CN112763555A - Multi-target heavy metal microfluidic electrochemical sensor and preparation and application thereof - Google Patents
Multi-target heavy metal microfluidic electrochemical sensor and preparation and application thereof Download PDFInfo
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- 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
- G01N27/308—Electrodes, e.g. test electrodes; Half-cells at least partially made of carbon
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- B01L3/00—Containers or dishes for laboratory use, e.g. laboratory glassware; Droppers
- B01L3/50—Containers for the purpose of retaining a material to be analysed, e.g. test tubes
- B01L3/502—Containers for the purpose of retaining a material to be analysed, e.g. test tubes with fluid transport, e.g. in multi-compartment structures
- B01L3/5027—Containers for the purpose of retaining a material to be analysed, e.g. test tubes with fluid transport, e.g. in multi-compartment structures by integrated microfluidic structures, i.e. dimensions of channels and chambers are such that surface tension forces are important, e.g. lab-on-a-chip
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- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
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- C25D3/48—Electroplating: Baths therefor from solutions of gold
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- G—PHYSICS
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- 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
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- G01N27/48—Systems using polarography, i.e. measuring changes in current under a slowly-varying voltage
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- G—PHYSICS
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- B01L2200/00—Solutions for specific problems relating to chemical or physical laboratory apparatus
- B01L2200/02—Adapting objects or devices to another
- B01L2200/026—Fluid interfacing between devices or objects, e.g. connectors, inlet details
- B01L2200/027—Fluid interfacing between devices or objects, e.g. connectors, inlet details for microfluidic devices
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01L—CHEMICAL OR PHYSICAL LABORATORY APPARATUS FOR GENERAL USE
- B01L2200/00—Solutions for specific problems relating to chemical or physical laboratory apparatus
- B01L2200/10—Integrating sample preparation and analysis in single entity, e.g. lab-on-a-chip concept
Abstract
The invention provides a multi-target heavy metal microfluidic electrochemical sensor and preparation and application thereof, wherein the sensor comprises a screen printing electrode and a microfluidic chip, and the screen printing electrode comprises a substrate, a working electrode, a counter electrode, a reference electrode and an insulating layer; the working electrode, the counter electrode and the reference electrode are arranged on the substrate, and the insulating layer is arranged above the working electrode, the counter electrode and the reference electrode; the working electrode is a carbon electrode, the counter electrode is a carbon electrode, the reference electrode is a silver and silver chloride electrode, and the insulating layer is an insulating ink layer; the surface of the working electrode is provided with gold nanoparticle electrode modification and bismuth membrane electrode modification; the microfluidic chip and the screen printing electrode are bonded and packaged into a whole. According to the invention, the microfluidic electrochemical sensor is rapidly constructed, so that ultra-high-sensitivity multi-target synchronous rapid detection of heavy metal lead and cadmium ions can be realized, and the detection sensitivity is highest; has the advantages of low manufacturing cost, high sensitivity, good reproducibility and the like.
Description
Technical Field
The invention relates to the field of heavy metal detection, in particular to a multi-target heavy metal microfluidic electrochemical sensor and preparation and application thereof.
Background
With the large-scale development of the industry and the breeding industry, the pollution of heavy metals is increasingly aggravated, serious harm is caused to the environment and human bodies, and various serious diseases are induced, so that how to develop a method for quickly detecting the heavy metals such as lead, mercury, cadmium and the like in the environment has very important significance.
At present, the main methods for detecting heavy metals in the environment comprise atomic absorption spectrometry, fluorescence spectrometry, plasma mass spectrometry, spectrophotometry, chemiluminescence and the like, but the methods have the disadvantages of large required instrument, high price, complex sample treatment and time consumption. The electrochemical method has the advantages of simple and convenient operation, high sensitivity, quick response, less cost and the like, and draws wide attention. The square wave stripping voltammetry is developed based on a suspended mercury polarography, a mercury film is used as a working electrode to detect the contents of heavy metals such as lead and cadmium, however, mercury has high toxicity and great harm to human bodies and test environment. At present, heavy metal detection is mainly carried out by using a disc electrode, a columnar microelectrode and the like, and then re-modification is needed, so that the repeatability is poor.
Through retrieval, the chinese patent with application number 201910237188.4 discloses a three-electrode system, an electrochemical sensor and a preparation method thereof, an electrochemical workstation and an application thereof, wherein the three-electrode system comprises a working electrode, a conductive layer on the surface of a conductive area of the working electrode, a reference electrode, a conductive layer on the surface of a conductive area of the reference electrode, a counter electrode and a conductive layer on the surface of a conductive area of the counter electrode; the conductive layer is a mixture of carbon paste ink and silver paste ink. The three-electrode system has better sensitivity and sensing effect and good responsiveness to current change by printing the mixed slurry layer of carbon slurry ink and silver slurry ink on the surface of the conductive area of the three electrodes; the electrochemical workstation comprises an electrochemical analysis system and a sensor, the sensor comprises a substrate, and an insulating layer and a contact reaction layer which are arranged on the substrate, the contact reaction layer is the three-electrode system, and the electrochemical workstation can be used for detecting the content of lead ions and cadmium ions in food by converting an electric signal into an optical signal. However, the sensitivity of the detection of heavy metal ions in the above patent is not high, and the detection can only reach 50ppb level generally.
Through search and discovery, the Chinese patent with the application number of 201910573506.4 discloses a preparation method of a cadmium ion electrochemical sensor, and the structure of the sensor consists of an electrochemical workstation, an electrolytic cell and electrodes. The electrodes include a silver/silver chloride reference electrode, a platinum wire counter electrode and a working electrode. The working electrode is a glassy carbon electrode modified by a bismuth film and sodium carboxymethyl cellulose. The electrochemical sensor can realize the sensitivity detection of trace heavy metal cadmium ions and can be used for detecting the heavy metal cadmium ions of an actual water sample. However, the above patents have the following disadvantages: the electrochemical sensor can only detect single-target heavy metal, and cannot detect a plurality of heavy metals. In addition, the platinum wire is used as the counter electrode, and the cost of the electrode sensor is high.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a multi-target heavy metal microfluidic electrochemical sensor and preparation and application thereof.
According to a first aspect of the invention, a multi-target heavy metal microfluidic electrochemical sensor is provided, which comprises a screen printing electrode and a microfluidic chip, wherein the screen printing electrode comprises a substrate, a working electrode, a counter electrode, a reference electrode and an insulating layer; wherein the content of the first and second substances,
the working electrode, the counter electrode and the reference electrode are disposed on the substrate, and the insulating layer is disposed over the working electrode, the counter electrode and the reference electrode;
the working electrode is a carbon electrode, the counter electrode is a carbon electrode, the reference electrode is a silver and silver chloride electrode, and the insulating layer is an insulating ink layer;
gold nanoparticles and a bismuth film are arranged on the surface of the working electrode, and after modification, the gold nanoparticles are distributed on the surface of the working electrode, and the bismuth film is distributed on the gold nanoparticles;
the lower surface of the microfluidic chip and the upper surface of the screen printing electrode are bonded and packaged into a whole.
Preferably, the substrate is a PP synthetic paper or a polyester film.
Preferably, the working electrode, the counter electrode and the reference electrode are respectively led out through carbon.
According to a second aspect of the present invention, there is provided a method for preparing a multi-target heavy metal microfluidic electrochemical sensor, comprising:
respectively printing conductive carbon paste, silver and silver chloride paste and insulating ink on a substrate through a printing screen, drying, obtaining a working electrode, a counter electrode and a reference electrode on the substrate to obtain a full-page screen printing electrode slice, and cutting the full-page screen printing electrode slice to obtain a single screen printing electrode;
respectively carrying out gold nanoparticle electrode modification and bismuth membrane electrode modification on the electrode surface of the screen printing electrode, and depositing a layer of gold nanoparticles on the surface of the working electrode through electrodeposition to obtain electrode modification of the gold nanoparticles; preparing a bismuth film on the gold nanoparticles by an in-situ bismuth plating method to obtain electrode modification of the bismuth film;
and bonding and packaging the lower surface of the microfluidic chip and the upper surface of the screen printing electrode into a whole to obtain the microfluidic electrochemical sensor.
Preferably, the pattern of the printing screen is designed by AutoCAD drawing software, and the aperture size of the printing screen is 100-200 meshes.
Preferably, a layer of gold nanoparticles is deposited on the surface of the working electrode by electrodeposition, which means that the gold nanoparticles are obtained by applying alternating oxidation potentials +1-2V, 40-60s and reduction potentials-0.2-0.5V, 1-5s in 2-5mM chloroauric acid, and the times of oxidation and reduction are 5-10 times.
Preferably, the electrode modification of the bismuth film is prepared on the working electrode by an orthotopic bismuth plating method, which means that 100-.
Preferably, the microfluidic chip is designed by AutoCAD, CroelDRAW or Photoshop drawing software; the micro-fluidic chip is prepared by adopting PMMA organic glass as a chip substrate and printing and outputting the PMMA organic glass by a laser engraving cutting machine.
According to the third aspect of the invention, a method for detecting heavy metal lead and cadmium ions in a water sample by using a multi-target heavy metal microfluidic electrochemical sensor is provided, an electrochemical anodic stripping voltammetry method is adopted, the potential is 8-10mV, the amplitude is 50-80mV, and the frequency is 20-30 Hz, a water quality sample of heavy metal ions to be detected is injected into the microfluidic electrochemical sensor through an injection pump at the flow rate of 50-200ul/min, the sample to be detected is continuously enriched, and finally, the measurement is carried out, so that the synchronous detection of the lead and cadmium multi-target heavy metal ions in the water sample is realized, and the detection limit reaches the level of 2 ppb.
Compared with the prior art, the invention has at least one of the following beneficial effects:
in the structure, the micro-fluidic electrochemistry is adopted to detect the heavy metal ions, and the surface of the gold nanoparticles is modified, namely a layer of colloidal gold is modified through electrochemical deposition, so that the specific surface area of the electrode can be further improved, the electron transfer is accelerated, and the detection sensitivity of the heavy metal ions is improved; meanwhile, an environment-friendly bismuth film is adopted to replace a mercury film, and bismuth ions and heavy metal ions are co-deposited on the surface of the electrode, so that the detection sensitivity is improved; meanwhile, the micro-fluidic chip is constructed on the screen printing electrode, so that continuous and stable enrichment of a sample to be detected is realized, and the detection sensitivity is further improved.
In the structure, the PP synthetic paper is adopted on the printing substrate, so that the electrode cost is further reduced, the electrode can be thrown as soon as needed, the price is low, and batch preparation is realized; the chip is directly printed by a laser engraving and cutting integrated machine, the microfluidic electrochemical sensor is quickly constructed, and the microfluidic electrochemical sensor has high sensitivity and good reproducibility.
The method is applied to the synchronous and rapid detection of heavy metal ions such as lead, cadmium and the like in the environment; the advantages of gold nanoparticle electrode modification, an in-situ bismuth plating film method and microfluidic chip enrichment are realized through a screen printing electrode, and ultra-high-sensitivity rapid synchronous detection of heavy metal ions is realized.
Drawings
Other features, objects and advantages of the invention will become more apparent upon reading of the detailed description of non-limiting embodiments with reference to the following drawings:
FIG. 1a is a schematic structural diagram of a microfluidic electrochemical sensor according to a preferred embodiment of the present invention;
FIG. 1b is a schematic diagram of a screen printed electrode according to a preferred embodiment of the present invention;
FIG. 1c is a schematic structural diagram of a microfluidic chip according to a preferred embodiment of the present invention;
FIG. 2 is a diagram illustrating the detection results of cadmium ions and lead ions in a water sample according to a preferred embodiment of the present invention;
the scores in the figure are indicated as: 1 is an outgoing line, 2 is a substrate, 3 is an insulating layer, 4 is a reference electrode, 5 is a working electrode, 6 is gold nanoparticles, 7 is a bismuth film, 8 is a counter electrode, 9 is organic glass, 10 is a sample inlet tube, 11 is a microfluidic chip channel, 12 is a sample outlet tube, and 13 is double-sided adhesive tape.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the spirit of the invention. All falling within the scope of the present invention.
Example 1
Referring to fig. 1a, 1b and 1c, which are schematic structural diagrams of a multi-target heavy metal microfluidic electrochemical sensor according to an embodiment of the present invention, referring to fig. 1a, the multi-target heavy metal microfluidic electrochemical sensor includes a screen-printed electrode and a microfluidic chip, referring to fig. 1b, the screen-printed electrode includes a substrate 2, an insulating layer 3, and a three-electrode system composed of a working electrode 5, a counter electrode 8 and a reference electrode 4; the working electrode 5, the counter electrode 8 and the reference electrode 4 are respectively arranged on the substrate 2, and the insulating layer 3 is arranged above the working electrode 5, the counter electrode 8 and the reference electrode 4; the working electrode 5 is a carbon electrode, the counter electrode 8 is a carbon electrode, the reference electrode 4 is a silver and silver chloride electrode, and the insulating layer 3 is an insulating ink layer; gold nanoparticles and a bismuth film are arranged on the surface of the working electrode 5, and after modification, the gold nanoparticles 6 are distributed on the surface of the working electrode, and the bismuth film 7 is distributed on the gold nanoparticles 6; the working electrode 5, the counter electrode 8 and the reference electrode 4 are respectively taken as leading-out wires 1 through carbon; and bonding and packaging the lower surface of the microfluidic chip and the upper surface of the screen printing electrode into a whole to form the microfluidic electrochemical sensor.
Referring to fig. 1c, the microfluidic chip includes a chip substrate, a microfluidic channel, a sample inlet tube 10, a sample outlet tube 12, and a double-sided adhesive tape 13. The structure of the microfluidic chip channel 11 is shown in fig. 1c, the middle part is an elliptical area (wherein the short radius of the ellipse is 2.1 mm, the long radius is 2.5 mm), the groove depth of the chip is 50-200 microns, the channel width at both sides is 100-200 microns, and the channel depth is 50-200 microns.
As a preferable mode, PP synthetic paper or polyester film may be used as the substrate 2. The PP synthetic paper is adopted, so that the cost of the electrode is reduced, the electrode can be thrown immediately after use, the price is low, the mass preparation is realized, and the high sensitivity and the good reproducibility are realized.
The preparation method of the multi-target heavy metal microfluidic electrochemical sensor can adopt the following steps:
1, preparing a screen printing plate pattern by adopting AutoCAD (computer-aided design) drawing software, wherein the aperture size of the screen printing plate is 200 meshes.
2, preparing printing slurry comprising conductive carbon slurry, conductive silver and silver chloride slurry, insulating ink and PP synthetic paper.
And 3, respectively printing conductive carbon paste, conductive silver paste, silver chloride paste and insulating ink on the PP synthetic paper by adopting a screen printer, drying for 2 hours in a 60-degree oven when printing a layer of paste, namely obtaining a working electrode 5, a counter electrode 8 and a reference electrode 4 on the PP synthetic paper, wherein the diameter of the working electrode 5 is 4mm, obtaining a full-page screen printing electrode slice, and cutting the full-page screen printing electrode slice to obtain a single screen printing electrode.
And 4, respectively carrying out electrode modification of gold nanoparticles 6 and electrode modification of a bismuth film 7 on the surface of a working electrode 5 of the screen printing electrode, and depositing a layer of gold nanoparticles 6 on the surface of the working electrode 5 through electrodeposition, specifically, in 2.5mM chloroauric acid, finishing the electrode modification of the gold nanoparticles 6 by applying alternate oxidation potentials of +1.5V, 40s and reduction potentials of-0.2V and 5s for 5 times of oxidation and reduction. Preparing a bismuth film 7 on the gold nanoparticles 6 by an orthotopic bismuth plating method, specifically, transferring 150ul of bismuth standard solution (1000.00mg/L), fixing the volume by 0.1mol/L acetic acid-sodium acetate buffer solution (pH is 5), and finishing electrode modification of the bismuth film 7 by adopting the orthotopic bismuth plating method under a set potential of-1.5V and setting the enrichment time to be 180 s.
And 5, preparing the microfluidic electrochemical sensor, designing chip channel drawing by adopting drawing software, directly printing and preparing on the organic glass 9 by using a laser engraving cutting machine, controlling the laser power to be 20%, and controlling the cutting/engraving speed to be 60 mm/s, and directly packaging the lower part of the microfluidic chip above the modified screen printing electrode by using the adhesion effect of the double-sided adhesive 13 to construct the microfluidic electrochemical sensor. The mapping software may employ AutoCAD, croeldaw, Photoshop, etc. PMMA organic glass 9 is selected as a chip base material.
Further, the obtained multi-target heavy metal electrochemical sensor is used for detecting heavy metal lead and cadmium ions in a water sample, and the detection method comprises the following steps: an electrochemical anodic stripping voltammetry method is adopted, the potential is 8mV, the amplitude is 50mV, the frequency is 20 Hz, a water quality sample of heavy metal ions to be detected is injected into the microfluidic electrochemical sensor from the sample inlet pipe 10 at the flow rate of 20ul/min by using an injection pump, the sample to be detected is continuously enriched for 3min, is discharged from the sample outlet pipe 12, is kept still for 10s before stripping, and is finally measured through an electrochemical workstation, and the result shows that the method can realize the synchronous detection of the heavy metal ions of lead and cadmium in the water sample, the detection limit of the method reaches 2ppb level, and the detection range is 2ppb-2 ppm.
Example 2
Referring to fig. 1a, 1b and 1c, which are schematic structural diagrams of a multi-target heavy metal microfluidic electrochemical sensor according to an embodiment of the present invention, referring to fig. 1a, the multi-target heavy metal microfluidic electrochemical sensor includes a screen-printed electrode and a microfluidic chip, referring to fig. 1b, the screen-printed electrode includes a substrate 2, an insulating layer 3, and a three-electrode system composed of a working electrode 5, a counter electrode 8 and a reference electrode 4; the working electrode 5, the counter electrode 8 and the reference electrode 4 are respectively arranged on the substrate 2, and the insulating layer 3 is arranged above the working electrode 5, the counter electrode 8 and the reference electrode 4; working electrode 5 is the carbon electrode, and counter electrode 8 is the carbon electrode, and reference electrode 4 is silver and silver chloride electrode, and insulating layer 3 is the insulating ink layer, and working electrode 5, counter electrode 8 and reference electrode 4 pass through carbon respectively and are as lead-out wire 1. Gold nanoparticles 6 and a bismuth film 7 are arranged on the surface of the working electrode 5, and after modification, the gold nanoparticles 6 are distributed on the surface of the working electrode, and the bismuth film 7 is distributed on the gold nanoparticles 6; and bonding and packaging the lower surface of the microfluidic chip and the upper surface of the screen printing electrode into a whole to form the microfluidic electrochemical sensor.
Referring to fig. 1c, the microfluidic chip includes a chip substrate, a microfluidic channel, a sample inlet tube 10, a sample outlet tube 12, and a double-sided adhesive tape 13. The structure of the microfluidic chip channel 11 is shown in fig. 1c, the middle part is an elliptical area (wherein the short radius of the ellipse is 2.1 mm, the long radius is 2.5 mm), the groove depth of the chip is 50-200 microns, the channel width at both sides is 100-200 microns, and the channel depth is 50-200 microns.
As a preferable mode, PP synthetic paper or polyester film may be used as the substrate 2. The substrate 2 adopts PP synthetic paper, so that the cost of the electrode is reduced, the electrode can be thrown immediately after use, the price is low, the mass preparation is realized, and the sensitivity is high and the reproducibility is good.
The preparation method of the multi-target heavy metal microfluidic electrochemical sensor can adopt the following steps,
1, preparing a screen printing plate pattern by adopting AutoCAD (computer-aided design) drawing software, wherein the aperture size of the screen printing plate is 200 meshes.
2, preparing printing slurry comprising conductive carbon slurry, conductive silver and silver chloride slurry, insulating ink and a polyester film;
and 3, respectively printing conductive carbon paste, conductive silver/silver chloride paste and insulating ink on the polyester film by adopting a screen printer, drying each layer of paste for 2 hours in an oven at 80 ℃, namely obtaining a working electrode 5, a counter electrode 8 and a reference electrode 4 on the polyester film, wherein the diameter of the working electrode 5 can be 4mm, obtaining a full-page screen printing electrode slice, and cutting the full-page screen printing electrode slice to obtain a single screen printing electrode.
And 4, respectively carrying out electrode modification of gold nanoparticles 6 and electrode modification of a bismuth film 7 on the surface of an electrode of the screen printing electrode, and depositing a layer of gold nanoparticles 6 on a working electrode 5 through electrodeposition, specifically, in 5mM chloroauric acid, applying alternate oxidation potential +1.5V, 30s and reduction potential for-0.2V and 10s for 5 times, and finishing the electrode modification of the gold nanoparticles 6. Preparing a bismuth film 7 on the gold nanoparticles 6 by an orthotopic bismuth plating method, specifically, transferring 200ul of bismuth standard solution (1000.00mg/L), fixing the volume by 0.1mol/L acetic acid-sodium acetate buffer solution (pH is 5), and finishing electrode modification of the bismuth film 7 by adopting the orthotopic bismuth plating method under a set potential of-1.5V and setting the enrichment time to 300 s.
And 5, preparing the microfluidic electrochemical sensor, adopting AutoCAD (auto computer aided design) drawing software to carry out chip channel drawing design, selecting PMMA (polymethyl methacrylate) organic glass 9 as a chip base material, controlling the laser power to be 30%, and the cutting/engraving speed to be 100 mm/s, directly printing and preparing the microfluidic chip on the organic glass 9, and then directly bonding and packaging the lower surface of the microfluidic chip and a screen printing electrode into a whole by adopting a double-sided adhesive 13 to prepare the heavy metal microfluidic electrochemical sensor.
Further, the obtained multi-target heavy metal electrochemical sensor is used for detecting heavy metal lead and cadmium ions in a water sample, and the detection method comprises the following steps: an electrochemical anodic stripping voltammetry method is adopted, the potential is 8mV, the amplitude is 50mV, the frequency is 20 Hz, a water quality sample of heavy metal ions to be detected is injected into the microfluidic electrochemical sensor from the sample inlet pipe 10 at the flow rate of 10ul/min by using an injection pump, the sample to be detected is continuously enriched for 6min, is discharged from the sample outlet pipe 12, stands still for 10s before stripping, and finally, the measurement is carried out through an electrochemical workstation, the result shows that the method can realize the synchronous detection of the heavy metal ions of lead and cadmium in the water sample, the detection limit of the method reaches 2ppb level, and the detection range is 2ppb-2 ppm.
The foregoing description of specific embodiments of the present invention has been presented. It is to be understood that the present invention is not limited to the specific embodiments described above, and that various changes and modifications may be made by one skilled in the art within the scope of the appended claims without departing from the spirit of the invention.
Claims (9)
1. A multi-target heavy metal micro-fluidic electrochemical sensor is characterized in that: the micro-fluidic chip comprises a screen printing electrode and a micro-fluidic chip, wherein the screen printing electrode comprises a substrate, a working electrode, a counter electrode, a reference electrode and an insulating layer; wherein the content of the first and second substances,
the working electrode, the counter electrode and the reference electrode are disposed on the substrate, and the insulating layer is disposed over the working electrode, the counter electrode and the reference electrode;
the working electrode is a carbon electrode, the counter electrode is a carbon electrode, the reference electrode is a silver and silver chloride electrode, and the insulating layer is an insulating ink layer;
gold nanoparticles and a bismuth film are arranged on the surface of the working electrode, and after modification, the gold nanoparticles are distributed on the surface of the working electrode, and the bismuth film is distributed on the gold nanoparticles;
the lower surface of the microfluidic chip and the upper surface of the screen printing electrode are bonded and packaged into a whole.
2. The multi-target heavy metal microfluidic electrochemical sensor according to claim 1, wherein: the substrate is PP synthetic paper or polyester film.
3. The multi-target heavy metal microfluidic electrochemical sensor according to claim 1, wherein:
the working electrode, the counter electrode and the reference electrode are respectively taken as leading-out wires through carbon.
4. A method for preparing a multi-target heavy metal micro-fluidic electrochemical sensor according to any one of claims 1 to 3, wherein the method comprises the following steps: the method comprises the following steps:
respectively printing conductive carbon paste, silver and silver chloride paste and insulating ink on a substrate through a printing screen, drying, obtaining a working electrode, a counter electrode and a reference electrode on the substrate to obtain a full-page screen printing electrode slice, and cutting the full-page screen printing electrode slice to obtain a single screen printing electrode;
respectively carrying out gold nanoparticle electrode modification and bismuth membrane electrode modification on the electrode surface of the screen printing electrode, and depositing a layer of gold nanoparticles on the surface of the working electrode through electrodeposition to obtain electrode modification of the gold nanoparticles; preparing a bismuth film on the gold nanoparticles by an in-situ bismuth plating method to obtain electrode modification of the bismuth film;
and bonding and packaging the lower surface of the microfluidic chip and the upper surface of the screen printing electrode into a whole to obtain the microfluidic electrochemical sensor.
5. The method for preparing the multi-target heavy metal micro-fluidic electrochemical sensor according to claim 4, wherein the method comprises the following steps: the pattern of the printing screen plate is designed by AutoCAD drawing software, and the aperture size of the printing screen plate is 100-200 meshes.
6. The method for preparing the multi-target heavy metal micro-fluidic electrochemical sensor according to claim 4, wherein the method comprises the following steps: depositing a layer of gold nanoparticles on the surface of the working electrode by electrodeposition, which is obtained by applying alternating oxidation potentials of +1-2V, 40-60s and reduction potentials of-0.2-0.5V, 1-5s in 2-5mM chloroauric acid, wherein the times of oxidation and reduction are 5-10.
7. The method for preparing the multi-target heavy metal micro-fluidic electrochemical sensor according to claim 4, wherein the method comprises the following steps: preparing electrode modification of the bismuth film on the working electrode by an orthotopic bismuth plating method, namely transferring 100-.
8. The method for preparing the multi-target heavy metal micro-fluidic electrochemical sensor according to claim 4, wherein the method comprises the following steps: the microfluidic chip is designed through AutoCAD, CroelDRAW or Photoshop drawing software; the micro-fluidic chip is prepared by adopting PMMA organic glass as a chip substrate and printing and outputting the PMMA organic glass by a laser engraving cutting machine.
9. A method for detecting heavy metal lead and cadmium ions in a water sample by using the multi-target heavy metal microfluidic electrochemical sensor as claimed in any one of claims 1 to 7, wherein the method comprises the following steps: and injecting a water quality sample of heavy metal ions to be detected into the microfluidic electrochemical sensor at a flow rate of 50-200ul/min by using an electrochemical anodic stripping voltammetry with a potential of 8-10mV, an amplitude of 50-80mV and a frequency of 20-30 Hz through an injection pump, continuously enriching the sample to be detected, and finally measuring to realize synchronous detection of the lead and cadmium multi-target heavy metal ions in the water sample.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114216949A (en) * | 2021-11-18 | 2022-03-22 | 佛山科学技术学院 | Screen printing electrode, manufacturing method and detection method thereof |
| CN114441619A (en) * | 2022-01-28 | 2022-05-06 | 安徽大学 | Electrode substrate of solid electrochemical gas sensor and sensor manufacturing method |
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| CN114216949A (en) * | 2021-11-18 | 2022-03-22 | 佛山科学技术学院 | Screen printing electrode, manufacturing method and detection method thereof |
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| CN114441619A (en) * | 2022-01-28 | 2022-05-06 | 安徽大学 | Electrode substrate of solid electrochemical gas sensor and sensor manufacturing method |
| CN114700123A (en) * | 2022-03-02 | 2022-07-05 | 天津工业大学 | Membrane-based micro-fluidic coupling chip for detecting multiple heavy metal ions in water environment |
| CN114700123B (en) * | 2022-03-02 | 2023-10-10 | 天津工业大学 | Membrane-based microfluidic coupling chip for detecting multiple heavy metal ions in water environment |
| CN115047053A (en) * | 2022-04-13 | 2022-09-13 | 哈尔滨工业大学 | Preparation method of bismuth-containing screen-printed electrode and application of bismuth-containing screen-printed electrode in heavy metal ion detection |
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