CN114935591B - Photoelectrochemical sensor, preparation method thereof and application thereof in tetracycline detection - Google Patents

Photoelectrochemical sensor, preparation method thereof and application thereof in tetracycline detection Download PDF

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CN114935591B
CN114935591B CN202111385745.0A CN202111385745A CN114935591B CN 114935591 B CN114935591 B CN 114935591B CN 202111385745 A CN202111385745 A CN 202111385745A CN 114935591 B CN114935591 B CN 114935591B
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CN114935591A (en
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韩得满
陈逢灶
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Taizhou University
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Abstract

The invention relates to the technical field of photoelectrochemical sensing, in particular to a photoelectrochemical sensor, a preparation method thereof and application thereof in tetracycline detection. The invention provides a photoelectrochemical sensor, which comprises an FTO electrode and a ZnInS@ZIF-8 composite modification layer modified on the conductive surface of the FTO electrode; the ZnInS@ZIF-8 composite modification layer comprises a ZnInS nano-sheet array and a ZIF-8 nano-film grown on the surface of the ZnInS nano-sheet array. The ZIF-8 film can adsorb TC, so that the TC can be enriched on the surface of the film, the two-dimensional structure of the ZnInS nanosheet array can improve the conduction path of photoelectrons, and the weak light energy signal change generated when the ZnInS@ZIF-8 structure captures trace TC can be quickly and stably converted into a detectable electric energy signal, so that the detection limit and response time of the TC are reduced, and the sensitivity of the photoelectrochemical sensor is improved.

Description

Photoelectrochemical sensor, preparation method thereof and application thereof in tetracycline detection
Technical Field
The invention relates to the technical field of photoelectrochemical sensing, in particular to a photoelectrochemical sensor, a preparation method thereof and application thereof in tetracycline detection.
Background
Tetracyclines (TC) are multifunctional broad-spectrum antibiotics that are widely used in the treatment of bacterial infections in humans or animals due to their ability to effectively inhibit bacterial protein synthesis. In addition, TC is often used as a feed additive in animal husbandry due to its effect of promoting animal growth. TC is very stable in chemical structure and is difficult to metabolize or naturally degrade by humans and animals. The excessive use of TC may result in small amounts of TC remaining in dairy, meat, fish and other foods and even contaminating drinking water. Through the above dietary route, long-term small dose of TC can cause serious harm to human health, such as adverse reactions of anaphylaxis, intestinal disorder, hepatotoxicity and the like, and can also enhance the drug resistance of bacteria to antibiotics. Therefore, the method has important significance for rapid and sensitive detection of trace TC.
Traditional methods for detecting TC mainly include colorimetry, spectrophotometry, liquid chromatography, liquid-mass spectrometry and the like. Although these methods have achieved qualitative or quantitative analysis of TC to some extent, there are also significant disadvantages such as expensive equipment, complicated operation, time consuming, low sensitivity, poor selectivity, etc. Photoelectrochemical analysis is an emerging analysis technology in recent years, and has the advantages of low equipment cost, simple operation, high sensitivity, high response speed and the like compared with the traditional detection method.
However, the detection limit of the existing photoelectrochemical analysis method on TC is nM, the response time is tens of seconds, and the sensitivity still needs to be improved.
Disclosure of Invention
In view of the above, the present invention aims to provide a photoelectrochemical sensor, a preparation method thereof and an application thereof in detecting tetracycline. The photoelectrochemical sensor provided by the invention has the characteristics of high sensitivity and strong anti-interference capability when detecting TC.
In order to achieve the above object, the present invention provides the following technical solutions:
a photoelectrochemical sensor comprises an FTO electrode and a ZnInS@ZIF-8 composite modification layer modified on a conductive surface of the FTO electrode; the ZnInS@ZIF-8 composite modification layer comprises a ZnInS nano-sheet array growing on the conductive surface of the FTO electrode and a ZIF-8 nano-film growing on the surface of the ZnInS nano-sheet array.
Preferably, the thickness of the ZnInS nano sheet in the ZnInS nano sheet array is less than or equal to 8nm; the thickness of the ZIF-8 nano film is less than or equal to 4nm.
The invention also provides a preparation method of the photoelectrochemical sensor, which comprises the following steps:
dissolving soluble zinc salt, soluble indium salt and thioacetamide in water to obtain a precursor solution;
placing the conductive surface of the FTO electrode into the precursor liquid for hydrothermal reaction, and growing a ZnInS nanosheet array on the conductive surface of the FTO electrode to obtain a ZnInS modified FTO electrode;
soaking the ZnInS modified FTO electrode in a methanol solution of dimethyl imidazole, and adding zinc nitrate into the methanol solution of dimethyl imidazole to perform self-template in-situ reaction to obtain the photoelectrochemical sensor.
Preferably, the soluble zinc salt comprises ZnCl 2 、Zn(NO 3 ) 2 、Zn(COOH) 2 Or ZnSO 4 The soluble indium salt comprises InCl 3 、In 2 (SO 4 ) 3 Or In (NO) 3 ) 3 。
Preferably, the stoichiometric ratio of zinc atoms in the soluble zinc salt, indium atoms in the soluble indium salt and thioacetamide is 1: 1-2: 0.1 to 5; the concentration of zinc atoms in the precursor solution is 9-20 mmol/L.
Preferably, the temperature of the hydrothermal reaction is 80-240 ℃, and the time of the hydrothermal reaction is 3-12 h.
Preferably, the concentration of the dimethylimidazole in the methanol solution of the dimethylimidazole is 0.5-1 mol/L, and the concentration of the zinc nitrate in the mixed solution obtained after the zinc nitrate is added is 50-100 mmol/L.
Preferably, the soaking time is 3-8 hours; the temperature of the in-situ reaction of the self-template is 40-100 ℃, and the time of the in-situ reaction of the self-template is 1-4 h.
The invention also provides an application of the photochemical sensor in detecting tetracycline, which is prepared by the photochemical sensor or the preparation method.
Preferably, the application comprises: detecting tetracycline in the electrolyte under illumination by adopting a three-electrode system; the working electrode of the three-electrode system is the photoelectrochemical sensor, the reference electrode is an Ag/AgCl electrode, and the counter electrode is a Pt wire; the electrolyte is PBS buffer solution; the wavelength of the illumination is 365-400 nm.
The invention provides a photoelectrochemical sensor, which comprises an FTO electrode and a ZnInS@ZIF-8 composite modification layer modified on the conductive surface of the FTO electrode; the ZnInS@ZIF-8 composite modification layer comprises a ZnInS nano-sheet array growing on the conductive surface of the FTO electrode and a ZIF-8 nano-film growing on the surface of the ZnInS nano-sheet array. According to the invention, the FTO electrode and the ZnInS@ZIF-8 composite modification layer are combined, the ZIF-8 film can adsorb TC, so that the TC is enriched on the surface of the film, the two-dimensional structure of the ZnInS nanosheet array improves the photoelectron conduction path, and the weak light energy signal change generated when the ZnInS@ZIF-8 structure captures trace TC can be quickly and stably converted into a detectable electric energy signal, so that the detection limit and response time of TC are reduced, and the sensitivity of the photoelectrochemical sensor is improved.
The invention provides a preparation method of a photoelectrochemical sensor, which adopts a hydrothermal method and a self-template in-situ growth method to prepare the photoelectrochemical sensor, and has the advantages of simple operation, no pollution, low cost and mass production.
The invention provides application of the photoelectrochemical sensor in detecting tetracycline. In the photoelectrochemical sensor, the ZnInS@ZIF-8 composite modification layer can be complexed with TC, and the number of stimulated electrons generated by light excitation of the ZnInS@ZIF-8 composite modification layer and transferred to the FTO is reduced, so that the original photocurrent is weakened, and the purpose of detecting TC is achieved. Experimental data in the embodiment of the invention show that the detection limit of the three-electrode system composed of the photoelectrochemical sensor prepared by the invention to TC reaches 0.1pM, the response time is 6s, the sensitivity is high, the response speed is high, when other antibiotics such as kanamycin, terramycin, hygromycin, puromycin, levofloxacin and the like are simultaneously added, only the three-electrode system is responsive to TC, and the three-electrode system has single selectivity to TC detection and strong anti-interference capability.
Drawings
FIG. 1 is a scanning electron microscope image of a ZnInS modified FTO electrode prepared in example 1;
FIG. 2 is an atomic force microscope image of a ZnInS modified FTO electrode prepared in example 1;
FIG. 3 is a scanning electron microscope image of the photoelectrochemical sensor prepared in example 1;
FIG. 4 is an atomic force microscope image of the photoelectrochemical sensor prepared in example 1;
FIG. 5 is a graph showing the contrast of X-ray photoelectron spectra of the ZnInS modified FTO electrode and the photoelectrochemical sensor prepared in example 1;
FIG. 6 is an i-t plot of the photoelectrochemical sensing system response to tetracycline prepared in application example 1;
FIG. 7 is an i-t diagram of a response TC cycling stability experiment of the photoelectrochemical sensing system prepared in application example 1;
FIG. 8 is a graph showing the response current change rate of the photochemical induction system prepared in application example 1 according to the concentration change of TC;
FIG. 9 is a graph showing the comparison of the response current change rates of the photochemical induction system prepared in application example 1 to 5 kinds of 100. Mu.M interferon antibiotics and 10. Mu.M TC.
Detailed Description
The invention provides a photoelectrochemical sensor, which comprises an FTO electrode and a ZnInS@ZIF-8 composite modification layer modified on the conductive surface of the FTO electrode; the ZnInS@ZIF-8 composite modification layer comprises a ZnInS nano-sheet array growing on the conductive surface of the FTO electrode and a ZIF-8 nano-film growing on the surface of the ZnInS nano-sheet array.
In the invention, the thickness of the ZnInS nano sheet in the ZnInS nano sheet array is preferably less than or equal to 8nm, more preferably 1-3 nm, and even more preferably 2nm; the ZIF-8 nano film preferably has a thickness of 4nm or less, more preferably 1 to 3nm, and still more preferably 2nm. According to the invention, the thickness of the ZnInS nanosheets and the ZIF-8 nanomembrane is controlled within the range, so that the two-dimensional composite structure of the sensor has certain strength, meanwhile, the thinner film layer enables the contact between TC and the sensor receiving site to be better, and the signal transmission path can be further reduced, so that the transmission speed of the signal variation when the sensor is contacted with TC is improved, and the sensitivity of the sensor is improved.
The invention also provides a preparation method of the photoelectrochemical sensor, which comprises the following steps:
dissolving soluble zinc salt, soluble indium salt and thioacetamide in water to obtain a precursor solution;
placing the conductive surface of the FTO electrode into the precursor liquid for hydrothermal reaction, and growing a ZnInS nanosheet array on the conductive surface of the FTO electrode to obtain a ZnInS modified FTO electrode;
soaking the ZnInS modified FTO electrode in a methanol solution of dimethyl imidazole, and adding zinc nitrate into the methanol solution of dimethyl imidazole to perform self-template in-situ reaction to obtain the photoelectrochemical sensor.
The invention dissolves soluble zinc salt, soluble indium salt and thioacetamide in water to obtain precursor liquid. In the present invention, the soluble zinc salt preferably comprises ZnCl 2 、Zn(NO 3 ) 2 、Zn(COOH) 2 Or ZnSO 4 More preferably ZnCl 2 Or Zn (NO) 3 ) 2 More preferably ZnCl 2 The method comprises the steps of carrying out a first treatment on the surface of the The soluble indium salt preferably comprises InCl 3 、In 2 (SO 4 ) 3 Or In (NO) 3 ) 3 More preferably InCl 3 Or In (NO) 3 ) 3 More preferably InCl 3 . In the present invention, the stoichiometric ratio of zinc atoms in the soluble zinc salt, indium atoms in the soluble indium salt, and thioacetamide is preferably 1: 1-2: 0.1 to 5, more preferably 1:1.3 to 2:1 to 4.5, more preferably 1:1.3 to 1.5:2 to 3.5, most preferably 1:1.32:2.42. in the present invention, the concentration of zinc atoms in the precursor solution is preferably 9 to 20mmol/L, more preferably 11 to 17mmol/L, and still more preferably 16.74mmol/L. The method controls the zinc atom, the indium atom and the thioacetamide in the precursor liquid within the range, is favorable for improving the purity of ZnInS and obtains thinner nano sheet thickness.
After the precursor liquid is obtained, the conductive surface of the FTO electrode is placed in the precursor liquid to perform hydrothermal reaction, and a ZnInS nano-sheet array is grown on the conductive surface of the FTO electrode to obtain the ZnInS modified FTO electrode. In the present invention, the aspect ratio of the FTO electrode is preferably 7:3, and in the specific embodiment of the present invention, the FTO electrode is used to have a length of 7mm and a width of 3mm. The hydrothermal reaction is preferably carried out in a hydrothermal kettle. In carrying out the hydrothermal reaction, the shorter side of the FTO electrode is preferably placed as the bottom side, and the FTO electrode is preferably placed vertically to the bottom of the hydrothermal kettle or is placed obliquely to the side wall. When the FTO electrode is placed, the conductive surface of the FTO electrode needs to face the side wall of the reaction kettle so as to enable the ZnInS nano-sheet array to grow on the conductive surface of the FTO electrode during hydrothermal reaction.
In the present invention, the temperature of the hydrothermal reaction is preferably 80 to 240 ℃, more preferably 120 to 200 ℃, still more preferably 160 to 180 ℃; the time of the hydrothermal reaction is preferably 3 to 12 hours, more preferably 4 to 10 hours, and still more preferably 6 to 8 hours. The invention preferably controls the hydrothermal reaction temperature and time within the above range, which is beneficial to loading the nano ZnInS nano-sheet array with proper thickness on the conductive surface of the FTO electrode.
After the ZnInS modified FTO electrode is obtained, the obtained ZnInS modified FTO electrode is soaked in a methanol solution of dimethyl imidazole, and then zinc nitrate is added into the methanol solution of dimethyl imidazole to perform self-template in-situ reaction, so that the photoelectrochemical sensor is obtained. In the present invention, the concentration of dimethylimidazole in the methanol solution of dimethylimidazole is preferably 0.5 to 1mol/L, more preferably 0.5 to 0.8mol/L, and still more preferably 0.5 to 0.6mol/L. The concentration of zinc nitrate in the mixed solution obtained after the zinc nitrate is added is preferably 50 to 100mmol/L, more preferably 50 to 80mmol/L, and still more preferably 50 to 60mmol/L. In the invention, the obtained ZnInS modified FTO electrode is soaked in a methanol solution of dimethyl imidazole for preferably 1-6 h, more preferably 2-5 h, further preferably 2-4 h and most preferably 4h, and the dimethyl imidazole is coordinated with Zn on the ZnInS nano-sheet in a soaking mode, so that a precursor for preparing the ZIF-8 film is uniformly formed on the surface of the nano-sheet, and then the precursor reacts with zinc nitrate in situ under the heating condition to form the ZIF-8 film.
In the present invention, the temperature of the in-situ reaction of the self-template is preferably 40 to 100 ℃, more preferably 60 to 80 ℃, still more preferably 80 ℃, and the time of the in-situ reaction of the self-template is preferably 1 to 4 hours, more preferably 1 to 3 hours, still more preferably 2 hours. According to the invention, the ZIF-8 nano film uniformly grows on the surface of the ZnInS nano sheet array by controlling the consumption of raw materials, the soaking time and the self-template reaction time and temperature, and the nano film has a thinner thickness, so that the contact between TC and a sensor receiving site can be effectively improved, the transmission path of photoelectric signals is reduced, and the sensitivity of the sensor is improved.
The invention also provides the application of the photoelectrochemical sensor in the technical scheme or the photoelectrochemical sensor obtained by the preparation method in the technical scheme in the detection of tetracycline.
In the present invention, the use of the photoelectrochemical sensor in detecting tetracycline includes: and detecting the tetracycline in the electrolyte under illumination by adopting a three-electrode system. The working electrode of the three-electrode system is the photoelectrochemical sensor, the reference electrode is an Ag/AgCl electrode, and the counter electrode is a Pt wire; the electrolyte is PBS buffer solution; the wavelength of the illumination is 365-400 nm. In an embodiment of the invention, the concentration of PBS buffer is 10mM under light irradiation at 380 nm. The sensor in the detection system can instantaneously generate strong photocurrent and keep stable current output for a long time, and after TC is added, the photocurrent which is originally kept stable output can be obviously reduced in a very short time, and good photoelectric response and sensitivity are shown.
The following is a detailed description of the present invention with reference to examples, but they should not be construed as limiting the scope of the invention.
Example 1
102.70mg of ZnCl 2 、219.90mg InCl 3 And 137.00mg of thioacetamide is dissolved in 45mL of water to prepare a precursor solution, then 20mL of the precursor solution is weighed and transferred into a polytetrafluoroethylene reaction kettle provided with an FTO electrode, the length of the FTO electrode is 7mm, the width of the FTO electrode is 3mm, the FTO electrode is placed in a manner that the shorter side is the bottom edge, the FTO electrode is obliquely leaned against the side wall of the reaction kettle, the electrode surface faces the side wall, the reaction kettle is heated for 6h at 160 ℃, after the reaction is finished, the FTO electrode after the hydrothermal reaction is taken out, and the ZnInS modified FTO electrode is obtained after the distilled water is washed. Then, the obtained ZnInS modified FTO electrode is soaked in a methanol solution containing dimethyl imidazole for 4 hours, and the concentration of the dimethyl imidazole is 0.5mol/L. And then adding zinc nitrate into the solution, wherein the concentration of the zinc nitrate in the obtained mixed solution is 60mmol/L. Then carrying out in-situ reaction of the self-template for 2 hours at 80 ℃, and washing with methanol after the reaction is finished to obtain the photoelectric sensor.
Performing morphology characterization on the ZnInS modified FTO electrode obtained in the embodiment 1 by adopting a scanning electron microscope, wherein the characterization result is shown in figure 1; fig. 1 is a scanning electron microscope image of a ZnInS-modified FTO electrode, and a small image at the upper right corner of fig. 1 is a partial enlarged image of the morphology of the ZnInS-modified FTO electrode, and it can be seen from fig. 1 that a ZnInS nano-sheet array is generated on the FTO electrode, and the nano-sheet has a good ordered two-dimensional structure, so that the corresponding stability of the photoelectric device can be improved, and abundant pore channels exist in the array, so that the capturing and enriching capability of the electric sensor on a target detection object can be improved. From the small graph at the upper right corner in fig. 1, it can be seen that the thickness of the nanosheets is less than 10nm, in order to obtain a more accurate thickness of the nanosheets, an atomic force microscope is used to measure the thickness of the ZnInS nanosheets, the measurement result is shown in fig. 2, and fig. 2 is an atomic force microscope diagram of the ZnInS modified FTO electrode prepared in example 1. According to the relation curve of the distance and the height in the graph, the thickness of the ZnInS nano sheet is calculated to be 2-3 nm, and the thinner nano sheet is beneficial to improving the transmission rate of photoelectric signals in the photoelectric sensor.
The photoelectrochemical sensor obtained in example 1 was subjected to morphology characterization by using a scanning electron microscope, the characterization result is shown in fig. 3, fig. 3 is a scanning electron microscope image of the photoelectrochemical sensor, the small image at the upper right corner of fig. 3 is a partial enlarged image of the morphology of the photoelectrochemical sensor, and according to fig. 3, it can be seen that the morphology of the nanosheet array in the electric sensor is well maintained. From the small drawing in the upper right corner of fig. 3, it can be seen that the surface of the nanoplatelets is not smooth but roughened, and that a structure of evenly distributed protrusions is seen, which further increases the contact area of the sensor surface with TC. In order to obtain the accurate thickness of the ZIF-8 film, the thickness of the ZnInS@ZIF-8 composite modification layer of the photoelectrochemical sensor is measured by adopting an atomic force microscope, the measurement result is shown in FIG. 4, and FIG. 4 is an atomic force microscope image of the photoelectrochemical sensor prepared in example 1. From the relation curve of the distance and the height in the graph, the thickness of the composite modification layer is calculated to be 4-5 nm, and the thickness data of the ZnInS nanosheets are combined to calculate that the thickness of the ZIF-8 film is calculated to be 1-3 nm and is closer to 2nm. The thinner ZIF-8 film ensures better contact between TC and the sensor receiving site, and the sensor is matched with the nano-sheet array with a two-dimensional structure, so that the sensitivity of the sensor is further improved.
Elemental analysis was performed on the ZnInS-modified FTO electrode and photoelectrochemical sensor of example 1 using an X-ray electron spectrometer, and the results are shown in fig. 5.
Fig. 5 is an X-ray photoelectron spectrum contrast diagram of the ZnInS-modified FTO electrode and the photoelectrochemical sensor, wherein the left side is a contrast diagram of each element, and the right side is a contrast diagram of the N element. As can be seen from fig. 5, the N content in the photoelectrochemical sensor is higher than that in the ZnInS-modified FTO electrode, and it is proved that ZIF-8 indeed grows onto the ZnInS nanoplatelets in combination with the morphology of fig. 3 and the measurement results of fig. 4.
Example 2
ZnCl in example 1 2 、InCl 3 And thioacetamide were used in amounts of 68.2mg, 221.2mg and 152.2mg, respectively, and the precursor solution was prepared by dissolving in 50mL of water, and the temperature of the in-situ reaction from the template was adjusted to 50℃under the same conditions as in example 1.
Application example 1
The photoelectric test was performed in the three-electrode system described above using the FTO/ZnInS@ZIF-8 sensor prepared in example 1 as the working electrode, ag/AgCl as the reference electrode, pt wire as the counter electrode, and PBS buffer solution as the electrolyte. The method comprises the following steps: the three electrodes were placed in the same cell with a concentration of 10mM PBS in PBS buffer. Light with a wavelength of 380nm is used as an excitation light source, and then an electrochemical workstation with a model CHI750 is used for collecting photocurrent generated in the system.
The test result shows that under the dark condition, no current is generated in the system, the light source is turned on, under the 380nm light irradiation condition, the sensor instantaneously generates strong photocurrent and keeps stable current output for a long time, and after the light source is turned off, the current instantaneously returns to the initial value under the dark condition, so that the sensor has good photoelectric response. When the concentration of TC is changed by 10 mu M each time, the photocurrent which is originally kept stably output is obviously reduced.
FIG. 6 is an i-t plot of the photoelectrochemical sensing system prepared in example 1 in response to tetracycline, with time on the abscissa and photocurrent on the ordinate. As can be seen from the real-time current record in fig. 6, the sensor can completely detect the change of the TC content within 6 seconds, which indicates that the photoelectrochemical sensor can realize rapid and real-time detection of TC.
Application example 2
The three-electrode system in application example 2 was the same as in application example 1, and was cycled on/Guan Guangzhao under initial dark conditions for 500 seconds, and the results of the current change in the system over time were recorded. The results are shown in FIG. 7, wherein FIG. 7 is an i-t diagram of a photoelectrochemical sensing system in response to a tetracycline cycling stability test, and the abscissa is time and the ordinate is the intensity of photocurrent. As can be seen from fig. 7, the three electrode system rapidly generates or quenches a cyclically reversible photocurrent with cyclical on/off illumination, and maintains a relatively stable signal output in each state. The sensor prepared by the invention has good structure and photoelectric response stability. After the sensor responds to the TC, the sensor can still output stable and reversible electric signals under the cyclic on-off illumination, so that the prepared photoelectrochemical sensor has good stability and can accurately detect the TC.
Application example 3
The three-electrode system in application example 3 was the same as in application example 1, and the response current in the recording system under the illumination condition was I 0 Then, the concentration of TC in the system is regulated, the response current in the system is recorded as I under each TC concentration, the logarithm of the TC concentration is taken as the abscissa, and the change rate (I 0 -I)/I is the ordinate, and the change rate of the response current is plotted with the change of the concentration of TC, and the result is shown in fig. 8. As can be seen from fig. 8, as the TC concentration increases, the photocurrent generated by the sensor gradually decreases under the illumination condition, and when the TC concentration in the system reaches 400 μm, the trend of current decrease in the system becomes gentle. By plotting the TC concentration on the abscissa and the response photocurrent on the ordinate in Origin9.8.5, a graph of the TC concentration in the range of 1pM to 100nM versus the rate of change of sensor response current was obtained, with specific results being shown in the small graph of FIG. 8. As can be seen from the graph, R of the curve is in the concentration range of 1pM to 100nM 2 =0.995. Indicating a good linear relationship between TC concentration and sensor response current rate of change.
Then, the detection limit of the sensor to TC can reach 0.1pM through three times of signal-to-noise ratio calculation. The photoelectrochemical sensor prepared by the invention has higher sensitivity and can realize the sensitive detection of trace TC.
Application example 4
The three-electrode system in application example 4 was the same as in application example 1, and the initial response current I in the system was recorded under the illumination condition 0 Thereafter, respectively at a three-electrode systemThe antibiotics used as the interferents were Kanamycin, oxytetracycline, hygromycin, puromycin and levofloxacin. The concentration of each interferent was 100. Mu.M. Recording the response current I when each interferon is independently added into the system, and calculating to obtain the change rate of the response current. The three-electrode system of application example 4 was separately charged with tetracycline, the concentration thereof was adjusted to 10. Mu.M, the response current I when tetracycline was charged into the system was recorded, and the rate of change of the response current was calculated. The types of the antibiotics and the change rates of the response currents at the time of addition were compared, and the comparison results are shown in FIG. 9.
As can be seen from FIG. 9, the photoelectrochemical sensor prepared by the invention has extremely high selectivity to tetracycline, and the photocurrent of the sensor is obviously reduced when the concentration of the tetracycline is changed from 0 to 10 mu M. However, for the other antibiotics, the concentration change amount of the antibiotics is far larger than that of tetracycline when the concentration is changed from 0 to 100 mu M, but the photocurrent of the sensor is not changed obviously. The photoelectrochemical sensor has high selectivity for detecting tetracycline and strong anti-interference capability.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.

Claims (9)

1. The photoelectrochemical sensor for detecting the tetracycline is characterized by comprising an FTO electrode and a ZnInS@ZIF-8 composite modification layer modified on the conductive surface of the FTO electrode; the ZnInS@ZIF-8 composite modification layer comprises a ZnInS nano-sheet array growing on the conductive surface of the FTO electrode and a ZIF-8 nano-film growing on the surface of the ZnInS nano-sheet array;
the thickness of the ZnInS nano sheet in the ZnInS nano sheet array is less than or equal to 8nm; the thickness of the ZIF-8 nano film is less than or equal to 4nm;
the preparation method of the photoelectrochemical sensor for tetracycline detection comprises the following steps:
dissolving soluble zinc salt, soluble indium salt and thioacetamide in water to obtain a precursor solution;
placing the conductive surface of the FTO electrode into the precursor liquid for hydrothermal reaction, and growing a ZnInS nanosheet array on the conductive surface of the FTO electrode to obtain a ZnInS modified FTO electrode;
soaking the ZnInS modified FTO electrode in a methanol solution of dimethyl imidazole, and adding zinc nitrate into the methanol solution of dimethyl imidazole to perform self-template in-situ reaction to obtain the photoelectrochemical sensor;
the stoichiometric ratio of zinc atoms in the soluble zinc salt, indium atoms in the soluble indium salt and thioacetamide is 1: 1-2: 0.1 to 5.
2. The method for preparing a photoelectrochemical sensor for the detection of tetracycline as defined in claim 1, comprising the steps of:
dissolving soluble zinc salt, soluble indium salt and thioacetamide in water to obtain a precursor solution;
placing the conductive surface of the FTO electrode into the precursor liquid for hydrothermal reaction, and growing a ZnInS nanosheet array on the conductive surface of the FTO electrode to obtain a ZnInS modified FTO electrode;
soaking the ZnInS modified FTO electrode in a methanol solution of dimethyl imidazole, and adding zinc nitrate into the methanol solution of dimethyl imidazole to perform self-template in-situ reaction to obtain the photoelectrochemical sensor;
the stoichiometric ratio of zinc atoms in the soluble zinc salt, indium atoms in the soluble indium salt and thioacetamide is 1: 1-2: 0.1 to 5.
3. The preparation method according to claim 2, characterized in that the soluble zinc salt comprises ZnCl 2 、Zn(NO 3 ) 2 、Zn(COOH) 2 Or ZnSO 4 The soluble indium salt comprises InCl 3 、In 2 (SO 4 ) 3 Or In (NO) 3 ) 3 。
4. The method according to claim 2 or 3, wherein the concentration of zinc atoms in the precursor solution is 9 to 20mmol/L.
5. The preparation method according to claim 2, wherein the temperature of the hydrothermal reaction is 80-240 ℃, and the time of the hydrothermal reaction is 3-12 hours.
6. The preparation method according to claim 2, wherein the concentration of dimethyl imidazole in the methanol solution of dimethyl imidazole is 0.5-1 mol/L, and the concentration of zinc nitrate in the mixed feed liquid obtained after adding zinc nitrate is 50-100 mmol/L.
7. The preparation method according to claim 2, wherein the soaking time is 3-8 hours; the temperature of the in-situ reaction of the self-template is 40-100 ℃, and the time of the in-situ reaction of the self-template is 1-4 hours.
8. Use of the photoelectrochemical sensor for tetracycline detection of claim 1 or the photoelectrochemical sensor for tetracycline detection obtained by the preparation method of any one of claims 2 to 7 for detecting tetracycline.
9. The application according to claim 8, characterized in that it comprises: detecting tetracycline in the electrolyte under illumination by adopting a three-electrode system; the working electrode of the three-electrode system is the photoelectrochemical sensor, the reference electrode is an Ag/AgCl electrode, and the counter electrode is a Pt wire; the electrolyte is PBS buffer solution; the wavelength of illumination is 365-400 nm.
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