Electrochemical sensor

• US 9,851,326 B2
• Filed: 11/22/2013
• Issued: 12/26/2017
• Est. Priority Date: 11/22/2012
• Status: Active Grant

• Current Assignee: Universite Laval
• Original Assignee: Universite Laval
• Inventors: Viens, Jean-Franois, Normandeau, Charles-Olivier, Messaddeq, Younes
• Primary Examiner(s): Ball, J. Christopher
• Application Number:
  US14/646,488
• Publication Number:
  US 20150338368A1
• Time in Patent Office: 1,495 Days
• CPC Class Codes: G01N 27/026 Dielectric impedance spectroscopy electrochemical impedance spectroscopy for measuring corrosion G01N17/02
• 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 27/36 Glass electrodes
• CPC Class Codes: G01N 27/406 Cells and probes with solid electrolytes
• CPC Class Codes: G01N 27/4112 Composition or fabrication of the solid electrolyte
• CPC Class Codes: G01N 27/4146 involving nanosized elements, e.g. nanotubes, nanowires
• CPC Class Codes: G01N 27/4148 Integrated circuits therefor, e.g. fabricated by CMOS processing CMOS processing per se H01L21/82

Abstract

An electrochemical ion sensor and a method for sensing a presence of at least one ion species in a solution are provided. The electrochemical sensor includes a solid-state electrolyte medium doped with an organometallic material, having an electrochemical affinity with the ion species, and a pair of electrodes electrically contacting the solid-state electrolyte. The electrochemical sensor also includes an electrical circuit configured to drive the pair of electrodes with an AC electrical excitation and to measure at least one parameter related to a complex electrical impedance of the doped solid-state electrolyte medium in response to the AC electrical excitation. The parameter may be an electrical resistance, an inductance or a combination of both, and represents the presence of the ion species in the solution when the solid-state electrolyte medium is exposed to the solution.

Claims

1. An electrochemical ion sensor for sensing a presence of at least one ion species in a solution, the electrochemical sensor comprising, for each of said at least one ion species:

a) a solid-state electrolyte medium, doped with an organometallic material, the organometallic material having an electrochemical affinity with the ion species;

b) a pair of electrodes electrically contacting the solid-state electrolyte medium; and

c) an electrical circuit configured to drive the pair of electrodes with an AC electrical excitation and to measure at least one parameter related to a complex electrical impedance of said doped solid-state electrolyte medium in response to the AC electrical excitation, said at least one parameter being representative of the presence of the ion species in said solution when the solid-state electrolyte medium is exposed to the solution.

2. The electrochemical sensor according to claim 1, wherein the solid-state electrolyte medium comprises a polymer material, a glass material, a ceramic material, a semiconductor material or a combination thereof.

3. The electrochemical sensor according to claim 1, wherein the solid-state electrolyte medium further comprises at least one additive, the at least one additive comprising at least one of a cationic additive, an anionic additive, a plasticizer material, an elastomer material, a crown ether material, a carbon nanotube material or a silane material.

4. The electrochemical sensor according to claim 1, configured for sensing the presence of phosphate as one of said at least one ion species, the corresponding organometallic material consisting of phosphate-selective vanadyl salophen having VO(N₂O₂) coordination modes.

5. The electrochemical sensor according to claim 1, configured for sensing the presence of nitrate as one of said at least one ion species, the corresponding organometallic material consisting of one of:

a) a nitrate-selective tetramethyl cyclotetra-decanato-nickel(II) complex;

b) a nitrate-selective Bis(2-hydroxyanil)acetylacetone Lead(II) complex;

c) a nitrate-selective cobalt(II) metallo-salen complex;

d) a nitrate-selective chromium(III) metallo-salen complex; and

e) a nitrate-selective aluminum(III) metallo-salen complex.

6. The electrochemical sensor according to claim 5, wherein

a) the nitrate-selective tetramethyl cyclotetra-decanato-nickel(II) complex is (6,8,15,17-tetramethyl-7H,16H-5,9,14,18-tetraazidobenzo [b,i]-cyclotetra-decanato-(2-)-K4-N,N0,N00,N000) Ni(II);

b) the nitrate-selective cobalt(II) metallo-salen complex is (R,R)-(−

)-N,N-bis(3,5-di-tert-butylsalicylidene)-1,2-cyclohexanediaminocobalt(II);

c) the nitrate-selective chromium(III) metallo-salen complex is (R,R)-(−

)-N,N-bis(3,5-di-tert-butylsalicylidene)-1,2-cyclohexanediaminochromium(III) chloride; and

d) the nitrate-selective aluminum(III) metallo-salen complex is (R,R)-N,N-bis(3,5-di-tert-butyl-salicylidene)-1,2-cyclohexane diamino aluminum(III) chloride.

7. The electrochemical sensor according to claim 1, configured for sensing the presence of sulfate as one of said at least one ion species, the corresponding organometallic material consisting of a sulfate-selective Zinc(II)-2,2′

-[4,4′

-diphenylmethane bis(nitrilomethylidyne)]-bis(phenol) complex.

8. The electrochemical sensor according to claim 1, wherein the electrodes are buried within the solid-state electrolyte medium.

9. The electrochemical sensor according to claim 1, further comprising, for each of said at least one ion species, a substrate supporting the corresponding solid-state electrolyte medium and pair of electrodes.

10. The electrochemical sensor according to claim 9, wherein the substrate comprises an electrical patch cord having at last two electrical wires defining the pair of electrodes.

11. The electrochemical sensor according to claim 1, wherein, for each of said ion species, the electrical circuit comprises a load electrical component for measuring at least one parameter representative of the presence of the corresponding ion species, the load electrical component comprises at least one LCR electronic circuit, at least one electronic bridge circuit or a combination thereof.

12. The electrochemical sensor according to claim 1, wherein, for at least one of said ion species, at least one parameter representative of the presence of the corresponding ion species is a resistance, a reactance or a combination of the resistance and the reactance of the corresponding solid-state electrolyte medium in response to the AC electrical excitation.

13. A method for sensing a presence of an ion species in a solution, the method comprising the steps of:

a) exposing a solid-state electrolyte medium doped with an organometallic material to the solution, the organometallic material having an electrochemical affinity with the ion species;

b) driving a pair of electrodes electrically contacting the solid-state electrolyte medium with an AC electrical excitation; and

c) measuring at least one parameter related to a complex electrical impedance of said solid-state electrolyte medium in response to the AC electrical excitation, said at least one parameter being representative of the presence of the ion species in said solution when the solid-state electrolyte medium is exposed to the solution.

14. The method according to claim 13, wherein the ion species comprises one of nitrogen (N), phosphorus (P), potassium (K) and sulfur (S) atoms.

15. The method according to claim 13, wherein said ion species comprises

i) phosphate, and the organometallic material consists of phosphate-selective vanadyl salophen having VO(N₂O₂) coordination modes

ii) nitrate, and the organometallic material consists of one of a nitrate-selective tetramethyl cyclotetra-decanato-nickel(II) complex, a nitrate-selective Bis(2-hydroxyanil)acetylacetone Lead(II) complex, a nitrate-selective cobalt(II) metallo-salen complex;

a nitrate-selective chromium(III) metallo-salen complex, and a nitrate-selective aluminum(III) metallo-salen complex;

or

iii) sulfate, and the organometallic material consists of a sulfate-selective Zinc(II)-2,2′

-[4,4′

-diphenylmethane bis(nitrilomethylidyne)]-bis(phenol) complex.

16. The method according to claim 13, further comprising a step d) of determining a concentration of the ion species in the solution.

17. A sensing component for use in combination with an electrical circuit in an electrochemical ion sensor for sensing a presence of at least one an ion species in a solution, the sensing component comprising, for each of said at least one ion species:

i) a solid-state electrolyte medium, doped with an organometallic material, the organometallic material having an electrochemical affinity with the ion species;

ii) a pair of electrodes electrically contacting the solid-state electrolyte medium; and

iii) a connecting interface electrically connected to the pair of electrodes and detachably connectable to the electrical circuit;

whereby the pair of electrodes is drivable by the electrical circuit, when the connecting interface is connected thereto, with an AC electrical excitation to measure at least one parameter related to a complex electrical impedance of said doped solid-state electrolyte medium in response to the AC electrical excitation, said at least one parameter being representative of the presence of the ion species in said solution when the solid-state electrolyte medium is exposed to the solution.

18. The sensing component according to claim 17, wherein said ion species comprises

i) phosphate, and the organometallic material consists of phosphate-selective vanadyl salophen having VO(N₂O₂) coordination modes

ii) nitrate, and the organometallic material consists of one of a nitrate-selective tetramethyl cyclotetra-decanato-nickel(II) complex, a nitrate-selective Bis(2-hydroxyanil)acetylacetone Lead(II) complex, a nitrate-selective cobalt(II) metallo-salen complex;

a nitrate-selective chromium(III) metallo-salen complex, and a nitrate-selective aluminum(III) metallo-salen complex;

or

iii) sulfate, and the organometallic material consists of a sulfate-selective Zinc(II)-2,2′

-[4,4′

-diphenylmethane bis(nitrilomethylidyne)]-bis(phenol) complex.

19. The sensing component according to claim 17, further comprising, for each of said at least one ion species, a substrate supporting the corresponding solid-state electrolyte medium and pair of electrodes.