CN111521657A - Dopamine biosensor based on porous boron-doped diamond electrode and preparation method and application thereof - Google Patents
Dopamine biosensor based on porous boron-doped diamond electrode and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a dopamine biosensor based on a porous boron-doped diamond electrode and a preparation method and application thereof. The porous boron-doped diamond electrode has a high specific surface area, the response current of the sensor can be increased, the modified nano carbon black particles and the naphthalene film are used as a protective film and a functional interlayer of the electrode, the carbon black particles can advance the oxidation potential of interferents, signal interference is reduced, and the naphthalene film plays the roles of inhibiting the interferents and stabilizing the carbon black particles.
Description
Technical Field
The invention belongs to the technical field of electrochemical biosensors, and particularly relates to a dopamine biosensor based on a porous boron-doped diamond electrode, and a preparation method and application thereof.
Background
Dopamine is a precursor substance of NA, is a key neurotransmitter in hypothalamic dopamine and pituitary gland, the concentration of dopamine in the central nervous system is influenced by mental factors, axonal connection and interaction exist between GnRH of nerve endings and dopamine, and dopamine has the effect of inhibiting GnRH secretion. The detection of dopamine content is of great significance to human health and diagnosis, treatment and control of diseases.
Biosensors (biosensors) are instruments or devices that organically combine a physical transducer with bioactive materials (enzymes, proteins, DNA, antibodies, antigens, biofilms, etc.), are an advanced detection method and monitoring method essential for the development of biotechnology, and are also rapid, micro-analysis methods of substance molecular levels. The structure (composition) of the biosensor, by definition, comprises two parts: 1. bioactive materials (also called bio-sensitive membranes, molecular recognition elements). 2. Physical transducers (also called sensors); in which a sensor part functions to convert various biological, chemical and physical information into an electric signal. Currently, many methods for detecting blood dopamine are reported, and a gas-liquid chromatography-mass spectrometry method, a temperature measurement method, a molecular luminescence method, a colorimetric method, an electrochemical method and the like are common, but the selectivity of the detection methods mostly depends on an enzyme or an antibody specifically recognizing the dopamine, and the methods are destructive and quite expensive.
The electrochemical non-enzyme biosensor has the advantages of simple operation, high sensitivity, short response time, and better stability and usability than enzyme sensors.
Currently, the mainstream dopamine biosensors can be classified into two categories. One is that non-dopamine micromolecule substances are blocked by a selective ion permeation membrane, and only dopamine molecules selectively pass through the membrane, so that only the dopamine molecules on the surface of an electrode react, and oxidation current of the dopamine molecules is obtained; the other type is that active substances are modified on the surface of an electrode, and the purpose of selectively detecting dopamine is achieved through the difference of oxidation potentials of the modified substances on dopamine and dopamine interferents. However, both methods cannot completely ensure that the detection process is not interfered, the former loses selectivity when facing some positive ions similar to dopamine, and the latter still has the problem that the detection result is not correct because the reaction product of the interferent and dopamine is reacted with the dopamine quinone, even if the oxidation potential of the interferent and dopamine is sufficiently separated, for example, even if the oxidation potential of the main interferent, namely ascorbic acid and dopamine is sufficiently separated by the electrode modified by the carbon nanotube, the oxidation product of dopamine still reacts with ascorbic acid in the solution to generate new dopamine, the newly generated dopamine changes the concentration of the original detected dopamine, and the detection result is naturally not correct.
Disclosure of Invention
In view of the shortcomings of the prior art, the first object of the present invention is to provide a dopamine biosensor based on a porous boron-doped diamond electrode.
The second purpose of the invention is to provide a preparation method of the dopamine biosensor based on the porous boron-doped diamond electrode.
The second purpose of the invention is to provide the application of the dopamine biosensor based on the porous boron-doped diamond electrode.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention discloses a dopamine biosensor based on a porous boron-doped diamond electrode, which comprises a working electrode, a counter electrode and a reference electrode, wherein a substrate electrode of the working electrode is a porous boron-doped diamond electrode, and the surface of the porous boron-doped diamond electrode is modified with nano carbon black particles and a naphthalene-phenol film.
In the invention, the working electrode of the dopamine biosensor is a porous boron-doped diamond electrode with the surface modified with nano carbon black particles and a naphthalene-phenol film, the porous boron-doped diamond electrode has a high specific surface area and can increase the response current of the sensor, the modified nano carbon black particles and the naphthalene-phenol film are used as a protective film and a functional interlayer of the electrode, the carbon black particles can advance the oxidation potential of an interferent and reduce signal interference, and the naphthalene-phenol simultaneously plays the roles of inhibiting the interferent and stabilizing the carbon black particles.
The invention relates to a dopamine biosensor based on a porous boron-doped diamond electrode.
The invention relates to a dopamine biosensor based on a porous boron-doped diamond electrode, wherein the thickness of a porous boron-doped diamond layer is 5-20 mu m; the diamond grain size ranges from 5 to 10 μm.
The surface of the porous boron-doped diamond layer is of a porous structure, the porous structure is regulated and controlled by controlling the thickness (5-50nm) of the nickel layer and the heat treatment etching time (100-300min), and the performance of the electrode can reach the optimal value by controlling the porous structure and matching the nano carbon black particles with the most suitable particle size.
The invention relates to a dopamine biosensor based on a porous boron-doped diamond electrode, wherein the size of nano carbon black particles is 50-100 nm. The inventors have found that when the nano-carbon black has a particle size of 50-100nm, the resulting electrode performs optimally.
The invention relates to a dopamine biosensor based on a porous boron-doped diamond electrode, which takes a platinum sheet as a counter electrode and an Ag/AgCl electrode as a reference electrode.
The invention relates to a preparation method of a dopamine biosensor based on a porous boron-doped diamond electrode, which comprises the following steps:
step 1 deposition of boron-doped diamond layer
Depositing a boron-doped diamond layer on the silicon-based substrate by adopting a chemical vapor deposition method, and controlling the thickness of the boron-doped diamond layer to be 5-20 mu m;
step 2 preparation of porous boron-doped diamond electrode
Sputtering a nickel layer with the thickness of 5-50nm on the surface of the boron-doped diamond layer by adopting a magnetron sputtering method, then placing the boron-doped diamond layer in a hydrogen atmosphere for heat treatment to etch the surface of the boron-doped diamond layer into a porous structure, then removing nickel particles in holes by adopting an acid solution to obtain a porous boron-doped diamond electrode,
step 3 modification of porous boron-doped diamond electrode
Dripping a solution containing nano carbon black particles on the surface of the porous boron-doped diamond electrode obtained in the step 2, drying, dripping a naphthylene solution, and airing to obtain the porous boron-doped diamond electrode with the surface modified with the nano carbon black particles and the naphthylene film;
step 4 preparation of the sensor
And (3) assembling the porous boron-doped diamond electrode with the surface modified with the nano carbon black particles and the nafil film obtained in the step (3) as a working electrode, a platinum sheet as a counter electrode and an Ag/AgCl electrode as a reference electrode to obtain the dopamine biosensor.
The invention relates to a preparation method of a dopamine biosensor based on a porous boron-doped diamond electrode, wherein in step 1, the technological parameters of chemical vapor deposition are as follows: the surface temperature of the silicon-based substrate is 700-900 ℃, the deposition pressure is 2.5-5KPa, and the deposition time is 4-10 h; the ratio of the introduced methane, the borane and the hydrogen is 1-20: 0.3-1: 30-49.
The invention relates to a preparation method of a dopamine biosensor based on a porous boron-doped diamond electrode, wherein in step 1, the chemical vapor deposition is hot wire chemical vapor deposition, the number of turns of a hot wire is 10-20, and the temperature of the hot wire is 2000-.
The invention relates to a preparation method of a dopamine biosensor based on a porous boron-doped diamond electrode, which comprises the following steps of 1, placing a silicon-based substrate in an acetone solution, carrying out ultrasonic cleaning for 5-20min, then carrying out ultrasonic cleaning in deionized water for 10-20min, drying and then carrying out deposition.
The invention relates to a preparation method of a dopamine biosensor based on a porous boron-doped diamond electrode, wherein in step 2, a nickel target with the purity of more than or equal to 99.99% is adopted, the magnetron sputtering power is 50-150W, and the air pressure is 0.5-2 Pa.
The invention relates to a preparation method of a dopamine biosensor based on a porous boron-doped diamond electrode, wherein in step 2, the introduction amount of a hydrogen atmosphere is 40-100SCCM, the heat treatment temperature is 600-1000 ℃, the heat treatment time is 100-300min, and the air pressure in the furnace is 10-20KPa during heat treatment.
The invention relates to a preparation method of a dopamine biosensor based on a porous boron-doped diamond electrode, which comprises the step 2 of soaking a boron-doped diamond layer with a surface etched into a porous structure for 100-150min in an acid pickling solution at 80-100 ℃ to obtain the porous boron-doped diamond electrode, wherein the acid solution is a nitric acid solution, and the mass fraction of the nitric acid is 10-30%.
The invention relates to a preparation method of a dopamine biosensor based on a porous boron-doped diamond electrode, which comprises the following steps of in step 3, dropwise coating 5-20 mu l of solution containing nano carbon black particles on the surface of the porous boron-doped diamond electrode obtained in step 2; the solution containing the nano carbon black particles is obtained by the following method: adding the nano carbon black particles into isopropanol, and performing ultrasonic treatment for 100-200min, wherein the mass-volume ratio of the nano carbon black particles to the isopropanol is 0.1-1g:10 ml.
The invention relates to a preparation method of a dopamine biosensor based on a porous boron-doped diamond electrode, wherein in step 3, the amount of a dripping nafil solution is 1-50 mu l, preferably 5-10 mu l; in the naftifine solution, the mass fraction of the raw material naftifine is 1-10%; the solvent is isopropanol.
The invention discloses application of a dopamine biosensor based on a porous boron-doped diamond electrode, and the dopamine biosensor is applied to quantitative dopamine detection.
Advantageous effects
The invention provides a dopamine biosensor based on a porous boron-doped diamond electrode, wherein the porous boron-doped diamond electrode has a high specific surface area and can increase the response current of the sensor, and the modified nano carbon black particles and a nafil film are used as a protective film and a functional interlayer of the electrode, so that the oxidation potential of ascorbic acid is advanced through the strong oxidizing property of the carbon black nanoparticles, and thus, the ascorbic acid capable of reacting with the dopamine quinone generated by dopamine oxidation can be greatly reduced due to the depletion effect of the reaction; second, the modified naftifine membrane can further prevent the small amount of ascorbic acid still present after depletion from reaching the electrode surface, thereby substantially eliminating the effect of ascorbic acid.
The preparation method adopts a CVD diamond growth method to grow a layer of uniform and compact diamond film on a silicon substrate, then the diamond is etched into a porous structure, so that the specific surface area of an electrode can be effectively increased, the active area of a sensor is increased, a larger response current is obtained, and finally functional nano carbon black particles and a naphthylene film are modified on the porous diamond to realize the selective detection of dopamine.
Drawings
FIG. 1 is a Scanning (SEM) image of the unetched diamond film of example 1;
FIG. 2 is a Scanning (SEM) image of the etched porous morphology of the diamond film in example 1;
FIG. 3 is a Scanning (SEM) image of the morphology of porous diamond-modified nano carbon black particles of example 1;
FIG. 4 is a Scanning (SEM) image of the morphology of the porous diamond modified nano carbon black particles and the nafion film in example 1.
Detailed Description
The essential features and the remarkable developments of the invention are further illustrated by the following examples, but the invention is by no means limited to these examples.
Example 1
Step 1, preparing the boron-doped diamond film. Firstly, placing a silicon wafer substrate in an acetone solution, and ultrasonically cleaning for 5 minutes to remove surface oil stains; then ultrasonically cleaning the substrate in deionized water for 10 minutes, drying the substrate in a drying furnace, and then placing the substrate in a chemical vapor deposition chamber for growing the boron-doped diamond, wherein the number of turns of a hot wire in the growth process is 10, the temperature of the hot wire is controlled at 2000 ℃, the surface temperature of the substrate is 700 ℃, the gas ratio is that methane/borane/hydrogen is equal to 1/0.3/49, the chamber pressure is about 2.5 kilopascals, the grain size of the grown diamond film is 5-7 micrometers in diameter, and the thickness range of the diamond film is 5-10 micrometers, as shown in figure 1.
And 2, sputtering a nickel layer. The method comprises the steps of using physical magnetron sputtering equipment, using a high-purity nickel target with the purity of 99.99 percent under the air pressure of 0.5 Pa, and uniformly sputtering a layer of nickel film on the diamond film in the step 1, wherein the sputtering power is 50 watts, and the thickness of the nickel layer is 5-20 nm.
And 3, carrying out high-temperature heat treatment etching in a hydrogen environment. The method comprises the steps of putting the sheet prepared in the step 2 into a cold wall heat treatment furnace, introducing 40SCCM hydrogen, controlling the etching temperature at 600 ℃, controlling the etching pressure at 10 kilopascals, controlling the etching time at 100 minutes, and showing the etching morphology as shown in figure 2.
And 4, removing nickel particles. The method comprises the steps of putting the electrode slice etched in the step 3 into a 10% nitric acid solution, adding the nitric acid solution to 80 ℃, preserving the temperature for 100 minutes, and removing nickel particles.
And 5, modifying the carbon black particles and the naphthylene solution. The method comprises the steps of melting 0.5 g of carbon black particles with the average particle size of 75nm into 10ml of isopropanol solution, carrying out ultrasonic treatment for 100 minutes to obtain a carbon black suspension solution, dropwise coating 5 microliters of the carbon black suspension solution on the surface of an electrode by using a pipette, wherein the carbon black modified morphology is shown in figure 3; then drying in a drying oven, dripping 5 microliter of 5% naphthylene solution diluted by isopropanol on the surface of the carbon black, and drying at room temperature, wherein the final modified morphology is shown in figure 4.
And 6, preparing and detecting the sensor. The method is that after the electrode obtained in the step 5 is packaged, the reference electrode, the counter electrode and the packaged electrode are used together to form the three-electrode detection sensor. The detection object is a dopamine solution with the concentration range of 0.01-500 mu M, the interference object is an ascorbic acid solution with the concentration range of 500 mu M and a uric acid solution with the concentration range of 500 mu M, and base solutions of the three solutions are PBS solutions with the concentration range of 0.01M. Adding interferents into dopamine solutions with different concentrations respectively, and performing detection analysis by using the encapsulated electrodes, wherein the detection analysis process adopts cyclic voltammetry (the scanning speed is 20mV per second) and square wave voltammetry (the pulse amplitude is 30mV, and the frequency is 5 Hz). And (3) displaying a detection result: the detection limit 50nM. of the electrode for dopamine reaches 5-50 mu M in a linear range.
Example 2
Step 1, preparing the boron-doped diamond film. Firstly, placing a silicon wafer substrate in an acetone solution, and ultrasonically cleaning for 10 minutes to remove surface oil stains; then ultrasonically cleaning the substrate in deionized water for 15 minutes, drying the substrate in a drying furnace, and then placing the substrate in a chemical vapor deposition chamber for growing the boron-doped diamond, wherein the number of turns of a hot wire in the growth process is 15, the temperature of the hot wire is controlled at 2250 ℃, the surface temperature of the substrate is 800 ℃, the gas ratio is that methane/borane/hydrogen is equal to 1/0.3/49, the chamber pressure is about 3.0 kilopascal, the grain size of the grown diamond film is 6-8 microns in diameter, and the film thickness range is 10-15 microns.
And 2, sputtering a nickel layer. The method comprises the steps of using physical magnetron sputtering equipment, using a high-purity nickel target with the purity of 99.99 percent under the air pressure of 1 Pa, and uniformly sputtering a layer of nickel film on the diamond film in the step 1, wherein the sputtering power is 100 watts, and the thickness of the nickel layer is 20-40 nm.
And 3, carrying out high-temperature heat treatment etching in a hydrogen environment. The method comprises the steps of putting the sheet prepared in the step 2 into a cold wall heat treatment furnace, introducing 60SCCM hydrogen, controlling the etching temperature at 800 ℃, controlling the etching pressure at 15 kilopascals, and etching for 200 minutes.
And 4, removing nickel particles. The method comprises the steps of putting the electrode slice etched in the step 3 into a 10% nitric acid solution, adding the nitric acid solution to 90 ℃, preserving the temperature for 125 minutes, and removing nickel particles.
And 5, modifying the carbon black particles and the naphthylene solution. The method comprises the steps of melting 0.5 g of carbon black particles with the average particle size of 75nm into 10ml of isopropanol solution, carrying out ultrasonic treatment 150 to obtain a carbon black suspension solution, dropwise coating 10 microliters of the carbon black suspension solution on the surface of an electrode by using a transfer pipette, drying in a drying furnace, dropwise coating 7 microliters of 5% naphthylene solution diluted by isopropanol on the surface of the carbon black, and airing at room temperature.
And 6, preparing and detecting the sensor. The method is that after the electrode obtained in the step 5 is packaged, the reference electrode, the counter electrode and the packaged electrode are used together to form the three-electrode detection sensor. The detection object is dopamine solution with concentration range of 0.01-500 μ M, the interference object is ascorbic acid solution with concentration range of 1000 μ M and uric acid solution with concentration range of 1000 μ M, and the base solutions of the three solutions are PBS solution with concentration range of 0.01M. Adding interferents into dopamine solutions with different concentrations respectively, and performing detection analysis by using the encapsulated electrodes, wherein the detection analysis process adopts cyclic voltammetry (the scanning speed is 30mV per second) and square wave voltammetry (the pulse amplitude is 35mV, and the frequency adopts 10 Hz). And (3) displaying a detection result: the linear range of the detection limit 30nM. of the electrode for dopamine reaches 1-80 mu M.
Example 3
Step 1, preparing the boron-doped diamond film. Firstly, placing a silicon wafer substrate in an acetone solution, and ultrasonically cleaning for 20 minutes to remove surface oil stains; then ultrasonically cleaning the substrate in deionized water for 20 minutes, drying the substrate in a drying furnace, and then placing the substrate in a chemical vapor deposition chamber for growing the boron-doped diamond, wherein the number of turns of a hot wire in the growth process is 20, the temperature of the hot wire is controlled at 2500 ℃, the surface temperature of the substrate is 900 ℃, the gas ratio is that methane/borane/hydrogen is equal to 1/0.3/49, the chamber pressure is about 5 kilopascals, the grain size of the grown diamond film is 8-10 micrometers in diameter, and the film thickness range is 15-20 micrometers.
And 2, sputtering a nickel layer. The method comprises the steps of using physical magnetron sputtering equipment, using a high-purity nickel target with the purity of 99.99 percent under the air pressure of 2Pa, and uniformly sputtering a layer of nickel film on the diamond film in the step 1, wherein the sputtering power is 150 watts, and the thickness of the nickel layer is 50nm.
And 3, carrying out high-temperature heat treatment etching in a hydrogen environment. The method comprises the steps of putting the sheet prepared in the step 2 into a cold wall heat treatment furnace, introducing 100SCCM hydrogen, controlling the etching temperature at 1000 ℃, controlling the etching pressure at 20 kilopascals, and etching for 300 minutes.
And 4, removing nickel particles. The method comprises the steps of putting the electrode slice etched in the step 3 into a 10% nitric acid solution, adding the nitric acid solution to 100 ℃, preserving the temperature for 150 minutes, and removing nickel particles.
And 5, modifying the carbon black particles and the naphthylene solution. The method comprises the steps of melting 0.5 g of carbon black particles with the average particle size of 75nm into 10ml of isopropanol solution, carrying out ultrasonic treatment for 200 minutes to obtain a carbon black suspension solution, dropwise coating 20 microliters of the carbon black suspension solution on the surface of an electrode by using a pipette, drying in a drying furnace, dropwise coating 10 microliters of 5% naphthylene solution diluted by isopropanol on the surface of the carbon black, and airing at room temperature.
And 6, preparing and detecting the sensor. The method is that after the electrode obtained in the step 5 is packaged, the reference electrode, the counter electrode and the packaged electrode are used together to form the three-electrode detection sensor. The detection object is dopamine solution with concentration range of 0.01-500 μ M, the interference object is ascorbic acid solution with concentration range of 1500 μ M and uric acid solution with concentration range of 1500 μ M, and the base solution of the three solutions adopts PBS solution with concentration range of 0.01M. Adding interferents into dopamine solutions with different concentrations respectively, and performing detection analysis by using the encapsulated electrodes, wherein the detection analysis process adopts cyclic voltammetry (the scanning speed is 40mV per second) and square wave voltammetry (the pulse amplitude is 40mV, and the frequency is 15 Hz). And (3) displaying a detection result: the linear detection range of the electrode to the detection limit 16nM. of dopamine reaches 0.1-100 mu M.
Comparative example 1
The other conditions of the comparative example 1 are the same as those of the example 1, the number of turns of the hot wire for growing the diamond film is 8, but the grown diamond film cannot completely cover the substrate, and the main reason is that the number of turns is too small, so that the heat radiation coverage area under the hot wire is insufficient, the temperature of the part of the substrate cannot reach the nucleation and growth temperature of the diamond, and finally, a continuous diamond layer cannot grow.
Comparative example 2
Other conditions of the comparative example 2 are the same as those of the example 1, and the number of turns of the hot wire is 25 turns only when the diamond film is grown, but the hot wire is very seriously deformed during the growth of the diamond film and is fused at the initial stage of nucleation, thereby causing the failure of the experiment. The main reason is that the tungsten wire has too many turns and too large total length, which brings excessive thermal deformation, thereby generating a phenomenon of serious deformation, further, the excessive deformation can generate thermal stress, finally, the hot wire can not be used for a long time, and the hot wire can be directly fused.
Comparative example 3
The other conditions of the comparative example 3 are the same as those of the example 1, the temperature of the hot wire is controlled to be 1800 ℃ when only the diamond film is grown, but the diamond film can not be grown on the substrate, mainly because the temperature of the hot wire is too low, the number of cracked C atoms is less, and in addition, the temperature of the substrate is too low, and the two aspects directly result in that effective nucleation can not be formed on the substrate, and finally the diamond growth fails.
Comparative example 4
Other conditions of the comparative example 4 are the same as those of the example 3, the thickness of the nickel layer for etching the diamond is only 80nm, after etching, nickel particles are found to be agglomerated into micron particles with larger sizes, and the surface of the nickel layer presents a black graphite layer, so that the porous layer can be effectively etched. The main reason is that the nickel layer is too thick, the size of the agglomerated nickel particles is too large, and carbon atoms etched below the nickel particles cannot be well taken away by hydrogen, so that the graphite layer is accumulated and etching is stopped.
Comparative example 5
This comparative example 5 was otherwise identical to example 1 except that no modification of the naftifine solution was performed. However, two major significant deficiencies were found in the selective detection of dopamine. Firstly, although the electrode modified by only carbon black solution can separate oxidation potentials of dopamine and ascorbic acid (the potential difference reaches 200mV), compared with the dopamine solution with the same concentration (0.01-500 mu M of the dopamine solution without interfering substance ascorbic acid), the detection signal of each concentration is obviously increased (the increased signal reaches 30% of the original value), which indicates that the electrode modified by only carbon black can reduce the influence of ascorbic acid, but can not completely eliminate the interference of ascorbic acid on the detection signal of dopamine, thereby causing inaccuracy of the detection result; the other problem is that although the carbon black particles on the electrode are embedded into diamond pores, the stability is enhanced compared with non-porous modification, but the stability is still insufficient, which shows that the carbon black particles obviously drop after 3-5 days of detection, and the effect of further fixing the naphthalene film modification cannot be achieved.
Comparative example 6
This comparative example 6 was otherwise the same as example 1 except that the carbon black particles had a particle diameter of 20 nm. When detecting dopamine solution (0.01-500 μ M), the electrode activity is found to be seriously insufficient, and the detection current signal is only about 20% of that in real-time example 1. The main reason is that the particle size of the carbon black particles is too small, so that most of the particles are completely embedded into the back of the hole, the exposed active area of the carbon black particles is greatly reduced, and the effective area for detecting dopamine is naturally seriously insufficient.
Claims (10)
1. A dopamine biosensor based on a porous boron-doped diamond electrode is characterized in that: the electrode comprises a working electrode, a counter electrode and a reference electrode, wherein a substrate electrode of the working electrode is a porous boron-doped diamond electrode, and the surface of the porous boron-doped diamond electrode is modified with nano carbon black particles and a naphthalene-phenol film.
2. The dopamine biosensor based on the porous boron-doped diamond electrode according to claim 1, wherein: the porous boron-doped diamond electrode comprises a silicon wafer substrate and a porous boron-doped diamond layer arranged on the surface of the silicon wafer substrate.
3. The dopamine biosensor based on the porous boron-doped diamond electrode according to claim 1, wherein: the thickness of the porous boron-doped diamond layer is 5-20 mu m; the diamond grain size is 5-10 μm.
4. The dopamine biosensor based on the porous boron-doped diamond electrode according to claim 1, wherein: the size of the nano carbon black particles is 50-100 nm.
5. Method for preparing a dopamine biosensor based on a porous boron doped diamond electrode according to any of claims 1-4, characterized in that: the method comprises the following steps:
step 1 deposition of boron-doped diamond layer
Depositing a boron-doped diamond layer on the silicon-based substrate by adopting a chemical vapor deposition method, and controlling the thickness of the boron-doped diamond layer to be 5-20 mu m;
step 2 preparation of porous boron-doped diamond electrode
Sputtering a nickel layer with the thickness of 5-50nm on the surface of the boron-doped diamond layer by adopting a magnetron sputtering method, then placing the boron-doped diamond layer in a hydrogen atmosphere for heat treatment to etch the surface of the boron-doped diamond layer into a porous structure, then removing nickel particles in holes by adopting an acid solution to obtain a porous boron-doped diamond electrode,
step 3 modification of porous boron-doped diamond electrode
Dripping a solution containing nano carbon black particles on the surface of the porous boron-doped diamond electrode obtained in the step 2, drying, dripping a naphthylene solution, and airing to obtain the porous boron-doped diamond electrode with the surface modified with the nano carbon black particles and the naphthylene film;
step 4 preparation of the sensor
And (3) assembling the porous boron-doped diamond electrode with the surface modified with the nano carbon black particles and the nafil film obtained in the step (3) as a working electrode, a platinum sheet as a counter electrode and an Ag/AgCl electrode as a reference electrode to obtain the dopamine biosensor.
6. The preparation method of the dopamine biosensor based on the porous boron-doped diamond electrode, according to claim 5, is characterized in that: in step 1, the chemical vapor deposition process parameters are as follows: the surface temperature of the silicon-based substrate is 700-900 ℃, the deposition pressure is 2.5-5KPa, and the deposition time is 4-10 h; the ratio of the introduced methane, the borane and the hydrogen is 1-20: 0.3-1: 30-49;
in step 1, the chemical vapor deposition is hot wire chemical vapor deposition, the number of hot wire turns is 10-20, and the temperature of the hot wire is 2000-.
7. The preparation method of the dopamine biosensor based on the porous boron-doped diamond electrode, according to claim 5, is characterized in that: in the step 2, a nickel target with the purity of more than or equal to 99.99 percent is adopted, the magnetron sputtering power is 50-150W, and the air pressure is 0.5-2 Pa;
in the step 2, the introduction amount of the hydrogen atmosphere is 40-100SCCM, the heat treatment temperature is 600-1000 ℃, the heat treatment time is 100-300min, and the air pressure in the furnace is 10-20KPa during the heat treatment;
in the step 2, soaking the boron-doped diamond layer with the surface etched into the porous structure in an acid washing solution at the temperature of 80-100 ℃ for 100-150min to obtain the porous boron-doped diamond electrode, wherein the acid solution is a nitric acid solution, and the mass fraction of the nitric acid is 10-30%.
8. The preparation method of the dopamine biosensor based on the porous boron-doped diamond electrode, according to claim 5, is characterized in that: in step 3, 5-20 mul of solution containing nano carbon black particles is dripped on the surface of the porous boron-doped diamond electrode obtained in step 2; the solution containing the nano carbon black particles is obtained by the following method: adding the nano carbon black particles into isopropanol, and performing ultrasonic treatment for 100-200min, wherein the mass-volume ratio of the nano carbon black particles to the isopropanol is 0.1-1g:10 ml.
9. The preparation method of the dopamine biosensor based on the porous boron-doped diamond electrode, according to claim 5, is characterized in that: in the step 3, the amount of the dripping nafil solution is 1-50 mu l, and the mass fraction of the nafil in the nafil solution is 1-10%; the solvent is isopropanol.
10. Use of a porous boron doped diamond electrode based dopamine biosensor according to any of claims 1-4, characterized in that: the dopamine biosensor is applied to quantitative detection of dopamine.
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