CN109270146B - Electrochemical chlorine sensor - Google Patents

Electrochemical chlorine sensor Download PDF

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CN109270146B
CN109270146B CN201811145538.6A CN201811145538A CN109270146B CN 109270146 B CN109270146 B CN 109270146B CN 201811145538 A CN201811145538 A CN 201811145538A CN 109270146 B CN109270146 B CN 109270146B
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electrode
chlorine
working electrode
electrolyte
counter electrode
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CN109270146A (en
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陈震
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Jingzhou Aeritech Co ltd
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Jingzhou Aeritech Co ltd
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    • 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
    • G01N27/403—Cells and electrode assemblies
    • G01N27/404—Cells with anode, cathode and cell electrolyte on the same side of a permeable membrane which separates them from the sample fluid, e.g. Clark-type oxygen sensors
    • G01N27/4045—Cells with anode, cathode and cell electrolyte on the same side of a permeable membrane which separates them from the sample fluid, e.g. Clark-type oxygen sensors for gases other than oxygen

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Abstract

The invention relates to an electrochemical chlorine sensor, which comprises a shell, an electrolyte, a working electrode, a reference electrode and a counter electrode, wherein the working electrode, the reference electrode and the counter electrode form ion conduction in the electrolyte, the working electrode, the reference electrode and the counter electrode respectively comprise an electrode film and a mixture attached to the electrode film, and the mixture comprises a catalyst and fluoropolymer particles. The technical scheme provided by the invention can quickly and accurately measure the concentration of the chlorine.

Description

Electrochemical chlorine sensor
Technical Field
The invention relates to the technical field of sensors, in particular to an electrochemical chlorine sensor.
Background
Chlorine gas is used in industry to produce various chlorides such as plastics, synthetic fibers, dyes, pesticides, disinfectants, bleaches, etc. because it can react with organic and inorganic substances to produce various chlorides. At the same time, chlorine gas is toxic and, in the event of leakage, can invade the body through the respiratory tract and dissolve in the water contained in the mucosa, causing damage to the mucosa of the upper respiratory tract. At present, in order to monitor the concentration of chlorine in real time and judge whether chlorine leakage occurs or not, a methyl orange spectrophotometry is commonly used for detecting the chlorine in the prior art, bromine in potassium bromide is replaced by the chlorine in an acid solution, the bromine destroys a molecular structure of the methyl orange to enable the methyl orange to fade, and then the content of the chlorine is determined by measuring the fading degree of the methyl orange by using the spectrophotometry.
Disclosure of Invention
In order to accurately and quickly measure the concentration of chlorine, the invention provides an electrochemical chlorine sensor.
The technical scheme for solving the technical problems is as follows: an electrochemical chlorine sensor comprising a housing, an electrolyte, and a working electrode, a reference electrode, and a counter electrode that form ionic communication in the electrolyte, the working electrode, the reference electrode, and the counter electrode each comprising an electrode film and a mixture attached to the electrode film, the mixture comprising a catalyst and fluoropolymer particles.
The invention has the beneficial effects that: when the electrochemical chlorine sensor measures the concentration of chlorine, the electrochemical chlorine sensor is connected with an external circuit, the input of the external circuit is respectively connected with a working electrode, a reference electrode and a counter electrode, a catalyst on the working electrode catalyzes chlorine to generate a reduction reaction on the surface of the working electrode, a catalyst on the counter electrode catalyzes an oxidation reaction on the surface of the counter electrode, the reduction reaction on the surface of the working electrode and the oxidation reaction on the surface of the counter electrode can generate current in the external circuit, the intensity of the current is in direct proportion to the concentration of the chlorine, and the real-time concentration value of the chlorine can be obtained by measuring and processing the current in the external circuit. The electrochemical chlorine sensor has the advantages of high response speed, high sensitivity and accurate measurement result. The reference electrode does not participate in the oxidation-reduction reaction, the potential is kept constant, the potential of the working electrode is used for working in a correct area, the sensitivity of the sensor can be kept, the sensor has good linearity, and the interference of interference gas is reduced. The electrode membrane is used for bearing the mixture and can allow chlorine molecules to pass through, so that the chlorine is fully contacted with the catalyst on the working electrode, and the chlorine is fully reacted. The fluoride particles have a porous structure, have hydrophobic and air-permeable functions and can promote the oxidation-reduction reaction.
On the basis of the technical scheme, the invention can be further improved as follows:
further: the electrode film is a polytetrafluoroethylene film.
Further: the catalyst on the working electrode and the reference electrode comprises carbon.
Further: the fluoropolymer particles on the working electrode and the reference electrode are polytetrafluoroethylene particles or perfluorosulfonic acid resin.
Further: the catalyst on the counter electrode comprises a noble metal nanomaterial.
Further: the noble metal nanomaterial includes at least one of a platinum nanomaterial, a ruthenium nanomaterial, and a rhodium nanomaterial.
Further: the fluoropolymer particles on the counter electrode comprise polytetrafluoroethylene particles.
Further: the electrolyte is sulfuric acid solution or phosphoric acid solution.
Further: the concentration of the sulfuric acid solution is 4-10mol/L.
Further: the mass ratio of the catalyst to the fluoropolymer particles is 1:1 to 10:1.
drawings
FIG. 1 is a cross-sectional view of an electrochemical chlorine sensor in accordance with an embodiment of the present invention;
FIG. 2 is an external circuit diagram of an electrochemical chlorine sensor in accordance with an embodiment of the present invention;
FIG. 3 is a chlorine response graph of an electrochemical chlorine sensor in accordance with an embodiment of the present invention.
In the drawings, the components represented by the respective reference numerals are listed below:
1. the liquid absorbing device comprises a shell, 2, a working electrode, 3, a reference electrode, 4, a counter electrode, 5, a liquid storage tank, 6, pins, 7, electrolyte, 8, a liquid absorbing material strip, 9, a first liquid absorbing material layer, 10, a second liquid absorbing material layer, 11, a third liquid absorbing material layer, 12 and an O-shaped sealing ring.
Detailed Description
The principles and features of this invention are described below in conjunction with the following drawings, which are set forth by way of illustration only and are not intended to limit the scope of the invention.
As shown in fig. 1, the electrochemical chlorine sensor according to an embodiment of the present invention includes a casing 1, an electrolyte 7, and a working electrode 2, a reference electrode 3, and a counter electrode 4 that form ionic conduction in the electrolyte 7, a vent is disposed at the top of the casing 1, a liquid storage tank 5 is disposed in the casing 1, the electrolyte 7 is stored in the liquid storage tank 5, and the counter electrode 4, the reference electrode 3, and the working electrode 2 are sequentially disposed above the liquid storage tank 5 from bottom to top.
A first liquid absorbing material layer 9 is arranged between the counter electrode 4 and the liquid storage tank 5, a second liquid absorbing material layer 10 is arranged between the counter electrode 4 and the reference electrode 3, a third liquid absorbing material layer 11 is arranged between the reference electrode 3 and the working electrode 2, and the first liquid absorbing material layer 9, the counter electrode 4, the second liquid absorbing material layer 10, the reference electrode 3, the third liquid absorbing material layer 11 and the working electrode 2 are sequentially pressed on the liquid storage tank 5 from bottom to top. The counter electrode 4 is of an annular structure, the middle part of the first liquid absorbing material layer 9 is in contact with the middle part of the second liquid absorbing material layer 10, the edge of the second liquid absorbing material layer 10 is in contact with the edge of the third liquid absorbing material layer 11, and the first liquid absorbing material is connected with the electrolyte 7 in the liquid storage tank 5 through the liquid absorbing material strip 8. Each of the wicking material layers has stored therein an electrolyte 7, the wicking material layers are in contact to allow capillary transport of the electrolyte 7, the electrolyte 7 provides ionic electrical contact between the electrodes, and when the electrolyte 7 content in each of the wicking material layers is insufficient, the electrolyte 7 in the reservoir 5 can be transported to each of the wicking material layers by the wicking material strip 8, the electrolyte 7 content in each of the wicking material layers is maintained, ionic conduction between the electrodes is ensured, and flow of the electrolyte 7, even leakage, is avoided.
An O-shaped sealing ring 12 is arranged between the upper surface of the working electrode 2 and the inner wall of the shell 1, the O-shaped sealing ring 12 enables chlorine to be in direct contact with the working electrode 2 only, reduction reaction occurs on the surface of the working electrode 2, and meanwhile, the chlorine is prevented from reacting with other electrodes or electrolyte 7 to influence a measurement result. The bottom of the shell 1 is provided with three pins 6, and the three pins 6 are respectively connected with the counter electrode 4, the reference electrode 3 and the working electrode 2. The first liquid-absorbent material layer 9, the second liquid-absorbent material layer 10, the third liquid-absorbent material layer 11 and the absorbent material strips 8 are of glass fiber material.
The electrochemical chlorine sensor comprises a shell 1, an electrolyte 7, a working electrode 2, a reference electrode 3 and a counter electrode 4, wherein the working electrode 2, the reference electrode 3 and the counter electrode 4 form ion conduction in the electrolyte 7, the working electrode 2, the reference electrode 3 and the counter electrode 4 respectively comprise an electrode film and a mixture attached to the electrode film, and the mixture comprises a catalyst and fluoropolymer particles.
In this embodiment, when the electrochemical chlorine sensor measures the concentration of chlorine, the electrochemical chlorine sensor is connected to an external circuit, an input of the external circuit is respectively connected to the working electrode 2, the reference electrode 3 and the counter electrode 4, the catalyst on the working electrode 2 catalyzes chlorine to perform a reduction reaction on the surface of the working electrode 2, the catalyst on the counter electrode 4 catalyzes an oxidation reaction on the surface of the counter electrode 4, the reduction reaction on the surface of the working electrode 2 and the oxidation reaction on the surface of the counter electrode 4 generate current in the external circuit, the intensity of the current is proportional to the concentration of chlorine, and the real-time concentration value of chlorine can be obtained by measuring and processing the current in the external circuit. The electrochemical chlorine sensor has the advantages of high response speed, high sensitivity and accurate measurement result. The reference electrode 3 does not participate in the oxidation-reduction reaction, the potential is kept constant, the potential of the working electrode 2 is used for working in a correct area, the sensitivity of the sensor can be kept, the sensor has good linearity, and the interference of interference gas is reduced. The electrode film is used for bearing the mixture and can allow chlorine molecules to pass through, so that the chlorine is fully contacted with the catalyst on the working electrode 2, and the chlorine is fully reacted. The fluoride particles have a porous structure, have hydrophobic and air-permeable functions, and can promote the oxidation-reduction reaction.
Preferably, the electrode film is a polytetrafluoroethylene film.
Preferably, the catalyst on the working electrode 2 and the reference electrode 3 comprises carbon.
Preferably, the fluoropolymer particles on the working electrode 2 and the reference electrode 3 are polytetrafluoroethylene particles or perfluorosulfonic acid resin.
Preferably, the catalyst on the counter electrode 4 comprises a noble metal nanomaterial.
Preferably, the noble metal nanomaterial comprises at least one of a platinum nanomaterial, a ruthenium nanomaterial, and a rhodium nanomaterial.
Preferably, the fluoropolymer particles on the counter electrode 4 comprise polytetrafluoroethylene particles.
Preferably, the electrolyte 7 is a sulfuric acid solution or a phosphoric acid solution.
Preferably, the concentration of the sulfuric acid solution is 4-10mol/L.
Preferably, the mass ratio of the catalyst to the fluoropolymer particles is 1:1 to 10:1.
specifically, the reaction principle on the working electrode 2 and the counter electrode 4 is as follows:
working electrode 2: cl2+2H++2e-→2HCl
The counter electrode 4:2H2O→O2+4H++4e-
And (3) total reaction: 2Cl2+2H2O→4HCl+O2
Chlorine gas is subjected to reduction reaction on the surface of the working electrode 2, electrons obtained from the chlorine gas are reduced into hydrochloric acid, water is reduced into oxygen gas on the counter electrode 4 for balancing the reaction of the working electrode 2, certain ions and electrons are generated at the same time, the ions reach the working electrode 2 through the electrolyte 7, the electrons reach the working electrode 2 through an external circuit, the number of the electrons generated by the reaction is in direct proportion to the concentration of the chlorine gas, and the concentration value of the chlorine gas can be obtained by measuring and processing the current of the external circuit.
As shown in fig. 2, in the present embodiment, an external circuit is provided in which a working electrode 2, a reference electrode 3, and a counter electrode 4 are connected to terminals W, R, and C in fig. 2, respectively. RFAs a load resistance, when RFWhen the value of (c) is small, noise is increased, but response is fast; when R isFWhen the value of (a) is large, noise is reduced, but the response is slow. C1And C2The signal noise and electromagnetic interference of the sensor can be reduced.
The electrochemical chlorine sensor of the present invention is first placed in the air for one minute and then the chlorine is introduced for four minutes, and the response current curve finally obtained is shown in fig. 3, wherein the direction of the generated response current is a negative direction.
Example 1, method for preparing working electrode 2 and reference electrode 3: mixing the components in a mass ratio of 1:1 with polytetrafluoroethylene particles or perfluorosulfonic acid resin to obtain a mixture, and rolling, spraying or printing the mixture on an electrode film to obtain a working electrode 2 and a reference electrode 3, wherein the electrode film can adopt a polytetrafluoroethylene film.
Example 2, preparation method of counter electrode 4: mixing the components in a mass ratio of 10:1, mixing the noble metal nano material with polytetrafluoroethylene particles to obtain a mixture, rolling, spraying or printing the mixture on an electrode film, wherein the noble metal nano material comprises at least one of a platinum nano material, a ruthenium nano material and a rhodium nano material, and the electrode film can adopt a polytetrafluoroethylene film.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.

Claims (1)

1. An electrochemical chlorine sensor comprising a housing, an electrolyte, and a working electrode, a reference electrode, and a counter electrode that form ionic communication in the electrolyte, wherein the working electrode, the reference electrode, and the counter electrode each comprise an electrode film and a mixture attached to the electrode film, the mixture comprising a catalyst and fluoropolymer particles;
the catalyst on the working electrode and the reference electrode is carbon;
the catalyst on the counter electrode is a platinum nano material;
the fluoropolymer particles on the working electrode and the reference electrode are polytetrafluoroethylene particles or perfluorosulfonic acid resin; the fluoropolymer particles on the counter electrode comprise polytetrafluoroethylene particles;
the electrolyte is a sulfuric acid solution or a phosphoric acid solution;
the mass ratio of the catalyst to the fluoropolymer particles is 1:1 to 10:1.
CN201811145538.6A 2018-09-29 2018-09-29 Electrochemical chlorine sensor Active CN109270146B (en)

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CN102200525B (en) * 2010-03-25 2014-02-26 华瑞科学仪器(上海)有限公司 Chlorine dioxide measurement component and method, and gas sensor with component
CN103926277B (en) * 2013-01-11 2017-02-15 深圳市深安旭传感技术有限公司 Carbon monoxide sensor and carbon monoxide sensor electrode production method
CN103217464B (en) * 2013-03-22 2016-03-23 无锡高顿传感技术有限公司 A kind of gas sensor

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