WO1992001219A1 - Ion-selective electrochemical sensor device - Google Patents
Ion-selective electrochemical sensor device Download PDFInfo
- Publication number
- WO1992001219A1 WO1992001219A1 PCT/NO1991/000099 NO9100099W WO9201219A1 WO 1992001219 A1 WO1992001219 A1 WO 1992001219A1 NO 9100099 W NO9100099 W NO 9100099W WO 9201219 A1 WO9201219 A1 WO 9201219A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- sensor device
- ion
- accordance
- water
- ions
- Prior art date
Links
- 150000002500 ions Chemical class 0.000 claims abstract description 15
- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 11
- 239000000758 substrate Substances 0.000 claims abstract description 8
- -1 nitrate ions Chemical class 0.000 claims abstract description 7
- 239000007787 solid Substances 0.000 claims abstract description 5
- 239000011248 coating agent Substances 0.000 claims abstract description 3
- 238000000576 coating method Methods 0.000 claims abstract description 3
- 229910052751 metal Inorganic materials 0.000 claims abstract 3
- 239000002184 metal Substances 0.000 claims abstract 3
- 229920000620 organic polymer Polymers 0.000 claims abstract 3
- 229920001746 electroactive polymer Polymers 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 4
- 239000002861 polymer material Substances 0.000 claims description 4
- QENGPZGAWFQWCZ-UHFFFAOYSA-N Methylthiophene Natural products CC=1C=CSC=1 QENGPZGAWFQWCZ-UHFFFAOYSA-N 0.000 claims description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 claims description 2
- 239000000956 alloy Substances 0.000 claims 1
- 229910045601 alloy Inorganic materials 0.000 claims 1
- 229910052697 platinum Inorganic materials 0.000 claims 1
- 239000007864 aqueous solution Substances 0.000 abstract description 4
- 229920000642 polymer Polymers 0.000 description 9
- 239000000243 solution Substances 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 4
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 4
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Inorganic materials [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 4
- 229910021607 Silver chloride Inorganic materials 0.000 description 3
- 238000012544 monitoring process Methods 0.000 description 3
- 230000035945 sensitivity Effects 0.000 description 3
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 3
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 239000012088 reference solution Substances 0.000 description 1
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
- G01N27/333—Ion-selective electrodes or membranes
Definitions
- the present invention concerns an ion-selective electro ⁇ chemical sensor device for analytical laboratory purposes, for process monitoring and for monitoring polluting discharges into the environment of special ions, particularly nitrate ions from industry and agriculture.
- Previously known commercial nitrate sensors are based on measurement of potentials over an ion-selective diaphragm with an internal reference solution and a reference electrode.
- the response time of commercial sensors is relatively long, and the precision is strongly influenced by interference from other ion types.
- the sensors must be calibrated at short intervals, and the service life is very limited.
- the purpose of the present invention is primarily to be able to detect and measure the concentration of nitrate ions in a aqueous solution containing other ions, in a fast and efficient manner, by means of a new type of nitrate sensor which can be regenerated and calibrated while in use.
- the main component of the present invention is an electro ⁇ active polymer material which is applied on an electronically conducting solid state substrate, e.g. of platinum metal.
- an electronically conducting solid state substrate e.g. of platinum metal.
- the electroactive polymer material is manufactured by a direct, electrochemical polymerization on the substrate.
- the polymer may first be provided by a chemical method, and subsequently be applied to the substrate.
- An example of an electroactive polymer which can be used as a coating on the substrate in order to provide a sensor device in accordance with the invention is poly-(3-methyl- thiophene) .
- the polymer electrode is included as an active (sensor) part of an electrochemical cell system.
- An adjustable voltage is applied to the cell, and the current through the electroactive polymer electrode is recorded.
- the current response at a certain potential, or the integrated charge which has passed through the polymer electrode, can be put in relation to the concentration of the particular ion it is desirable to detect in the solution.
- the sensitivity and specificity regarding one particular ion type can be adjusted by selecting the electroactive polymer material.
- the sensitivity can also be adjusted by adapting potential range and potential scan rate.
- fig. 1 shows a cyclic voltammogram for a polymer electrode in accordance with the invention
- fig. 2 shows the current response of the polymer electrode for different ion types
- fig. 3 shows the current response of a polymer electrode in accordance with the invention as a function of potential scan rate.
- fig. 1 shows curves recorded for a sensor device in accordance with the invention, with a poly-(3-methylthiophene) polymer electrode in aqueous solution of respectively 0.1 M KN0 3 and 0.1 M KCL.
- the current response of the electrode is substantially stronger than in the chloride solution in the potential range about 700 mV (versus an Ag/AgCl reference electrode) .
- Further experiments with sulfate and phosphate solutions result in current responses which are correspondingly weak as the chloride response.
- fig. 2 is shown (in a log-log diagram) the current response (current density) of the polymer electrode at 700 mV (versus an Ag/AgCl reference electrode) as a function of the concentration of some ion-types in an aqueous solution (respec ⁇ tively KCIO4, KNO 3 , KC1 and K2SO4) .
- the current response in the nitrate and perchlorate solutions shows a strong dependence of the ion concentrations, while sulfate and chloride merely exhibit a weak current response.
- Fig. 3 shows the influence of potential scan rate on the current response (current density) of the polymer electrode at 700 V potential (versus an Ag/AgCl reference electrode) , for pure 0.1 M solutions of KC10 4 , KN0 3 , KC1 and K 2 S0 . It appears that the response in chloride and sulfate solutions is little influenced by the scan rate, while the response in nitrate and perchlorate solutions on the contrary depends strongly on the scan rate. This implies that it is possible to increase the sensitivity to nitrate ions (and possibly perchlorate ions) in relation to chloride and sulfate ions by increasing the scan rate.
- the sensor device in accordance with the present invention exhibits clear advantages as to a strong response to nitrate ions, and little interference from other ion types.
- this electrode is also sensitive to perchlorate ions in water.
- the response time is short, and the sensor device can be regenerated and calibrated while in use.
- the measurement procedure can be automatized, and can operate in a completely automatic environment monitoring system.
- the active sensor material can be manufactured in a relatively simple manner, which makes reconditioning of the sensor device easy.
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Molecular Biology (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Investigating Or Analyzing Materials By The Use Of Fluid Adsorption Or Reactions (AREA)
- Measuring Oxygen Concentration In Cells (AREA)
Abstract
A sensor device for detecting a special ion type in an aqueous solution, particularly nitrate ions, consists of a coating of an electroactive organic polymer applied to an electronically conducting solid state substrate, preferably of a metal.
Description
ION-SELECTIVE ELECTROCHEMICAL SENSOR DEVICE
The present invention concerns an ion-selective electro¬ chemical sensor device for analytical laboratory purposes, for process monitoring and for monitoring polluting discharges into the environment of special ions, particularly nitrate ions from industry and agriculture.
Previously known commercial nitrate sensors are based on measurement of potentials over an ion-selective diaphragm with an internal reference solution and a reference electrode. The response time of commercial sensors is relatively long, and the precision is strongly influenced by interference from other ion types. The sensors must be calibrated at short intervals, and the service life is very limited.
The purpose of the present invention is primarily to be able to detect and measure the concentration of nitrate ions in a aqueous solution containing other ions, in a fast and efficient manner, by means of a new type of nitrate sensor which can be regenerated and calibrated while in use.
This purpose is achieved by putting into use a sensor device of the type appearing from the enclosed patent claims, which claims also indicate a manufacturing method for such a sensor device.
The main component of the present invention is an electro¬ active polymer material which is applied on an electronically conducting solid state substrate, e.g. of platinum metal. Preferably the electroactive polymer material is manufactured by a direct, electrochemical polymerization on the substrate. Alternatively, the polymer may first be provided by a chemical method, and subsequently be applied to the substrate.
An example of an electroactive polymer which can be used as a coating on the substrate in order to provide a sensor device in accordance with the invention, is poly-(3-methyl- thiophene) .
The polymer electrode is included as an active (sensor) part of an electrochemical cell system. An adjustable voltage is applied to the cell, and the current through the electroactive polymer electrode is recorded. The current response at a
certain potential, or the integrated charge which has passed through the polymer electrode, can be put in relation to the concentration of the particular ion it is desirable to detect in the solution.
The sensitivity and specificity regarding one particular ion type can be adjusted by selecting the electroactive polymer material. The sensitivity can also be adjusted by adapting potential range and potential scan rate.
In order to illuminate the invention further, it is now referred to the enclosed drawing figures, where fig. 1 shows a cyclic voltammogram for a polymer electrode in accordance with the invention, fig. 2 shows the current response of the polymer electrode for different ion types, and fig. 3 shows the current response of a polymer electrode in accordance with the invention as a function of potential scan rate.
It is first referred to fig. 1 which shows curves recorded for a sensor device in accordance with the invention, with a poly-(3-methylthiophene) polymer electrode in aqueous solution of respectively 0.1 M KN03 and 0.1 M KCL. As appears from the cyclic voltammogram in the drawing, the current response of the electrode is substantially stronger than in the chloride solution in the potential range about 700 mV (versus an Ag/AgCl reference electrode) . Further experiments with sulfate and phosphate solutions result in current responses which are correspondingly weak as the chloride response.
In fig. 2 is shown (in a log-log diagram) the current response (current density) of the polymer electrode at 700 mV (versus an Ag/AgCl reference electrode) as a function of the concentration of some ion-types in an aqueous solution (respec¬ tively KCIO4, KNO3, KC1 and K2SO4) . The current response in the nitrate and perchlorate solutions shows a strong dependence of the ion concentrations, while sulfate and chloride merely exhibit a weak current response.
Fig. 3 shows the influence of potential scan rate on the current response (current density) of the polymer electrode at 700 V potential (versus an Ag/AgCl reference electrode) , for
pure 0.1 M solutions of KC104 , KN03 , KC1 and K2S0 . It appears that the response in chloride and sulfate solutions is little influenced by the scan rate, while the response in nitrate and perchlorate solutions on the contrary depends strongly on the scan rate. This implies that it is possible to increase the sensitivity to nitrate ions (and possibly perchlorate ions) in relation to chloride and sulfate ions by increasing the scan rate.
The sensor device in accordance with the present invention exhibits clear advantages as to a strong response to nitrate ions, and little interference from other ion types. However, this electrode is also sensitive to perchlorate ions in water. The response time is short, and the sensor device can be regenerated and calibrated while in use. The measurement procedure can be automatized, and can operate in a completely automatic environment monitoring system. The active sensor material can be manufactured in a relatively simple manner, which makes reconditioning of the sensor device easy.
Claims
1. Ion-selective electrochemical sensor device for detecting ions of a special type in water, particularly nitrate ions in water, c h a r a c t e r i z e d i n that it comprises an electrode coating consisting of an electroactive organic polymer applied on an electronically conducting solid state substrate.
2. Sensor device in accordance with claim 1, c h a r a c t e r i z e d i n that said solid state substrate comprises a metal or an alloy.
3. Sensor device in accordance with claim 1, c h a r a c t e r i z e d i n that said metal is platinum.
4. Sensor device in accordance with claim 1, 2 or 3, c h a r a c t e r i z e d i n that said organic polymer is constituted by poly-(3-methylthiophene) .
5. A method for manufacturing an ion-selective electrochemical sensor device for detecting ions of a special type in water, particularly nitrate ions in water, c h a r a c t e r i z e d i n that an electroactive polymer material is deposited by direct electrochemical polymerization on an electronically conducting solid state substrate.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| NO903011 | 1990-07-05 | ||
| NO90903011A NO903011L (en) | 1990-07-05 | 1990-07-05 | ELECTROCHEMICAL ION SELECTIVE SENSOR. |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO1992001219A1 true WO1992001219A1 (en) | 1992-01-23 |
Family
ID=19893329
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/NO1991/000099 WO1992001219A1 (en) | 1990-07-05 | 1991-07-04 | Ion-selective electrochemical sensor device |
Country Status (3)
| Country | Link |
|---|---|
| AU (1) | AU8008191A (en) |
| NO (1) | NO903011L (en) |
| WO (1) | WO1992001219A1 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5584979A (en) * | 1994-05-27 | 1996-12-17 | Kone Instruments Oy | Ion-selective electrode and procedure for producing an ion-selective electrode |
| US5700922A (en) * | 1991-12-24 | 1997-12-23 | Isis Pharmaceuticals, Inc. | PNA-DNA-PNA chimeric macromolecules |
| WO1999045376A1 (en) * | 1998-03-03 | 1999-09-10 | Unisense Aps | Method for regulating the sensitivity of a microsensor, and a microsensor that makes use of this method |
| US9281219B2 (en) | 2013-09-18 | 2016-03-08 | Suprasensor Technologies, Llc | Molecular receptor-based chemical field-effect transistor (CHEMFET) devices, systems, and methods for in-situ nitrate monitoring in field soils |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08505476A (en) * | 1993-03-05 | 1996-06-11 | ユニヴァーシティー オブ ウーロンゴング | Pulsed electrochemical detection method using electroactive polymer electrode |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1989007262A1 (en) * | 1988-01-29 | 1989-08-10 | Terumo Kabushiki Kaisha | Film-coated sensor |
-
1990
- 1990-07-05 NO NO90903011A patent/NO903011L/en unknown
-
1991
- 1991-07-04 AU AU80081/91A patent/AU8008191A/en not_active Abandoned
- 1991-07-04 WO PCT/NO1991/000099 patent/WO1992001219A1/en unknown
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1989007262A1 (en) * | 1988-01-29 | 1989-08-10 | Terumo Kabushiki Kaisha | Film-coated sensor |
Non-Patent Citations (2)
| Title |
|---|
| DERWENT'S ABSTRACT No. 633 38 E/30; & SU,A,868 527, publ. week 8230. * |
| ELECTROANALYSIS, Vol. 2, 1990, HANS ZIMMER et al., "Conductivity Monitoring by an Amperometric Detector with a Cu(II)-Containing Poly(3-methylthiophene) Electrode", see page 1 - page 2. * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5700922A (en) * | 1991-12-24 | 1997-12-23 | Isis Pharmaceuticals, Inc. | PNA-DNA-PNA chimeric macromolecules |
| US5584979A (en) * | 1994-05-27 | 1996-12-17 | Kone Instruments Oy | Ion-selective electrode and procedure for producing an ion-selective electrode |
| EP0684466A3 (en) * | 1994-05-27 | 1998-06-10 | KONE Instruments Oy | Ion-selective electrode and procedure for producing an ion-selective electrode |
| WO1999045376A1 (en) * | 1998-03-03 | 1999-09-10 | Unisense Aps | Method for regulating the sensitivity of a microsensor, and a microsensor that makes use of this method |
| US9281219B2 (en) | 2013-09-18 | 2016-03-08 | Suprasensor Technologies, Llc | Molecular receptor-based chemical field-effect transistor (CHEMFET) devices, systems, and methods for in-situ nitrate monitoring in field soils |
| US9535031B2 (en) | 2013-09-18 | 2017-01-03 | Suprasensor Technologies, Llc | Molecular receptor-based chemical field-effect transistor (CHEMFET) devices, systems, and methods for in-situ nitrate monitoring in field soils |
Also Published As
| Publication number | Publication date |
|---|---|
| AU8008191A (en) | 1992-02-04 |
| NO903011L (en) | 1992-01-06 |
| NO903011D0 (en) | 1990-07-05 |
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