IP Library Granted Patent US 12,365,998
Granted Patent B2
US 12,365,998 · App. 17/356,203 · Granted Jul 22, 2025

Ion exchange membrane separated two electrode flow analyzer for continuous aqueous electrochemical heavy metal detection

Inventors: Tybur Quinton Casuse (Albuquerque, NM); Fernando Garzon (Santa Fe, NM); Jose Manuel Cerrato Corrales (Albuquerque, NM)
Assignee: UNM RAINFOREST INNOVATIONS
C25B11/081C25B9/23C25B11/032C25B11/065C25B13/00G01N27/304G01N27/333
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Quick Facts
Patent No.
US 12,365,998
App. No.
17/356,203
Granted
Jul 22, 2025
Kind
B2
Abstract

An ion exchange membrane separated two electrode flow analyzer for continuous aqueous electrochemical heavy metal detection is disclosed. The electrochemical cell includes a gas diffusion counter/reference electrode, a flooded flow through working electrode, and an ion exchange membrane that separates the gas diffusion counter/reference electrode and the flooded flow through working electrode. A method of continuous fluid analysis using a multi-electrode flow analyzer is also disclosed, including passing an aqueous sample through a first inlet flow area and into a working electrode of a multi-electrode flow analyzer, passing a gas mixture through a second inlet flow area and into a counter/reference electrode of the multi-electrode flow analyzer, depositing an analyte onto a surface of the working electrode, stripping the analyte from the surface of the working electrode by sweeping a range of a potential applied to the surface of the working electrode.

Claims (52)

1. An electrochemical cell for detecting heavy metals in water, comprising:

a gas diffusion counter/reference electrode;

a gas inlet in communication with the gas diffusion counter/reference electrode, wherein the gas inlet is connected to a hydrogen source that is external to the electrochemical cell;

a flooded flow through working electrode;

a water inlet in communication with the flooded flow through working electrode, wherein the water inlet is configured to be connected to a water source that is external to the electrochemical cell; and

an ion exchange membrane comprising a composition selected based on a heavy metal being detected and disposed to separate the gas diffusion counter/reference electrode and the flooded flow through working electrode; and

a flooded zone; and wherein:

the working electrode comprises a physically vapor deposited gold (Au) film, the working electrode configured to receive deposition of a heavy metal on a surface of the working electrode, and configured to remove the heavy metal from the surface of the working electrode; and

the flooded flow through working electrode is positioned in the flooded zone and separated from the gas diffusion counter/reference electrode by the ion exchange membrane, wherein the ion exchange membrane directly contacts both the flooded flow through working electrode and the gas diffusion counter/reference electrode.

2. The electrochemical cell of claim 1 , wherein the counter/reference electrode comprises a platinum (Pt) electrode.

3. The electrochemical cell of claim 1 , wherein the working electrode further comprises a hydrophilic surface.

4. The electrochemical cell of claim 1 , wherein the working electrode further comprises a porous carbon media.

5. The electrochemical cell of claim 1 , wherein the working electrode further comprises an internal serpentine fluidic pathway.

6. The electrochemical cell of claim 1 , wherein the ion exchange membrane comprises a cationic exchange membrane.

7. The electrochemical cell of claim 1 , wherein the ion exchange membrane comprises an anionic exchange membrane.

8. The electrochemical cell of claim 1 , wherein the ion exchange membrane comprises an exchange membrane designed for use in a pH range of from about 6 to about 9.

9. The electrochemical cell of claim 1 further comprising a single stack fuel cell casing that encases the counter/reference electrode, the working electrode, and the ion exchange membrane.

10. The electrochemical cell of claim 1 further comprising at least one inlet on a first side of the electrochemical cell, and at least one outlet on a second side of the electrochemical cell.

11. The electrochemical cell of claim 1 further comprising a first inlet and a first outlet on a first side of the electrochemical cell, and a second inlet and a second outlet on a second side of the electrochemical cell.

12. An array of two or more electrochemical cells for detecting heavy metals in water, comprising:

a first electrochemical cell comprising:

a first gas diffusion counter/reference electrode;

a first flooded flow through working electrode comprising a porous, hydrophilic media coated with a physically vapor deposited gold (Au) surface;

a first flooded zone; and

a first ion exchange membrane comprising a first ion exchange membrane composition selected based on a heavy metal being detected and disposed to separate the first gas diffusion counter/reference electrode and the first flooded flow through working electrode;

a second electrochemical cell comprising:

a second gas diffusion counter/reference electrode;

a second flooded flow through working electrode comprising a porous, hydrophilic media coated with a bismuth surface; and

a second ion exchange membrane comprising a second ion exchange membrane composition selected based on a heavy metal being detected that is disposed to separate the second gas diffusion counter/reference electrode and the second flooded flow through working electrode to form an anoxic environment around the gas diffusion counter/reference electrode;

a gas inlet in communication with the first gas diffusion counter/reference electrode and the second gas diffusion counter/reference electrode connected to a hydrogen source that is external to the electrochemical cell;

a water inlet in communication with the first flooded flow through working electrode and the second flooded flow through working electrode and configured to be connected to a water source that is external to the electrochemical cell;

a second flooded zone; and wherein:

each working electrode is configured to receive deposition of a heavy metal on a surface of the working electrode, and configured to remove the heavy metal from the surface of the working electrode;

the first flooded flow through working electrode is positioned in the first flooded zone and separated from the first gas diffusion counter/reference electrode by the first ion exchange membrane, wherein the first ion exchange membrane directly contacts both the first flooded flow through working electrode and the first gas diffusion counter/reference electrode; and

the second flooded flow through working electrode is positioned in the second flooded zone and separated from the second gas diffusion counter/reference electrode by the second ion exchange membrane, wherein the first ion exchange membrane directly contacts both the first flooded flow through working electrode and the first gas diffusion counter/reference electrode.

13. The array of two or more electrochemical cells of claim 12 , further comprising a single stack fuel cell casing that encases the first electrochemical cell and the second electrochemical cell.

14. The array of two or more electrochemical cells of claim 12 , wherein the first ion exchange membrane further comprises an anionic exchange membrane.

15. The array of two or more electrochemical cells of claim 12 , wherein the second ion exchange membrane further comprises a cationic exchange membrane.

16. The array of two or more electrochemical cells of claim 12 , wherein the first electrochemical cell and the second electrochemical cell are configured in series.

17. A method of continuous fluid analysis for heavy metals in water using a multi-electrode flow analyzer, comprising:

passing an aqueous sample through a first water inlet flow area and into a flooded flow working electrode of a multi-electrode flow analyzer;

passing a gas mixture through a second gas inlet flow area and into a gas diffusion counter/reference electrode of the multi-electrode flow analyzer;

depositing an analyte onto a surface of the working electrode, which comprises a physically vapor deposited gold (Au) film;

stripping the analyte from the surface of the working electrode by sweeping a range of a potential applied to the surface of the working electrode; and

determining a peak current over the range of the potential to determine a quantity of analyte deposited on the working electrode; and wherein:

the flooded flow through working electrode is positioned in a flooded zone and separated from the gas diffusion counter/reference electrode by an ion exchange membrane, the ion exchange membrane comprising a composition selected based on a heavy metal being detected and disposed to directly contact both the flooded flow through working electrode and the gas diffusion counter/reference electrode and separate the gas diffusion counter/reference electrode from the flooded flow through working electrode;

the water inlet is configured to be connected to a water source that is external to the multi-electrode flow analyzer; and

wherein the gas inlet is connected to a hydrogen source that is external to the multi-electrode flow analyzer.

18. The method of continuous fluid analysis using a multi-electrode flow analyzer of claim 17 , further comprising reducing any aqueous metal ions present on the surface of the working electrode prior to stripping the analyte from the surface of the working electrode.

19. The method of continuous fluid analysis using a multi-electrode flow analyzer of claim 17 , further comprising oxidizing any aqueous metal ions present on the surface of the working electrode prior to stripping the analyte from the surface of the working electrode.

20. The method of continuous fluid analysis using a multi-electrode flow analyzer of claim 17 , wherein depositing an analyte onto a surface of the working electrode further comprises holding the working electrode at a negative potential.

21. The method of continuous fluid analysis using a multi-electrode flow analyzer of claim 17 , wherein sweeping a range of a potential on the surface of the working electrode is from a positive value to a negative value.

Assignments (3)
CONFIRMATORY LICENSE Recorded Feb 26, 2025
From: UNIVERSITY OF NEW MEXICO
To: NATIONAL SCIENCE FOUNDATION
Reel/Frame 070336/0427 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Feb 2, 2022
From: GARZON, FERNANDO; CASUSE, TYBUR; CORRALES, JOSE
To: THE REGENTS OF THE UNIVERSITY OF NEW MEXICO
Reel/Frame 058866/0479 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Feb 2, 2022
From: THE REGENTS OF THE UNIVERSITY OF NEW MEXICO
To: UNM RAINFOREST INNOVATIONS
Reel/Frame 058866/0590 →
Continuity (2)
Provisional Application 63042921 · Jun 23, 2020
Related Publication 20210395910A1 · Dec 23, 2021
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