Electrochemical sensor

• US 8,758,593 B2
• Filed: 08/06/2010
• Issued: 06/24/2014
• Est. Priority Date: 01/08/2004
• Status: Active Grant

• Current Assignee: Schlumberger Technology Corporation (Schlumberger NV)
• Original Assignee: Schlumberger Technology Corporation (Schlumberger NV)
• Inventors: Lawrence, Nathan, Lafitte, Valerie
• Primary Examiner(s): LEONG, SUSAN DANG
• Application Number:
  US12/852,315
• Publication Number:
  US 20110048969A1
• Time in Patent Office: 1,418 Days
• Field of Search: 204/403.03, 204/403.06, 204/403.13, 204/406, 204/407, 204/412, 204/415, 204/416, 204/419, 204/433, 205/787.5, 205/792, 205/793
• US Class Current: 205/787.5
• CPC Class Codes: B82Y 30/00 Nanotechnology for materials or surface science, e.g. nanocomposites
• CPC Class Codes: G01N 27/302 pH sensitive, e.g. quinhydron, antimony or hydrogen electrodes ion selective electrodes G01N27/333, glass electrodes G01N27/36
• CPC Class Codes: G01N 27/308 at least partially made of carbon
• CPC Class Codes: G01N 27/3335 the membrane containing at least one organic component G01N27/3271 takes precedence; aspects concerning the enzyme reagent in enzyme electrodes C12Q1/001

Abstract

An electrochemical sensor and a method for using an electrochemical sensor are described where the electrochemical sensor comprises a working electrode having thereon one or more redox species that are sensitive to an analyte to be measured and a polymer coating that provides for interaction between the redox species and the analyte.

Claims

1. A working electrode for an electrochemical sensor for measuring pH of a fluid, comprising:

a conducting substrate;

a first set of redox species coupled with the conducting substrate, wherein the first set of redox species comprises one or more non-polymeric redox species that are sensitive to pH, and wherein the coupling of the first set of redox species with the conducting substrate comprises one of the first set of redox species being chemically coupled with the conducting substrate, the first set of redox species being coated on the conducting substrate and the first set of redox species being deposited on the conducting substrate; and

a polymer layer which consists of polymer and which directly covers at least an area of the conducting substrate where the conducting substrate is coupled with the first set of redox species so that the polymer layer directly covers the first set of redox species, the polymer layer being configured to allow hydrogen ions to diffuse through the polymer layer to interact with the first set of redox species and to prevent diffusion of the non-polymeric redox species from the working electrode.

2. The working electrode of claim 1, further comprising:

a second set of non-polymeric redox species disposed between the conducting substrate and the polymer layer, wherein the polymer layer is configured to prevent diffusion of the second set of non-polymeric redox species from the working electrode.

3. The working electrode of claim 2, wherein the second set of redox species is chemically bound to the conducting substrate.

4. The working electrode of claim 1, wherein the working electrode comprises an electrode having a diameter between 1 and 5 millimeters and the polymer layer comprises less than 1000 micrograms of polymer.

5. The working electrode of claim 1, wherein the polymer layer consists of a polystyrene polymer.

6. The working electrode of claim 5, wherein the working electrode has a diameter between 1 and 5 millimeters and the polymer layer consists of less than 600 micrograms of the polystyrene polymer.

7. The working electrode of claim 5, wherein the working electrode has a diameter between 1 and 5 millimeters and the polymer layer consists of between 100 and 500 micrograms of the polystyrene polymer.

8. The electrochemical sensor of claim 1, wherein the polymer layer consists of a polysulphone polymer.

9. The electrochemical sensor of claim 8, wherein the working electrode has a diameter between 1 and 5 millimeters and the polymer layer consists of less than 600 micrograms of the polysulphone polymer.

10. The working electrode of claim 8, wherein the working electrode has a diameter between 1 and 5 millimeters and the polymer layer consists of between 10 and 500 micrograms of the polysulphone polymer.

11. An electrochemical sensor for measuring pH in a fluid, comprising:

a working electrode, the working electrode comprising a conducting substrate, a first set of redox species, a second set of redox species and a polymer layer, wherein;

the first set of redox species comprises one or more non-polymeric redox species that are sensitive to pH;

the second set of redox species comprises one or more non-polymeric redox species that are insensitive to pH;

the first set of redox species is either chemically coupled with the conducting substrate, coated on the conducting substrate, directly immobilized on the conducting substrate or deposited on the conducting substrate and

the polymer layer consists of polymer and is disposed on top of the conducting substrate and the first set of redox species thereon, and wherein the polymer layer is configured to prevent diffusion of at least the first set of non-polymeric redox species from the working electrode and to allow hydrogen ions to diffuse through the polymer layer to interact with at least the first set of redox species;

a counter electrode;

a reference electrode;

means to apply a varying potential to the working electrode;

means to measure a potential difference between the working electrode and the reference electrode;

means to measure a current flow between the working electrode and the counter electrode as the applied potential causes the first and the second set of redox species to undergo at least one of oxidation and reduction; and

a processor configured to process a measurement of pH from at least one of the measured potential difference and the measured current.

12. The electrochemical sensor of claim 11, wherein the working electrode comprises a first working electrode and a second working electrode and the first working electrode comprises the first set of redox species and the second working electrode comprises the second set of redox species.

13. The electrochemical sensor of claim 11, wherein the second set of redox species is chemically coupled with the working electrode.

14. The electrochemical sensor of claim 11, wherein the second set of redox species is coated or deposited onto the working electrode.

15. The electrochemical sensor of claim 11, wherein the working electrode has a diameter between 1 and 5 millimeters and the polymer layer consists of less than 1000 micrograms of polymer.

16. The electrochemical sensor of claim 11, wherein the polymer layer consists of a polystyrene polymer.

17. The electrochemical sensor of claim 16, wherein the working electrode has a diameter between 1 and 5 millimeters and the polymer layer consists of less than 600 micrograms of the polystyrene polymer.

18. The electrochemical sensor of claim 16, wherein the working electrode has a diameter between 1 and 5 millimeters and the polymer layer consists of between 100 and 500 micrograms of the polystyrene polymer.

19. The electrochemical sensor of claim 11, wherein the polymer layer consists of a polysulphone polymer.

20. The electrochemical sensor of claim 19, wherein the working electrode has a diameter between 1 and 5 millimeters and the polymer layer consists of less than 600 micrograms of the polysulphone polymer.

21. The electrochemical sensor of claim 19, wherein the working electrode has a diameter between 1 and 5 millimeters and the polymer layer consists of between 10 and 500 micrograms of the polysulphone polymer.

22. The electrochemical sensor of claim 11, wherein the means for measuring at least one of the potential difference and the current flow comprises at least one of a voltammetric device and a potentiostat.

23. The electrochemical sensor of claim 11, wherein the one or more redox species sensitive to pH contains a hydroquinone or quinone moiety.

24. The electrochemical sensor in accordance with claim 11, wherein the one or more species insensitive to pH contain one of a ferrocene moiety, a ruthenocene moiety and a hexacyanometallate moiety.

25. The electrochemical sensor of claim 11, wherein a first surface area of the counter electrode is of the order of one to ten times that of a second surface area of the working electrode.

26. The electrochemical sensor of claim 11, wherein a first surface area of the counter electrode is less than one hundred times that of a second surface area of the working electrode.

27. The electrochemical sensor of claim 11, further comprising a temperature probe for measuring a temperature of the fluid.

28. The electrochemical sensor of claim 27, wherein the processor uses the temperature to process the presence or the measurement of the analyte.

29. The electrochemical sensor of claim 11, wherein the reference electrode comprises one of silver and silver chloride.

30. The electrochemical sensor of claim 12, wherein the second working electrode comprises carbon particles solvent cast with a ferrocene.

31. The electrochemical sensor of claim 11, wherein the processor processes the presence or measurement of pH from peak current flows produced by the oxidation or reduction of the first and the second sets of the redox species.

32. A method for electrochemically measuring pH of a fluid comprising:

contacting a working electrode with the fluid, wherein the working electrode comprises a conducting substrate coupled with a first set of redox species which comprises one or more non-polymeric redox species that are sensitive to pH wherein the coupling of the first set of redox species with the conducting substrate comprises one of the first set of redox species being chemically coupled with the conducting substrate, the first set of redox species being coated on the conducting substrate and the first set of redox species being deposited on the conducting substrate, a second set of non-polymeric redox species that are insensitive to pH and a polymer layer which consists of polymer and which directly covers at least an area of the conducting substrate where the conducting substrate is coupled with the redox species so that the polymer layer directly covers the redox species;

using the polymer layer to prevent diffusion of at least one of the first set of redox species and the second set of redox species from the working electrode;

applying a varying potential between the working electrode and a reference electrode;

making voltammetric measurements of at least a current flow between the working electrode and a counter electrode as the varying potential causes the first and the second set of redox species to undergo at least one of oxidation and reduction and a potential difference between the working electrode and the reference electrode; and

processing the measurement of pH from the voltammetric measurements.

33. The method of claim 32, further comprising:

measuring a temperature of the fluid; and

using the measured temperature to calibrate the measurement of pH.