CN112209369A - Preparation and application of indium oxide nanosheet array/foamed graphene electrode - Google Patents
Preparation and application of indium oxide nanosheet array/foamed graphene electrode Download PDFInfo
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- CN112209369A CN112209369A CN201910633824.5A CN201910633824A CN112209369A CN 112209369 A CN112209369 A CN 112209369A CN 201910633824 A CN201910633824 A CN 201910633824A CN 112209369 A CN112209369 A CN 112209369A
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- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
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- 239000010453 quartz Substances 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G15/00—Compounds of gallium, indium or thallium
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/184—Preparation
- C01B32/186—Preparation by chemical vapour deposition [CVD]
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
- G01N27/308—Electrodes, e.g. test electrodes; Half-cells at least partially made of carbon
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/416—Systems
- G01N27/48—Systems using polarography, i.e. measuring changes in current under a slowly-varying voltage
Abstract
The invention relates to preparation and application of an indium oxide nanosheet array/foamed graphene electrode, and belongs to the technical field of novel functional materials and biosensor detection. The preparation method comprises the following steps: the first, chemical vapor deposition method, the second, hydrothermal synthesis method. According to the method, foamed nickel is used as a template, a chemical vapor deposition method is used for preparing three-dimensional foamed graphene, an indium sulfide nanosheet array grows on the three-dimensional foamed graphene through a hydrothermal synthesis method, and high-temperature heat treatment is carried out to obtain an indium oxide nanosheet array/foamed graphene. The prepared indium oxide nanosheet array/foamed graphene electrode is applied to the field of biosensors, has the advantages of high sensitivity, good selectivity, good repeatability, good stability and the like, and solves the problem of low sensitivity of the existing material in detecting dopamine in the biosensors.
Description
Technical Field
The invention relates to preparation and application of an indium oxide nanosheet array/foamed graphene electrode.
Background
Graphene is a two-dimensional crystal consisting of carbon atoms in sp2The hexagonal honeycomb-lattice two-dimensional carbon nanomaterial formed by hybrid tracks has excellent conductivity, chemical stability, high transparency and mechanical properties, and can be applied to materials science, micro-nano processing, biomedicine and medicinesHas important application prospect in aspects such as object transfer and the like. The graphene synthesis methods reported in the literature at present mainly comprise a mechanical stripping method, a chemical oxidation method and a chemical vapor deposition method. The mechanical stripping method is the method which is firstly applied to preparing graphene, but the size of the graphene obtained by the method is not easy to control, the yield is relatively low, and the method is not suitable for industrial production. The chemical oxidation method has low cost and high yield, but the interior of the chemical oxidation method contains a large number of defects, and a large number of chemical groups are remained at the edge of a sheet layer, so that the conductivity of the sheet layer is greatly reduced, and therefore, the application is limited. Compared with the former two, the graphene prepared by the chemical vapor deposition method has attracted much attention for its superior electrical properties, in which the graphene prepared by using foamed nickel as a template and methane as a carbon source has a large porosity, high conductivity and few defects and a three-dimensional network structure. However, the hydrophobic nature of graphene makes it difficult to combine with metal oxides.
Indium oxide is an important wide-bandgap N-type semiconductor material, has a direct bandgap width of 3.65eV at room temperature, has relatively low resistivity and relatively high catalytic activity, and is widely applied to the fields of lithium ion batteries, gas sensors, supercapacitors and the like. The indium oxide nanosheet can provide a large specific surface area and a large number of active sites, and therefore is considered to have potential application value in the field of electrochemical biosensors. But their relatively poor electrical conductivity has somewhat hindered their use. The preparation method of the indium oxide nanosheet array generally comprises the methods of metal organic vapor phase epitaxial growth, chemical vapor deposition, physical vapor deposition, hydrothermal synthesis and the like. The hydrothermal synthesis method has the advantages of low synthesis temperature, low cost, large-scale production and the like, and is concerned about.
Parkinson's disease is a common degenerative disease of the nervous system, and its clinical manifestations mainly include resting tremor, bradykinesia, myotonia and postural gait disorder, while patients may be accompanied by non-motor symptoms such as depression, constipation and sleep disorder. The main pathology of parkinson is due to degenerative death of mesencephalic dopaminergic neurons, resulting in a marked reduction of striatal dopamine content. Dopamine is a key neurotransmitter produced by hypothalamus and pituitary gland, and is used to help cells transmit impulses, which are closely related to human emotion and sensation and can transmit exciting and happy information to brain. Therefore, it becomes very important to monitor the content of dopamine in the human body at the early stage of the onset of parkinson's disease. The sensitivity of the currently reported application in dopamine detection is low, and is generally less than 1 muA/mumol/L.
Disclosure of Invention
The invention aims to solve the technical problem of low sensitivity when the existing material is applied to dopamine detection, thereby providing the biosensor capable of detecting dopamine more sensitively and more widely.
The preparation method of the indium oxide nanosheet array/foamed graphene composite material provided by the invention comprises the following steps:
chemical vapor deposition method
1) The density is 420g/m2～440g/m2Placing foamed nickel with the thickness of 1.6-2.0 mm in the center of a quartz tube furnace, heating the foamed nickel to 1000-1100 ℃ from room temperature at the heating rate of 20-40 ℃/min under the protection of argon with the flow rate of 480-500 sccm and hydrogen with the flow rate of 180-200 sccm, preserving the heat at 1000-1100 ℃ for 30-60 min, introducing methane gas into the tube furnace at the cooling rate of 5-10 sccm at the temperature of 1000-1100 ℃ for 5-20 min, and cooling the quartz tube furnace to the room temperature from 1000-1100 ℃ at the cooling rate of 80-100 ℃/min to obtain the foamed nickel wrapped by graphene;
2) dissolving 4-5% by mass of polymethyl methacrylate in ethyl lactate, heating and stirring for 1-2 h at 80-120 ℃ to obtain a mixed solution, dropwise adding the mixed solution to the graphene-coated foamed nickel obtained in the step 1) by using a sample adding gun according to the usage amount of 100-200 mu L per square centimeter, naturally drying at room temperature, and then preserving heat at 150-200 ℃ for 0.5-1 h to obtain the foamed graphene with the surface coated with the polymethyl methacrylate;
3) coating the surface obtained in the step one 2) with polymerFoamed graphene of methyl methacrylate was cut to a surface area of 0.5cm2～2cm2The cube is completely soaked in a hydrochloric acid solution with the temperature of 80-90 ℃ and the concentration of 3-4 mol/L for 4-6 h to obtain the nickel-removed three-dimensional foam graphene;
4) soaking the nickel-removed three-dimensional foam graphene obtained in the step one 3) in acetone at the temperature of 60-70 ℃ for 0.5-1.5 h to obtain foam graphene with the polymethyl methacrylate removed, then cleaning the foam graphene with the polymethyl methacrylate removed with distilled water to obtain cleaned foam graphene with the polymethyl methacrylate removed, then transferring the cleaned foam graphene with the polymethyl methacrylate removed to clean the foam graphene with the polymethyl methacrylate removed in acetone for 15-20 min, cleaning the foam graphene with ethanol for 15-20 min and deionized water for 15-20 min, naturally drying the cleaned foam graphene with the polymethyl methacrylate removed, then dropwise adding an indium sulfide seed layer solution onto the cleaned foam graphene with the polymethyl methacrylate removed by using a sample adding gun according to the usage amount of 50-100 mu L per square centimeter, then placing the glass at the temperature of 150-200 ℃ and preserving heat for 40-60 min to obtain three-dimensional foam graphene/ITO glass prefabricated with an indium sulfide seed layer; the indium sulfide seed layer solution in the step one 4) is synthesized by the following steps: dissolving indium chloride tetrahydrate and thioacetamide in ethanol, and magnetically stirring at the rotating speed of 450-550 r/min for 15-20 min to obtain an indium sulfide seed layer solution, wherein the concentration of the indium chloride tetrahydrate in the indium sulfide seed layer solution is 0.01-0.03 mol/L, and the concentration of the thioacetamide is 0.05-0.07 mol/L;
hydrothermal synthesis method
1) Using ethylene glycol as a solvent to respectively prepare an indium chloride solution with the concentration of 0.01-0.03 mol/L and a thioacetamide solution with the concentration of 0.05-0.07 mol/L, uniformly mixing the two solutions, and magnetically stirring at the rotating speed of 450-550 r/min for 15-20 min to obtain a hydrothermal reaction solution;
2) pouring the hydrothermal reaction solution obtained in the step two 1) into a reaction kettle, inversely placing the three-dimensional foam graphene/ITO glass prefabricated with the indium sulfide seed layer obtained in the step one 4) into a mixed solution in the reaction kettle, covering a cover of the reaction kettle, reacting for 8-14 h at the temperature of 190-210 ℃, taking out, naturally cooling to room temperature in the air to obtain an indium sulfide nanosheet array/foam graphene composite material, opening the reaction kettle, cleaning the composite material with distilled water, preserving heat for 2.5-3 h at the temperature of 450-500 ℃ in the air, and cooling to room temperature along with a furnace to obtain the indium oxide nanosheet array/foam graphene composite material.
The invention has the advantages that:
(1) the method comprises the steps of preparing high-conductivity defect-free three-dimensional foam graphene through chemical vapor deposition, and vertically growing an indium oxide nanosheet array with a high specific surface area on the surface of the foam graphene through hydrothermal synthesis to prepare a composite material with a novel structure;
(2) the composite material can play a synergistic role of high-conductivity graphene and the indium oxide nanosheet array with the high specific surface area, the combination of the indium oxide nanosheet array and the graphene can be improved by utilizing the seed layer preparation, countless active points are provided on the surface of the graphene due to the existence of the indium oxide nanosheet array, and the indium oxide nanosheet can directly transfer electrons generated by reaction to the graphene to realize the rapid transfer of the electrons, so that the electrocatalytic performance can be obviously improved. The sensitivity of electrochemical detection of dopamine can be remarkably improved to 2.69 mu A/mu mol/L by the indium oxide nanosheet array/foamed graphene composite material.
Drawings
Fig. 1 is a scanning electron micrograph of an indium oxide nanosheet array/graphene foam composite prepared by experiment one, at a magnification of 250 times;
fig. 2 is a scanning electron micrograph of an indium oxide nanosheet array/graphene foam composite prepared in experiment one at magnification of 40000 times;
fig. 3 is a scanning electron micrograph of an indium oxide nanosheet array/graphene foam composite prepared in experiment one, magnified 100000 times;
FIG. 4 is an X-ray diffraction pattern of a three-dimensional graphene and indium oxide nanowire array/graphene foam nanosheet composite;
FIG. 5 is a graph of dopamine concentration versus oxidation current obtained from trial two;
FIG. 6 is a graph of dopamine concentration versus oxidation current obtained from run two;
fig. 7 is a curve of dopamine concentration detection of the indium oxide nanosheet array/graphene foam composite material prepared in experiment two under the interference of 20 μ M uric acid.
Fig. 8 is a fitting graph of dopamine concentration detection of the indium oxide nanosheet array/graphene foam composite material prepared in experiment two under the interference of 20 μ M uric acid.
Detailed Description
The first embodiment is as follows: in the embodiment, the preparation method of the indium oxide nanosheet array/foamed graphene composite material is carried out according to the following steps:
chemical vapor deposition method
1) The density is 420g/m2～440g/m2Placing foamed nickel with the thickness of 1.6-2.0 mm in the center of a quartz tube furnace, heating the foamed nickel to 1000-1100 ℃ from room temperature at the heating rate of 20-40 ℃/min under the protection of argon with the flow rate of 480-500 sccm and hydrogen with the flow rate of 180-200 sccm, preserving the heat at 1000-1100 ℃ for 30-60 min, introducing methane gas into the tube furnace at the cooling rate of 5-10 sccm at the temperature of 1000-1100 ℃ for 5-20 min, and cooling the quartz tube furnace to the room temperature from 1000-1100 ℃ at the cooling rate of 80-100 ℃/min to obtain the foamed nickel wrapped by graphene;
2) dissolving 4-5% by mass of polymethyl methacrylate in ethyl lactate, heating and stirring for 1-2 h at 80-120 ℃ to obtain a mixed solution, dropwise adding the mixed solution to the graphene-coated foamed nickel obtained in the step 1) by using a sample adding gun according to the usage amount of 100-200 mu L per square centimeter, naturally drying at room temperature, and then preserving heat at 150-200 ℃ for 0.5-1 h to obtain the foamed graphene with the surface coated with the polymethyl methacrylate;
3)cutting the foamed graphene coated with the polymethyl methacrylate on the surface, which is obtained in the step one 2), into pieces with the surface area of 0.5cm2～2cm2The cube is completely soaked in a hydrochloric acid solution with the temperature of 80-90 ℃ and the concentration of 3-4 mol/L for 4-6 h to obtain the nickel-removed three-dimensional foam graphene;
4) soaking the nickel-removed three-dimensional foam graphene obtained in the step one 3) in acetone at the temperature of 60-70 ℃ for 0.5-1.5 h to obtain foam graphene with the polymethyl methacrylate removed, then cleaning the foam graphene with the polymethyl methacrylate removed with distilled water to obtain cleaned foam graphene with the polymethyl methacrylate removed, then transferring the cleaned foam graphene with the polymethyl methacrylate removed to clean the foam graphene with the polymethyl methacrylate removed in acetone for 15-20 min, cleaning the foam graphene with ethanol for 15-20 min and deionized water for 15-20 min, naturally drying the cleaned foam graphene with the polymethyl methacrylate removed, then dropwise adding an indium sulfide seed layer solution onto the cleaned foam graphene with the polymethyl methacrylate removed by using a sample adding gun according to the usage amount of 50-100 mu L per square centimeter, then placing the glass at the temperature of 150-200 ℃ and preserving heat for 40-60 min to obtain three-dimensional foam graphene/ITO glass prefabricated with an indium sulfide seed layer; the indium sulfide seed layer solution in the step one 4) is synthesized by the following steps: dissolving indium chloride tetrahydrate and thioacetamide in ethanol, and magnetically stirring at the rotating speed of 450-550 r/min for 15-20 min to obtain an indium sulfide seed layer solution, wherein the concentration of the indium chloride tetrahydrate in the indium sulfide seed layer solution is 0.01-0.03 mol/L, and the concentration of the thioacetamide is 0.05-0.07 mol/L;
hydrothermal synthesis method
1) Using ethylene glycol as a solvent to respectively prepare an indium chloride solution with the concentration of 0.01-0.03 mol/L and a thioacetamide solution with the concentration of 0.05-0.07 mol/L, uniformly mixing the two solutions, and magnetically stirring at the rotating speed of 450-550 r/min for 15-20 min to obtain a hydrothermal reaction solution;
2) pouring the hydrothermal reaction solution obtained in the step two 1) into a reaction kettle, inversely placing the three-dimensional foam graphene/ITO glass prefabricated with the indium sulfide seed layer obtained in the step one 4) into a mixed solution in the reaction kettle, covering a cover of the reaction kettle, reacting for 8-14 h at the temperature of 190-210 ℃, taking out, naturally cooling to room temperature in the air to obtain an indium sulfide nanosheet array/foam graphene composite material, opening the reaction kettle, cleaning the composite material with distilled water, preserving heat for 2.5-3 h at the temperature of 450-500 ℃ in the air, and cooling to room temperature along with a furnace to obtain the indium oxide nanosheet array/foam graphene composite material.
The second embodiment is as follows: the first difference between the present embodiment and the specific embodiment is: step one 3) cutting the foamed graphene coated with the polymethyl methacrylate on the surface and obtained in the step one 2) into pieces with the surface area of 0.8cm2～1.0cm2And completely soaking the three-dimensional foam graphene in hydrochloric acid solution with the temperature of 85-90 ℃ and the concentration of 3-4 mol/L for 4.5-5.5 h to obtain the nickel-removed three-dimensional foam graphene. The rest is the same as the first embodiment.
The third concrete implementation mode: this embodiment is different from the first or second embodiment in that: and step one 4) dropwise adding the indium sulfide seed layer solution onto the cleaned foamed graphene without the polymethyl methacrylate by using a sample adding gun according to the usage amount of 70-90 mu L per square centimeter, and then, placing the foamed graphene/ITO glass at the temperature of 180-200 ℃ for heat preservation for 50-60 min to obtain the three-dimensional foamed graphene/ITO glass prefabricated with the indium sulfide seed layer. The indium sulfide seed layer solution is synthesized by the following steps: dissolving indium chloride tetrahydrate and thioacetamide in ethanol, and magnetically stirring at the rotating speed of 480-520 r/min for 5-10 min to obtain an indium sulfide seed layer solution, wherein the concentration of the indium chloride tetrahydrate in the indium sulfide seed layer solution is 0.02-0.03 mol/L, and the concentration of the thioacetamide is 0.06-0.07 mol/L; the other is the same as in one or both of the first and second embodiments.
The fourth concrete implementation mode: the difference between this embodiment mode and one of the first to third embodiment modes is: in the second step 1), 0.02 mol/L-0.03 mol/L indium chloride tetrahydrate and 0.06 mol/L-0.07 mol/L thioacetamide are added into 70 mL-80 mL ethylene glycol and placed in a magnetic stirrer for stirring; the stirring speed of the magnetic stirrer in the step two 1) is 480-520 r/min; stirring for 18-20 min to obtain a hydrothermal reaction solution. The others are the same as in one of the first to third embodiments.
The fifth concrete implementation mode: the difference between this embodiment and one of the first to fourth embodiments is: pouring the hydrothermal reaction solution obtained in the step 1) into a reaction kettle, inversely placing the pre-three-dimensional foam graphene/ITO glass obtained in the step 4) into a mixed solution in the reaction kettle, covering a reaction kettle cover, reacting for 10-12 h at the temperature of 200-210 ℃, taking out, naturally cooling to room temperature in the air to obtain a composite material, opening the reaction kettle, cleaning the composite material with distilled water, preserving heat at 480-500 ℃ for 2.8-3.0 h, and cooling to room temperature along with a furnace to obtain the indium oxide nanosheet array/foam graphene. The other is the same as one of the first to fourth embodiments.
The following tests are adopted to verify the effect of the invention:
test one: the preparation method of the indium oxide nanosheet array/foamed graphene composite material is realized according to the following steps:
firstly, chemical vapor deposition:
1) placing foam nickel with the density of 420g/m2 and the thickness of 1.6mm in the center of a quartz tube furnace, heating the foam nickel from room temperature to 1000 ℃ at the heating rate of 30 ℃/min under the protection of argon with the flow rate of 500sccm and hydrogen with the flow rate of 200sccm, preserving the heat for 30min at the temperature of 1000 ℃, introducing methane gas into the tube furnace at the temperature of 1000 ℃ at the rate of 10sccm for 10min, and cooling the quartz tube furnace from the temperature of 1000 ℃ to room temperature at the cooling rate of 100 ℃/min to obtain the foam nickel wrapped by graphene;
2) dissolving polymethyl methacrylate with the mass fraction of 4% in ethyl lactate, heating and stirring for 2h at the temperature of 100 ℃ to obtain a mixed solution, dropwise adding the mixed solution to the surface of the graphene-coated foamed nickel obtained in the step 1) by using a sample adding gun according to the usage amount of 150 mu L per square centimeter, naturally drying at room temperature, and then preserving heat at the temperature of 200 ℃ for 0.5h to obtain the foamed graphene with the surface coated with the polymethyl methacrylate;
3) cutting the foamed graphene coated with the polymethyl methacrylate on the surface obtained in the step one 2) into cubes with the surface area of 1cm2, and completely soaking the cubes in a hydrochloric acid solution with the temperature of 90 ℃ and the concentration of 3mol/L for 5 hours to obtain nickel-removed three-dimensional foamed graphene;
4) soaking the nickel-removed three-dimensional foam graphene obtained in the step one 3) in acetone at the temperature of 60 ℃ for 1h to obtain foam graphene with the polymethyl methacrylate removed, then cleaning the foamed graphene without the polymethyl methacrylate by using distilled water, then transferring the cleaned foamed graphene without the polymethyl methacrylate to ultrasonic cleaning in acetone for 15min, ultrasonic cleaning in ethanol for 15min and ultrasonic cleaning in deionized water for 15min in sequence, naturally drying at room temperature to obtain clean ITO glass, dropwise adding the indium sulfide seed layer solution to the cleaned foamed graphene without polymethyl methacrylate by using a sample adding gun according to the usage amount of 80 mu L per square centimeter, and then placing the foamed graphene/ITO glass at the temperature of 200 ℃ for heat preservation for 60min to obtain the three-dimensional foamed graphene/ITO glass prefabricated with the indium sulfide seed layer; the indium sulfide seed layer solution in the step one 4) is prepared according to the following steps: dissolving indium chloride tetrahydrate and thioacetamide in ethanol, and magnetically stirring at the rotating speed of 500r/min for 5min to obtain an indium sulfide seed layer solution, wherein the concentration of the indium chloride tetrahydrate and the thioacetamide in the indium sulfide seed layer solution are respectively 0.024mol/L and 0.063 mol/L;
secondly, hydrothermal synthesis method:
1) dissolving 0.024mol/L indium chloride tetrahydrate and 0.063mol/L thioacetamide in 75ml ethylene glycol, and magnetically stirring at the rotating speed of 500r/min for 20min to obtain a hydrothermal reaction solution;
2) pouring the hydrothermal reaction solution obtained in the step two 1) into a reaction kettle, inversely placing the three-dimensional foam graphene/ITO glass prefabricated with the indium sulfide seed layer obtained in the step one 4) into a mixed solution in the reaction kettle, covering a cover of the reaction kettle, reacting for 12 hours at the temperature of 200 ℃, taking out the three-dimensional foam graphene/ITO glass, naturally cooling to room temperature in the air to obtain an indium sulfide nanosheet array/foam graphene composite material, opening the reaction kettle, cleaning the composite material with distilled water, preserving the heat for 3 hours at the temperature of 500 ℃ in the air, and cooling to the room temperature along with a furnace to obtain the indium oxide nanosheet array/foam graphene composite material.
Fig. 1-3 are scanning electron micrographs of the indium oxide nanosheet array/graphene foam composite prepared in experiment one at 250 times, 40000 times and 100000 times magnification. The figure clearly shows that the aperture of the three-dimensional graphene is-300 mu m, numerous indium oxide nanosheet arrays vertically grow on the surface of the graphene to form the indium oxide nanosheet array/foamed graphene three-dimensional composite material, and the size of the indium oxide nanosheet is-300 nm.
Fig. 4 is an X-ray diffraction pattern of a three-dimensional graphene and indium oxide nanowire array/graphene foam nanosheet composite. The existence of diffraction peaks of indium oxide and graphene is evident from the figure, which shows that the composite material is compounded by the two materials.
And (2) test II: the detection test of the indium oxide nanosheet array/foamed graphene composite material as the working electrode specifically comprises the following operations:
the indium oxide nanosheet array/foamed graphene composite material and ITO glass are used as working electrodes, and the effective material area is 0.7cm2The silver/silver chloride is used as a reference electrode, a platinum wire is used as a counter electrode, and the traditional three-electrode system is used for testing by a pulse voltammetry method, wherein the potential is increased by 50mV, the pulse height is 4mV, and the scanning rate is 8mV/s, so that the material is obtained to correspond to the currents of dopamine with different concentrations; the indium oxide nanosheet array/foamed graphene composite material is prepared by the first experiment.
5-6 are graphs and fitting graphs of dopamine concentration and oxidation current obtained in experiment two, and by performing tests in the concentration range of 0.05-60 mu mol/L, a linear relation straight line of dopamine concentration change and current can be obtained, and the slope of the straight line obtained in the range of dopamine concentration, namely the sensitivity for detecting dopamine, is 2.69 mu A/mu mol/L.
Fig. 7-8 are a curve and a fitting graph of dopamine concentration detection of the indium oxide nanosheet array/graphene foam composite material prepared in experiment two under the interference of 20 μ M uric acid. Through testing in the concentration range of 0.05-60 mu mol/L, the composite material can clearly distinguish dopamine from uric acid, and the sensitivity can still reach 2.47 mu A/mu mol/L under interference, which shows that the material has good selectivity.
Claims (2)
1. A preparation method of an indium oxide nanosheet array/foamed graphene electrode is characterized in that the synthesis method of the indium oxide nanosheet array/foamed graphene composite material is specifically carried out according to the following steps:
chemical vapor deposition method
1) The density is 420g/m2～440g/m2Placing foamed nickel with the thickness of 1.6-2.0 mm in the center of a quartz tube furnace, heating the foamed nickel to 1000-1100 ℃ from room temperature at the heating rate of 20-40 ℃/min under the protection of argon with the flow rate of 480-500 sccm and hydrogen with the flow rate of 180-200 sccm, preserving the heat at 1000-1100 ℃ for 30-60 min, introducing methane gas into the tube furnace at the cooling rate of 5-10 sccm at the temperature of 1000-1100 ℃ for 5-20 min, and cooling the quartz tube furnace to the room temperature from 1000-1100 ℃ at the cooling rate of 80-100 ℃/min to obtain the foamed nickel wrapped by graphene;
2) dissolving 4-5% by mass of polymethyl methacrylate in ethyl lactate, heating and stirring for 1-2 h at 80-120 ℃ to obtain a mixed solution, dropwise adding the mixed solution to the graphene-coated foamed nickel obtained in the step 1) by using a sample adding gun according to the usage amount of 100-200 mu L per square centimeter, naturally drying at room temperature, and then preserving heat at 150-200 ℃ for 0.5-1 h to obtain the foamed graphene with the surface coated with the polymethyl methacrylate;
3) cutting the foamed graphene coated with the polymethyl methacrylate on the surface, which is obtained in the step one 2), into pieces with the surface area of 0.5cm2～2cm2OfCompletely soaking the graphene in a hydrochloric acid solution with the temperature of 80-90 ℃ and the concentration of 3-4 mol/L for 4-6 h to obtain nickel-removed three-dimensional foam graphene;
4) soaking the nickel-removed three-dimensional foam graphene obtained in the step one 3) in acetone at the temperature of 60-70 ℃ for 0.5-1.5 h to obtain foam graphene with the polymethyl methacrylate removed, then cleaning the foam graphene with the polymethyl methacrylate removed with distilled water to obtain cleaned foam graphene with the polymethyl methacrylate removed, then transferring the cleaned foam graphene with the polymethyl methacrylate removed to clean the foam graphene with the polymethyl methacrylate removed in acetone for 15-20 min, cleaning the foam graphene with ethanol for 15-20 min and deionized water for 15-20 min, naturally drying the cleaned foam graphene with the polymethyl methacrylate removed, then dropwise adding an indium sulfide seed layer solution onto the cleaned foam graphene with the polymethyl methacrylate removed by using a sample adding gun according to the usage amount of 50-100 mu L per square centimeter, then placing the glass at the temperature of 150-200 ℃ and preserving heat for 40-60 min to obtain three-dimensional foam graphene/ITO glass prefabricated with an indium sulfide seed layer; the indium sulfide seed layer solution in the step one 4) is synthesized by the following steps: dissolving indium chloride tetrahydrate and thioacetamide in ethanol, and magnetically stirring at the rotating speed of 450-550 r/min for 15-20 min to obtain an indium sulfide seed layer solution, wherein the concentration of the indium chloride tetrahydrate in the indium sulfide seed layer solution is 0.01-0.03 mol/L, and the concentration of the thioacetamide is 0.05-0.07 mol/L;
hydrothermal synthesis method
1) Using ethylene glycol as a solvent to respectively prepare an indium chloride solution with the concentration of 0.01-0.03 mol/L and a thioacetamide solution with the concentration of 0.05-0.07 mol/L, uniformly mixing the two solutions, and magnetically stirring at the rotating speed of 450-550 r/min for 15-20 min to obtain a hydrothermal reaction solution;
2) pouring the hydrothermal reaction solution obtained in the step two 1) into a reaction kettle, inversely placing the three-dimensional foam graphene/ITO glass prefabricated with the indium sulfide seed layer obtained in the step one 4) into a mixed solution in the reaction kettle, covering a cover of the reaction kettle, reacting for 8-14 h at the temperature of 190-210 ℃, taking out, naturally cooling to room temperature in the air to obtain an indium sulfide nanosheet array/foam graphene composite material, opening the reaction kettle, cleaning the composite material with distilled water, preserving heat for 2.5-3 h at the temperature of 450-500 ℃ in the air, and cooling to room temperature along with a furnace to obtain the indium oxide nanosheet array/foam graphene composite material.
2. An application of an indium oxide nanosheet array/foamed graphene composite material is characterized in that the indium oxide nanosheet array/foamed graphene composite material is used as a working electrode.
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