Modified microelectrodes with renewable surface and method of making same

• US 5,002,651 A
• Filed: 03/07/1989
• Issued: 03/26/1991
• Est. Priority Date: 03/07/1989
• Status: Expired due to Fees

• Current Assignee: University of Connecticut (State of Connecticut)
• Original Assignee: University of Connecticut (State of Connecticut)
• Inventors: Creasy, Kenneth E., Shaw, Brenda R.
• Primary Examiner(s): Niebling, John F.
• Assistant Examiner(s): GORGOS, KATHRYN L
• Application Number:
  US07/319,984
• Time in Patent Office: 749 Days
• Field of Search: 204/290 R, 204/291, 429/42, 429/43, 427/58, 427/113, 427/355
• US Class Current: 204/400
• CPC Class Codes: G01N 27/30 Electrodes, e.g. test electrodes; Half-cells G01N27/414 takes precedence
• 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
• CPC Class Codes: G01N 27/38 Cleaning of electrodes
• CPC Class Codes: H01M 4/86 Inert electrodes with catalytic activity, e.g. for fuel cells
• CPC Class Codes: Y02E 60/50 Fuel cells

Abstract

Renewable composite microelectrodes for electrochemical applications are formed by an initial coating on an elongated conductive substrate of less than 500 micrometers over at least a portion of its length with a modifier composition, and a superposed coating of electronically resistive polymer. The initial coating is exposed only at the tip portion of the microelectrode. The initial coating may be an absorbed layer of the modifier, a homogeneous layer of a polymeric matrix with the modifier dispersed therein, or a layer of a polymer with a modifier in its chain. The modifier provides distinctive properties to the surface of the electrode which may be electroactivity, inclusion, acidic/basic, complexing/chelating or electrocatalysis. The microelectrode will normally be used with only the tip portion thereof immersed in the solution, and it may be renewed by removing the contaminated tip portion.

Claims

1. A renewable composite microelectrode for electrochemical applications comprising:

(a) at least one elongated conductive substrate having a cross section of less than 500 micrometers and selected from the group of conductive fibers and metallic wires, said substrate having a tip at one end thereof;

(b) an initial surface coating extending along at least a portion of the length of said substrate from said tip and containing a modifier providing to said electrode distinctive properties selected from the group consisting of electroactivity, inclusion, adsorption, acidic/basic, complexing/chelating and electrocatalysis, said coating being

a homogeneous layer of 1-99 percent by weight of a polymeric matrix and 1-99 percent by weight of said modifier dispersed therein; and

(c) an electronically resistive polymer coating superposed thereon, said electrode at said tip of said substrate being free from said resistive coating and said initial surface coating being exposed at said tip, said electrode being renewable by removing a portion thereof at the tip of said substrate to expose a fresh portion of said initial coating at said tip.

2. The electrode in accordance with claim 1 wherein said substrate is a conductive or semiconductive fiber.

3. The electrode in accordance with claim 1 wherein said initial and resistive coatings extend over substantially the entire length of the substrate from said tip.

4. The electrode in accordance with claim 1 wherein said initial coating comprises an initial deposit of said modifier and said polymer coating is a non-conductive polymer surrounding and encapsulating a multiplicity of initially coated substrates.

5. The electrode in accordance with claim 1 wherein said modifier exhibits said distinctive such properties only upon application of a potential to said electrode.

6. The electrode in accordance with claim 1 wherein said modifier is non-conductive and enhances electroactivity upon application of a potential to the electrode in a solution.

7. The electrode in accordance with claim 1 wherein said modifier exhibiting said distinctive properties is selected from the group consisting of organic compounds and polymers.

8. The electrode in accordance with claim 1 wherein said initial coating has a thickness has a thickness of 0.1 nanometers to 5 millimeters and said resistive polymer coating has a thickness of 0.01-10 micrometers.

9. In the method of making renewable composite microelectrodes for electrochemical applications, the steps comprising:

(a) selecting an elongated conductive substrate having a cross section of less than 500 micrometers and of the group consisting of conductive fibers and wires, said substrate having a tip at one end thereof;

(b) providing an initial surface coating extending along at least a portion of the length of said substrate from said tip to form an electrode, said coating containing a modifier providing to said electrode distinctive properties selected from the group consisting of electroactivity, inclusion, adsorption, acidic/basic, complexing/chelating and electrocatalysis, said initial coating being formed by

coating said substrate with a homogeneous layer comprising a mixture of 1-99 percent by weight of a polymeric matrix and 1-99 percent by weight of said modifier dispersed therein; and

(c) superposing on said initial coating an electronically resistive polymer coating; and

(d) removing said conductive polymer at the tip of said substrate to expose said initial coating at the tip of said substrate.

10. The method in accordance with claim 9 wherein there are included the additional steps of selecting a multiplicity of microelectrodes produced in accordance with steps (a), (b), (c) and (d) of claim 9 and having different coatings exhibiting different distinctive properties, and assembling such microelectrodes into a composite electrode providing more than one of said properties.

11. The method in accordance with claim 9 wherein there are included the additional steps of:

(a) immersing said electrode in a solution to perform a function involving one of said properties; and

(b) subsequently removing a portion of said electrode at said tip of said substrate to expose fresh surface of said initial coating for further use.

12. The method in accordance with claim 9 wherein said substrate is a conductive fiber.

13. The method in accordance with claim 9 wherein said initial and resistive coatings extend over substantially the entire length of the substrate from said tip.

14. The method in accordance with claim 9 wherein said initial coating comprises an initial deposit of said modifier and said resistive polymer coating is a non-conductive polymer surrounding and encapsulating a multiplicity of initially coated substrates produced in accordance with steps (a) and (b) of claim 11.

15. The method in accordance with claim 9 wherein said modifier exhibits such properties only upon application of a potential to said electrode.

16. The method in accordance with claim 9 wherein a multiplicity of initially coated substrates is encapsulated within said electronically resistive polymer coating and step (d) is performed therafter.

17. A renewable composite microelectrode for electrochemical applications comprising:

(a) at least one elongated conductive substrate having a cross section of less than 500 micrometers and selected from the group of conductive fibers and metallic wires, said substrate having a tip at one end thereof;

(b) an initial surface coating extending along at least a portion of the length of said substrate from said tip and containing a modifier providing to said electrode distinctive properties selected from the group consisting of electroactivity, inclusion, adsorption, acidic/basic, complexing/chelating and electrocatalysis, said coating being an adsorbed layer of said modifier; and

(c) an electronically resistive polymer coating superposed thereon, said electrode at said tip of said substrate being free from said resistive coating and said initial surface coating being exposed at said tip, said electrode being renewable by removing a portion thereof at the tip of said substrate to expose a fresh portion of said initial coating at said tip.

18. The electrode in accordance with claim 17 wherein said substrate is a conductive or semiconductive fiber.

19. The electrode in accordance with claim 17 wherein said initial coating comprises an initial deposit of said modifier and said polymer coating is a non-conductive polymer surrounding and encapsulating a multiplicity of initially coated substrates.

20. The electrode in accordance with claim 17 wherein said initial coating has a thickness of 0.1 nanometers to 5 millimeters and said nresistive polymer coating has a thickness of 0.01-10 micrometers.

21. A renewable composite microelectrode for electrochemical applications comprising:

(a) at least one elongated conductive substrate having a cross section of less than 500 micrometers and selected from the group of conductive fibers and metallic wires, said substrate having a tip at one end thereof;

(b) an initial surface coating extending along at least a portion of the length of said substrate from said tip and containing a modifier providing to said electrode distinctive properties selected from the group consisting of electroactivity, inclusion, adsorption, acidic/basic, complexing/chelating and electrocatalysis, said coating being a polymer having a polymer chain containing said modifier in the polymer chain; and

(c) an electronically resistive polymer coating superposed thereon, said electrode at said tip of said substrate being free from said resistive coating and said initial surface coating being exposed at said tip, said electrode being renewable by removing a portion thereof at the tip of said substrate to expose a fresh portion of said initial coating at said tip.

22. The electrode in accordance with claim 21 wherein said substrate is a conductive or semiconductive fiber.

23. The electrode in accordance with claim 21 wherein said initial coating comprises an initial deposit of said modifier and said polymer coating is a non-conductive polymer surrounding and encapsulating a multiplicity of initially coated substrates.

24. The electrode in accordance with claim 21 wherein said initial coating has a thickness of 0.1 nanometers to 5 millimeters and said nresistive polymer coating has a thickness of 0.01-10 micrometers.

25. In the method of making renewable composite microelectrodes for electrochemical applications, the steps comprising:

(a) selecting an elongated conductive substrate having a cross section of less than 500 micrometers and of the group consisting of conductive fibers and wires, said substrate having a tip at one end thereof;

(b) providing an initial surface coating extending along at least a portion of the length of said substrate from said tip to form an electrode, said coating containing a modifier providing to said electrode distinctive properties selected from the group consisting of electroactivity, inclusion, adsorption, acidic/basic, complexing/chelating and electrocatalysis, said initial coating being formed by absorbing said modifier onto said substrate;

(c) superposing on said initial coating an electronically resistive polymer coating; and

(d) removing said conductive polymer at the tip of said substrate to expose said initial coating at the tip of said substrate.

26. The method in accordance with claim 25 wherein there are included the additional steps of selecting a multiplicity of microelectrodes produces in accordance with steps (a), (b), (c) and (d) of claim 25 and having different coatings exhibiting different distinctive properties, and assembling such microelectrodes into a composite electrode providing more than one of said properties.

27. The method in accordance with claim 25 wherein there are included the additional steps of:

(a) immersing said electrode in a solution to perform a function involving one of said properties; and

(b) subsequently removing a portion of said electrode at said tip of said substrate to expose fresh surface of said initial coating for further use.

28. The method in accordance with claim 25 wherein said initial coating comprises an initial deposit of said modifier and said resistive polymer coating is a non-conductive polymer surrounding and encapsulating a multiplicity of initially coated substrates produced in accordance with steps (a) and (b) of claim 25.

29. The method in accordance with claim 25 wherein a multiplicity of initially coated substrates is encapsulated within said electronically resistive polymer coating and step (d) is performed therafter.

30. The method of making renewable composite microelectrodes for electrochemical applications, the steps comprising:

(a) selecting an elongated conductive substrate having a cross section of less than 500 micrometers and of the group consisting of conductive fibers and wires, said substrate having a tip at one end thereof;

(b) providing an initial surface coating extending along at least a portion of the length of said substrate from said tip to form an electrode, said coating containing a modifier providing to said electrode distinctive properties selected from the group consisting of electroactivity, inclusion, adsorption, acidic/basic, complexing/chelating and electrocatalysis, said initial coating being formed by coating and substrate with a non-conductive polymer having a polymer chain containing the modifier in the polymer chain;

(c) superposing on said initial coating an electronically resistive polymer coating; and

(d) removing said conductive polymer at the tip of said substrate to expose said initial coating at the tip of said substrate.

31. The method in accordance with claim 30 wherein said initial coating comprises a non-conductive polymer having the modifier in the polymer chain, said modifier being copolymerized with a polymerizable monomer to form said non-conductive polymer.

32. The method in accordance with claim 30 wherein said initial coating comprises a non-conductive polymer having the modifier in the polymer chain, said polymer being cross-linked.

33. The method in accordance with claim 30 wherein there are included the additional steps of selecting a multiplicity of microelectrodes produced in accordance with steps (a), (b), (c) and (d) of claim 30 and having different coatings exhibiting different distinctive properties, and assembling such microelectrodes into a composite electrode providing more than one of said properties.

34. The method in accordance with claim 30 wherein there are included the additional steps of:

(a) immersing said electrode in a solution to perform a function involving one of said properties; and

(b) subsequently removing a portion of said electrode at said tip of said substrate to expose fresh surface of said initial coating for further use.

35. The method in accordance with claim 30 wherein said initial coating comprises an initial deposit of said modifier and said resistive polymer coating is a non-conductive polymer surrounding and encapsulating a multiplicity of initially coated substrates produced in accordance with steps (a) and (b) of claim 30.

36. The method in accordance with claim 30 wherein a multiplicity of initially coated substrates is encapsulated within said electronically resistive polymer coating and step (d) is performed therafter.