CN113514519A - Carbendazim electrochemical sensor and application thereof - Google Patents
Carbendazim electrochemical sensor and application thereof Download PDFInfo
- Publication number
- CN113514519A CN113514519A CN202110406280.6A CN202110406280A CN113514519A CN 113514519 A CN113514519 A CN 113514519A CN 202110406280 A CN202110406280 A CN 202110406280A CN 113514519 A CN113514519 A CN 113514519A
- Authority
- CN
- China
- Prior art keywords
- carbendazim
- electrochemical sensor
- carbon material
- working electrode
- carbon
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- JNPZQRQPIHJYNM-UHFFFAOYSA-N carbendazim Chemical compound C1=C[CH]C2=NC(NC(=O)OC)=NC2=C1 JNPZQRQPIHJYNM-UHFFFAOYSA-N 0.000 title claims abstract description 57
- TWFZGCMQGLPBSX-UHFFFAOYSA-N Carbendazim Natural products C1=CC=C2NC(NC(=O)OC)=NC2=C1 TWFZGCMQGLPBSX-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 239000006013 carbendazim Substances 0.000 title claims abstract description 55
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 38
- 238000001514 detection method Methods 0.000 claims abstract description 12
- 239000000758 substrate Substances 0.000 claims abstract description 12
- 230000004913 activation Effects 0.000 claims abstract description 10
- 239000011159 matrix material Substances 0.000 claims abstract description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 25
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 16
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 14
- 229910021389 graphene Inorganic materials 0.000 claims description 14
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 13
- 150000001721 carbon Chemical class 0.000 claims description 12
- 229910052759 nickel Inorganic materials 0.000 claims description 12
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 11
- 229910021397 glassy carbon Inorganic materials 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- 238000000926 separation method Methods 0.000 claims description 8
- 239000002134 carbon nanofiber Substances 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 6
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 claims description 5
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 claims description 5
- 239000004744 fabric Substances 0.000 claims description 5
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 5
- 229910052737 gold Inorganic materials 0.000 claims description 5
- 239000010931 gold Substances 0.000 claims description 5
- 229910052697 platinum Inorganic materials 0.000 claims description 5
- 238000005507 spraying Methods 0.000 claims description 5
- HVBSAKJJOYLTQU-UHFFFAOYSA-N 4-aminobenzenesulfonic acid Chemical compound NC1=CC=C(S(O)(=O)=O)C=C1 HVBSAKJJOYLTQU-UHFFFAOYSA-N 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 239000008363 phosphate buffer Substances 0.000 claims description 3
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 2
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 2
- 239000002041 carbon nanotube Substances 0.000 claims description 2
- 239000003153 chemical reaction reagent Substances 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 238000007639 printing Methods 0.000 claims description 2
- 238000004528 spin coating Methods 0.000 claims description 2
- 229950000244 sulfanilic acid Drugs 0.000 claims description 2
- 238000006277 sulfonation reaction Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 230000035945 sensitivity Effects 0.000 abstract description 10
- 239000000575 pesticide Substances 0.000 abstract description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- 238000012360 testing method Methods 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 238000004140 cleaning Methods 0.000 description 5
- 239000012279 sodium borohydride Substances 0.000 description 5
- 229910000033 sodium borohydride Inorganic materials 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 208000019331 Foodborne disease Diseases 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000008055 phosphate buffer solution Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000002965 ELISA Methods 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 201000010099 disease Diseases 0.000 description 2
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 2
- 238000000840 electrochemical analysis Methods 0.000 description 2
- 238000004108 freeze drying Methods 0.000 description 2
- 238000004895 liquid chromatography mass spectrometry Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 238000002798 spectrophotometry method Methods 0.000 description 2
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 1
- 229920002749 Bacterial cellulose Polymers 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- 102000004316 Oxidoreductases Human genes 0.000 description 1
- 108090000854 Oxidoreductases Proteins 0.000 description 1
- 238000012271 agricultural production Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000005016 bacterial cellulose Substances 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000032823 cell division Effects 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 230000034994 death Effects 0.000 description 1
- 231100000517 death Toxicity 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 210000004602 germ cell Anatomy 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 231100001231 less toxic Toxicity 0.000 description 1
- 244000144972 livestock Species 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 230000003228 microsomal effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- -1 potassium ferricyanide Chemical compound 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 1
- 238000012546 transfer Methods 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
- G01N27/308—Electrodes, e.g. test electrodes; Half-cells at least partially made of carbon
Landscapes
- 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 Electric Means (AREA)
Abstract
The invention discloses a carbendazim electrochemical sensor and application thereof, and belongs to the technical field of pesticide detection. A carbendazim electrochemical sensor comprising a working electrode, the working electrode comprising: the conductive substrate is in a two-dimensional sheet shape, a two-dimensional net shape, a three-dimensional net shape or a honeycomb shape; the activation layer is arranged on the surface of the conductive matrix and comprises a carbon material, and a sulfonic group is modified on the carbon material. According to the carbendazim electrochemical sensor provided by the invention, the specific surface area of the working electrode is increased, and meanwhile, the surface of the working electrode is modified with the excellent conductive carbon material, so that the sensitivity of the carbendazim electrochemical sensor is improved, and the detection specificity of the carbendazim electrochemical sensor is improved as the surface of the carbon material is modified with the sulfonic group.
Description
Technical Field
The invention belongs to the technical field of pesticide detection, and particularly relates to a carbendazim electrochemical sensor and application thereof.
Background
The statistics of the world health organization show that in industrialized regions, about 30% of people are harmed by food-borne diseases every year, and nearly 4800 million cases of food-borne diseases and 3000 deaths occur in the United states every year. One of the causes of food-borne diseases is the abuse of pesticides.
Carbendazim (also known as carbendazim, benzimidazole number 44, carbendazim) is a broad-spectrum bactericide, can prevent and treat diseases caused by fungi, is widely applied in agricultural production, and has the action mechanism of preventing and treating the diseases to influence cell division. Although carbendazim is less toxic to human and livestock, the residual period is long, and carbendazim can be accumulated in human body through food chain to cause damage to microsomal membranes, influence the activity of oxidase and cause serious damage to germ cells.
In order to control the content of carbendazim in food, researchers have studied various methods for detecting carbendazim residues, among which spectrophotometry, liquid chromatography-mass spectrometry, enzyme-linked immunosorbent assay, and the like are mainly used. Although the spectrophotometry and the liquid chromatography-mass spectrometry are mature, the problems of complicated sample preparation and high cost exist, and the problem of difficult antibody preparation exists in the enzyme-linked immunosorbent assay. This limits the utility of the above method in detecting carbendazim residues.
The electrochemical analysis method for detecting the carbendazim is realized based on the electrochemical activity of the carbendazim, and is one of research hotspots for detecting the residual concentration of the carbendazim due to the fact that the electrochemical analysis method is low in cost, simple in equipment, easy to operate and short in detection time. The three-electrode system is the most widely used electrochemical sensing measurement system at present, and mainly comprises a Working Electrode (WE), a Reference Electrode (RE) and an auxiliary electrode (CE). In the system, the working electrode and the auxiliary electrode form a loop to ensure smooth measurement process, and the reference electrode provides a stable potential for the system to reduce the influence of the components of the solution to be measured on the detection result. However, the existing working electrode for detecting carbendazim has the characteristics of poor specificity, poor conductivity, poor sensitivity and the like.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art described above. Therefore, the specific surface area of the working electrode is increased, and the surface of the working electrode is modified with the excellent conductive carbon material, so that the sensitivity of the carbendazim electrochemical sensor is improved.
The invention also provides an application of the carbendazim electrochemical sensor in carbendazim concentration detection.
According to an aspect of the present invention, there is provided a carbendazim electrochemical sensor comprising a working electrode, the working electrode comprising:
the conductive substrate is in a two-dimensional sheet shape, a two-dimensional net shape, a three-dimensional net shape or a honeycomb shape;
the activation layer is arranged on the surface of the conductive matrix and comprises a carbon material, and sulfonic groups are modified on the carbon material.
According to a preferred embodiment of the present invention, at least the following advantages are provided:
(1) compared with the traditional carbendazim electrochemical sensor taking rod-shaped glassy carbon as a working electrode, the working electrode adopted by the invention is in a two-dimensional sheet shape, a two-dimensional net shape, a three-dimensional net shape or a honeycomb shape, and the specific surface area of the working electrode is increased due to the special shape, so that the sensitivity of the carbendazim electrochemical sensor in carbendazim detection is increased; in addition, the working electrode with the special shape reduces the weight of the working electrode (when the surface area of the working electrode is equal to that of the rod-shaped electrode and the material is the same), and saves the manufacturing cost of the working electrode.
(2) Compared with the traditional carbendazim electrochemical sensor taking rod-shaped glassy carbon as the working electrode, the carbon material is modified on the surface of the working electrode, so that the specific surface area of the working electrode is further increased, and the sensitivity of the carbendazim electrochemical sensor is improved.
(3) According to the invention, the surface of the working electrode is modified with the carbon material, and the carbon material has the characteristics of excellent conductivity, macroscopic tunnel effect and the like, so that the transfer rate of electrons can be increased, and the sensitivity and response speed of the carbendazim electrochemical sensor can be improved.
(4) According to the invention, the surface of the working electrode is modified with the carbon material, and the carbon material has lower apparent free energy, so that the anti-interference capability of the carbendazim electrochemical sensor can be improved.
(5) The carbon material modified on the surface of the working electrode is a sulfonated carbon material, so that the surface of the carbon material has a sulfonate group, and active groups such as hydroxyl, carboxyl and the like inherent on the surface of the carbon material, and the carbon material has excellent detection activity and specificity.
In some embodiments of the present invention, the conductive substrate is made of at least one of carbon, nickel, gold, platinum and glassy carbon.
In some preferred embodiments of the present invention, the conductive substrate is one of sheet glassy carbon, three-dimensional reticulated foamed nickel, two-dimensional reticulated platinum mesh, two-dimensional reticulated gold mesh, and two-dimensional reticulated carbon cloth.
These conductive matrices are both inert and conductive, and therefore have low interference signals when used in a carbendazim detection process.
The carbon cloth and the foamed nickel are light in weight and low in price, so that the working electrode taking the carbon cloth or the foamed nickel as the conductive substrate can be manufactured into an instant throwing type working electrode, the cleaning work of the working electrode is avoided, and the raw material cost of the working electrode is also reduced.
The platinum net and the gold net can be ultrasonically cleaned by sequentially adopting organic acid, inorganic base and organic solvent, can be reused after being dried, and are simple to clean.
In some embodiments of the present invention, the carbon material is at least one of graphene oxide, reduced graphene oxide, carbon nanotubes, and carbon nanofibers.
In some embodiments of the present invention, the method for preparing reduced graphene oxide comprises the steps of:
A1. dispersing graphene oxide in deionized water, wherein the mass ratio of the graphene oxide to the water is 1: (900-950);
A2. adjusting the pH of the system obtained from A1 to 9-10, adding a reducing agent, stirring at 60-70 ℃ for reaction for 1-3 h, adjusting the pH to be neutral, performing solid-liquid separation, cleaning and drying to obtain the reduced graphene oxide;
in some embodiments of the present invention, in step a2, the reducing agent is at least one of sodium borohydride or nano-iron simple substance.
In some embodiments of the invention, in step a2, the pH adjusting agent is at least one of sodium hydroxide, potassium hydroxide, hydrochloric acid and sulfuric acid.
In some embodiments of the present invention, the method for preparing the carbon nanofiber comprises preparing the carbon nanofiber by a high temperature pyrolysis method using bacterial cellulose as a carbon source.
In some embodiments of the invention, the high temperature pyrolysis process is carried out at a temperature of 850 ℃ to 900 ℃ in an atmosphere of nitrogen or an inert gas.
In some embodiments of the invention, the ratio of the mass of the activation layer to the surface area of the conductive substrate is 2mg/m2～5mg/m2。
Due to the active layer and the conductorThe partial connection relationship between the electric substrates is physical adhesion and weak connection, if the ratio of the mass of the carbon activation layer to the surface area of the electric conductive substrate is more than 5mg/m2The problem of the peeling of the active layer during the test is easily caused.
If the ratio of the mass of the active layer to the surface area of the conductive substrate is < 2mg/m2Then, the sensitivity and specificity of the carbendazim electrochemical sensor cannot be effectively improved by the active layer.
In some embodiments of the invention, the method of making the working electrode comprises the steps of:
s1, mixing a sulfonation reagent and the carbon material for reaction, and then carrying out solid-liquid separation and washing to obtain a sulfonated carbon material;
s2, dispersing the sulfonated carbon material obtained in the step S1 on the surface of the conductive matrix to form the activation layer, and drying to obtain the working electrode.
In some embodiments of the present invention, in step S1, the sulfonating agent is at least one of sulfuric acid, chlorosulfonic acid, ammonium sulfate and sulfanilic acid.
In some embodiments of the present invention, in step S2, the activation layer is formed by at least one of spraying, spin coating, and printing.
In some embodiments of the present invention, in step S2, the activated layer is formed by dispersing the sulfonated carbon material obtained in step S1 in a phosphate buffer and performing a current-time scan.
In some preferred embodiments of the present invention, the method for preparing the working electrode comprises the steps of:
B1. mixing the carbon material with a sulfuric acid aqueous solution for reaction for 6-10 h, carrying out solid-liquid separation, cleaning and drying to obtain a sulfonated carbon material;
B2. and C, preparing the sulfonated carbon material obtained in the step B1 into 0.1-0.9 mg/ml suspension, spraying the suspension onto the surface of the conductive substrate, and drying at normal temperature to obtain the working electrode.
In some preferred embodiments of the present invention, in step B1, the mass percentage of sulfuric acid in the aqueous sulfuric acid solution is 70% to 98%.
In some preferred embodiments of the present invention, the method for preparing the working electrode comprises the steps of:
C1. dispersing the carbon material into dichloromethane, adding chlorosulfonic acid into the dichloromethane, stirring the mixture to react, performing solid-liquid separation, and performing freeze drying to obtain a sulfonated carbon material;
C2. and D, adding the sulfonated carbon material obtained in the step C1 into a phosphate buffer solution to prepare a suspension of 0.1-0.9 mg/ml, taking the conductive matrix as a working electrode, taking saturated calomel as a reference electrode and a platinum wire as a counter electrode, carrying out current-time scanning in a range of-0.8V to-0.2V, and obtaining the working electrode after the current-time scanning is finished.
In some embodiments of the present invention, the carbendazim electrochemical sensor further comprises a counter electrode, a reference electrode, a power supply system, and a display system.
An application of a carbendazim electrochemical sensor in detecting the concentration of the carbendazim.
According to the invention, the working electrode of the carbendazim electrochemical sensor is optimized, so that the detection sensitivity, specificity and corresponding speed of the carbendazim electrochemical sensor on the carbendazim are improved.
Detailed Description
The concept and technical effects of the present invention will be clearly and completely described below in conjunction with the embodiments to fully understand the objects, features and effects of the present invention. It is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments, and those skilled in the art can obtain other embodiments without inventive effort based on the embodiments of the present invention, and all embodiments are within the protection scope of the present invention.
Example 1
The working electrode of the carbendazim electrochemical sensor is prepared in the embodiment, and the specific process is as follows:
s1, dispersing graphene oxide (purchased from a Sigma website, the purity is more than or equal to 97%) in deionized water, wherein the mass ratio of the graphene oxide to the water is 1: 900;
s2, adjusting the pH value of the system obtained in the step S1 to 9.5 by using a sodium hydroxide aqueous solution, adding sodium borohydride (the mass of the sodium borohydride is 15 times that of graphene oxide, the sodium borohydride is purchased from an Aladdin website, the purity of the sodium borohydride is more than or equal to 95%), stirring the mixture at 65 ℃ for reaction for 1.5 hours, adjusting the pH value to be neutral by using a hydrochloric acid aqueous solution, and carrying out solid-liquid separation, cleaning and drying on the mixture to obtain reduced graphene oxide;
s3, mixing the reduced graphene oxide obtained in the step S2 with a sulfuric acid aqueous solution (mass concentration is 70%) for reaction for 6 hours, and carrying out solid-liquid separation, cleaning and drying to obtain sulfonated reduced graphene oxide;
s4, preparing the sulfonated reduced graphene oxide obtained in the step S3 into 0.9mg/ml turbid liquid, and spraying the turbid liquid onto the surface of foamed nickel (three-dimensional mesh conductive matrix) (the spraying proportion is 2 mg/m)2) And forming an active layer, and drying at normal temperature to obtain the working electrode.
Example 2
The working electrode of the carbendazim electrochemical sensor is prepared in the embodiment, and the specific process is as follows:
s1, dispersing carbon nanofibers into dichloromethane (purchased from Aladdin, the purity is more than or equal to 99.5 percent), adding chlorosulfonic acid (purchased from Shenyang chemical industry) into the carbon nanofibers with the concentration of 2mg/ml, the mass ratio of the chlorosulfonic acid to the carbon nanofibers being 50:1, stirring and reacting for 30min, carrying out solid-liquid separation, and carrying out freeze drying to obtain sulfonated carbon nanofibers;
s2, adding the sulfonated carbon nanofibers obtained in the step S1 into a phosphate buffer solution to prepare 0.9mg/ml suspension, taking carbon cloth as a working electrode (a two-dimensional mesh conductive matrix), saturated calomel as a reference electrode and a platinum wire as a counter electrode, and carrying out current-time scanning for 800S in a range of-0.8V to-0.2V to obtain the working electrode.
Comparative example 1
The working electrode of the carbendazim electrochemical sensor is prepared according to the comparative example, and the specific process is different from that of the embodiment 1:
(1) step S3 is not carried out, namely, the reduced graphene oxide obtained in step S2 is directly modified to the surface of the foamed nickel.
Test examples
In the test example, the working electrodes of the carbendazim electrochemical sensors prepared in examples 1-2 and comparative example 1 were tested, and the detection performance of the unmodified glassy carbon bare electrode and the nickel foam used in example 1 as the working electrodes was also tested. Wherein:
the electrochemical behavior of the above-mentioned working electrode was tested in potassium ferricyanide solution (5mM) and carbendazim test substance (20 μ M) in phosphate buffer (pH 7) using cyclic voltammetry, with a scan rate of 100 mV/s. The impedance was also analyzed and measured, the whole experiment was carried out at room temperature, and carbendazim was diluted with phosphate buffer solution of pH 7. All tests were performed under the action of a coster electrochemical workstation, with a platinum wire as counter electrode and saturated calomel as reference electrode.
The test results are shown in table 1.
Table 1 test results for working electrodes.
As can be seen from the results in table 1, compared to the bare glassy carbon electrode and the foamed nickel, the sensitivity and the effective active area of the working electrode are both significantly improved after the carbon material is modified, and if the carbon material is a sulfonated carbon material, the analysis sensitivity can be further improved.
The alternating current impedance result shows that the impedance of the working electrode in the embodiment 1-2 is equivalent to that of the working electrode in the comparative example 1, is smaller than that of the bare glassy carbon electrode and the foamed nickel, and is obviously smaller than that of the bare glassy carbon electrode and the foamed nickel, so that the working electrode provided by the invention has small electrode impedance and better conductivity when being applied to a carbendazim electrochemical sensor, and can effectively promote the electron transfer rate on the surface of the electrode.
The embodiments of the present invention have been described in detail, but the present invention is not limited to the embodiments, and various changes can be made without departing from the gist of the present invention within the knowledge of those skilled in the art. Furthermore, the embodiments of the present invention and the features of the embodiments may be combined with each other without conflict.
Claims (10)
1. A carbendazim electrochemical sensor comprising a working electrode, the working electrode comprising:
the conductive substrate is in a two-dimensional sheet shape, a two-dimensional net shape, a three-dimensional net shape or a honeycomb shape;
the activation layer is arranged on the surface of the conductive matrix and comprises a carbon material, and sulfonic groups are modified on the carbon material.
2. The carbendazim electrochemical sensor of claim 1, wherein the conductive substrate is at least one of carbon, nickel, gold, platinum and glassy carbon.
3. The carbendazim electrochemical sensor according to claim 2, wherein the conductive matrix is one of sheet glassy carbon, three-dimensional reticulated foamed nickel, two-dimensional reticulated platinum mesh, two-dimensional reticulated gold mesh and two-dimensional reticulated carbon cloth.
4. The carbendazim electrochemical sensor according to claim 1, wherein the carbon material is at least one of graphene oxide, reduced graphene oxide, carbon nanotubes, and carbon nanofibers.
5. The carbendazim electrochemical sensor of claim 1, wherein the working electrode is prepared by a method comprising the steps of:
s1, mixing a sulfonation reagent and the carbon material for reaction, and then carrying out solid-liquid separation and washing to obtain a sulfonated carbon material;
s2, dispersing the sulfonated carbon material obtained in the step S1 on the surface of the conductive matrix to form the activation layer, and drying to obtain the working electrode.
6. The carbendazim electrochemical sensor according to claim 5, wherein in step S1, the sulfonating agent is at least one of sulfuric acid, chlorosulfonic acid, ammonium sulfate and sulfanilic acid.
7. The carbendazim electrochemical sensor according to claim 5, wherein in step S2, the activation layer is formed by at least one of spraying, spin coating and printing.
8. The carbendazim electrochemical sensor according to claim 5, wherein in step S2, the activation layer is formed by dispersing the sulfonated carbon material obtained in step S1 in a phosphate buffer and performing a current-time scan.
9. The carbendazim electrochemical sensor according to any one of claims 1 to 8, further comprising a counter electrode, a reference electrode, a power supply system and a display system.
10. Use of a carbendazim electrochemical sensor as claimed in any one of claims 1 to 9 in the detection of carbendazim concentration.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110406280.6A CN113514519A (en) | 2021-04-15 | 2021-04-15 | Carbendazim electrochemical sensor and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110406280.6A CN113514519A (en) | 2021-04-15 | 2021-04-15 | Carbendazim electrochemical sensor and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113514519A true CN113514519A (en) | 2021-10-19 |
Family
ID=78062530
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110406280.6A Pending CN113514519A (en) | 2021-04-15 | 2021-04-15 | Carbendazim electrochemical sensor and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113514519A (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103645237A (en) * | 2013-12-16 | 2014-03-19 | 江苏大学 | Electrochemical sensor for detecting content of carbendazim in fog drops as well as preparation and application methods |
| CN106124766A (en) * | 2016-07-05 | 2016-11-16 | 天津师范大学 | Use the method for carbendazim content in carbendazim detection of specific antibody edible fungi |
| CN106770551A (en) * | 2016-12-07 | 2017-05-31 | 信阳师范学院 | A kind of electrochemical sensor of quick measure carbendazim, preparation method and the application in carbendazim is determined |
| CN109187679A (en) * | 2018-07-26 | 2019-01-11 | 河北科技大学 | A kind of electrochemical sensor and its preparation method and application |
| US20190049400A1 (en) * | 2015-08-14 | 2019-02-14 | Razzberry, Inc. | Electrodes, and methods of use in detecting explosives and other volatile materials |
-
2021
- 2021-04-15 CN CN202110406280.6A patent/CN113514519A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103645237A (en) * | 2013-12-16 | 2014-03-19 | 江苏大学 | Electrochemical sensor for detecting content of carbendazim in fog drops as well as preparation and application methods |
| US20190049400A1 (en) * | 2015-08-14 | 2019-02-14 | Razzberry, Inc. | Electrodes, and methods of use in detecting explosives and other volatile materials |
| CN106124766A (en) * | 2016-07-05 | 2016-11-16 | 天津师范大学 | Use the method for carbendazim content in carbendazim detection of specific antibody edible fungi |
| CN106770551A (en) * | 2016-12-07 | 2017-05-31 | 信阳师范学院 | A kind of electrochemical sensor of quick measure carbendazim, preparation method and the application in carbendazim is determined |
| CN109187679A (en) * | 2018-07-26 | 2019-01-11 | 河北科技大学 | A kind of electrochemical sensor and its preparation method and application |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Xu et al. | Graphene/polyaniline/gold nanoparticles nanocomposite for the direct electron transfer of glucose oxidase and glucose biosensing | |
| Zhou et al. | Acetylcholinesterase biosensor based on SnO2 nanoparticles–carboxylic graphene–nafion modified electrode for detection of pesticides | |
| Fang et al. | A non-enzymatic hydrogen peroxide sensor based on poly (vinyl alcohol)–multiwalled carbon nanotubes–platinum nanoparticles hybrids modified glassy carbon electrode | |
| Zhang et al. | CuO nanowires based sensitive and selective non-enzymatic glucose detection | |
| Mahesh et al. | Flexible sensor for dopamine detection fabricated by the direct growth of α-Fe2O3 nanoparticles on carbon cloth | |
| Zheng et al. | Carbon nanohorns enhanced electrochemical properties of Cu-based metal organic framework for ultrasensitive serum glucose sensing | |
| CN102078826B (en) | Preparation method and application of ionic liquid modified carbon sphere loaded platinum nanoparticle catalyst | |
| Musameh et al. | Silk provides a new avenue for third generation biosensors: Sensitive, selective and stable electrochemical detection of nitric oxide | |
| Mohiuddin et al. | Alpha-glucosidase enzyme biosensor for the electrochemical measurement of antidiabetic potential of medicinal plants | |
| Gokoglan et al. | Paper based glucose biosensor using graphene modified with a conducting polymer and gold nanoparticles | |
| Wang et al. | Sensitive voltammetric sensor based on Isopropanol–Nafion–PSS–GR nanocomposite modified glassy carbon electrode for determination of Clenbuterol in pork | |
| CN110031521B (en) | Preparation of acetylcholinesterase biosensor and application of acetylcholinesterase biosensor in detection of organophosphorus | |
| Liu et al. | A novel non-enzymatic hydrogen peroxide sensor based on Mn-nitrilotriacetate acid (Mn-NTA) nanowires | |
| CN106383158A (en) | Hydrogen peroxide non-enzyme sensor based on silver-graphene nano composite and manufacturing method thereof | |
| CN103551591B (en) | Porous platinum-graphene oxide composite nano material and preparation method thereof | |
| CN113340947B (en) | Preparation method of polyaniline hollow sphere/MXene composite ammonia gas-sensitive material | |
| Sheng et al. | Bienzyme system for the biocatalyzed deposition of polyaniline templated by multiwalled carbon nanotubes: a biosensor design | |
| KR101765844B1 (en) | Nickel/Cobalt Oxide Based Electrode for Urea Detection and Method for Preparing the Same | |
| CN104034786B (en) | Based on the preparation of the superoxide anion sensor of precious metal alloys/carbon composite | |
| Ahammad et al. | Hydrogen peroxide biosensor based on the immobilization of horseradish peroxidase onto a gold nanoparticles-adsorbed poly (brilliant cresyl blue) film | |
| CN114920228B (en) | Transition metal phosphate nano enzyme material and preparation method and application thereof | |
| CN110441368B (en) | Construction of glucose photoelectrochemical self-powered sensor based on NiO/RGO/BiOI | |
| Zhao et al. | Synthesis of mesoporous grooved ZnFe2O4 nanobelts as peroxidase mimetics for improved enzymatic biosensor | |
| Chairam et al. | A novel hydrogen peroxide biosensor based on horseradish peroxidase immobilized on poly (aniline-co-o-aminobenzoic acid) modified glassy carbon electrode coated with chitosan film | |
| CN109187687B (en) | Preparation of conjugated organic microporous material modified electrode and application of modified electrode as peroxynitroso anion electrochemical sensor |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |