CN111943179B - Nitrogen-doped three-dimensional porous graphene-based electrode material and preparation method and application thereof - Google Patents
Nitrogen-doped three-dimensional porous graphene-based electrode material and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a nitrogen-doped three-dimensional porous graphene-based electrode material and a preparation method and application thereof, and belongs to the technical field of electrochemistry. The preparation method comprises the following specific steps: 1) mixing the graphene oxide solution with a hydrogen peroxide solution, and reacting to obtain three-dimensional porous graphene oxide; 2) mixing three-dimensional porous graphene oxide and urea, and carrying out hydrothermal reaction to obtain nitrogen-doped three-dimensional porous graphene; 3) and preparing the nitrogen-doped three-dimensional porous graphene into a dispersion liquid, and dropwise adding the dispersion liquid to the center of the glassy carbon electrode substrate to obtain the nitrogen-doped three-dimensional porous graphene-based electrode material. The nitrogen-doped three-dimensional porous graphene-based electrode material prepared by the method is used in an electrochemical sensor, can detect the content of the organophosphorus pesticide methyl parathion, and has the advantages of high sensitivity, short response time, strong anti-interference capability, good repeatability, good long-term stability and high recovery rate.
Description
Technical Field
The invention belongs to the technical field of electrochemistry, and particularly relates to a nitrogen-doped three-dimensional porous graphene-based electrode material as well as a preparation method and application thereof.
Background
Organophosphorus Pesticides (OPs) have been used in agricultural production for many years to improve agricultural productivity due to their strong toxicity, good efficacy and the like, Methyl Parathion (MP) is the most commonly used organophosphorus pesticide in agricultural pest control, but its environmental pollution is not negligible, even a small amount of MP residue pollutes water and soil, and in addition, MP may permeate plant tissues and remain in plants, such as fruits and vegetables, once ingested by the human body, even a trace amount of MP residue may cause degeneration of human acetylcholinesterase (AChE) to cause interruption of nerve signal transmission, thereby causing severe consequences such as muscle paralysis, convulsion, bronchoconstriction and death. Therefore, rapid, accurate and sensitive detection is carried out on MP, and the method has important significance on human health and environmental safety.
Currently, residual MP can be detected by Gas Chromatography (GC), High Performance Liquid Chromatography (HPLC), gas chromatography-mass spectrometry (GC/MS), enzyme-linked immunoassay (EIA), surface enhanced raman spectroscopy, and other analytical methods. However, most of these methods require large-scale instruments, are complicated in process operation, cannot be detected on site, and have adverse effects on repeatability and accuracy of actual experiments due to the fact that enzymes are diverse in source and difficult to store. Therefore, finding a simple, low-cost, and time-consuming MP detection method is still a hot spot of research.
In contrast, electrochemical sensors have the advantages of small size, field-testability, low cost, short response time, and the like, and are an alternative detection method. In recent years, some electrode materials such as copper oxide-titanium dioxide, gold-zirconium oxide-graphene, gold nano/neutral red bio-functionalized graphene, etc. are used to construct electrochemical sensors for MP content detection. Graphene-based electrochemical sensors have received much attention due to their excellent electrochemical properties, high sensitivity and good stability.
However, in the application process, the graphene-based electrode materials are easy to agglomerate and overlap, the graphene does not have an energy gap, and the conductivity of the graphene cannot be easily controlled like that of a traditional semiconductor, so that the performance of the sensor is greatly influenced; in addition, the surface of graphene is smooth and inert, which is not beneficial to further compounding with other materials. These problems described above have severely hampered the use of graphene-based electrochemical sensors in the detection of pesticides.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a nitrogen-doped three-dimensional porous graphene-based electrode material, a preparation method and application thereof, which can enable the electrochemical active sites of the current graphene-based electrochemical electrode material to be more, and an electrochemical sensor prepared by adopting the electrode material has higher sensitivity and anti-interference capability, and good repeatability and stability.
The technical scheme of the invention is as follows:
the invention provides a preparation method of a nitrogen-doped three-dimensional porous graphene-based electrode material, which comprises the following steps:
1) ultrasonically mixing a graphene oxide solution and a hydrogen peroxide solution, placing the mixture in a reaction container for reaction, and then washing and drying the mixture to obtain three-dimensional porous graphene oxide;
2) dissolving the three-dimensional porous graphene oxide obtained in the step 1) in ultrapure water, mixing with urea, performing ultrasonic treatment, placing in a reaction container for hydrothermal reaction, and then washing and drying to obtain nitrogen-doped three-dimensional porous graphene; the mass concentration of the three-dimensional porous graphene oxide is 1-3 mg/mL, and the mass ratio of urea to the three-dimensional porous graphene oxide is 60: 1-30: 1; the temperature of the hydrothermal reaction is 170-195 ℃, and the time is 10-14 h;
3) preparing the nitrogen-doped three-dimensional porous graphene obtained in the step 2) into a dispersion liquid, dropwise adding the dispersion liquid to the center of the glassy carbon electrode substrate, and carrying out vacuum-pumping drying at 15-30 ℃ to obtain the nitrogen-doped three-dimensional porous graphene-based electrode material.
Optionally, in the step 1), the graphene oxide solution is an aqueous solution of graphene oxide, and the mass concentration of the graphene oxide is 1-5 mg/mL; the hydrogen peroxide solution is a hydrogen peroxide aqueous solution, and the mass percentage of the hydrogen peroxide is 20-40%; the volume ratio of the graphene oxide solution to the hydrogen peroxide solution is 5: 1-15: 1.
Optionally, in the step 1), the time of the ultrasonic treatment is 15-20 min, the reaction temperature is 95-105 ℃, and the reaction time is 2-5 h.
Alternatively, in step 1), the washing refers to dialyzing the product of the reaction for 4 to 7 days.
Optionally, in the step 2), the time of the ultrasonic treatment is 20-30 min; the washing means immersing the reaction product in water for 1 to 2 days.
Optionally, in step 2), the drying is freeze drying, and the specific process is as follows: and (3) quickly freezing the washing product in liquid nitrogen, and then placing the washing product in a freeze dryer for freeze drying, wherein the temperature in the freeze drying process is between 55 ℃ below zero and 45 ℃ below zero, and the time is 10 to 15 hours.
The invention also provides the nitrogen-doped three-dimensional porous graphene-based electrode material prepared by the preparation method and an electrochemical sensor prepared from the nitrogen-doped three-dimensional porous graphene-based electrode material.
The invention also provides application of the nitrogen-doped three-dimensional porous graphene-based electrode material or the electrochemical sensor in detecting the content of the organophosphorus pesticide methyl parathion.
According to the invention, the nitrogen-doped three-dimensional porous graphene not only has a microporous structure in a three-dimensional space, but also has in-plane nanopores in a two-dimensional plane, and the abundant pore structures effectively increase the exposed edge number and defect density of the graphene, so that the aggregation of graphene nanosheets on a sensor substrate is inhibited, the graphene has a larger specific surface area, and after nitrogen doping, the content of pyrrole nitrogen in the graphene structure is greatly increased, the electrochemical active sites of the graphene are increased, the adsorption capacity is improved, and the improvement of the material transmission capacity is facilitated. Therefore, the structures greatly improve the electrochemical performance of the nitrogen-doped three-dimensional porous graphene.
Compared with the prior art, the invention has the following beneficial effects:
1) the nitrogen-doped three-dimensional porous graphene-based electrode material prepared by the invention can be used in an electrochemical sensor, can quickly detect the concentration of methyl parathion, has the characteristics of high sensitivity, short response time, strong anti-interference capability, good repeatability, good long-term stability and high recovery rate, and has good application potential in the aspect of quickly detecting the content of methyl parathion;
2) firstly, preparing three-dimensional porous graphene oxide by using hydrogen peroxide as an etching agent; then, urea is used as a nitrogen source, and a hydrothermal method is adopted to prepare the nitrogen-doped three-dimensional porous graphene which is rich in three-dimensional micropores and two-dimensional in-plane nanopores and has a high specific surface area; and finally, dropwise adding the suspension of the nitrogen-doped three-dimensional porous graphene to the center of the substrate, and depositing the nitrogen-doped three-dimensional porous graphene by a vacuum-pumping drying method at room temperature to obtain the nitrogen-doped three-dimensional porous graphene-based electrode material, wherein the preparation method is simple and rapid.
Drawings
Fig. 1 is an SEM image of the nitrogen-doped three-dimensional porous graphene prepared in example 3.
Fig. 2 is a TEM image of the nitrogen-doped three-dimensional porous graphene prepared in example 3.
Fig. 3 shows (a) a full spectrum and (b) an N1s high resolution XPS spectrum of the nitrogen-doped three-dimensional porous graphene prepared in example 3.
Fig. 4(a) is a cyclic voltammogram of the nitrogen-doped three-dimensional porous graphene-based electrode material (N-HG50/GCE) prepared in example 3 and a common Glassy Carbon Electrode (GCE) in 0.1M phosphate buffer (pH 7) containing MP (25 μ M) at a scan rate of 0.05V/s; (b) is the corresponding differential pulse voltammogram.
Fig. 5(a) is a differential pulse voltammogram of the nitrogen-doped three-dimensional porous graphene-based electrode material prepared in example 3 after sequentially adding a series of concentrations of MP solution to 0.1M phosphate buffer (pH 7); (b) fitting curve corresponding to differential pulse voltammogram
FIG. 6 is a graph showing the peak current of differential pulse voltammetry measured after adding a concentration of interfering substance 100 times to the MP test substance solution.
Fig. 7 is a repetitive bar graph of the electrode after the nitrogen-doped three-dimensional porous graphene-based electrode material prepared in example 3 is repeatedly used 10 times in 0.1M phosphate buffer (pH 7.0) containing MP (10 μ M).
Fig. 8 is a bar graph of the long-term stability of the nitrogen-doped three-dimensional porous graphene-based electrode material prepared in example 3 in 0.1M phosphate buffer (pH 7.0) containing MP (10 μ M) for 21 days.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments. The following examples are carried out on the premise of the technical scheme of the present invention, and detailed embodiments and specific operation procedures are given, but the scope of the present invention is not limited to the following examples.
As used herein, "room temperature" means a temperature of 15 to 30 ℃.
Example 1
A preparation method of a nitrogen-doped three-dimensional porous graphene-based electrode material comprises the following steps:
1) taking 50mL of graphene oxide (2mg/mL) solution, adding a hydrogen peroxide solution (30 wt.%) according to the volume ratio of the graphene oxide solution to the hydrogen peroxide solution of 15:1, carrying out ultrasonic treatment for 15min, transferring the mixed solution of the graphene oxide and the hydrogen peroxide into a round-bottom flask, and reacting for 5h at the temperature of 95 ℃; soaking the obtained product in ultrapure water for dialysis for 4 days to remove excessive hydrogen peroxide impurities, then quickly freezing in liquid nitrogen, and continuously freezing and drying for 10 hours in a freeze dryer to obtain a three-dimensional porous graphene oxide solid;
2) dissolving 70mg of the obtained three-dimensional porous graphene oxide solid in 70mL of ultrapure water, and then mixing the urea solid with the three-dimensional porous graphene oxide according to the mass ratio of 60: 1, adding urea, carrying out ultrasonic treatment for 20min, then transferring to a high-pressure reaction kettle, reacting for 14h at the high temperature of 170 ℃, immersing the obtained product in ultrapure water, washing for 1 day to remove excessive urea impurities, then quickly freezing in liquid nitrogen, and continuously freezing and drying for 12h in a freeze dryer to obtain a nitrogen-doped three-dimensional porous graphene solid;
3) and (3) dropwise adding 6 mu L of nitrogen-doped three-dimensional porous graphene suspension (0.2 mg/mL of nitrogen-doped three-dimensional porous graphene suspension prepared by using ultrapure water as a nitrogen-doped three-dimensional porous graphene solid) to the center of the glassy carbon electrode substrate, and vacuumizing and drying at room temperature to obtain the nitrogen-doped three-dimensional porous graphene-based electrode material.
Example 2
A preparation method of a nitrogen-doped three-dimensional porous graphene-based electrode material comprises the following steps:
1) taking 50mL of graphene oxide (2mg/mL) solution, adding a hydrogen peroxide solution (20 wt.%) according to the volume ratio of the graphene oxide solution to the hydrogen peroxide solution of 12:1, carrying out ultrasonic treatment for 20min, transferring the mixed solution of the graphene oxide and the hydrogen peroxide into a round-bottom flask, and reacting for 3h at the temperature of 100 ℃; soaking the obtained product in ultrapure water for dialysis for 5 days to remove excessive hydrogen peroxide impurities, then quickly freezing in liquid nitrogen, and continuously freezing and drying in a freeze dryer for 12 hours to obtain a three-dimensional porous graphene oxide solid;
2) dissolving 70mg of the obtained three-dimensional porous graphene oxide solid in 50mL of ultrapure water, and then mixing the urea solid with the three-dimensional porous graphene oxide according to a mass ratio of 45: 1, adding urea, carrying out ultrasonic treatment for 25min, then transferring to a high-pressure reaction kettle, reacting for 12h at a high temperature of 180 ℃, immersing the obtained product in ultrapure water, washing for 2 days to remove excessive urea impurities, then quickly freezing in liquid nitrogen, and continuously freezing and drying for 12h in a freeze dryer to obtain a nitrogen-doped three-dimensional porous graphene solid;
3) and (3) dropwise adding 6 mu L of nitrogen-doped three-dimensional porous graphene suspension (0.2 mg/mL of nitrogen-doped three-dimensional porous graphene suspension prepared by using ultrapure water as a nitrogen-doped three-dimensional porous graphene solid) to the center of the glassy carbon electrode substrate, and vacuumizing and drying at room temperature to obtain the nitrogen-doped three-dimensional porous graphene-based electrode material.
Example 3
A preparation method of a nitrogen-doped three-dimensional porous graphene-based electrode material comprises the following steps:
1) taking 50mL of graphene oxide (2mg/mL) solution, adding a hydrogen peroxide solution (40 wt.%) according to the volume ratio of the graphene oxide solution to the hydrogen peroxide solution of 10:1, carrying out ultrasonic treatment for 15min, transferring the mixed solution of the graphene oxide and the hydrogen peroxide into a round-bottom flask, and reacting for 3.5h at the temperature of 100 ℃; soaking the obtained product in ultrapure water for dialysis for 6 days to remove excessive hydrogen peroxide impurities, then quickly freezing in liquid nitrogen, and continuously freezing and drying in a freeze dryer for 12 hours to obtain a three-dimensional porous graphene oxide solid;
2) dissolving 70mg of the obtained three-dimensional porous graphene oxide solid in 35mL of ultrapure water, wherein the mass ratio of the urea solid to the three-dimensional porous graphene oxide is 50: 1, adding urea, carrying out ultrasonic treatment for 30min, then transferring to a high-pressure reaction kettle, reacting for 13h at a high temperature of 188 ℃, immersing the obtained product in ultrapure water, washing for 2 days to remove excessive urea impurities, then quickly freezing in liquid nitrogen, and continuously freezing and drying for 12h in a freeze dryer to obtain a nitrogen-doped three-dimensional porous graphene solid (N-HG 50);
3) and (3) dropwise adding 6 mu L of nitrogen-doped three-dimensional porous graphene suspension (0.2 mg/mL of nitrogen-doped three-dimensional porous graphene suspension prepared by using ultrapure water as a nitrogen-doped three-dimensional porous graphene solid) to the center of the glassy carbon electrode substrate, and performing vacuum drying at room temperature to obtain the nitrogen-doped three-dimensional porous graphene-based electrode material (N-HG 50/GCE).
Example 4
A preparation method of a nitrogen-doped three-dimensional porous graphene-based electrode material comprises the following steps:
1) taking 50mL of graphene oxide (2mg/mL) solution, adding a hydrogen peroxide solution (30 wt.%) according to the volume ratio of the graphene oxide solution to the hydrogen peroxide solution of 5:1, carrying out ultrasonic treatment for 20min, transferring the mixed solution of the graphene oxide and the hydrogen peroxide into a round-bottom flask, and reacting for 2h at the temperature of 105 ℃; soaking the obtained product in ultrapure water for dialysis for 7 days to remove excessive hydrogen peroxide impurities, then quickly freezing in liquid nitrogen, and continuously freezing and drying for 12 hours in a freeze dryer to obtain a three-dimensional porous graphene oxide solid;
2) dissolving 70mg of the obtained three-dimensional porous graphene oxide solid in 50mL of ultrapure water, and then mixing the urea solid with the three-dimensional porous graphene oxide according to the mass ratio of 30: 1, adding urea, carrying out ultrasonic treatment for 25min, then transferring to a high-pressure reaction kettle, reacting for 10h at a high temperature of 195 ℃, immersing the obtained product in ultrapure water, washing for 2 days to remove excessive urea impurities, then quickly freezing in liquid nitrogen, and continuously freezing and drying for 12h in a freeze dryer to obtain a nitrogen-doped three-dimensional porous graphene solid;
3) and (3) dropwise adding 6 mu L of nitrogen-doped three-dimensional porous graphene suspension (0.2 mg/mL of nitrogen-doped three-dimensional porous graphene suspension is prepared from nitrogen-doped three-dimensional porous graphene solid by ultrapure water) to the center of the electrode substrate, and vacuumizing and drying at room temperature to obtain the nitrogen-doped three-dimensional porous graphene-based electrode material.
Test example
Scanning Electron Microscope (SEM) and Transmission Electron Microscope (TEM) characterization was performed on the nitrogen-doped three-dimensional porous graphene prepared in example 3. FIG. 1 is an SEM image of nitrogen-doped three-dimensional porous graphene, which shows that the graphene material has abundant three-dimensional network micropores, and the pore size range of the graphene material is 0.1-10 μm; fig. 2 is a TEM image of the nitrogen-doped three-dimensional porous graphene, which shows that a large number of two-dimensional in-plane nanopores are distributed on the basal plane of the graphene, and the pore size ranges from 1 nm to 4.8 nm.
X-ray photoelectron spectroscopy (XPS) was performed on the nitrogen-doped three-dimensional porous graphene prepared in example 3, and the result is shown in fig. 3. Fig. 3(a) shows that nitrogen doping was successfully performed on porous graphene oxide, and fig. 3(b) analyzes 4 different N-functional group contents of the nitrogen-doped three-dimensional porous graphene prepared in example 3, wherein the pyrrole nitrogen content is the highest.
The solution containing 25 μ M MP was detected using the nitrogen-doped three-dimensional porous graphene-based electrode material prepared in example 3, and a cyclic voltammogram and a differential pulse voltammogram were obtained, and the results are shown in fig. 4. As shown in fig. 4(a), when 25 μ M methyl parathion was added to 0.1M phosphate buffer (pH 7), the glassy carbon electrode exhibited a pair of redox reaction peaks and one reduction peak, but the redox reaction peaks were not distinct and the peak current was weak. However, 3 good resolution peaks can be observed in the nitrogen-doped three-dimensional porous graphene-based electrode material prepared in example 3, which proves that the nitrogen-doped three-dimensional porous graphene-based electrode material can sensitively, rapidly and accurately detect MP. The results are also shown in fig. 4(b), and the nitrogen-doped three-dimensional porous graphene-based electrode material prepared in example 3 not only reduces the position of the reduction peak, but also has a peak current 2.27 times that of a glassy carbon electrode.
Preparation of the resin composition of example 3The obtained nitrogen-doped three-dimensional porous graphene-based electrode material is used for detecting MP solutions with different concentrations to obtain differential pulse voltammograms, and the results are respectively shown in fig. 5 (a). The results showed that the peak current was gradually increased as the concentration of MP was increased by continuously adding MP to each of 0.1M phosphate buffers (pH 7). Fitting a Linear plot of electrode peak current and MP concentration at-0.6V Voltage, as shown in FIG. 5 (b), R of the equation is linearly fitted when the MP concentration is between 3.8nM and 570. mu.M20.999. The above data show that there is a good linear relationship between the concentration of MP and the electrode peak current.
MP and other interfering substances are detected by using the nitrogen-doped three-dimensional porous graphene-based electrode material prepared in the embodiment 3, such as: p-nitrophenol, Na+,K+,CO3 2-,PO4 2-,Cl-,Fe2+/Fe3+,NO3 -and chloritropifos to obtain a differential pulse volt-ampere peak current response histogram. Differential pulse voltammetry is adopted to record differential pulse voltammetry peak current of MP (10 mu M) in 0.1M phosphate buffer solution (pH 7), and then a plurality of interfering substances with 100-fold concentration are respectively added, so that as shown in FIG. 6, when the concentration of the interfering substances is 100 times of the concentration of the detection substance, the influence on the MP current response detected by the nitrogen-doped three-dimensional porous graphene-based electrode material can be ignored. The electrochemical sensor based on the nitrogen-doped three-dimensional porous graphene-based electrode material has good selectivity and anti-interference capability for detecting MP.
MP is detected by using the nitrogen-doped three-dimensional porous graphene-based electrode material prepared in the embodiment 3, and a repetitive histogram is obtained. The nitrogen-doped three-dimensional porous graphene-based electrode material is repeatedly measured in a 10 mu M methyl parathion standard solution for 10 times by adopting a differential pulse voltammetry method, and the result is shown in fig. 7, wherein the relative standard deviation RSD of the detection result is 2.17%, which shows that the nitrogen-doped three-dimensional porous graphene-based electrode material has good repeatability for MP detection.
MP is detected by using the nitrogen-doped three-dimensional porous graphene-based electrode material prepared in the embodiment 3, and a long-term stability histogram is obtained. As shown in fig. 8, a differential pulse voltammetry is used for detecting a 10 μ M methyl parathion standard solution, the peak current response of the nitrogen-doped three-dimensional porous graphene-based electrode material for detecting MP is recorded once every three days, the peak current response is continuously recorded for 21 days (three weeks), the non-detection time three-dimensional porous nitrogen-doped graphene modified electrode is stored in a 4 ℃ refrigerator, and after three weeks, the MP peak current detected by the nitrogen-doped three-dimensional porous graphene-based electrode material is 95.4% of the first detection peak current, which indicates that the nitrogen-doped three-dimensional porous graphene-based electrode material has good long-term stability.
The content of MP in apple, broccoli, and river water was measured using the nitrogen-doped three-dimensional porous graphene-based electrode material prepared in example 3, and the results are shown in table 1, where the test method employs a standard addition method, MP of different concentrations was added to phosphate buffer (pH 7) containing a certain volume of test sample, differential pulse voltammetry curves of each measurement were recorded, and the content of MP in the test solution was calculated according to the standard equation curve. As can be seen from Table 1, the recovery rate of MP is very good, the recovery value is as high as 99.66-101.00%, and the RSD is less than 2.35%.
TABLE 1
| Actual sample | Addition amount (μ M) | Detection value (μ M) | Recovery (%) | RSD(n＝5，％) |
| Apple (Malus pumila) | 100 | 99.86 | 99.86 | 2.35 |
| 150 | 150.98 | 100.65 | 2.14 | |
| 200 | 199.32 | 99.66 | 1.94 | |
| 250 | 249.26 | 99.70 | 2.34 | |
| 350 | 350.43 | 100.12 | 1.97 | |
| Broccoli (Broccoli) | 50 | 50.5 | 101.00 | 2.31 |
| 150 | 149.68 | 99.79 | 2.47 | |
| 200 | 201.80 | 100.90 | 1.15 | |
| 300 | 300.40 | 100.13 | 1.25 | |
| 350 | 352.05 | 100.59 | 1.33 | |
| |
100 | 100.65 | 100.65 | 1.68 |
| 150 | 150.93 | 100.62 | 1.74 | |
| 200 | 199.90 | 99.95 | 1.69 | |
| 350 | 350.40 | 100.11 | 1.26 | |
| 450 | 449.60 | 99.91 | 1.39 |
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (7)
1. A preparation method of a nitrogen-doped three-dimensional porous graphene-based electrode material is characterized by comprising the following steps: the method comprises the following steps:
1) ultrasonically mixing a graphene oxide solution and a hydrogen peroxide solution, placing the mixture in a reaction container for reaction, and then washing and drying the mixture to obtain three-dimensional porous graphene oxide;
2) dissolving the three-dimensional porous graphene oxide obtained in the step 1) in ultrapure water, mixing with urea, performing ultrasonic treatment, placing in a reaction container for hydrothermal reaction, and then washing and drying to obtain nitrogen-doped three-dimensional porous graphene; the mass concentration of the three-dimensional porous graphene oxide is 1-3 mg/mL, and the mass ratio of urea to the three-dimensional porous graphene oxide is 60: 1-30: 1; the temperature of the hydrothermal reaction is 170-195 ℃, and the time is 10-14 h;
3) preparing the nitrogen-doped three-dimensional porous graphene obtained in the step 2) into a dispersion liquid, dropwise adding the dispersion liquid to the center of a glassy carbon electrode substrate, and carrying out vacuum-pumping drying at 15-30 ℃ to obtain a nitrogen-doped three-dimensional porous graphene-based electrode material;
in the step 1), the washing refers to dialyzing the reaction product for 4-7 days;
step 2), the nitrogen-doped three-dimensional porous graphene is provided with three-dimensional network micropores, and the pore diameter of each micropore is 0.1-10 mu m; and the two-dimensional in-plane nano-pores are distributed on the substrate plane of the nitrogen-doped three-dimensional porous graphene, and the pore diameter is 1-4.8 nm.
2. The method of claim 1, wherein: in the step 1), the graphene oxide solution is an aqueous solution of graphene oxide, and the mass concentration of the graphene oxide is 1-5 mg/mL; the hydrogen peroxide solution is a hydrogen peroxide aqueous solution, wherein the mass percentage of the hydrogen peroxide is 20-40%; the volume ratio of the graphene oxide solution to the hydrogen peroxide solution is 5: 1-15: 1.
3. The method of claim 1, wherein: in the step 1), the time of ultrasonic treatment is 15-20 min, the reaction temperature is 95-105 ℃, and the reaction time is 2-5 h.
4. The method of claim 1, wherein: in the step 2), the ultrasonic treatment time is 20-30 min; the washing means immersing the reaction product in water for 1 to 2 days.
5. The method of claim 1, wherein: in the step 2), the drying is freeze drying, and the specific process is as follows: and (3) quickly freezing the washing product in liquid nitrogen, and then placing the washing product in a freeze dryer for freeze drying, wherein the temperature in the freeze drying process is between 55 ℃ below zero and 45 ℃ below zero, and the time is 10 to 15 hours.
6. The nitrogen-doped three-dimensional porous graphene-based electrode material prepared by the preparation method of any one of claims 1 to 5.
7. The application of the nitrogen-doped three-dimensional porous graphene-based electrode material of claim 6 in detecting the content of organophosphorus pesticide methyl parathion.
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