CN109632923B - Method for detecting carbendazim by using differential pulse voltammetry - Google Patents
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Abstract
The invention discloses a method for simultaneously detecting methyl parathion and carbendazim by using a differential pulse voltammetry method. The method can effectively solve the problems of complicated steps and difficult on-line detection of the traditional methyl parathion and carbendazim detection method, has the characteristics of simple and convenient process, accurate determination, high specificity, quick reaction, high sensitivity, simple operation and the like, realizes the simultaneous detection of the mixture of the methyl parathion and the carbendazim, and has wide application prospect.
Description
Technical Field
The invention relates to a method for simultaneously detecting methyl parathion and carbendazim in a water sample, in particular to a method for simultaneously detecting methyl parathion and carbendazim by using a differential pulse voltammetry. Belongs to the field of electrochemical analysis and test.
Background
In recent years, researches on detection and treatment schemes of pesticide residues in agricultural products are becoming hot spots in the field of food safety monitoring. Due to unreasonable use of pesticides, pesticides can remain in environmental water samples and soil in large quantities, and potential threats are caused to human health, so that the pesticide residue problem is increasingly concerned by the public and the society. The pollution problem of methyl parathion and carbendazim is more prominent.
Methyl Parathion (MP) is a high-toxicity organic phosphate pesticide, and can inhibit cholinesterase activity in organisms, cause acute poisoning and abnormal neurobehavioral, and has immunotoxicity and carcinogenic risk. Carbendazim (CBM) belongs to benzimidazole pesticides, and is a systemic fungicide with broad-spectrum, high efficiency and low toxicity. Although carbendazim has low acute toxicity, the carbendazim has certain carcinogenicity to mammals, is a suspected endocrine disruptor, has certain reproductive toxicity and fetal teratogenicity, and can also cause chromosome aberration.
The currently known detection methods for methyl parathion and carbendazim are:
1. the method comprises the steps of chromatography-mass spectrometry (Zhang Shi Yong, Gong Yong, single Wei force. QuEChERS-high performance liquid chromatography-tandem mass spectrometry for measuring thiophanate-methyl and carbendazim [ J ] in cucumber and soil, chromatography, 2012,30(1): 91-94. Wang Haifeng, Wang Jun, Liu Hao science, and the like. gas chromatography-mass spectrometry is used for simultaneously measuring various organophosphorus pesticide residues [ J ] in fruits and vegetables, 2013,29(1): 92-94.).
2. Chromatography (Gaojie, Hudiyu, Huangrong. HPLC method for detecting the residual amount of carbendazim in cucumber and soil [ J ]. Processary of agriculture biology in mountain region, 2011,30(2): 161. 164. Libeini, Wanyilin, Jiajinping. solid phase microextraction gas chromatography of carbon fiber derived from carbendazim in fruit [ J ]. journal of environment and health, 2008,25(3): 255-257. K.Seebunrugg, Y. Santaladchai kit, P.Soisun, S.Srijarai, cationic surfactant immobilized group condensation point extraction high-performance-chromatography method for synthesis of microorganisms and analysis of inorganic nanoparticles of polysaccharides condensate resin, sample and biological sample of Biochemical engineering, 1703. Bioproduct of Biochemical engineering and Biochemical engineering, 3. 1703. Bioproduct, Biochemical engineering, 3. Biochemical engineering, Biochemical engineering and Biochemical engineering, 3. Biochemical engineering.
3. Spectrophotometry (Qufengying, Li Xiaodong, Chen Ruo, et al. ultraviolet spectroscopy of carbendazim in Mulberry leaves [ J ]. proceedings of Zhongshan university: Nature science edition, 1995,34(1): 118-.
However, there are critical problems to be solved in the detection methods of methyl parathion and carbendazim, such as:
1) the above method 1 requires a cumbersome derivatization process and sample handling.
2) The method 2 needs to consume a large amount of organic solvent which is easy to cause secondary pollution to the environment, and the instrument and equipment are expensive and need to be operated by professional personnel.
3) The method 3 has low test accuracy and high detection limit.
4) In the method, the sample must be subjected to complicated and tedious processes such as concentration or enrichment, pretreatment and the like, an instrument is expensive and cannot be carried, the detection time is long, the simultaneous detection of the methyl parathion and the carbendazim cannot be realized while the online and rapid detection cannot be met.
Based on the method, an accurate, specific, rapid, sensitive and simple analysis means is established to simultaneously detect the methyl parathion and the carbendazim, so that the method has important practical significance and market demand.
Disclosure of Invention
Aiming at the defects of the existing detection method, the invention aims to provide a method for simultaneously detecting methyl parathion and carbendazim by using a differential pulse voltammetry method.
The invention relates to a method for simultaneously detecting methyl parathion and carbendazim by using a differential pulse voltammetry, which is to detect methyl parathion and carbendazim by using a nano porous gold sensor in an acetic acid-sodium acetate buffer system through the differential pulse voltammetry;
the method is characterized in that:
the nano-porous gold sensor is a three-electrode system, a nano-porous gold (NPG)/Glassy Carbon Electrode (GCE) is used as a working electrode, a platinum electrode is used as a counter electrode, and a saturated calomel electrode is used as a reference electrode;
wherein, the nano-porous gold/glassy carbon electrode is prepared by the following steps:
1) preparing nano porous gold: placing the Au/Ag alloy sheet with the thickness of 100 +/-10 nm in pure nitric acid, and corroding for 10-60min at the temperature of 20-60 ℃ to prepare a nano porous gold film;
2) preparing an electrode: sticking the prepared nano porous gold film on the surface of a glassy carbon electrode, then dropwise adding 2-8 mu L of Nafion solution with the concentration of 0.01-5% (w/v), and baking for 5-30min by infrared to obtain a nano porous gold/glassy carbon electrode;
wherein the nanoporous gold/glassy carbon electrode is characterized by the following method:
the prepared nano porous gold/glassy carbon electrode is at 0.5M H2SO4Scanning for 5-30 circles by cyclic voltammetry to represent the effective area of the nano porous gold/glassy carbon electrode by reducing peak current;
the method for simultaneously detecting methyl parathion and carbendazim by using the differential pulse voltammetry comprises the following steps:
1) performance characterization of the sensor: detecting the current response of a sample to be detected by using a nano porous gold sensor in a 0-1.0V interval through a differential pulse voltammetry, wherein the peak potential of methyl parathion is 0.25V, the peak potential of carbendazim is 0.95V, and whether the peak potential appears is the basis for judging whether the methyl parathion or the carbendazim exists in the solution;
2) sensor calibration or calibration: simultaneously adding a methyl parathion standard substance with final concentration of 5-25 mu M and a carbendazim standard substance with final concentration of 10-75 mu M into a deoxygenated acetic acid-sodium acetate buffer system with pH 4 and 100mM, detecting the current response of the added methyl parathion standard substance with known concentration and carbendazim standard substance within the interval of 0-1.0V by using a sensor, and respectively making a concentration-current standard curve of the current response for later use; wherein the peak potential of the methyl parathion standard substance is 0.25V, the peak potential of the carbendazim standard substance is 0.95V, and whether the peak potential appears is the basis for judging whether the methyl parathion and the carbendazim exist in the solution; when the sensor is used again, the sensor is placed into a reaction system of acetic acid-sodium acetate buffer solution with pH 4 and 100mM, a methyl parathion standard substance with the final concentration of 20 mu M and a carbendazim standard substance with the final concentration of 30 mu M are added, the current response of the two standard substances is detected by the sensor within the interval of 0-1.0V, the obtained response current is substituted into a concentration-current standard curve, the actually measured concentration of the curve is calculated, and the electrode error is calibrated; after the electrode error is calibrated, the electrode is reserved;
3) detection of methyl parathion and carbendazim in actual samples: placing the calibrated or calibrated sensor into a reaction system of a deoxidized synthetic water sample, adding a sample to be detected, detecting the current response of the sample to be detected within a 0-1.0V interval by using the sensor, and judging that the sample contains methyl parathion when the peak potential is 0.25V; when the peak potential is 0.95V, the sample can be judged to contain the carbendazim; and further substituting the current response of the sample to be detected into the corresponding concentration-current standard curve for calculation, so as to respectively and correspondingly obtain the relevant contents of the methyl parathion and the carbendazim in the sample to be detected.
In the above method for simultaneously detecting methyl parathion and carbendazim by using differential pulse voltammetry, the nanoporous gold/glassy carbon electrode is preferably prepared by the following steps:
1) preparing nano porous gold: placing the Au/Ag alloy sheet with the thickness of 100 +/-10 nm in pure nitric acid, and corroding for 20-30min at the temperature of 30-50 ℃ to prepare a nano porous gold film;
2) preparing an electrode: and (3) sticking the prepared nano porous gold film on the surface of a glassy carbon electrode, dripping 4-6 mu L of 0.5% (w/v) Nafion solution, and baking for 15-20min by infrared to obtain the nano porous gold/glassy carbon electrode.
In the method for simultaneously detecting methyl parathion and carbendazim by using the differential pulse voltammetry, the deoxygenated acetic acid-sodium acetate buffer system with the pH value of 4 and the concentration of 100mM is realized by blowing high-purity nitrogen into the system for 1-30min before each electrochemical measurement. Preferably, it is maintained under high purity nitrogen throughout the experiment.
The invention discloses a method for simultaneously detecting methyl parathion and carbendazim by using a differential pulse voltammetry, which adopts a three-Electrode system with a Nano Porous Gold (NPG) and Glassy Carbon Electrode (GCE) as a working Electrode, a platinum Electrode as a counter Electrode and a saturated calomel Electrode as a reference Electrode. The method has the outstanding advantages that the nano-porous gold can be used for directly detecting the sample, the sample does not need to be subjected to complex pretreatment, further modification is not needed, and the generation of secondary pollution is effectively avoided. The method is simple and efficient, has good stability, high selectivity, low detection limit and low measurement standard deviation, and has wide application prospect.
In conclusion, the invention has the beneficial effects that:
1. the method is based on the characteristic that the nano-porous gold catalyzes and oxidizes the methyl parathion and the carbendazim, and the constructed nano-porous gold sensor is used for simultaneously detecting the methyl parathion and the carbendazim by adopting an electrochemical method. The method can effectively solve the problems that the traditional detection method for detecting the methyl parathion and the carbendazim has complicated steps and is difficult to detect simultaneously on line.
2. The detection method provided by the invention has the advantages that the performance of the experimental test electrode shows that: the linear detection range of the electrode pair methyl parathion and carbendazim is 5-25 mu M and 10-75 mu M respectively, the detection limit is as low as 0.085 mu M and 0.27 mu M respectively, and the sensitivity is 629.68 mu A cm-2mM-1And 20.53. mu.A cm-2mM-1. Therefore, the method realizes the simultaneous detection of the methyl parathion and the carbendazim with high sensitivity and high accuracy by utilizing the unique physical and chemical properties and structural functions of the nano porous gold, greatly improves the working efficiency and has wide application prospect.
3. The invention also shows that the nano porous gold sensor shows good stability and high selectivity for detecting methyl parathion and carbendazim through an anti-interference capability test.
Drawings
Fig. 1 is a diagram of the detection of methyl parathion and carbendazim standard products respectively based on a nano porous gold sensor.
Wherein: panel A is methyl parathion; and the figure B is carbendazim.
Figure 2 is a detection map of a nanoporous gold-based sensor for a mixture of parathion-methyl and carbendazim standards.
Fig. 3 is a graph of interference rejection detection for a nanoporous gold based sensor.
Detailed Description
Example 1
Preparing and characterizing a sensor: assembling a nano porous gold sensor of a three-electrode system by taking an NPG/GCE electrode as a working electrode, a platinum electrode as a counter electrode and a saturated calomel electrode as a reference electrode; at 0.5M H2SO4Carrying out cyclic voltammetry scanning for 15 circles to reduce peak-to-peak current to characterize the effective area of the NPG/GCE electrode;
and (3) detecting standard substances of methyl parathion and carbendazim: purging 15mL of acetic acid-sodium acetate buffer solution with the pH of 4.0 and the concentration of 100mM for 5min by using high-purity nitrogen, putting the prepared sensor into a deoxygenated acetic acid-sodium acetate buffer solution reaction system, respectively adding methyl parathion with the final concentration of 0.5-150 mu M and carbendazim standard substance with the final concentration of 3-120 mu M, and detecting the current response of the added standard substance with the known concentration in a 0-0.5V interval and a 0.7-1.0V interval by using the sensor; in a very short time, obvious oxidation peaks appear at 0.25V and 0.95V respectively, and the detection result is shown in FIG. 1. The peak potential is the basis for judging whether the methyl parathion and the carbendazim exist in the solution or not; the constructed electrode shows good catalytic performance on methyl parathion and carbendazim, and has good rapidity and accuracy.
The preparation method of the NPG/GCE electrode comprises the following steps:
1) preparing nano porous gold: placing the Au/Ag alloy sheet with the thickness of 100nm in pure nitric acid, and corroding for 60min at the temperature of 20 ℃ to prepare a nano porous gold film;
2) preparing an electrode: and (2) sticking the nano porous gold prepared in the step 1) on the surface of a glassy carbon electrode, then dropwise adding 8 mu L of Nafion solution (0.01%, w/v), and carrying out infrared baking for 5min to obtain the NPG/GCE electrode.
Example 2
Preparing and characterizing a sensor: assembling the nano-porous gold sensor of a three-electrode system by taking the prepared NPG/GCE electrode as a working electrode, a platinum electrode as a counter electrode and a saturated calomel electrode as a reference electrode; at 0.5M H2SO4Carrying out cyclic voltammetry scanning for 15 circles to reduce peak-to-peak current to characterize the effective area of the NPG/GCE electrode;
sensor calibration or calibration: blowing 15mL of acetic acid-sodium acetate buffer solution with the pH value of 4.0 and the concentration of 100mM for 5min by using high-purity nitrogen, putting the prepared sensor into a deoxygenated acetic acid-sodium acetate buffer solution reaction system, simultaneously adding a methyl parathion standard substance with the final concentration of 5-25 mu M and a carbendazim standard substance with the final concentration of 10-75 mu M, detecting corresponding current responses of the added methyl parathion standard substance with known concentration and the carbendazim standard substance within the interval of 0-1.0V by using the sensor, and respectively making a concentration-current standard curve of the current responses for later use; wherein the peak potential of the methyl parathion standard substance is 0.25V, the peak potential of the carbendazim standard substance is 0.95V, and whether the peak potential appears is the basis for judging whether the methyl parathion and the carbendazim exist in the solution; when the sensor is used again, the sensor is placed into a reaction system of acetic acid-sodium acetate buffer solution, a methyl parathion standard substance with the final concentration of 20 mu M and a carbendazim standard substance with the final concentration of 30 mu M are added, the current response of the two standard substances is detected within the interval of 0-1.0V by using the sensor, the obtained response current is substituted into a concentration-current standard curve, the actual measurement concentration of the standard substance is calculated, and the electrode error is calibrated; after the electrode error is calibrated, the electrode is reserved; the constructed sensor can realize the simultaneous and sensitive detection of the methyl parathion and the carbendazim.
The preparation method of the NPG/GCE electrode comprises the following steps:
1) preparing nano porous gold: placing the Au/Ag alloy sheet with the thickness of 100nm in pure nitric acid, and corroding for 30min at the temperature of 30 ℃ to prepare a nano porous gold film;
2) preparing an electrode: and (2) sticking the nano porous gold prepared in the step 1) on the surface of a glassy carbon electrode, then dropwise adding 6 mu L of Nafion solution (1%, w/v), and carrying out infrared baking for 10min to obtain the NPG/GCE electrode.
Example 3
Preparing and characterizing a sensor: assembling the nano-porous gold sensor of a three-electrode system by taking the prepared NPG/GCE electrode as a working electrode, a platinum electrode as a counter electrode and a saturated calomel electrode as a reference electrode; at 0.5M H2SO4Carrying out cyclic voltammetry scanning for 15 circles to reduce peak-to-peak current to characterize the effective area of the NPG/GCE electrode;
sensor calibration or calibration: blowing 15mL of acetic acid-sodium acetate buffer solution with the pH value of 4 and the concentration of 100mM for 5min by using high-purity nitrogen, putting the prepared sensor into a deoxygenated acetic acid-sodium acetate buffer solution reaction system, respectively adding a methyl parathion standard substance with the final concentration of 5-25 mu M and a carbendazim standard substance with the final concentration of 10-75 mu M, detecting the current response of the added carbendazim standard substance with known concentration and the added methyl parathion standard substance within the interval of 0-1.0V by using the sensor, and respectively making a concentration-current standard curve of the current response for later use; wherein the peak potential of the methyl parathion standard substance is 0.25V, the peak potential of the carbendazim standard substance is 0.95V, and whether the peak potential appears is the basis for judging whether the methyl parathion and the carbendazim exist in the solution; when the sensor is used again, the sensor is placed into a reaction system of acetic acid-sodium acetate buffer solution, a methyl parathion standard substance with the final concentration of 20 mu M and a carbendazim standard substance with the final concentration of 30 mu M are added, the current response of the two standard substances is detected within the interval of 0-1.0V by using the sensor, the obtained response current is substituted into a concentration-current standard curve, the actual measurement concentration of the standard substance is calculated, and the electrode error is calibrated; after the electrode error is calibrated, the electrode is reserved;
anti-interference detection: putting the sensor calibrated or calibrated in the step (2) into a reaction system of acetic acid-sodium acetate buffer solution, and adding four cations (Mg) with the concentration of 100 times of that of a target substance2+、NH4 +、K+、Na+) And four anions (SO)4 2-、PO4 3-、 CO3 2-、NO3 -) Adding into acetic acid-sodium acetate buffer containing 5 μ M methyl parathion and 50 μ M carbendazimIn the liquid system, the current response of the added methyl parathion and carbendazim standard substance with known concentration is respectively detected by using a sensor in the range of 0-1.0V, and when the peak potential is 0.25V, the methyl parathion in the detection system can be judged; when the peak potential is 0.95V, the detection system can be judged to contain the carbendazim. And further substituting the current response of the sample to be detected into a concentration-current standard curve for calculation, so as to correspondingly obtain the contents of the related carbendazim and the methyl parathion in the sample to be detected. After the interferents are added, the peak potential and the peak current density of carbendazim and methyl parathion are not obviously interfered, the change of current signals is below 3.51 percent, and the detection result is shown in figure 3. The constructed sensor has strong anti-interference capability.
The preparation method of the NPG/GCE electrode comprises the following steps:
1) preparing nano porous gold: placing the Au/Ag alloy sheet with the thickness of 100nm in pure nitric acid, and corroding for 20min at the temperature of 40 ℃ to prepare a nano porous gold film;
2) preparing an electrode: and (2) sticking the nano porous gold prepared in the step 1) on the surface of a glassy carbon electrode, then dropwise adding 4 mu L of Nafion solution (5%, w/v), and carrying out infrared baking for 30min to obtain the NPG/GCE electrode.
Example 4
Preparing and characterizing a sensor: assembling the nano-porous gold sensor of a three-electrode system by taking the prepared NPG/GCE electrode as a working electrode, a platinum electrode as a counter electrode and a saturated calomel electrode as a reference electrode; at 0.5M H2SO4Carrying out cyclic voltammetry scanning for 15 circles to reduce peak-to-peak current to characterize the effective area of the NPG/GCE electrode;
sensor calibration or calibration: blowing 15mL of acetic acid-sodium acetate buffer solution with the pH value of 4.0 and the concentration of 100mM for 5min by using high-purity nitrogen, putting the prepared sensor into a deoxygenated acetic acid-sodium acetate buffer solution reaction system, respectively adding a methyl parathion standard substance with the final concentration of 5-25 mu M and a carbendazim standard substance with the final concentration of 10-75 mu M, detecting the current response of the added methyl parathion standard substance with known concentration and carbendazim standard substance by using the sensor within the interval of 0-1.0V, and respectively making a concentration-current standard curve of the current response for later use; wherein the peak potential of the methyl parathion standard substance is 0.25V, the peak potential of the carbendazim standard substance is 0.95V, and whether the peak potential appears is the basis for judging whether the methyl parathion and the carbendazim exist in the solution; when the sensor is used again, the sensor is placed into a reaction system of acetic acid-sodium acetate buffer solution, a methyl parathion standard substance with the final concentration of 20 mu M and a carbendazim standard substance with the final concentration of 30 mu M are added, the current response of the two standard substances is detected within the interval of 0-1.0V by using the sensor, the obtained response current is substituted into a concentration-current standard curve, the actual measurement concentration of the standard substance is calculated, and the electrode error is calibrated; after the electrode error is calibrated, the electrode is reserved;
detecting methyl parathion and carbendazim in an actual sample: placing the calibrated or calibrated sensor into a reaction system of a deoxidized synthetic water sample, respectively adding a sample to be detected, detecting the current response of the sample to be detected within a 0-1.0V interval by using the sensor, and judging that the sample contains methyl parathion when the peak potential is 0.25V; when the peak potential is 0.95V, the sample can be judged to contain the carbendazim. And further substituting the current response of the sample to be detected into the corresponding concentration-current standard curve for calculation, so as to respectively and correspondingly obtain the contents of the relevant methyl parathion and carbendazim in the sample to be detected, wherein the detection results are shown in table 1. Indicating that the constructed sensor can be used for actual detection.
The preparation method of the NPG/GCE electrode comprises the following steps:
1) preparing nano porous gold: placing the Au/Ag alloy sheet with the thickness of 100nm in pure nitric acid, and corroding for 10min at the temperature of 50 ℃ to prepare a nano porous gold film;
2) preparing an electrode: and (2) sticking the nano porous gold prepared in the step 1) on the surface of a glassy carbon electrode, then dropwise adding 4 mu L of Nafion solution (0.5%, w/v), and carrying out infrared baking for 15min to obtain the NPG/GCE electrode.
Table 1 is a detection table for detecting methyl parathion and carbendazim in actual samples by utilizing a sensor based on nanoporous gold
From the table 1, under the conditions of low concentration, high concentration and intermediate concentration, the recovery rate of the electrode for the simultaneous detection of methyl parathion and carbendazim is good, and the deviation rate is less than 5.1%, which indicates that the constructed NPG/GCE electrode has good practical applicability and can be used for the detection of practical samples.
Claims (1)
1. A method for detecting carbendazim by using differential pulse voltammetry is characterized in that a nano porous gold sensor is used for detecting in an acetic acid-sodium acetate buffer system by using differential pulse voltammetry;
wherein: the nano porous gold sensor is a three-electrode system, a nano porous gold/glassy carbon electrode is used as a working electrode, a platinum electrode is used as a counter electrode, and a saturated calomel electrode is used as a reference electrode;
wherein, the nano-porous gold/glassy carbon electrode is prepared by the following steps:
1) preparing nano porous gold: placing the Au/Ag alloy sheet with the thickness of 100 +/-10 nm in pure nitric acid, and corroding for 20-30min at the temperature of 40-50 ℃ to prepare a nano porous gold film;
2) preparing an electrode: sticking the prepared nano porous gold film on the surface of a glassy carbon electrode, dripping 4-6 mu L of Nafion solution with the concentration of 0.5% (w/v), and baking for 15-20min by infrared to prepare a nano porous gold/glassy carbon electrode;
wherein the nanoporous gold/glassy carbon electrode is characterized by the following method:
the prepared nano porous gold/glassy carbon electrode is at 0.5M H2SO4Scanning for 5-30 circles by cyclic voltammetry to represent the effective area of the nano porous gold/glassy carbon electrode by reducing peak current;
the method is characterized in that:
the method for detecting carbendazim by using the differential pulse voltammetry comprises the following steps:
1) performance characterization of the sensor: detecting the current response of a sample to be detected by using a nano porous gold sensor in a 0-1.0V interval through a differential pulse voltammetry, wherein the peak potential of the carbendazim is 0.95V, and whether the peak potential appears is a basis for judging whether the carbendazim exists in a solution;
2) sensor calibration or calibration: adding a carbendazim standard substance with the final concentration of 10-75 mu M into a deoxygenated acetic acid-sodium acetate buffer system with the pH value of 4 and the concentration of 100mM, detecting the current response of the added carbendazim standard substance with the known concentration within the interval of 0-1.0V by using a sensor, and making a concentration-current standard curve of the current response for later use; wherein the deoxygenated pH 4, 100mM acetic acid-sodium acetate buffer system is achieved by blowing high purity nitrogen into the system for 1-30min before each electrochemical measurement; wherein the peak potential of the carbendazim standard product is 0.95V, and whether the peak potential appears is a basis for judging whether the carbendazim exists in the solution; when the sensor is used again, the sensor is placed into a reaction system of acetic acid-sodium acetate buffer solution with pH 4 and 100mM, carbendazim standard substance with final concentration of 30 mu M is added, the current response of the standard substance is detected by the sensor within the interval of 0-1.0V, the obtained response current is substituted into a concentration-current standard curve, and the actually measured concentration is calculated to calibrate the electrode error; after the electrode error is calibrated, the electrode is reserved;
3) detection of carbendazim in actual samples: placing the calibrated or calibrated sensor into a reaction system of a deoxidized synthetic water sample, adding a sample to be detected, detecting the current response of the sample to be detected within a 0-1.0V interval by using the sensor, and judging that the sample contains the carbendazim when the peak potential is 0.95V; and further substituting the current response of the sample to be detected into the corresponding concentration-current standard curve for calculation, so as to correspondingly obtain the related content of the carbendazim in the sample to be detected.
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| KR101047115B1 (en) * | 2009-07-28 | 2011-07-07 | 광운대학교 산학협력단 | Fusion electrode for sensor and manufacturing method thereof |
| CN102636537A (en) * | 2012-04-19 | 2012-08-15 | 湖南大学 | Enzyme-free methyl parathion detection sensor, and preparation and application methods thereof |
| 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 |
| CN105588869B (en) * | 2015-12-03 | 2018-02-23 | 山东大学 | A kind of method of aromatic pollution in hydrogen peroxide sersor quick detection waste water using nano-porous gold |
| JP6441282B2 (en) * | 2016-09-27 | 2018-12-19 | 三井化学アグロ株式会社 | Agro-horticultural wettable powder with improved physicochemical properties |
| CN107151807B (en) * | 2017-04-28 | 2018-12-21 | 中国科学院合肥物质科学研究院 | Porous golden micro-nano structure of hemispherical shell and its preparation method and application |
| CN107976473A (en) * | 2017-11-22 | 2018-05-01 | 陕西盛迈石油有限公司 | A kind of preparation method of L-cysteine modified nano gold pore membrane electrode |
| CN108593729A (en) * | 2018-06-27 | 2018-09-28 | 中山大学 | A kind of preparation method of the porous golden blood glucose micropin electrochemical sensor module of no proteins carry enzyme |
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