CN114563454A - Based on Au/Ti3C2TxDopamine electrochemical sensor for modifying glassy carbon working electrode and preparation method thereof - Google Patents
Based on Au/Ti3C2TxDopamine electrochemical sensor for modifying glassy carbon working electrode and preparation method thereof Download PDFInfo
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- G—PHYSICS
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- 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
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Abstract
Based on Au/Ti3C2TxA dopamine electrochemical sensor for modifying a glassy carbon working electrode and a preparation method thereof belong to the technical field of biosensors. The sensor consists of a reference electrode AgCl/Ag, a counter electrode Pt sheet and Au/Ti3C2TxThe modified glassy carbon working electrode consists of electrolyte 0.1M, pH ═ 7 phosphate buffer solution. The invention uses Au/Ti3C2TxAs a working electrode modifying material, Ti3C2TxThe dopamine-containing porous material has large specific surface area, excellent conductivity, hydrophilic surface, good biocompatibility and good adsorption effect on dopamine; the Au nanoparticles are used for catalyzing the oxidation-reduction reaction on the surface of the electrode, and the conductivity, the electron transfer capacity and the electrochemical active area are improved. The electrode modification material is a nano composite material,the purpose of improving the sensitivity of the sensor is achieved by utilizing the synergistic effect of the composite materials.
Description
Technical Field
The invention belongs to the technical field of biosensors, and particularly relates to a biosensor based on Au/Ti3C2TxThe dopamine electrochemical sensor with the modified glassy carbon working electrode can be used for detecting the concentration of dopamine in a liquid environment.
Background
Dopamine is an important neurotransmitter in the human body and plays a very important role in the kidney, hormones, cardiovascular and central nervous systems. The health-care food has the regulation effect on multiple activities of a human body, has certain correlation on emotion and feeling, and has important effect on the regulation of heart rate and blood pressure. However, abnormal dopamine concentration in humans may lead to neurological disorders such as addictive behaviors, schizophrenia, parkinsonism, alzheimer's disease, and the like. Therefore, the method has important medical value for accurately detecting the concentration of the dopamine. For many years, there have been many conventional techniques for detecting dopamine, such as high performance liquid chromatography, fluorescence analysis, electrophoresis, spectrophotometry. However, these detection methods usually require expensive instruments, good experimental conditions, and technically sophisticated experimenters, and thus cannot satisfy the popular demands. And these instruments are bulky and cannot be monitored in real time. Therefore, the construction of a low-cost, portable and high-performance dopamine sensor becomes a research hotspot.
The electrochemical analysis method has the characteristics of portable instrument, low cost, simple operation and low requirement on experimental environment, has the advantages of high sensitivity, low detection limit and high selectivity of an optical method, and has more possibility of practical application. Because dopamine molecules are electroactive substances and are easy to oxidize, an electrochemical analysis technology is widely applied to detection of dopamine content. When dopamine is measured by an electrochemical method, a solution to be measured is placed in an electrolytic cell. The concentration of the dopamine is analyzed through the relation between the measured electrochemical parameters (Current, electric quantity Charge, Voltage and Conductivity) and the measured dopamine. Electrochemical methods are largely classified into differential pulse voltammetry, cyclic voltammetry, chronoamperometry, polarography, potentiometry, and voltammetry, wherein differential pulse voltammetry is considered as an effective method for detecting dopamine in an aqueous environment. The principle is that a constant potential rectifier superposes a series of forward and reverse pulse signals as excitation signals on the basis of step linear scanning, and the currents of the forward and reverse pulses in a period are subtracted to obtain the electrolytic current in the period. The electrolytic current is measured continuously over a plurality of cycles as the potential increases and plotted against potential to obtain a differential pulse curve. Recording an I-V curve obtained in scanning, wherein oxidation peak current is the response value of the sensor to dopamine, and further judging the concentration according to the current value of the oxidation peak of the dopamine.
In the design of electrochemical sensors, the design of the working electrode is of the utmost importance, and the properties of the electrode modification material have an important influence on the working electrode. The original electrode has no molecular recognition capability, low response signal and difficult dopamine detection, so the working electrode needs to be modified. Most sensing materials have certain limitations, such as small specific surface area, poor biocompatibility, low catalytic activity and the like, and the selection of a modifying material is very important. In the detection of dopamine, the design of the electrode modification material is mainly based on the fact that the redox reaction occurring at the interface of the electrolyte and the electrode can be promoted. The electrode modification material should be selected with attention paid to its adsorption to dopamine, catalytic ability to redox reaction, and electron transfer ability.
The electrode modification material Ti designed by the invention3C2TxThe nano-composite material has the advantages of large specific surface area, excellent conductivity, good biocompatibility and good adsorption capacity on dopamine; and Au nano particles are introduced to catalyze the oxidation-reduction reaction on the surface of the electrode, so that the conductive capacity, the electron transfer capacity and the electrochemical active area are improved.
Disclosure of Invention
The invention aims to provide a catalyst based on Au/Ti3C2TxThe invention discloses a dopamine electrochemical sensor with a modified glassy carbon working electrode and a preparation method thereof.
The invention relates to a method based on Au/Ti3C2TxThe dopamine electrochemical sensor for modifying the glassy carbon working electrode is characterized in that: the reference electrode AgCl/Ag, the counter electrode Pt sheet and Au/Ti3C2TxThe modified glassy carbon working electrode consists of electrolyte of 0.1M NaH2PO4And 0.1M Na2HPO4The solution was prepared as a 0.1M, pH ═ 7 Phosphate (PBS) buffer solution (i.e., phosphate ion concentration of 0.1M). Precursor Ti3AlC2The powder is from Jilin province, science and technology limited (Changchun, China). All other chemicals were purchased commercially and were analytically pure and used without further purification. All solutions were prepared with deionized water. Au/Ti of the invention3C2TxThe preparation method comprises the following steps:
(1) adding 1-5 g of Ti3AlC2Slowly adding the powder into 30-60 mL of 40 wt% hydrofluoric acid solution, and magnetically stirring for 20-40 h at 40-60 ℃; then adding deionized water to centrifugally wash the reaction product for multiple times until the pH value of the supernatant is 5.8-6.2, and freeze-drying the obtained precipitate to obtain Ti3C2TxPowder; wherein T isxThe functional group is the abbreviation of the functional group on the surface of the material, and mainly contains functional groups such as-OH, -F and ═ O;
(2) weighing 50-100 mg of Ti prepared in the step (1)3C2TxDissolving the powder in 30-60 mL of deionized water, uniformly mixing, and then adding 0.2-0.6 mL and 20mg/mL of HAuCl into the mixed solution4Mixing the solution evenly, and slowly adding 0.01-0.05 mg NaBH4Magnetically stirring and reacting for 3-6 h;
(3) centrifugally cleaning the reaction product obtained in the step (2) with deionized water for 3-5 times at 10000-12000 rpm, and drying for 20-30 hours at 40-60 ℃ in vacuum to obtain the catalystAu/Ti3C2TxA nanocomposite powder.
The invention relates to a method based on Au/Ti3C2TxThe preparation method of the dopamine electrochemical sensor for modifying the glassy carbon working electrode comprises the following steps:
(1) preparing an electrode modification material: taking Au/Ti3C2TxDispersing the nano composite material powder in deionized water, and carrying out ultrasonic treatment for 5-15 min to form uniform Au/Ti3C2TxSuspension of Au/Ti3C2TxThe concentration of (A) is 0.5-1.5 mg/mL;
(2) polishing the glassy carbon electrode: firstly wiping off dirt on the surface of the glassy carbon electrode by using wet absorbent cotton, and then adding deionized water and polishing powder Al2O3Mixed to form a rice paste, and then pulverized and polished to form Al powder2O3The size of the particles is 0.02-1.2 mm, and Al2O3The mass volume dosage ratio of the deionized water to the deionized water is 1 mL: 0.5-2 mg; tightly holding the glassy carbon electrode, and polishing the surface of the glassy carbon electrode by utilizing mutual contact friction of rice paste-shaped polishing powder and the glassy carbon electrode; in the process, the glassy carbon electrode is ensured to move vertically and in a circular or 8-shaped mode all the time; moving the glassy carbon electrode clockwise and anticlockwise for the same number of turns respectively, and then washing the glassy carbon electrode by using deionized water; then, forming a three-electrode system by taking the washed glassy carbon electrode as a working electrode, silver chloride/silver as a reference electrode and a platinum sheet as a counter electrode, and detecting the glassy carbon electrode by cyclic voltammetry scanning in a 5mM potassium ferricyanate solution by using an electrochemical workstation, wherein when the oxidation reduction peak potential difference of the glassy carbon electrode is 60-70 mV, the glassy carbon electrode is completely polished and can be subjected to subsequent electrode modification; finally, respectively placing the glassy carbon electrodes in dilute sulfuric acid (the concentration of the dilute sulfuric acid is 0.05-0.1 mol/L), ethanol and deionized water for cumulative ultrasonic treatment for 0.5-1 min, taking out and drying by using nitrogen;
(3) preparation of Au/Ti3C2TxModifying a glassy carbon electrode: 8-12 mu L of Au/Ti prepared in the step (1)3C2TxThe suspension liquid is dripped on the surface (1 cm) of the glassy carbon electrode polished in the step (2)2Au/Ti used on unit area glassy carbon electrode surface3C2TxThe volume consumption of the suspension is 110-180 mu L), and drying at room temperature to obtain Au/Ti3C2TxModifying a glassy carbon electrode;
(4) Au/Ti obtained in the step (3)3C2TxThe modified glassy carbon electrode is a working electrode, silver chloride/silver is a reference electrode, a platinum sheet is a counter electrode to form a three-electrode system, PBS (phosphate buffer solution) containing 0.1M, pH-7 is used as electrolyte, and the Au/Ti-based three-electrode system is prepared and obtained3C2TxA dopamine electrochemical sensor for modifying a glassy carbon working electrode.
The glassy carbon electrode is adopted as the working electrode of the sensor, and has the advantages of good conductivity, high chemical stability, hard texture, good air tightness and wide potential application range. And using Au/Ti3C2TxAs a working electrode modifying material, Ti3C2TxThe dopamine adsorption material has large specific surface area, excellent conductivity, hydrophilic surface, good biocompatibility and good adsorption effect on dopamine; the Au nano particles are used for catalyzing the oxidation-reduction reaction on the surface of the electrode, so that the conductivity, the electron transfer capability and the electrochemical active area are improved, the advantages of various materials are combined, and the purpose of improving the sensitivity of the sensor is achieved by utilizing the synergistic effect of the composite materials. The sensor is an electrochemical sensor, and has the advantages of small volume, simple operation, suitability for field analysis and detection and the like.
The invention has the advantages that:
(1) the sensor uses the glassy carbon electrode as a working electrode, and has the characteristics of good conductivity, high chemical stability, hard texture, wide potential application range and the like.
(2) The preparation method of the sensor electrode modification material is simple, the conditions are easy to control, and the method is suitable for batch industrial production.
(3) The sensor is an electrochemical sensor, has small volume and simple operation, and is suitable for field analysis and detection.
(4) The electrode modification material is Au/Ti3C2TxThe nano composite material combines the characteristics of good catalysis, conductivity and biocompatibility, so that the sensor has advantages in both lower detection limit and sensitivity.
Drawings
FIG. 1: XRD (X-ray diffraction) spectrum of electrode modification material prepared by the invention, wherein a curve 1 is Ti3AlC2XRD pattern of (D), curve 2 being Ti3C2TxXRD pattern of (1), curve 3 is Au/Ti3C2TxIn which the abscissa is angle and the ordinate is intensity.
As shown in FIG. 1, Ti before etching3AlC2The diffraction peak at 2 θ of 39 ° is strongest and is a diffraction peak of aluminum. Post-etch Ti3C2TxThe peak of aluminum at 2 θ of 39 ° completely disappeared, Ti3C2TxDiffraction peaks at 8.9 °, 27.3 °, 34.2 °, 53.4 ° and 60.7 ° respectively correspond to Ti3C2TxThe (002), (006), (008), (0012), and (110) crystal planes of (a) indicate that the Al layer is etched and Ti3AlC2Conversion to Ti3C2Tx。Au/Ti3C2TxIn the XRD pattern of (A), not only Ti is included3C2TxAlmost all diffraction peaks at 2 θ ═ 38.2 °, 44.4 °, 64.6 °, and 77.6 ° correspond to the (111), (200), (220), and (311) crystal planes of the Au nanoparticles. FIG. 1 demonstrates Au/Ti3C2TxSuccessful synthesis of nanocomposites.
FIG. 2: the electrode modification material Ti prepared by the invention3C2Tx(FIGS. A to B), Au/Ti3C2TxSEM pictures of (FIGS. (c) to (d)).
As shown in FIG. 2, the electrode modified material Ti prepared by the invention3C2Tx(FIGS. A to B), Au/Ti3C2TxSEM pictures of (FIGS. (c) to (d)). By the pair of Ti3AlC2The powder is selectively etched to remove the Al layer to prepare Ti3C2TxThe material obtained after etching is shown in FIGS. (a) to (b)Ti of (A)3C2TxThe distance between the material layers becomes larger, Ti3C2TxThe material has the appearance similar to an accordion structure and consists of a plurality of layers, and the single layer thickness is about 50 nm. Synthetic Ti3C2TxThe material has a unique two-dimensional layered structure and can provide a large specific surface area. As can be seen from FIGS. (c) to (d), reduction with sodium borohydride is carried out on Ti3C2TxAu NPs and Pt NPs grow on the surface, and the particle size is about 20-30 nm.
FIG. 3: with GCE, Ti3C2Tx/GCE、Au/Ti3C2TxThe sensor with/GCE as the working electrode has a differential pulse voltammetry curve for 1mM dopamine (wherein the abscissa is potential and the ordinate is response value, 0.1M PBS (pH 7.0) buffer solution is used as electrolyte, and the concentration of the added dopamine during detection is 10 μ M).
As shown in FIG. 3, GCE and Ti are used3C2Tx/GCE、Au/Ti3C2TxDevices fabricated with/GCE working electrodes correspond to examples 1, 2, and 3, respectively. In the differential pulse voltammetry test for 1mM dopamine, the oxidation peak current value of the detected dopamine is taken as a response value, the response value of the device is obviously different, the response value of the dopamine in example 2 is 1.71 times of that of example 1, and when Au/Ti is adopted3C2TxIn example 3, the response value of dopamine is further increased on the basis of example 2, and the response value of dopamine in example 3 is 1.24 times that of example 2. It can be seen that when Au/Ti is used3C2TxWhen the glassy carbon electrode is modified as an electrode modification material, the dopamine sensor of example 3 has a larger response value than those of examples 1 and 2, and exhibits good sensing characteristics.
FIG. 4 is a schematic view of: using Au/Ti3C2TxA differential pulse voltammogram of a dopamine sensor as an electrode modification material (0.1M PBS (pH 7.0) buffer solution was used as an electrolyte, the abscissa was a potential, and the ordinate was a response value). The detection is carried out by 0.5 mu M, 1.0 mu M and,Differential pulse voltammograms of 2 μ M, 5 μ M, 10 μ M, 20 μ M, 50 μ M dopamine.
As can be seen from FIG. 4, Au/Ti is realized by using differential pulse voltammetry3C2TxThe GCE carries out quantitative detection on dopamine with different concentrations. The results show that as the concentration of dopamine is increased from 0.5 mu M to 50 mu M, the oxidation peak current is also increased, namely the response value is gradually increased, and the detection range is wide.
FIG. 5 is a schematic view of: using Au/Ti3C2TxThe response concentration curve of the dopamine sensor as an electrode modification material (wherein the abscissa represents the concentration of dopamine, and the ordinate represents the response value).
As shown in fig. 5, the response value of the device manufactured in example 3 varies with the dopamine concentration, and it can be seen from the graph that the response value and the dopamine concentration of the device respectively show a better linear relationship. The slope was defined as the sensitivity of the sensor, which was measured to be 0.29 μ A/μ M. The lower limit of detection actually measured was 0.267. mu.M. Thus, it can be seen that Au/Ti3C2TxThe dopamine sensor used as the electrode modification material has good sensing performance.
FIG. 6: using Au/Ti3C2TxReproducibility test pattern of dopamine sensor as electrode modification material (wherein, abscissa is sensor prepared at nth time, and ordinate is response value).
As shown in fig. 6, differential pulse voltammetry tests were performed on 10 μ M dopamine for example 3 using the same method for 6 devices prepared separately. As can be seen from the graph, the response value does not change greatly in 6 independent device preparations, wherein the standard deviation of the response value for dopamine detection is 6.71%, and the device is proved to have good reproducibility and a stable and reliable preparation method.
FIG. 7: using Au/Ti3C2TxStability test chart of dopamine sensor as electrode modification material (wherein, abscissa is electric potential, ordinate is response value).
As shown in fig. 7, the device fabricated in example 3 first measured the initial response value of the differential pulse voltammogram in 0.1MPBS (pH 7.0) buffer solution containing 10 μ M dopamine, and after 14 days, again measured the response value of the differential pulse voltammogram in 0.1M PBS (pH 7.0) buffer solution containing 10 μ M dopamine with the electrode, and the response value after 14 days was 91.2% of the initial value, which proved that the sensor had good stability.
Detailed Description
Example 1
A glassy carbon electrode is used as a working electrode, a dopamine electrochemical sensor is manufactured based on a three-electrode working system, and the related performance of the sensor is tested, wherein the specific process is as follows:
1. polishing the glassy carbon electrode: before polishing the glassy carbon electrode, lightly wiping the glassy carbon electrode with wet absorbent cotton to remove dirt and ensure that the surface of the electrode is smooth; 2mg of polishing powder Al with the particle size of 0.05 mu m2O3Adding 2mL of deionized water dropwise on the chamois, and uniformly stirring the mixture and polishing powder; and the glassy carbon electrode is held tightly, so that the glassy carbon electrode is ensured to vertically move in a circular or 8-shaped mode all the time. And respectively rotating clockwise and anticlockwise for 100 circles until the surface of the glassy carbon electrode presents a mirror surface state, and washing with deionized water. Then, a washed glassy carbon electrode is taken as a working electrode, silver chloride/silver is taken as a reference electrode, a platinum sheet is taken as a counter electrode to form a three-electrode system, the state of the glassy carbon electrode is detected by cyclic voltammetry scanning in a 5mM potassium ferricyanate solution by virtue of an electrochemical workstation, when the potential difference of an oxidation reduction peak is closer to 64mV, the surface treatment of the glassy carbon electrode is cleaner, and in order to avoid variable influence caused by different surface treatment results of the glassy carbon electrode, the cyclic voltammetry potential difference is strictly controlled to 64mV in the design; and finally, respectively placing the glassy carbon electrode in 0.08mol/L dilute sulfuric acid, ethanol and deionized water for ultrasonic treatment, wherein the total ultrasonic treatment time is not more than 1min, the damage to the glassy carbon electrode is reduced, the glassy carbon electrode is dried by nitrogen for standby, and the polishing process of the glassy carbon electrode is completed.
2. The dopamine electrochemical sensor is manufactured by taking a bare glassy carbon electrode as a working electrode without modifying any electrode material, taking silver chloride/silver as a reference electrode and a platinum sheet as a counter electrode, and respectively connecting green, white and red connecting wires of an electrochemical workstation to form a three-electrode system.
Example 2
With Ti3C2TxModification of Glassy Carbon Electrodes (GCE), i.e. Ti, as electrode modifying materials3C2TxThe method is characterized in that the/GCE is a working electrode and is used for manufacturing a dopamine electrochemical sensor, and the manufacturing process is as follows:
1. the procedure for polishing the glassy carbon electrode was the same as in example 1.
2. Preparation of Ti3C2TxThe working electrode of/GCE: first, Ti is prepared3C2TxA nanocomposite material.
2g of Ti3AlC2The powder was slowly added to 40mL of 40 wt% hydrofluoric acid solution and reacted for 24h at 40 ℃ with magnetic stirring. Then, the precipitate was freeze-dried to obtain Ti by adding deionized water and centrifuging for several times (4000rpm for 10min) until the pH of the supernatant was 63C2TxAnd (3) powder.
With Ti3C2TxIs an electrode modification material and is modified on a glassy carbon electrode: taking 3mg of Ti3C2TxAdding 3mL of deionized water into the powder, and carrying out ultrasonic treatment for 5min to form uniform Ti3C2TxSuspending liquid; 10. mu.L of Ti was aspirated with a micropipette gun3C2TxThe suspension liquid is dripped on a glassy carbon electrode (the area is about 7.07 mm)2) Drying at room temperature to obtain Ti3C2Txa/GCE working electrode.
3. To modify Ti3C2TxA glassy carbon electrode of (i) or Ti3C2Txthe/GCE is a working electrode, the silver chloride/silver is a reference electrode, the platinum sheet is a counter electrode, and the working electrode, the silver chloride/silver and the platinum sheet are respectively connected with green, white and red connection wires of an electrochemical workstation to form a three-electrode system, so that the dopamine electrochemical sensor is manufactured.
Example 3
With Au/Ti3C2TxModification of Glassy Carbon Electrodes (GCE), i.e. Au/Ti, as electrode-modifying materials3C2TxThe method is characterized in that the/GCE is a working electrode and is used for manufacturing a dopamine electrochemical sensor, and the manufacturing process is as follows:
1. the procedure for polishing the glassy carbon electrode was the same as in example 1.
2. Preparation of Au/Ti3C2TxThe GCE working electrode: first, Au/Ti is prepared3C2TxA nanocomposite material.
Weigh 80mg Ti3C2TxThe powder was dissolved in 40mL of deionized water and mixed well, and 0.4mL of HAuCl and 20mg/mL of HAuCl were added to the mixed solution4The solution was mixed well and weighed 0.019mg NaBH was added slowly4After magnetically stirring for 3h, the reaction was centrifugally washed 3 times at 12000rpm and finally dried in a vacuum oven at 60 ℃ for 24h to obtain Au/Ti3C2TxAnd (3) powder.
With Au/Ti3C2TxFor electrode modification materials, glassy carbon electrodes were modified according to the procedure described in example 2, and the modification solution was changed to Au/Ti3C2TxObtaining Au/Ti by electrode modification liquid3C2Txa/GCE working electrode.
3. To modify Au/Ti3C2TxOf glassy carbon electrode, i.e. Au/Ti3C2Txthe/GCE is a working electrode, the silver chloride/silver is a reference electrode, the platinum sheet is a counter electrode, and the working electrode, the silver chloride/silver and the platinum sheet are respectively connected with green, white and red connection wires of an electrochemical workstation to form a three-electrode system, so that the dopamine electrochemical sensor is manufactured.
Table 1: with GCE (example 1), Ti3C2Tx(example 2) Au/Ti3C2TxThe differential pulse voltammetry curve of the sensor with the working electrode as the/GCE (example 3) for 1mM dopamine oxidizes peak current value data, wherein the oxidation peak current value is the response value detected by the sensor.
Table 2: with Au/Ti3C2TxGCE (example 3) response values for sensors with working electrodes to detect different concentrations of dopamine
| Dopamine concentration (μ M) in PBS buffer | Response value (μ A) |
| 0.5 | 1.72 |
| 1 | 2.152 |
| 2 | 2.891 |
| 5 | 3.534 |
| 10 | 5.388 |
| 20 | 7.604 |
| 50 | 16.28 |
The sensors were attached to a CHI760E electrochemical workstation and the 3 sensors were each subjected to current signal testing sequentially in 0.1M PBS (pH 7) buffer containing 10 μ M dopamine; will be in Au/Ti3C2TxThe sensor with the working electrode/GCE (example 3) was placed in the container with dopamineCurrent signal testing was performed in 0.1M PBS (pH 7) buffer at concentrations of 0.5 μ M, 1.0 μ M, 2 μ M, 5 μ M, 10 μ M, 20 μ M, 50 μ M.
Table 1 shows the results of the tests using GCE (example 1) and Ti, respectively3C2Tx(example 2) Au/Ti3C2TxDifferential pulse voltammogram oxidation peak current values for a sensor with/GCE (example 3) as the working electrode in 0.1MPBS (pH 7) buffered solution containing 10 μ M dopamine. As can be seen from the table, the response characteristics of the 3 devices to dopamine were not the same, using Au/Ti3C2TxThe oxidation peak current value, i.e., the response value, of the sensor having the working electrode was the largest in the case of the/GCE (example 3). The response value to dopamine in the buffer solution to be tested is 4.761 muA, which is relatively larger than that of other devices. It can be seen that Au/Ti was used3C2Txthe/GCE shows the best sensing characteristic for the sensor with the working electrode.
In the meantime, Table 2 shows Au/Ti3C2TxThe response of the dopamine sensor manufactured for the working electrode in PBS (pH 7) buffer solution for different concentrations of dopamine was calculated by/GCE (example 3). The response value increases with increasing dopamine concentration. Therefore, the oxidation-reduction reaction generated on the interface of the working electrode and the solution is promoted by constructing the electrode modification material so that the interface of the working electrode has good electrocatalytic activity, conductivity and dopamine adsorption, and thus the dopamine sensor with good sensing performance is constructed.
Claims (5)
1. Based on Au/Ti3C2TxThe dopamine electrochemical sensor for modifying the glassy carbon working electrode is characterized in that: the reference electrode AgCl/Ag, the counter electrode Pt sheet and Au/Ti3C2TxThe electrolyte is composed of 0.1M NaH2PO4And 0.1M Na2HPO40.1M, pH ═ 7 phosphate buffer solution prepared from the solution; and Au/Ti3C2TxThe nano composite material is prepared by the following method，
(1) Adding 1-5 g of Ti3AlC2Slowly adding the powder into 30-60 mL of 40 wt% hydrofluoric acid solution, and magnetically stirring for 20-40 h at 40-60 ℃; then adding deionized water to centrifugally wash the reaction product for multiple times until the pH value of the supernatant is 5.8-6.2, and freeze-drying the obtained precipitate to obtain Ti3C2TxPowder;
(2) weighing 50-100 mg of Ti prepared in the step (1)3C2TxDissolving the powder in 30-60 mL of deionized water, uniformly mixing, and then adding 0.2-0.6 mL and 20mg/mL of HAuCl into the mixed solution4The solution is evenly mixed, and then 0.01-0.05 mg of NaBH is slowly added4Magnetically stirring for reaction for 3-6 h;
(3) centrifugally cleaning the reaction product obtained in the step (2) with deionized water at 10000-12000 rpm for 3-5 times, and then drying at 40-60 ℃ in vacuum for 20-30 hours to obtain Au/Ti3C2TxA nanocomposite powder.
2. An Au/Ti-based alloy according to claim 13C2TxThe preparation method of the dopamine electrochemical sensor for modifying the glassy carbon working electrode comprises the following steps:
(1) preparing an electrode modification material: taking Au/Ti3C2TxDispersing the nano composite material powder in deionized water, and performing ultrasonic treatment for 5-15 min to form uniform Au/Ti3C2TxSuspension of Au/Ti3C2TxThe concentration of (A) is 0.5-1.5 mg/mL;
(2) polishing the glassy carbon electrode: firstly, wiping off dirt on the surface of the glassy carbon electrode by using wet absorbent cotton, and then, adding deionized water and polishing powder Al2O3Mixed into a rice-paste-like milled powder, Al2O3Has a particle size of 0.02 to 1.2mm and Al2O3The mass volume dosage ratio of the deionized water to the deionized water is 1 mL: 0.5-2 mg; polishing the surface of the glassy carbon electrode by utilizing mutual contact friction of the rice paste-shaped polishing powder and the glassy carbon electrode, so that the oxidation reduction peak potential difference of the glassy carbon electrode is 60-70 mV; finally after washingRespectively placing the glassy carbon electrodes in dilute sulfuric acid, ethanol and deionized water, performing cumulative ultrasonic treatment for 0.5-1 min, taking out, and drying by using nitrogen;
(3) preparation of Au/Ti3C2TxModifying a glassy carbon electrode: 8-12 mu L of Au/Ti prepared in the step (1)3C2TxThe suspension liquid is dripped on the surface of the glassy carbon electrode polished in the step (2) by 1cm2Au/Ti used on unit area glassy carbon electrode surface3C2TxThe volume consumption of the suspension is 110-180 mu L; drying at room temperature to obtain Au/Ti3C2TxModifying the glassy carbon electrode;
(4) Au/Ti obtained in the step (3)3C2TxThe modified glassy carbon electrode is a working electrode, silver chloride/silver is a reference electrode, a platinum sheet is a counter electrode to form a three-electrode system, phosphate buffer solution containing 0.1M, pH-7 is used as electrolyte, and Au/Ti-based alloy is prepared3C2TxA dopamine electrochemical sensor for modifying a glassy carbon working electrode.
3. An Au/Ti-based alloy as claimed in claim 23C2TxThe preparation method of the dopamine electrochemical sensor for modifying the glassy carbon working electrode is characterized by comprising the following steps: in the step (2), the glassy carbon electrode is held tightly, and the surface of the glassy carbon electrode is polished by utilizing mutual contact friction between the rice paste-shaped polishing powder and the glassy carbon electrode; in the process, the glassy carbon electrode is ensured to be always vertical and move in a circular or 8-shaped mode, and the glassy carbon electrode is moved for the same number of turns clockwise and anticlockwise respectively.
4. An Au/Ti-based alloy as claimed in claim 23C2TxThe preparation method of the dopamine electrochemical sensor of the modified glassy carbon working electrode is characterized by comprising the following steps: in the step (2), a three-electrode system is formed by taking the washed glassy carbon electrode as a working electrode, silver chloride/silver as a reference electrode and a platinum sheet as a counter electrode, and the oxidation-reduction peak potential of the glassy carbon electrode is detected by cyclic voltammetry scanning in a 5mM potassium ferricyanate solution by utilizing an electrochemical workstation.
5. An Au/Ti-based alloy according to claim 23C2TxThe preparation method of the dopamine electrochemical sensor for modifying the glassy carbon working electrode is characterized by comprising the following steps: the concentration of the dilute sulfuric acid in the step (2) is 0.05-0.1 mol/L.
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