CN110308189B - Silk-screen printing electrochemical sensor for mercury ion detection and application thereof - Google Patents
Silk-screen printing electrochemical sensor for mercury ion detection and application thereof Download PDFInfo
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- 238000001514 detection method Methods 0.000 title claims abstract description 37
- BQPIGGFYSBELGY-UHFFFAOYSA-N mercury(2+) Chemical compound [Hg+2] BQPIGGFYSBELGY-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 238000007650 screen-printing Methods 0.000 title abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 54
- 229910052753 mercury Inorganic materials 0.000 claims abstract description 48
- -1 mercury ions Chemical class 0.000 claims abstract description 45
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 30
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 24
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 19
- 239000010941 cobalt Substances 0.000 claims abstract description 19
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000011258 core-shell material Substances 0.000 claims abstract description 12
- 239000002105 nanoparticle Substances 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 11
- 239000003480 eluent Substances 0.000 claims description 19
- 238000007789 sealing Methods 0.000 claims description 15
- 239000000523 sample Substances 0.000 claims description 14
- 239000000758 substrate Substances 0.000 claims description 9
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 229910052709 silver Inorganic materials 0.000 claims description 6
- 239000004332 silver Substances 0.000 claims description 6
- 229920002873 Polyethylenimine Polymers 0.000 claims description 5
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 5
- 230000002378 acidificating effect Effects 0.000 claims description 5
- 125000000524 functional group Chemical group 0.000 claims description 5
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 5
- 239000004952 Polyamide Substances 0.000 claims description 3
- 125000003277 amino group Chemical group 0.000 claims description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052737 gold Inorganic materials 0.000 claims description 3
- 239000010931 gold Substances 0.000 claims description 3
- 229920002647 polyamide Polymers 0.000 claims description 3
- 238000007639 printing Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 2
- 239000012488 sample solution Substances 0.000 claims description 2
- 238000003556 assay Methods 0.000 claims 1
- 230000009471 action Effects 0.000 abstract description 7
- 230000004044 response Effects 0.000 abstract description 7
- 230000035945 sensitivity Effects 0.000 abstract description 6
- 239000012141 concentrate Substances 0.000 abstract description 2
- 238000005259 measurement Methods 0.000 description 8
- 238000012544 monitoring process Methods 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000000835 electrochemical detection Methods 0.000 description 3
- 229910001385 heavy metal Inorganic materials 0.000 description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 241001465754 Metazoa Species 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 238000000559 atomic spectroscopy Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 239000012472 biological sample Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000412 dendrimer Substances 0.000 description 1
- 229920000736 dendritic polymer Polymers 0.000 description 1
- 238000001903 differential pulse voltammetry Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000013020 embryo development Effects 0.000 description 1
- 238000004993 emission spectroscopy Methods 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000002773 nucleotide Substances 0.000 description 1
- 125000003729 nucleotide group Chemical group 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Classifications
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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
- G01N27/28—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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- 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
- G01N27/3335—Ion-selective electrodes or membranes the membrane containing at least one organic component
-
- 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
- G01N27/416—Systems
- G01N27/48—Systems using polarography, i.e. measuring changes in current under a slowly-varying voltage
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- Health & Medical Sciences (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Molecular Biology (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
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Abstract
The invention discloses a screen printing electrochemical sensor for mercury ion detection and an application method thereof. The screen printing electrochemical sensor for mercury ion detection comprises a reaction device, a detection electrode and a mercury ion capturing agent; the reaction device is used for enriching the trapping agent for trapping mercury ions and separating the trapping agent from a sample; the detection electrode is used for detecting the concentration of mercury ions released by the mercury ion capturing agent. The functionalized carbon coated core-shell magnetic cobalt nanoparticle is used as a mercury ion capturing agent to enrich and concentrate mercury ions under the action of an external magnetic field, so that the response sensitivity of the screen printing electrochemical sensor to the mercury ions is improved, and the trace mercury ions in the water environment are measured by matching with an electrochemical device.
Description
Technical Field
The invention relates to an electrochemical measuring device, in particular to a screen printing electrochemical sensor for mercury ion detection and application thereof.
Background
In recent years, heavy metal pollution of water environment is increasingly serious, and the pollution to human bodies, animals and plants is very serious, and the pollution has an accumulation effect. Wherein mercury (Hg) is one of the most toxic heavy metal elements in the environment, and the mercury in the environment is converted into organic mercury under the action of microorganisms, and then finally enters the human body through food chain enrichment, thereby influencing the aspects of embryo development, cell chemical activity and histopathology. Therefore, the rapid on-site detection technology of mercury ions in the water environment is developed, and the method has important significance in the fields of environmental protection, health care, food monitoring and the like. In recent years, the analysis and detection means of mercury ions have been developed remarkably, and methods such as inductively coupled plasma mass spectrometry, inductively coupled plasma emission spectrometry, atomic spectroscopy, X-ray, chromatography and the like have been widely adopted. However, the above-mentioned required equipment is expensive, the processing steps are complicated, and the operation is complicated.
The electrochemical detection technology has the advantages of low instrument cost, high detection speed, convenient operation, easy automation realization and the like, and is widely applied to multiple fields such as environmental monitoring, biological sample analysis, food and drug monitoring and the like. However, most of the conventional electrochemical detection methods are columnar glassy carbon electrodes or gold electrodes, which need to be reprocessed after use, the electrodes are difficult to maintain the stability of response in continuous monitoring, the long-term reproducibility is poor, the electrodes are inevitably polluted and corroded in online analysis, the batch and continuous measurement of samples are not facilitated, and the application of the electrodes is limited to a certain extent. On the other hand, the electrode has less ideal selectivity, detection limit and sensitivity in heavy metal detection. In order to improve the detection performance of the electrode, the electrode is often modified with biological materials such as DNA or nucleotide chains for enriching mercury ions, the modification preparation process is complex, and the factors influencing the stability and consistency of the electrode are more, so that the inaccurate measurement result is caused by detection, and the problem of reproducibility is faced.
Disclosure of Invention
In order to solve the technical problems, the invention provides a screen printing electrochemical sensor for mercury ion detection and application thereof. The sensor can improve the response sensitivity of the screen printing electrochemical sensor to mercury ions, and is matched with an electrochemical device to measure mercury ions in water environment and trace mercury ions.
The mercury ion capturing agent adopted by the invention is a functionalized carbon coated core-shell type magnetic cobalt nanoparticle, which takes magnetic material cobalt as the center, the magnetic core cobalt has good magnetic guidance property, and high molecular carbon is coated to form a core-shell structure so as to increase stability and dispersibility. Polyamine polymers can chelate metal ions, especially mercury ions, so that functional groups such as amino groups, polyethyleneimine (PEI), polyamide-amine dendrimer (PAMAM) and the like are connected to the surface of a carbon shell, and can be combined with the mercury ions, so that the mercury ions can be selectively combined from water environment. Under the action of an external magnetic field, the functionalized carbon-coated core-shell magnetic cobalt nanoparticles enriched with mercury ions are attracted to the surface of the working electrode to be in close contact.
The separation and concentration of the functionalized carbon coated core-shell magnetic cobalt nanoparticle on mercury ions can improve the sensitivity of measuring mercury ions in the electrochemical detection process. After the measurement is finished, mercury ions in the acidic eluent can be released from the functionalized carbon coated core-shell magnetic cobalt nanoparticles, the surface of the screen printing electrochemical sensor is cleaned under the action of external magnetic force, the acidic eluent containing the mercury ions is removed, the update of a detection electrode can be conveniently realized, and the cost is reduced.
The technical scheme provided by the invention is as follows:
a screen printing electrochemical sensor for mercury ion detection comprises a reaction device, a detection electrode and a mercury ion capturing agent;
the reaction device is used for enriching the trapping agent for trapping mercury ions and separating the trapping agent from a sample;
the detection electrode is used for detecting the concentration of mercury ions released by the mercury ion capturing agent.
Specifically, the reaction device comprises a reaction tank, a base and a magnet;
the reaction tank consists of an outer layer and an inner layer; the outer layer is of a cylinder structure; the inner layer is a cylinder body which gradually transits downwards to be conical, and the bottom of the inner layer is provided with a through hole; the outer layer is sleeved with a sealing pad for sealing;
the reaction tank is arranged on the base;
a clamping groove is formed in one side of the base, and a magnet is arranged on the clamping groove.
Specifically, the detection electrode comprises a substrate; the substrate is printed with a guide rail, a working electrode, a reference electrode and an auxiliary electrode, and is covered with an insulating layer.
Specifically, the guide rail electrode is formed by printing conductive silver ink or conductive carbon ink on a substrate to form three parallel guide rails and consists of two rectangular blocks with different widths, wherein the end parts are wider and used for connecting an electrochemical workstation, and the middle parts are narrower and used for connecting the electrodes.
Specifically, the working electrode is a carbon electrode; the reference electrode is an Ag/AgCl electrode; the auxiliary electrode is a carbon electrode or a gold electrode;
wherein,
the working electrode body is a round block and is connected to the tail end of the narrower part of the middle guide rail electrode in an expanding way;
the reference electrode is a small arc ring formed by extending the tail end of the narrower part of the left guide rail electrode to the middle electrode, wherein silver/silver chloride ink is printed on the reference electrode;
the auxiliary electrode body is a large arc-shaped ring formed from the lower part of the tail end of the narrower part of the left guide rail electrode to the tail end of the narrower part of the right guide rail electrode, and the part close to the right guide rail electrode extends onto the guide rail electrode.
Specifically, the mercury ion capturing agent is functionalized carbon coated core-shell magnetic cobalt nanoparticles; wherein the core center is cobalt; the shell is a high molecular carbon shell connected with a functional group.
Specifically, the functional groups include amino groups, polyethyleneimine, and polyamide.
Specifically, the dosage of the mercury ion capturing agent is 1-10 g per L of sample solution.
Another object of the present invention is to provide a method for applying the above electrochemical sensor to mercury ion measurement, comprising the steps of:
(1) Adding a water sample containing mercury ions and a mercury ion capturing agent into a reaction tank, uniformly mixing and sealing by using a sealing gasket, placing the reaction tank on a base, mounting a magnet on a clamping groove of the base, and adsorbing the capturing agent with the mercury ions on one side of an inner layer of the reaction tank close to the magnet by the magnet so as to enrich the capturing agent;
(2) Separating out the water sample in the reaction tank, separating the reaction tank and the base, removing the sealing pad, moving the reaction tank with the capturing agent to a region corresponding to the detection electrode, and placing the magnet below the detection electrode;
(3) Adding an eluent into the reaction tank, separating mercury ions from the capturing agent, and enabling the eluent containing the mercury ions to flow to the surface of the detection electrode through holes in the inner layer of the reaction tank; the cavity between the inner layer and the outer layer of the reaction tank forms a sample tank of eluent;
(4) And connecting the detection electrode with an electrochemical workstation, and measuring the content of mercury ions in the eluent.
Specifically, the eluent is an acidic eluent comprising dilute sulfuric acid.
The invention has the beneficial effects that:
1) The mercury ion capturing agent uses functionalized carbon coated core-shell magnetic cobalt nanoparticles to enrich and pre-concentrate mercury ions under the action of an external magnetic field, so that the selectivity and sensitivity of the mercury ions on the screen printing electrochemical sensor are improved, and trace mercury ions in a water sample can be detected;
2) The regeneration of the previous electrode is complicated, and the mercury ion capturing agent can very conveniently realize the update of the working electrode under the action of external magnetic force;
3) High measurement sensitivity and accuracy
4) The detection is quick and convenient, the sampling is less, the sample does not need complex pretreatment, and the method is very suitable for on-site quick detection;
5) The electrochemical sensor can be industrially produced, has low price and is easy to popularize.
Drawings
FIG. 1 is a schematic diagram of a screen printed electrochemical sensor according to the present invention;
FIG. 2 is a block diagram of a reaction device for use with a screen printed electrochemical sensor;
FIG. 3 is a schematic diagram of a reaction device for use with a screen printed electrochemical sensor;
FIG. 4 is a graph of the electrochemical response of a screen printed electrochemical sensor to mercury ions;
reference numerals: 11-substrate, 12-guide rail, 13-reference electrode, 14-working electrode, 15-auxiliary electrode and 16-insulating layer; 21-reaction tank, 211-reaction tank inner layer, 212-reaction tank outer layer, 213-holes, 22-base, 23-sealing pad, 24-clamping groove and 25-magnet.
Detailed Description
The invention is further illustrated below in connection with specific examples, the content of which is not limited at all.
The following functionalized carbon coated core-shell magnetic cobalt nanoparticles were prepared using the method described in document [ Synthesis of functionalized, dispersible carbon-coated cobalt nanoparticles for potential biomedical applications, faraday discuss, 2014,175,27 ].
Example 1
Fig. 1 shows a structure of a screen-printed electrochemical sensor, comprising a substrate 11 on which electrodes are printed, three guide rails 12, a reference electrode 13, a working electrode 14, an auxiliary electrode 15 and an insulating layer 16 are printed.
Wherein:
the guide rail electrode consists of three parallel guide rails formed by printing conductive silver ink or conductive carbon ink on a substrate and two rectangular blocks with different widths, wherein the end part is wider and is used for connecting an electrochemical workstation, and the middle part is narrower and is used for connecting each electrode; preferably, the wider portion is 2mm by 5mm and the narrower portion is 1mm by 17mm.
The working electrode body is a round block and is connected to the tail end of the narrower part of the middle guide rail electrode in an expanding way; preferably, the diameter of the circular block is 2mm; the extension is 1mm by 2mm.
The reference electrode is a small arc ring formed by extending the tail end of the narrower part of the left guide rail electrode to the middle electrode, wherein silver/silver chloride ink is printed on the reference electrode; preferably, the reference electrode is a 1/6 circular arc, the inner diameter is 4mm, and the outer diameter is 7mm.
The auxiliary electrode body is a large arc-shaped ring formed from the lower part of the tail end of the narrower part of the left guide rail electrode to the tail end of the narrower part of the right guide rail electrode, and the part close to the right guide rail electrode is expanded to the guide rail electrode; preferably, the main body part is a 2/3 circular arc, the inner diameter is 4mm, the outer diameter is 7mm, and the expansion part is 1mm multiplied by 5mm.
Fig. 2 shows a structural view of a reaction device for use with a screen-printed electrochemical sensor, comprising a reaction cell 21, a base 22, a sealing pad 23 and a magnet 25. The reaction tank 1 has a cylindrical structure composed of an inner layer (211) and an outer layer (212), and the inner layer 211 is nested in the outer layer 212. The outer layer 212 is a cylinder; the upper main body of the inner layer 211 is cylindrical, and the bottom is of an inverted cone structure with a hole 213 in the middle; the reaction tank 21 is sleeved with a sealing pad 23. The base 22 is square and is used for placing the reaction tank 21. The base 22 is provided with a clamping groove 24; the magnet 25 is inserted into the card slot 24.
Fig. 3 shows a schematic view of the usage state, and the usage method is as follows:
1) Adding a water sample containing mercury ions into a reaction tank 21 sleeved with a sealing pad 23, and coating functionalized carbon coated core-shell magnetic cobalt nanoparticles (cobalt nanoparticle-mercury ion compound) with the mercury ions in the water sample by the action of a side magnet 25, wherein the functionalized carbon comprises amino, polyethyleneimine and polyamide, and is attracted to the side, close to the magnet 25, of an inner layer 211 of the reaction tank 21 to the greatest extent;
2) Removing the water sample in the reaction tank 21 after the functionalized carbon coated core-shell type magnetic cobalt nano particles are adsorbed, separating the reaction tank 21 from the base 22, removing the sealing pad 23, moving the reaction tank 21 with the cobalt nano particles-mercury ion compound left to the position right above a reaction area (comprising a working electrode, an auxiliary electrode and a reference electrode) on the surface of the screen printing electrochemical sensor 1, wherein the outer layer 212 of the reaction tank 21 can comprise the reaction area of the screen printing electrochemical sensor 1, and the magnet 25 is arranged below the screen printing electrochemical sensor 1;
3) An acidic eluent (H) was added to the reaction tank 1 2 SO 4 ) After separating mercury ions from the cobalt nanoparticle-mercury ion compound by the eluent, the eluent containing concentrated mercury ions flows to the surface of the screen printing electrochemical sensor 1 through holes 213 at the bottom of the inner layer 211 of the reaction tank; the cavity between the inner layer 211 and the outer layer 212 of the reaction tank forms a sample tank for containing eluent of the screen printing electrochemical sensor 1;
the screen-printed electrochemical sensor 1 is connected to an electrochemical workstation and the content of mercury ions in the eluent is determined electrochemically.
Application example 1
Screen-printed electrochemical sensor electrochemical response to mercury ions.
The electrochemical response of the screen printed biosensor to mercury ions was observed using the screen printed biosensor of example 1 and a reaction device used in combination.
Measurement conditions: the measurement medium was a sulfuric acid solution (H) of 0.5mol/L 2 SO 4 )。
The measuring method comprises the following steps: differential pulse voltammetry, potential scanning range 0.1V-0.4V, parameter setting: pulse amplitude 50mV; pulse time 20ms; the potential increase was 0.005V. As shown in fig. 4, the response measurement results show that the screen-printed electrochemical sensor has a linear relationship (r=0.991) with a detection limit of 0.01 μg/L (S/n=3) for a concentration range of 0.02 to 0.8 μg/L of mercury ion concentration.
The results show that: the device provided by the invention has the advantages of good linear relation for detecting the concentration of mercury ions, low detection limit and high accuracy, and can be used for rapid detection.
The present invention is not limited to the above-mentioned embodiments, but any modifications, equivalents, improvements and modifications within the scope of the invention will be apparent to those skilled in the art.
Claims (7)
1. A screen printed electrochemical sensor for mercury ion detection, characterized by:
comprises a reaction device, a detection electrode and a mercury ion capturing agent;
the reaction device is used for enriching the trapping agent for trapping mercury ions and separating the trapping agent from a sample;
the detection electrode is used for detecting the concentration of mercury ions released by the mercury ion capturing agent; the detection electrode comprises a substrate; the substrate is printed with a guide rail electrode, a working electrode, a reference electrode and an auxiliary electrode, and is covered with an insulating layer;
the mercury ion capturing agent is functionalized carbon coated core-shell magnetic cobalt nanoparticles; wherein the core center is cobalt; the shell is a high molecular carbon shell connected with a functional group; the functional groups include amino groups, polyethylenimine and polyamides.
2. The electrochemical sensor according to claim 1, characterized in that:
the reaction device comprises a reaction tank, a base and a magnet;
the reaction tank consists of an outer layer and an inner layer; the outer layer is of a cylinder structure; the inner layer is a cylinder body which gradually transits downwards to be conical, and the bottom of the inner layer is provided with a through hole; the outer layer is sleeved with a sealing pad for sealing;
the reaction tank is arranged on the base;
a clamping groove is formed in one side of the base, and a magnet is arranged on the clamping groove.
3. The electrochemical sensor according to claim 1, characterized in that: the guide rail electrode is formed by printing conductive silver ink or conductive carbon ink on a substrate to form three parallel guide rail electrodes and consists of two rectangular blocks with different widths, wherein the end parts are wider and used for connecting an electrochemical workstation, and the middle parts are narrower and used for connecting the electrodes.
4. An electrochemical sensor according to claim 3, characterized in that:
the working electrode is a carbon electrode; the reference electrode is an Ag/AgCl electrode; the auxiliary electrode is a carbon electrode or a gold electrode;
wherein,
the working electrode body is a round block and is connected to the tail end of the narrower part of the middle guide rail electrode in an expanding way;
the reference electrode is a small arc ring formed by extending the tail end of the narrower part of the left guide rail electrode to the middle electrode, wherein silver/silver chloride ink is printed on the reference electrode;
the auxiliary electrode body is a large arc-shaped ring formed from the lower part of the tail end of the narrower part of the left guide rail electrode to the tail end of the narrower part of the right guide rail electrode, surrounds the working electrode, and the part close to the right guide rail electrode extends onto the right guide rail electrode.
5. The electrochemical sensor according to claim 1, characterized in that: the dosage of the mercury ion capturing agent is 1-10 g per L of sample solution.
6. A method of applying the electrochemical sensor of any one of claims 1-5 to mercury ion assays, comprising the steps of:
(1) Adding a water sample containing mercury ions and a mercury ion capturing agent into a reaction tank, uniformly mixing and sealing by using a sealing gasket, placing the reaction tank on a base, mounting a magnet on a clamping groove of the base, and adsorbing the capturing agent with the mercury ions on one side of an inner layer of the reaction tank close to the magnet by the magnet so as to enrich the capturing agent;
(2) Separating out the water sample in the reaction tank, separating the reaction tank and the base, removing the sealing pad, moving the reaction tank with the capturing agent to a region corresponding to the detection electrode, and placing the magnet below the detection electrode;
(3) Adding an eluent into the reaction tank, separating mercury ions from the capturing agent, and enabling the eluent containing the mercury ions to flow to the surface of the detection electrode through holes in the inner layer of the reaction tank; the cavity between the inner layer and the outer layer of the reaction tank forms a sample tank of eluent;
(4) And connecting the detection electrode with an electrochemical workstation, and measuring the content of mercury ions in the eluent.
7. The electrochemical sensor according to claim 6, wherein: the eluent is an acidic eluent comprising dilute sulfuric acid.
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Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101892294A (en) * | 2010-01-22 | 2010-11-24 | 华南师范大学 | Magnetic bead electrochemiluminescence gene sensor-based method for detecting mercury ions and application thereof |
| CN102698598A (en) * | 2012-05-21 | 2012-10-03 | 华中科技大学 | Method and apparatus for catalyzing and oxidizing elemental mercury in flue gas by magnetic balls in fly ash |
| CN103675054A (en) * | 2012-09-25 | 2014-03-26 | 方建辉 | Electrolytic tank and method for detecting dopamine |
| CN204359742U (en) * | 2014-12-26 | 2015-05-27 | 武汉华纳联合药业有限公司 | A kind of sensitive membrane and the screen printing electrode containing this sensitive membrane |
| CN104655473A (en) * | 2015-02-26 | 2015-05-27 | 中国科学院电子学研究所 | Method for detecting trace mercury in water |
| CN105866101A (en) * | 2016-05-23 | 2016-08-17 | 中国科学院生态环境研究中心 | Heavy metal mercury ion detection method based on nucleic acid aptamer labeling |
| CN106215912A (en) * | 2016-08-25 | 2016-12-14 | 中国石油大学(北京) | A kind of nano composite material and preparation method thereof and the method for detection mercury ion |
| CN208721607U (en) * | 2018-07-27 | 2019-04-09 | 湖北科技学院 | A kind of reaction unit for screen printing electrode measurement |
| CN210720238U (en) * | 2019-06-28 | 2020-06-09 | 湖北科技学院 | Screen printing electrochemical sensor for mercury ion detection |
-
2019
- 2019-06-28 CN CN201910582365.2A patent/CN110308189B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101892294A (en) * | 2010-01-22 | 2010-11-24 | 华南师范大学 | Magnetic bead electrochemiluminescence gene sensor-based method for detecting mercury ions and application thereof |
| CN102698598A (en) * | 2012-05-21 | 2012-10-03 | 华中科技大学 | Method and apparatus for catalyzing and oxidizing elemental mercury in flue gas by magnetic balls in fly ash |
| CN103675054A (en) * | 2012-09-25 | 2014-03-26 | 方建辉 | Electrolytic tank and method for detecting dopamine |
| CN204359742U (en) * | 2014-12-26 | 2015-05-27 | 武汉华纳联合药业有限公司 | A kind of sensitive membrane and the screen printing electrode containing this sensitive membrane |
| CN104655473A (en) * | 2015-02-26 | 2015-05-27 | 中国科学院电子学研究所 | Method for detecting trace mercury in water |
| CN105866101A (en) * | 2016-05-23 | 2016-08-17 | 中国科学院生态环境研究中心 | Heavy metal mercury ion detection method based on nucleic acid aptamer labeling |
| CN106215912A (en) * | 2016-08-25 | 2016-12-14 | 中国石油大学(北京) | A kind of nano composite material and preparation method thereof and the method for detection mercury ion |
| CN208721607U (en) * | 2018-07-27 | 2019-04-09 | 湖北科技学院 | A kind of reaction unit for screen printing electrode measurement |
| CN210720238U (en) * | 2019-06-28 | 2020-06-09 | 湖北科技学院 | Screen printing electrochemical sensor for mercury ion detection |
Non-Patent Citations (3)
| Title |
|---|
| A Mild and Facile Synthesis of Amino Functionalized CoFe2O4@SiO2 for Hg(II) Removal;Xi Wang 等;nanomaterials;20180829;第1-21页 * |
| Dansyl derivative functionalized Fe3O4@SiO2 fluorescent probe for detection and removal of Hg2+ in aqueous solution;Zhengping Dong 等;RSC Advances;20121121;第1082-1088页 * |
| 磁性Fe3O4@SiO2-SH的制备及环境水体中汞的富集与分析;宋娟 等;分析试验室;20141231;第33卷(第12期);第1374-1377页 * |
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