CN115112737B - Preparation and application of electrochemical sensor based on nitrogen-doped reduced graphene oxide composite tungsten disulfide nanosheet - Google Patents
Preparation and application of electrochemical sensor based on nitrogen-doped reduced graphene oxide composite tungsten disulfide nanosheet Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 128
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 105
- ITRNXVSDJBHYNJ-UHFFFAOYSA-N tungsten disulfide Chemical compound S=[W]=S ITRNXVSDJBHYNJ-UHFFFAOYSA-N 0.000 title claims abstract description 87
- 239000002131 composite material Substances 0.000 title claims abstract description 85
- 239000002135 nanosheet Substances 0.000 title claims abstract description 83
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims abstract description 268
- 229960003638 dopamine Drugs 0.000 claims abstract description 134
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 23
- 239000000843 powder Substances 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 20
- 238000001514 detection method Methods 0.000 claims abstract description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 21
- KPGXUAIFQMJJFB-UHFFFAOYSA-H tungsten hexachloride Chemical compound Cl[W](Cl)(Cl)(Cl)(Cl)Cl KPGXUAIFQMJJFB-UHFFFAOYSA-H 0.000 claims description 20
- 239000002244 precipitate Substances 0.000 claims description 17
- 239000011259 mixed solution Substances 0.000 claims description 16
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims description 15
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 15
- 239000007788 liquid Substances 0.000 claims description 14
- 238000007650 screen-printing Methods 0.000 claims description 14
- 238000010992 reflux Methods 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 9
- 229920000642 polymer Polymers 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 150000003460 sulfonic acids Chemical class 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 229920000877 Melamine resin Polymers 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 7
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 7
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- 239000006185 dispersion Substances 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 5
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 5
- 239000010453 quartz Substances 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 abstract description 64
- LEHOTFFKMJEONL-UHFFFAOYSA-N Uric Acid Chemical compound N1C(=O)NC(=O)C2=C1NC(=O)N2 LEHOTFFKMJEONL-UHFFFAOYSA-N 0.000 abstract description 34
- TVWHNULVHGKJHS-UHFFFAOYSA-N Uric acid Natural products N1C(=O)NC(=O)C2NC(=O)NC21 TVWHNULVHGKJHS-UHFFFAOYSA-N 0.000 abstract description 34
- 229940116269 uric acid Drugs 0.000 abstract description 34
- 229960005070 ascorbic acid Drugs 0.000 abstract description 32
- 235000010323 ascorbic acid Nutrition 0.000 abstract description 28
- 239000011668 ascorbic acid Substances 0.000 abstract description 28
- 238000000926 separation method Methods 0.000 abstract description 6
- 239000000126 substance Substances 0.000 abstract description 3
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- 238000004458 analytical method Methods 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 230000002452 interceptive effect Effects 0.000 abstract description 2
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- 239000002994 raw material Substances 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 34
- 229910052757 nitrogen Inorganic materials 0.000 description 17
- 239000002064 nanoplatelet Substances 0.000 description 9
- 238000001318 differential pulse voltammogram Methods 0.000 description 8
- 238000001903 differential pulse voltammetry Methods 0.000 description 6
- 239000008363 phosphate buffer Substances 0.000 description 6
- 230000035945 sensitivity Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 235000000069 L-ascorbic acid Nutrition 0.000 description 4
- 239000002211 L-ascorbic acid Substances 0.000 description 4
- 238000000835 electrochemical detection Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000002484 cyclic voltammetry Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 229910021607 Silver chloride Inorganic materials 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 210000003169 central nervous system Anatomy 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000008204 material by function Substances 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 2
- 208000024827 Alzheimer disease Diseases 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- 238000001237 Raman spectrum Methods 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 150000003943 catecholamines Chemical class 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000002964 excitative effect Effects 0.000 description 1
- 238000001917 fluorescence detection Methods 0.000 description 1
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000005802 health problem Effects 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002055 nanoplate Substances 0.000 description 1
- 239000002858 neurotransmitter agent Substances 0.000 description 1
- 239000008055 phosphate buffer solution Substances 0.000 description 1
- 201000000980 schizophrenia Diseases 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
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- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
- G01N27/327—Biochemical electrodes, e.g. electrical or mechanical details for in vitro measurements
- G01N27/3275—Sensing specific biomolecules, e.g. nucleic acid strands, based on an electrode surface reaction
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- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
- G01N27/327—Biochemical electrodes, e.g. electrical or mechanical details for in vitro measurements
- G01N27/3275—Sensing specific biomolecules, e.g. nucleic acid strands, based on an electrode surface reaction
- G01N27/3278—Sensing specific biomolecules, e.g. nucleic acid strands, based on an electrode surface reaction involving nanosized elements, e.g. nanogaps or nanoparticles
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- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/416—Systems
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Abstract
The invention relates to preparation and application of a nitrogen-doped reduced graphene oxide-based composite tungsten disulfide nanosheet electrochemical sensor. Firstly, preparing a reduced graphene oxide composite tungsten disulfide nano sheet; then preparing a nitrogen-doped reduced graphene oxide composite tungsten disulfide nano sheet; and then modifying the nitrogen-doped reduced graphene oxide composite tungsten disulfide nanosheet powder with the screen-printed carbon electrode to prepare the electrochemical sensor. Meanwhile, the nitrogen-doped reduced graphene oxide composite tungsten disulfide nanosheet electrochemical sensor is applied to detection of dopamine. The electrochemical separation detection of dopamine and interfering substances uric acid and ascorbic acid is realized. The modified material nitrogen-doped reduced graphene oxide composite tungsten disulfide nanosheets prepared by the method have the advantages of wide raw material sources, low cost, simple process and environmental friendliness. The constructed electrochemical sensor is simple in dopamine detection operation, does not need any treatment, is quick in test time, and improves analysis speed.
Description
Technical Field
The invention relates to the technical field of electrochemical sensors, in particular to a preparation method of a nitrogen-doped reduced graphene oxide-based composite tungsten disulfide nanosheet electrochemical sensor and application of the sensor in dopamine detection.
Background
Dopamine (DA) is a catecholamine neurotransmitter that plays a vital role in the human central nervous system and can carry excitatory information that affects communication with the human central nervous system. When abnormal Dopamine (DA) levels occur in the body, serious health problems such as Alzheimer's disease, schizophrenia, etc. occur. Therefore, it is necessary to develop a highly sensitive and highly selective Dopamine (DA) detection method. The existing common Dopamine (DA) detection methods comprise a Raman spectrum method, a liquid chromatography method and a fluorescence detection method, but the methods have the defects of high cost, large instrument and equipment, inflexibility, limitation and the like. Therefore, in order to better detect dopamine, electrochemical sensors have been rapidly developed due to their advantages of excellent sensitivity, stability, low cost, reliability, and the like. In an electrochemical sensor, an electrode is an important device for detecting an electric signal, and the exposed electrode has the problems of poor conductivity, low stability and the like. Modification of functional materials to the electrode surface is a good strategy to improve current signals and high stability. Therefore, the electrochemical detection signal is enhanced by adopting excellent functional materials to modify the electrode, so that the development of an electrochemical sensor with high sensitivity is advanced.
The tungsten disulfide nanosheets are two-dimensional transition metal halides with graphene nanosheets, and are widely applied to the electrochemical field due to high electrochemical activity. The structure is a sandwich structure formed by a metal tungsten (W) atomic layer and a sulfur (S) atomic layer through Van der Waals force, and the structure enables the structure to have a large number of active points. However, the re-stacking and low electron conduction between nanoplates limit their applications.
Disclosure of Invention
In order to solve the problems in the prior art, the reduced graphene oxide has good flexibility and conductivity, and the defects and holes of the reduced graphene oxide are increased by doping nitrogen, so that the electron transmission capability is further improved. Therefore, the invention constructs the electrochemical sensor based on the nitrogen doped reduced graphene oxide composite tungsten disulfide nanosheet, which not only realizes the sensitivity detection of Dopamine (DA) but also realizes the electrochemical separation detection of Dopamine (DA) and interfering substances Uric Acid (UA) and Ascorbic Acid (AA).
Therefore, the invention constructs the electrochemical sensor based on the nitrogen doped reduced graphene oxide composite tungsten disulfide nanosheet.
According to the invention, the nitrogen-doped reduced graphene oxide composite tungsten disulfide nanosheet composite material is synthesized, and the composite material is modified on a screen printing carbon electrode, so that a current signal is enlarged, dopamine (DA) can be sensitively detected, and electrochemical separation detection of Dopamine (DA), uric Acid (UA) and Ascorbic Acid (AA) can be realized.
The specific technical scheme of the invention is as follows:
a preparation method of an electrochemical sensor based on nitrogen-doped graphene composite tungsten disulfide nanosheets comprises the following steps:
(1) Preparation of a reduced graphene oxide composite tungsten disulfide nanosheet: dissolving tungsten hexachloride, thioacetamide and graphene oxide powder in deionized water, stirring, ultrasonically dispersing, and performing hydrothermal reaction; washing the precipitate after cooling to room temperature, carrying out reflux treatment on the obtained precipitate in a mixed solution of absolute ethyl alcohol and 3-aminopropyl trimethoxy silane, mixing the precipitate with a graphene oxide aqueous solution at room temperature, and finally drying in a vacuum oven to obtain reduced graphene oxide composite tungsten disulfide nanosheet powder;
(2) Preparation of nitrogen-doped reduced graphene oxide composite tungsten disulfide nanosheets: grinding and mixing the nano-sheet powder with melamine, and transferring the mixture into a quartz boat to perform high-temperature heat treatment in a nitrogen atmosphere to obtain nitrogen-doped reduced graphene oxide composite tungsten disulfide nano-sheet powder;
(3) Preparation of electrochemical sensor: dispersing nitrogen-doped reduced graphene oxide composite tungsten disulfide nanosheet powder in a mixed solution of absolute ethyl alcohol and perfluorinated sulfonic acid polymer solution, and performing ultrasonic dispersion; and (3) transferring the dispersed liquid drops to a screen printing carbon electrode by using a liquid transferring gun, and naturally drying at room temperature to obtain the nitrogen-doped reduced graphene oxide composite tungsten disulfide nanosheet modified screen printing carbon electrode, thereby preparing the electrochemical sensor.
The concentration of tungsten hexachloride in the step (1) is preferably 0.0297-0.0446 g/mL, the concentration of graphene oxide is preferably 7.2-8.1 mg/mL, and the concentration of thioacetamide is preferably 0.0595-0.0676 g/mL.
The hydrothermal reaction in the step (1) is carried out at a preferable hydrothermal temperature of 180-220 ℃ and a preferable hydrothermal reaction time of 18-24 h.
The concentration of the precipitate in the reflux treatment in the step (1) is preferably 8 to 13mg/mL.
The concentration of the graphene oxide aqueous solution in the step (1) is preferably 1.5-2 mg/mL.
The reflux temperature in the reflux treatment in the step (1) is preferably 60 to 80℃and the reflux time is preferably 4 to 6 hours.
In the step (1), the molar ratio of the tungsten hexachloride to the graphene oxide is preferably 1:6-1:8, and the mass ratio of the tungsten hexachloride to the thioacetamide is preferably 1:1.5-1:2.
The volume ratio of the 3-aminopropyl trimethoxysilane to the absolute ethyl alcohol in the step (1) is preferably 1:18-1:22.
In the step (2), the mass ratio of the nano-sheet powder to the melamine is preferably 1:5-1:7.
The high-temperature heat treatment temperature in the step (2) is preferably 600-800 ℃, and the heat treatment time is preferably 2-4 h.
The concentration of the nitrogen-doped reduced graphene oxide composite tungsten disulfide nanosheet dispersion liquid in the step (3) is preferably 2-5 mg/mL.
The volume ratio of the perfluorosulfonic acid polymer to the absolute ethanol in the step (3) is preferably 1:15 to 1:24.
The specific application method of the nitrogen-doped reduced graphene oxide composite tungsten disulfide nanosheet electrochemical sensor for detecting dopamine is as follows:
The method comprises the steps of modifying a silk-screen printing carbon electrode based on a nitrogen-doped reduced graphene oxide composite tungsten disulfide nano sheet, taking a silver/silver chloride electrode as a reference electrode, taking phosphate buffer liquid drops of dopamine by a pipette, dropping the phosphate buffer liquid drops on the silk-screen printing carbon electrode, characterizing electric signal enhancement of the electrochemical sensor to Dopamine (DA) by adopting a cyclic voltammetry technology (CV), and carrying out electrochemical scanning to the dopamine by adopting a differential pulse voltammetry technology (DPV) to obtain differential pulse voltammograms of the dopamine with different concentrations. Meanwhile, in the mixed solution of Ascorbic Acid (AA), dopamine (DA) and Uric Acid (UA), electrochemical separation detection of the Ascorbic Acid (AA), the Dopamine (DA) and the Uric Acid (UA) is realized by a differential pulse voltammetry technology.
The concentration of phosphate buffer solution for removing dopamine by a liquid-transfering gun in the specific application method of the invention is preferably 1-100 mu mol/L.
The pH of the phosphate buffer of dopamine in the specific application method of the invention is preferably 6-8.
The concentration of the Ascorbic Acid (AA), dopamine (DA) and Uric Acid (UA) mixed solution in the specific application method of the present invention is preferably 500 to 1000. Mu. Mol/L of Ascorbic Acid (AA), 50 to 100. Mu. Mol/L of Dopamine (DA) and 100 to 1000. Mu. Mol/L of Uric Acid (UA).
The invention has the following beneficial effects:
(1) The modified material nitrogen-doped reduced graphene oxide composite tungsten disulfide nanosheets prepared by the method have the advantages of wide raw material sources, low cost, simple process, environmental friendliness and no harm to the health of operators.
(2) The constructed electrochemical sensor is simple in dopamine detection operation, does not need any treatment, is quick in test time (the test time is 70 s), and improves the analysis speed.
(3) The constructed electrochemical sensor has high sensitivity and high selectivity. The electrochemical signal of dopamine can be obviously improved, the detection limit is 0.2 mu mol/L, and the interference of ascorbic acid and uric acid can be avoided.
Drawings
FIG. 1 is a scanning electron microscope image of a nitrogen doped reduced graphene oxide composite tungsten disulfide nanosheet at different magnifications;
wherein (a) the nitrogen doped reduced graphene oxide composite tungsten disulfide nanoplatelets have a magnification of 15000; (b) The magnification is 60000 nitrogen doped reduced graphene oxide composite tungsten disulfide nano-sheet; (c) Magnification 100000 nitrogen doped reduced graphene oxide composite tungsten disulfide nanoplatelets.
FIG. 2 is an X-ray diffraction pattern of a nitrogen doped reduced graphene oxide composite tungsten disulfide nanoplatelet.
FIG. 3 cyclic voltammograms of Dopamine (DA) on different electrodes;
wherein (a) an unmodified screen-printed carbon electrode; (b) Nitrogen doped reduced graphene oxide composite tungsten disulfide nanosheets modify screen printed carbon electrodes.
Fig. 4 differential pulse voltammograms of different concentrations of Dopamine (DA) nitrogen doped reduced graphene oxide composite tungsten disulfide nanoplatelet electrochemical sensors.
Wherein the concentration of Dopamine (DA) is sequentially from bottom to top 1μmol/L、2.5μmol/L、5μmol/L、7.5μmol/L、10μmol/L、25μmol/L、37.5μmol/L、50μmol/L、62.5μmol/L、75μmol/L、87.5μmol/L、100μmol/L.
FIG. 5 is a graph showing the oxidation peak current of Dopamine (DA) plotted against the concentration.
Wherein the concentration of Dopamine (DA) is in turn 1μmol/L、2.5μmol/L、5μmol/L、7.5μmol/L、10μmol/L、25μmol/L、37.5μmol/L、50μmol/L、62.5μmol/L、75μmol/L、87.5μmol/L、100μmol/L.
FIG. 6 differential pulse voltammograms of Dopamine (DA) nitrogen doped reduced graphene oxide composite tungsten disulfide nanoplatelet electrochemical sensors at different pH values;
Wherein (a) 80 mu mol/L, the nitrogen doped reduced graphene oxide of Dopamine (DA) with pH value of 6 is used for preparing a differential pulse voltammogram of the electrochemical sensor of the tungsten disulfide nano-sheet; (b) Differential pulse voltammogram of 100 mu mol/L Dopamine (DA) nitrogen doped reduced graphene oxide composite tungsten disulfide nanosheet electrochemical sensor with pH value of 8.
FIG. 7 differential pulse voltammogram of 500. Mu. Mol/L Ascorbic Acid (AA), 50. Mu. Mol/L Dopamine (DA) and 100. Mu. Mol/L Uric Acid (UA) mixed solution of nitrogen doped reduced graphene oxide composite tungsten disulfide nanoplatelet electrochemical sensors.
Detailed Description
The preparation method and the application of the electrochemical sensor based on the nitrogen-doped reduced graphene oxide composite tungsten disulfide nanosheet are further explained below by combining specific examples.
Example 1
A preparation method of a nitrogen-doped graphene composite tungsten disulfide nanosheet electrochemical sensor.
(1) Preparation of a reduced graphene oxide composite tungsten disulfide nanosheet: 0.8923g of tungsten hexachloride, 189mg of graphene oxide powder and 1.6904g of thioacetamide are dissolved in 25mL of deionized water (wherein the molar ratio of the tungsten hexachloride to the graphene oxide is 1:7, the mass ratio of the tungsten hexachloride to the thioacetamide is 1:1.8, the concentration of the tungsten hexachloride is 0.0357g/mL, the concentration of the graphene oxide is 7.56mg/mL and the concentration of the thioacetamide is 0.0676 g/mL), and the solution is stirred, dispersed in an ultrasonic manner and transferred into a reaction kettle. And carrying out hydrothermal reaction for 24 hours at 200 ℃, cooling to room temperature, washing the precipitate, refluxing the obtained precipitate in a mixed solution of 20mL of absolute ethyl alcohol and 1mL of 3-aminopropyl trimethoxy silane at 80 ℃ for 4 hours (the precipitation concentration is 10mg/mL, the volume ratio of 3-aminopropyl trimethoxy silane to absolute ethyl alcohol is 1:20), mixing the precipitate with a graphene oxide aqueous solution (1.5 mg/mL) at room temperature, and finally drying in a vacuum oven to obtain the reduced graphene oxide composite tungsten disulfide nano-sheet powder.
(2) Preparation of nitrogen-doped reduced graphene oxide composite tungsten disulfide nanosheets: grinding and mixing 0.2g of reduced graphene oxide composite tungsten disulfide nano-sheet powder with melamine according to a mass ratio of 1:6, transferring into a quartz boat, and performing heat treatment at 800 ℃ for 2 hours in a nitrogen atmosphere to obtain the nitrogen-doped reduced graphene oxide composite tungsten disulfide nano-sheet powder. FIG. 1 shows scanning electron microscope images of nitrogen-doped reduced graphene oxide composite tungsten disulfide nanoplatelets at different magnifications, wherein (a) is a nitrogen-doped reduced graphene oxide composite tungsten disulfide nanoplatelet at a magnification of 15000; (b) The magnification is 60000 nitrogen doped reduced graphene oxide composite tungsten disulfide nano-sheet; (c) The magnification is 100000 nitrogen doped reduced graphene oxide composite tungsten disulfide nano-sheet. From the figure, it can be seen in turn that the tungsten disulfide nanoplatelets randomly grow on the nitrogen doped reduced graphene oxide sheets, and this structure increases the electroactive area of the electrode.
(3) Preparation of electrochemical sensor: the screen-printed carbon electrode was first washed with absolute ethanol and deionized water and dried at room temperature. 1mg of nitrogen-doped reduced graphene oxide composite tungsten disulfide nanosheet powder is dispersed in 480 mu L of mixed solution of absolute ethyl alcohol and 20 mu L of perfluorinated sulfonic acid type polymer solution (the concentration of the nitrogen-doped reduced graphene oxide composite tungsten disulfide nanosheets is 2mg/mL, and the volume ratio of the perfluorinated sulfonic acid type polymer to the absolute ethyl alcohol is 1:24) for ultrasonic dispersion. And (3) transferring 2 mu L of dispersion liquid drops by using a liquid transferring gun, landing on the screen printing carbon electrode, and naturally drying at room temperature to obtain the nitrogen-doped reduced graphene oxide composite tungsten disulfide nanosheet modified screen printing carbon electrode. And connecting the electrode with an electrochemical workstation to construct the nitrogen-doped reduced graphene oxide composite tungsten disulfide nanosheet electrochemical sensor.
Example 2
(1) Preparation of a reduced graphene oxide composite tungsten disulfide nanosheet: 0.8923g of tungsten hexachloride, 162mg of graphene oxide powder and 1.3385g of thioacetamide are dissolved in 20mL of deionized water (wherein the molar ratio of the tungsten hexachloride to the graphene oxide is 1:6, the mass ratio of the tungsten hexachloride to the thioacetamide is 1:1.5, the concentration of the tungsten hexachloride is 0.0446g/mL, the concentration of the graphene oxide is 8.1mg/mL and the concentration of the thioacetamide is 0.0669 g/mL), and the solution is stirred, dispersed in an ultrasonic manner and transferred into a reaction kettle. And carrying out hydrothermal reaction for 20h at 220 ℃, cooling to room temperature, washing the precipitate, refluxing the obtained precipitate in a mixed solution of 22mL of absolute ethyl alcohol and 1mL of 3-aminopropyl trimethoxy silane at 70 ℃ for 5h (the precipitation concentration is 13mg/mL, the volume ratio of 3-aminopropyl trimethoxy silane to absolute ethyl alcohol is 1:22), mixing the precipitate with a graphene oxide aqueous solution (2 mg/mL) at room temperature, and finally drying in a vacuum oven to obtain the reduced graphene oxide composite tungsten disulfide nano-sheet powder.
(2) Preparation of nitrogen-doped reduced graphene oxide composite tungsten disulfide nanosheets: grinding and mixing 0.2g of reduced graphene oxide composite tungsten disulfide nano-sheet powder with melamine according to a mass ratio of 1:7, transferring into a quartz boat, and performing heat treatment for 3 hours at 700 ℃ in a nitrogen atmosphere to obtain the nitrogen-doped reduced graphene oxide composite tungsten disulfide nano-sheet powder. Fig. 2 is an X-ray diffraction diagram of the nitrogen-doped reduced graphene oxide composite tungsten disulfide nanosheets of example 2, and it can be seen that the main diffraction peaks of the nitrogen-doped reduced graphene oxide composite tungsten disulfide nanosheets are (002), (004), (100), (103), (006), (105), (110), (112) and (108), which are the same as the diffraction peaks of the tungsten disulfide nanosheets, indicating successful preparation of the nitrogen-doped reduced graphene oxide composite tungsten disulfide nanosheets.
(3) Preparation of electrochemical sensor: the screen-printed carbon electrode was first washed with absolute ethanol and deionized water and dried at room temperature. 2mg of nitrogen-doped reduced graphene oxide composite tungsten disulfide nanosheet powder is dispersed in 375 mu L of absolute ethyl alcohol and 25 mu L of mixed solution of perfluorinated sulfonic acid type polymer solution (the concentration of the nitrogen-doped reduced graphene oxide composite tungsten disulfide nanosheets is 5mg/mL, and the volume ratio of perfluorinated sulfonic acid type polymer to absolute ethyl alcohol is 1:15), and the mixture is subjected to ultrasonic dispersion. And (3) transferring 4 mu L of dispersion liquid drops by a liquid transferring gun, landing on the screen printing carbon electrode, and naturally drying at room temperature to obtain the nitrogen-doped reduced graphene oxide composite tungsten disulfide nanosheet modified screen printing carbon electrode. And connecting the electrode with an electrochemical workstation to construct the nitrogen-doped reduced graphene oxide composite tungsten disulfide nanosheet electrochemical sensor.
Example 3
(1) Preparation of a reduced graphene oxide composite tungsten disulfide nanosheet: 0.8923g of tungsten hexachloride, 216mg of graphene oxide powder and 1.7864g of thioacetamide are dissolved in 30mL of deionized water (wherein the molar ratio of the tungsten hexachloride to the graphene oxide is 1:8, the mass ratio of the tungsten hexachloride to the thioacetamide is 1:2, the concentration of the tungsten hexachloride is 0.0297g/mL, the concentration of the graphene oxide is 7.2mg/mL, the concentration of the thioacetamide is 0.0595 g/mL), and the solution is stirred, dispersed in an ultrasonic manner and transferred into a reaction kettle. And carrying out hydrothermal reaction for 18h at 180 ℃, cooling to room temperature, washing the precipitate, refluxing the obtained precipitate in a mixed solution of 18mL of absolute ethyl alcohol and 1mL of 3-aminopropyl trimethoxy silane at 60 ℃ for 6h (the precipitation concentration is 8mg/mL, the volume ratio of 3-aminopropyl trimethoxy silane to absolute ethyl alcohol is 1:18), mixing the precipitate with a graphene oxide aqueous solution (1.8 mg/mL) at room temperature, and finally drying in a vacuum oven to obtain the reduced graphene oxide composite tungsten disulfide nano-sheet powder.
(2) Preparation of nitrogen-doped reduced graphene oxide composite tungsten disulfide nanosheets: grinding and mixing 0.2g of nitrogen-doped reduced graphene oxide composite tungsten disulfide nano-sheet powder with melamine according to a mass ratio of 1:5, transferring into a quartz boat, and performing heat treatment at 600 ℃ for 4 hours in a nitrogen atmosphere to obtain the nitrogen-doped reduced graphene oxide composite tungsten disulfide nano-sheet powder.
(3) Preparation of electrochemical sensor: the screen-printed carbon electrode was first washed with absolute ethanol and deionized water and dried at room temperature. 2mg of nitrogen-doped reduced graphene oxide composite tungsten disulfide nanosheet powder is dispersed in 475 mu L of absolute ethyl alcohol and 25 mu L of mixed solution of perfluorinated sulfonic acid type polymer solution (nafion) (the concentration of the nitrogen-doped reduced graphene oxide composite tungsten disulfide nanosheets is 4mg/mL, and the volume ratio of the perfluorinated sulfonic acid type polymer to the absolute ethyl alcohol is 1:19), and the mixture is subjected to ultrasonic dispersion. And (3) transferring 1 mu L of dispersion liquid drops by using a liquid transferring gun, landing on the screen printing carbon electrode, and naturally drying at room temperature to obtain the nitrogen-doped reduced graphene oxide composite tungsten disulfide nanosheet modified screen printing carbon electrode. And connecting the electrode with an electrochemical workstation to construct the nitrogen-doped reduced graphene oxide composite tungsten disulfide nanosheet electrochemical sensor.
Example 4
Based on the electrochemical sensor prepared in example 1, a nitrogen-doped reduced graphene oxide composite tungsten disulfide nanosheet modified screen-printed carbon electrode is used as a working electrode, a silver/silver chloride electrode is used as a reference electrode, a carbon electrode is used as a counter electrode, 60 mu L of phosphate buffer droplets with the concentration of 50 mu mol/L and the pH value of 7 of dopamine are removed by a pipette and fall on the screen-printed carbon electrode, the potential is in the range from-0.3V to 0.4V, the pulse amplitude is 0.05V, the pulse period is 0.5s, and the Differential Pulse Voltammetry (DPV) technology is adopted to carry out electrochemical scanning on Dopamine (DA) for 70s. Cyclic voltammograms of Dopamine (DA) on different electrodes as in fig. 3, where (a) is an unmodified screen-printed carbon electrode; (b) And (3) modifying the screen printing carbon electrode by using the nitrogen-doped reduced graphene oxide composite tungsten disulfide nano sheet. As can be seen from the figure, the unmodified screen-printed electrode (fig. 3 (a)) shows a smaller electrochemical signal to Dopamine (DA), and the nitrogen-doped reduced graphene oxide composite tungsten disulfide nanosheet modified screen-printed electrode (fig. 3 (b)) significantly enhances the electrochemical signal of Dopamine (DA), which indicates that the nitrogen-doped reduced graphene oxide composite tungsten disulfide nanosheet electrochemical sensor can significantly improve the sensitivity of Dopamine (DA). In fig. 4, in the range of potential-0.3V to 0.4V, the electrochemical sensor prepared in example 1 is used to detect a Dopamine (DA) solution with the concentration range of 1 μmol/L to 100 μmol/L by using a differential pulse voltammetry technology, wherein the concentration of Dopamine (DA) is 1μmol/L、2.5μmol/L、5μmol/L、7.5μmol/L、10μmol/L、25μmol/L、37.5μmol/L、50μmol/L、62.5μmol/L、75μmol/L、87.5μmol/L、100μmol/L. from bottom to top, as can be seen from fig. 4, the peak current of the oxidation peak of Dopamine (DA) increases with the increase of the concentration of Dopamine (DA), the linear relation between the oxidation peak current and the concentration of Dopamine (DA) is shown in fig. 5, the linear relation between the concentration of Dopamine (DA) is 1μmol/L、2.5μmol/L、5μmol/L、7.5μmol/L、10μmol/L、25μmol/L、37.5μmol/L、50μmol/L、62.5μmol/L、75μmol/L、87.5μmol/L、100μmol/L., the linear relation between the concentration of Dopamine (DA) is I pa(μA)＝0.5593CDA+4.6214(R2 = 0.9986, and the detection limit of Dopamine (DA) is calculated to be 0.2 μmol/L according to the linear relation between the peak current and the concentration, so that the electrochemical signal and the concentration of Dopamine (DA) have good linear relation, and the electrochemical sensor has excellent detection sensitivity to Dopamine (DA).
Example 5
Example 5 differs from example 4 in that the concentration of dopamine phosphate buffer removed by the pipette is 100. Mu. Mol/L and the pH is 8. As shown in fig. 6 (b), a differential pulse voltammogram of the electrochemical sensor of the Dopamine (DA) nitrogen-doped reduced graphene oxide composite tungsten disulfide nanosheet with the pH value of 8 is shown, and as can be seen from the figure, the Dopamine (DA) undergoes an oxidation reaction on the modified electrode of the Dopamine (DA) nitrogen-doped reduced graphene oxide composite tungsten disulfide nanosheet, which indicates that the electrochemical sensor can still realize electrochemical detection on dopamine, and the same effect as that of example 4 is achieved.
Example 6
Example 6 differs from example 4 in that the pipette is used to remove a volume of dopamine phosphate buffer of 80. Mu. Mol/L at a pH of 6. As shown in fig. 6 (a), a differential pulse voltammogram of a Dopamine (DA) nitrogen-doped reduced graphene oxide composite tungsten disulfide nanosheet electrochemical sensor with a pH of 6 is shown, and it can be seen from the figure that the Dopamine (DA) undergoes an oxidation reaction on the modified electrode of the Dopamine (DA) nitrogen-doped reduced graphene oxide composite tungsten disulfide nanosheet, and the sensor can still realize electrochemical detection on dopamine, so that the same effect as that of example 4 is achieved.
Example 7
Based on the electrochemical sensor prepared in the embodiment 1, the electrochemical detection separation of substances Ascorbic Acid (AA) and Uric Acid (UA) with extremely strong interference on the detection of Dopamine (DA) is realized, so that the electrochemical sensor is verified to have good selectivity on the Dopamine (DA). As shown in FIG. 7, a mixed solution of 500. Mu. Mol/L Ascorbic Acid (AA), 50. Mu. Mol/L Dopamine (DA) and 100. Mu. Mol/L Uric Acid (UA) was electrochemically analyzed by differential pulse voltammetry in the range of potential-0.3V to 0.4V. From the figure, it is clear that the electrochemical sensor clearly distinguishes between Dopamine (DA), ascorbic Acid (AA) and Uric Acid (UA), wherein the potential difference between Uric Acid (UA) and Dopamine (DA) is 142mV. This indicates that the electrochemical sensor realizes electrochemical separation detection of Dopamine (DA), ascorbic Acid (AA) and Uric Acid (UA), and shows excellent selectivity to Dopamine (DA).
Example 8
Example 8 is different from example 7 in that the electrochemical sensor can achieve the same effect as example 7 with respect to the volume of the Ascorbic Acid (AA), dopamine (DA) and Uric Acid (UA) mixed solution of 1000 μmol/L Ascorbic Acid (AA), 100 μmol/L Dopamine (DA) and 1000 μmol/L Uric Acid (UA).
Example 9
Example 9 is different from example 7 in that the electrochemical sensor can achieve the same effect as example 7 with respect to the volume of the Ascorbic Acid (AA), dopamine (DA) and Uric Acid (UA) mixed solution of 800 μmol/L Ascorbic Acid (AA), 80 μmol/L Dopamine (DA) and 800 μmol/L Uric Acid (UA).
Claims (8)
1. The sensor prepared by the preparation method of the nitrogen-doped graphene composite tungsten disulfide nanosheet electrochemical sensor is applied to detection of dopamine and is characterized by comprising the following steps of:
Dissolving tungsten hexachloride, thioacetamide and graphene oxide powder in deionized water, stirring, ultrasonically dispersing, and performing hydrothermal reaction; washing the precipitate after cooling to room temperature, carrying out reflux treatment on the obtained precipitate in a mixed solution of absolute ethyl alcohol and 3-aminopropyl trimethoxy silane, mixing the precipitate with a graphene oxide aqueous solution at room temperature, and finally drying in a vacuum oven to obtain reduced graphene oxide composite tungsten disulfide nanosheet powder;
Grinding and mixing the nano-sheet powder with melamine, and transferring the mixture into a quartz boat to perform high-temperature heat treatment in a nitrogen atmosphere to obtain nitrogen-doped reduced graphene oxide composite tungsten disulfide nano-sheet powder;
Dispersing nitrogen-doped reduced graphene oxide composite tungsten disulfide nanosheet powder in a mixed solution of absolute ethyl alcohol and perfluorinated sulfonic acid polymer solution, and performing ultrasonic dispersion; and (3) transferring the dispersed liquid drops to a screen printing carbon electrode by using a liquid transferring gun, and naturally drying at room temperature to obtain the nitrogen-doped reduced graphene oxide composite tungsten disulfide nanosheet modified screen printing carbon electrode, thereby preparing the electrochemical sensor.
2. The method for detecting dopamine according to claim 1, wherein in the step (1), the molar ratio of tungsten hexachloride to graphene oxide is 1:6-1:8, and the mass ratio of tungsten hexachloride to thioacetamide is 1:1.5-1:2.
3. The method for detecting dopamine according to claim 1, wherein in the step (1), the concentration of tungsten hexachloride is 0.0297-0.0446 g/mL, the concentration of graphene oxide is 7.2-8.1-mg/mL, and the concentration of thioacetamide is 0.0595-0.0676 g/mL; the concentration of the graphene oxide aqueous solution is 1.5-2 mg/mL.
4. The method for detecting dopamine according to claim 1, wherein the hydrothermal reaction in the step (1) is carried out at a hydrothermal temperature of 180-220 ℃ for a hydrothermal reaction time of 18-24 h.
5. The method for detecting dopamine according to claim 1, wherein the concentration of precipitate in the reflux treatment in the step (1) is 8-13 mg/mL; the reflux temperature in the reflux treatment is 60-80 ℃ and the reflux time is 4-6 h.
6. The method for detecting dopamine according to claim 1, wherein the mass ratio of the nanosheet powder to the melamine in the step (2) is 1:5-1:7.
7. The method for detecting dopamine according to claim 1, wherein the high-temperature heat treatment temperature in the step (2) is 600-800 ℃, and the heat treatment time is 2-4 h.
8. The method for detecting dopamine according to claim 1, wherein the concentration of the nitrogen-doped reduced graphene oxide composite tungsten disulfide nanosheet dispersion liquid in the step (3) is 2-5 mg/mL.
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