Electrochemical sensor having a mediator compound

• US 7,883,611 B2
• Filed: 02/23/2007
• Issued: 02/08/2011
• Est. Priority Date: 03/30/2006
• Status: Active Grant

• Current Assignee: Dragerwerk AG
• Original Assignee: Dragerwerk AG
• Inventors: Kiesele, Herbert, Sommer, Sabrina, Mett, Frank
• Primary Examiner(s): Nguyen; Nam X
• Assistant Examiner(s): LEONG, SUSAN DANG
• Application Number:
  US11/678,279
• Publication Number:
  US 20070227909A1
• Time in Patent Office: 1,446 Days
• Field of Search: 204/400, 204/403.06, 204/431, 205/793, 205/794.5
• US Class Current: 204/431
• CPC Class Codes: B82Y 15/00 Nanotechnology for interacting, sensing or actuating, e.g. quantum dots as markers in protein assays or molecular motors
• CPC Class Codes: B82Y 30/00 Nanotechnology for materials or surface science, e.g. nanocomposites
• CPC Class Codes: G01N 27/4045 for gases other than oxygen
• CPC Class Codes: G01N 33/0042 for SO2, SO3
• CPC Class Codes: Y02A 50/20 Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters

Abstract

An electrochemical sensor, especially for gases, is provided having a mediator compound based on transition metal salts of polybasic acids and/or transition metal salts of polyhydroxycarboxylic acids. The electrochemical sensor also contains a DLC, BDD or a precious metal thin-layer measuring electrode (3). The electrochemical sensor may be used for determining SO₂ and H₂S.

Claims

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

a measuring electrode;

an auxiliary electrode; and

an electrolyte solution containing the mediator compound, said mediator compound comprising a transition metal salt of an acid compound, said acid compound containing one of at least two acid groups or at least one hydroxyl group and at least one acid group, said measuring electrode detecting a concentration of one of H₂S and SO₂ in a gas, wherein said electrolyte solution is in a saturated state, said mediator being provided as an excess solid in said electrolyte solution.

2. An electrochemical gas sensor in accordance with claim 1, wherein said acid compound is a carboxylic acid.

3. An electrochemical gas sensor in accordance with claim 1, wherein the carboxylic acid is an aromatic carboxylic acid with two or three carboxyl groups.

4. An electrochemical gas sensor in accordance with claim 1, wherein the carboxylic acid is phthalic acid, isophthalic acid or terephthalic acid.

5. An electrochemical gas sensor in accordance with at least claim 1, wherein the acid compound is an aliphatic polycarboxylic acid.

6. An electrochemical gas sensor in accordance with at least claim 1, wherein the acid compound is citric acid.

7. An electrochemical gas sensor in accordance with claim 1, wherein the acid compound is gluconic acid.

8. An electrochemical gas sensor in accordance with claim 1, wherein the acid compound is a boric acid.

9. An electrochemical gas sensor in accordance with claim 1, wherein the electrolyte solution contains alkali or alkaline earth metal salts.

10. An electrochemical gas sensor in accordance with claim 1, wherein the electrolyte solution contains LiCl.

11. An electrochemical gas sensor in accordance with at least claim 1, wherein water or organic solvents are used as a solvent.

12. An electrochemical gas sensor in accordance with at least claim 1, wherein ethylene and/or propylene carbonate are used as a solvent.

13. An electrochemical gas sensor in accordance with at least claim 1, wherein the measuring electrode is a diamond-like carbon, boron-doped diamond, a precious metal thin-layer electrode or carbon nanotubes.

14. An electrochemical gas sensor in accordance with claim 9, wherein the thickness of the precious metal thin-layer electrode is 100-500 nm.

15. An electrochemical gas sensor in accordance with at least claim 1, wherein the transition metal salt is a copper salt or a Cu²⁺ salt.

16. An electrochemical gas sensor in accordance with claim 11, 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.

17. An electrochemical gas sensor in accordance with claim 11, wherein the Cu²⁺ salt is CuCl₂ and the concentration of CuCl₂ is about 0.5 mol in a 2-10-molar LiCl solution.

18. An electrochemical gas sensor in accordance with claim 1, wherein the transition metal salt is an iron salt or an Fe³⁺ salt.

19. An 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 the analyte substance enters the area of said measuring electrode via said gas-permeable membrane.

20. An electrochemical gas sensor in accordance with claim 1, further comprising a reference electrode.

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

24. An electrochemical gas sensor in accordance with claim 1, wherein said mediator being formed from one of potassium hydrogen phthalate, sodium tetraborate and trisodium citrate.

22. A method of electrochemical gas sensing for detecting an analyte, the method comprising:

providing a measuring electrode;

providing an auxiliary electrode;

providing an electrolyte solution containing the mediator compound, said mediator compound comprising a transition metal salt of an acid compound, said acid compound containing one of at least two acid groups or at least one hydroxyl group and at least one acid group;

positioning said measuring electrode and said auxiliary electrode in said electrolyte solution containing the mediator compound to provide an electrochemical gas sensor; and

determining SO₂ concentration or H₂S concentration in a gas using said measuring electrode, said electrolyte being in a saturated state, said mediator being provided as an excess solid in said electrolyte solution.

23. A method according to claim 22, wherein said electrolyte is or contains a chloride, said mediator being formed from one of potassium hydrogen phthalate, sodium tetraborate and trisodium citrate.