim 1, wherein said measuring electrode comprises at least one of graphite, diamond-like carbon (DLC), carbon nanotubes (CNT) or boron-doped diamond (BDD).

3. An electrochemical gas sensor in accordance with claim 1, further comprising a reference electrode comprising at least one of graphite, diamond-like carbon (DLC) or boron-doped diamond (BDD) or carbon nanotubes.

4. An electrochemical gas sensor in accordance with claim 1, wherein said mediator comprises a mediator compound that is a transition metal salt of an acid compound, said acid compound containing at least two acid groups or at least one acid group and two hydroxyl groups.

5. An electrochemical gas sensor in accordance with claim 4, wherein said acid compound is a carboxylic acid.

6. An electrochemical gas sensor in accordance with claim 5, wherein said carboxylic acid is an aromatic carboxylic acid with two or three carboxyl groups, especially phthalic acid, isophthalic acid or terephthalic acid.

7. An electrochemical gas sensor in accordance with claim 4, wherein the acid compound is an aliphatic polycarboxylic acid, especially citric acid.

8. An electrochemical gas sensor in accordance with claim 4, wherein the acid compound is gluconic acid.

9. An electrochemical gas sensor in accordance with claim 4, wherein the acid compound is a boric acid.

10. An electrochemical gas sensor in accordance with claim 4, wherein said liquid electrolyte is a solution containing alkali or alkaline earth metal salts, preferably LiCl.

11. An electrochemical gas sensor in accordance with claim 4, wherein water or organic solvents including ethylene and/or propylene carbonate, are used as a solvent.

12. An electrochemical gas sensor in accordance with claim 4, wherein the transition metal salt is a copper salt or a Cu²⁺ salt.

13. An electrochemical gas sensor in accordance with claim 12, wherein the Cu2⁺ salt is CuCl₂ and the concentration of CuCl₂ is between 0.2 mol and 1.0 mol in a 2-10-molar LiCl solution.

14. An electrochemical gas sensor in accordance with claim 12, wherein the Cu2⁺ salt is CuCl₂ and the concentration of CuCl₂ is about 0.5 mol in a 2-10-molar LiCl solution.

15. An electrochemical gas sensor in accordance with claim 4, wherein the transition metal salt is an iron salt or an Fe³⁺ salt.

16. Electrochemical gas sensor in accordance with claim 1, further comprising a gas-permeable membrane, said housing having an opening with said gas-permeable membrane, wherein an analyte substance enters the area of said measuring electrode via said gas-permeable membrane.

17. An electrochemical gas sensor in accordance with claim 16, further comprising a reference electrode.

18. An electrochemical gas sensor in accordance with claim 1, further comprising a protective electrode arranged behind said measuring electrode.

21. An electrochemical gas sensor in accordance with claim 1, wherein said analyte-selective mediator comprises one of potassium hydrogen phthalate, sodium tetraborate and trisodium citrate.

19. A process of electrochemical gas sensing, the process comprising:

providing a housing defining an electrolyte space;

providing a measuring electrode comprising a carbon-containing material, said measuring electrode being disposed in said electrolyte space;

providing an auxiliary electrode disposed in said electrolyte space;

providing a liquid electrolyte disposed in said electrolyte space;

providing an analyte-selective mediator;

providing said analyte-selective mediator in a saturated form in said electrolyte;

providing said analyte-selective mediator as an excess solid in the electrolyte space; and

determining SO₂ concentration or H₂S concentration in a gas using said measuring electrode.

20. A process of electrochemical gas sensing according to claim 19, wherein said electrolyte is or contains a chloride, wherein said analyte-selective mediator comprises one of potassium hydrogen phthalate, sodium tetraborate and trisodium citrate.