CN111272857A - Molecularly imprinted photoelectrochemical sensor and preparation method and application thereof - Google Patents
Molecularly imprinted photoelectrochemical sensor and preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of photoelectrochemical sensing analysis and detection, food detection and sensing, and particularly relates to a sensor based on MIL-125-NH2/TiO2A molecular imprinting photoelectric chemical sensor of a composite material and a preparation method and application thereof are provided. The invention aims to solve the problems of complicated sample pretreatment steps, expensive instruments and equipment, requirement of professional technicians and the like in the traditional oxytetracycline detection method and the technical problems of low photoelectrochemical sensing detection sensitivity, poor selectivity and the like. The invention mainly solves the defects of complicated sample pretreatment process, expensive instrument, complex operation and the like in the existing oxytetracycline detection method based on the chromatographic technology, and is a complex sample in the practical application processThe terramycin in the product is detected by a simple, convenient, quick, sensitive and reliable analysis and detection means.
Description
Technical Field
The invention belongs to the technical field of photoelectrochemical sensing analysis and detection, food detection and sensing, and particularly relates to a sensor based on MIL-125-NH2/TiO2A molecular imprinting photoelectric chemical sensor of a composite material and a preparation method and application thereof are provided.
Background
Oxytetracycline (OTC) is a tetracycline antibiotic with good antibacterial and bactericidal effects, and is widely used in aquaculture and animal husbandry as a broad-spectrum antibiotic. However, improper use of terramycin often leads to excessive terramycin content in some animal food, ground water and production wastewater. The existing terramycin detection method is mainly high performance liquid chromatography, and the method has the advantages of high equipment cost, complex pretreatment, long time consumption and complex operation. Therefore, the development of a rapid and effective oxytetracycline detection method has very important practical significance.
The photoelectrochemical sensing detection technology adopts two different forms of energy as an excitation signal and a detection signal, light is used as the excitation signal to excite a light-activated material, and an electric signal is used as the detection signal. In the detection process, the effective separation of excitation and detection signals can reduce the interference of background signals and noise during detection, and improve the detection sensitivity. Meanwhile, electrochemical equipment is used for detection, so that the photoelectrochemical detection method has the advantages of simple and miniaturized equipment, quick response, convenience in operation and the like.
Metal-organic frameworks (MOFs) are porous materials that have been developed faster in recent years, and have greater porosity, specific surface area and stability than traditional inorganic porous materials, attracting the attention of more and more researchers. The MOF material is widely used at presentThe method is widely applied to the aspects of hydrogen storage, biosensing, substance adsorption and separation. MIL-125-NH2As one of metal organic framework materials, the material has excellent photoelectrochemical properties and photocatalytic activity, and is very suitable for developing photoelectrochemical sensors. However, the MOF material itself lacks specific recognition properties for the target, and has certain limitations in enriching and recognizing specific targets.
Molecular Imprinting Technique (MIT) refers to a process of preparing a Molecularly Imprinted Polymer (MIPs) having specific recognition properties for a specific target molecule using the molecule as a template. The MIPs can specifically identify a target object, and have the characteristics of simple preparation, excellent selectivity, excellent stability and the like.
Disclosure of Invention
The invention aims to solve the problems of complicated sample pretreatment steps, expensive instruments and equipment, requirement of professional technicians and the like in the traditional oxytetracycline detection method and the technical problems of low photoelectrochemical sensing detection sensitivity, poor selectivity and the like. The invention aims to provide a catalyst based on MIL-125-NH2/TiO2A preparation method of a molecular imprinting photoelectric chemical sensor of the composite material and application of terramycin detection. The invention firstly uses a hydrothermal synthesis method to prepare MOF and TiO2Composite material MIL-125-NH2/TiO2Then, by means of dripping, MIL-125-NH2/TiO2The surface of an Indium Tin Oxide (ITO) electrode is modified, a molecularly imprinted polymer film is modified by an electropolymerization method, and the modified electrode is used as a working electrode to successfully construct a substrate based on MIL-125-NH2/TiO2A molecular imprinting photoelectric chemical sensor of composite material. The sensor prepared by the invention can be used for high-selectivity and high-sensitivity detection of oxytetracycline. In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
based on MIL-125-NH2/TiO2The molecular imprinting photoelectrochemical sensor of the composite material comprises a working electrode and MIL-125-NH sequentially modified on the upper surface of the working electrode2/TiO2Photovoltaic deviceA conversion layer and a molecular imprinting film layer, wherein the working electrode is an indium tin oxide electrode.
Based on MIL-125-NH2/TiO2The preparation method of the molecular imprinting photoelectric chemical sensor of the composite material comprises the following steps:
Further, MIL-125-NH is prepared by a hydrothermal synthesis method in the step 12/TiO2The specific method of the composite material is that tetrabutyl titanate, 2-amino terephthalic acid, methanol, N-dimethylformamide and TiO are added in a 50mL hydrothermal reaction kettle in sequence2Sealing and reacting at 150 ℃; when the hydrothermal reaction kettle is cooled to 25 ℃, taking out the solution of the hydrothermal reaction kettle, centrifugally washing the solution by using N, N-dimethylformamide and methanol, and putting the precipitate into a vacuum drying oven to be dried to obtain MIL-125-NH2/TiO2A composite material.
Still further, the concentration of the tetrabutyl titanate is 0.05moL/L, the dosage of the tetrabutyl titanate is 0.18mL, the concentration of the 2-amino terephthalic acid is 1moL/L, the dosage of the 2-amino terephthalic acid is 0.16g, and the TiO is2The concentration is 6moL/L, the dosage is 0.16g, and the volume ratio of the methanol to the N, N-dimethylformamide is 1: 9; the reaction time is 20 hours when the mixture is sealed and placed at 150 ℃, and the drying temperature of the precipitate placed in a vacuum drying oven is 60 ℃.
Furthermore, the specific preparation method of the uniform dispersion liquid in the step 2 is to mix-125-NH prepared in the step 12/TiO2Dispersing the composite material in deionized water, and ultrasonically obtaining uniform MIL-125-NH by an ultrasonic cleaner2/TiO2Dispersing liquid, wherein the ultrasonic time of the ultrasonic cleaning instrument is 30-50min, and the uniform MIL-125-NH2/TiO2The concentration of the dispersion liquid is 0.5-1.5 mg/mL; the drying time under an infrared lamp in the step 2 is 30-60 min.
Furthermore, the scanning range of the electropolymerization method in the step 3 is 0-0.8V, and the scanning rate is as follows: 30-100mV/s, number of scan cycles: 10-20 circles; the concentration of the nitric acid solution is 5%, and the time for eluting the template molecule oxytetracycline is 5-10 min.
Furthermore, the molecularly imprinted polymer solution in step 3 is prepared from template molecules: oxytetracycline, functional monomers: o-phenylenediamine and solvent: acetate buffer solution, wherein the pH of the acetate buffer solution is 5.2; and 3, dissolving oxytetracycline and o-phenylenediamine in an acetate buffer solution, introducing nitrogen to remove oxygen for 5-10min, sealing and storing in a dark place to obtain the molecularly imprinted polymer solution, wherein the oxytetracycline concentration is 0.09-0.15mg/mL, and the o-phenylenediamine concentration is 0.06-0.15 mg/mL.
Based on MIL-125-NH2/TiO2The application of the molecular imprinting photoelectric chemical sensor of the composite material is to detect the oxytetracycline.
Further, the molecular imprinting photoelectric chemical sensor is applied to the detection of oxytetracycline, and the specific detection method comprises the following steps:
Further, Na in said step 1 and step 22SO4The concentration of the aqueous solution was 0.1 mmol/L.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention utilizes MIL-125-NH2/TiO2The novel photoelectric composite material has excellent photoelectrochemical property and excellent specificity recognition property of the molecular imprinting material, and a novel molecular imprinting photoelectric chemical sensor is constructed in a layer-by-layer assembling mode and is used for detecting the oxytetracycline with high sensitivity and high selectivity. Metal organic framework material MIL-125-NH2And TiO2The composite material can greatly improve the photoelectrochemical property of the composite material, so as to improve the detection sensitivity of the sensor, and the large specific surface area of the composite material can improve the subsequently modified molecularly imprinted materialTarget adsorption capacity of (2). The modification of the molecular imprinting material can improve the selectivity of the photoelectrochemical sensor.
2. The method mainly overcomes the defects of complicated sample pretreatment process, expensive instrument, complex operation and the like in the existing oxytetracycline detection method based on the chromatographic technology, and provides a simple, convenient, rapid, sensitive and reliable analysis and detection means for the detection of oxytetracycline in a complex sample in the practical application process.
3. The invention firstly constructs the MIL-125-NH-based2/TiO2The molecular imprinting photoelectric chemical sensor of the composite material is used for detecting oxytetracycline. The invention is based on MIL-125-NH2/TiO2The construction of the molecular imprinting sensing functional interface of the composite material provides a new idea and method for the construction of a high-sensitivity high-specificity photoelectrochemical sensor.
Drawings
FIG. 1 is a schematic diagram of the process and detection of preparing a photoelectric chemical sensor according to the present invention (a, b are photocurrent responses of the sensor before and after target recognition);
FIG. 2 is a graph showing the comparison of photocurrent response and corresponding linear comparison of the sensor in example 3 for detecting OTC at different concentrations, wherein the concentration of OTC is 0, 0.001. mu.M, 0.01. mu.M, 0.1. mu.M, 1. mu.M, 10. mu.M, 200. mu.M;
FIG. 3 is a comparison of the results of the specific detection of OTC by the sensor in the presence of different interfering substances in example 4: wherein the concentration of the analyte OTC is 0.01mM and the concentration of the interferent is 0.1 mM;
FIG. 4 is a comparison table of the reproducibility results of the sensor in example 5 for detecting OTC, wherein the concentration of the analyte OTC is 0.01 mM.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Based on MIL-125-NH2/TiO2The molecular imprinting photoelectrochemical sensor of the composite material comprises a working electrode and MIL-125-NH sequentially modified on the upper surface of the working electrode2/TiO2Photoelectric conversion layer and molecular imprinting rete, the working electrode is indium tin oxide electrode (ITO).
Example 2
Based on MIL-125-NH2/TiO2The preparation method of the molecular imprinting photoelectric chemical sensor of the composite material comprises the following steps:
The step 1 is a hydrothermal synthesis method for preparing MIL-125-NH2/TiO2The specific method of the composite material is that 0.05moL/L of tetra-N-butyl titanate with the dosage of 0.18mL, 1moL/L of 2-amino terephthalic acid with the dosage of 0.16g, methanol, N-Dimethylformamide (DMF) with the concentration of 6moL/L and 0.16g of TiO are sequentially added into a 50mL hydrothermal reaction kettle2Sealing and reacting for 20h at 150 ℃; cooling the hydrothermal reaction kettle to 25 ℃, taking out the solution of the hydrothermal reaction kettle, centrifugally washing the solution by using N, N-Dimethylformamide (DMF) and methanol, putting the precipitate into a vacuum drying oven, and drying the precipitate at the drying temperature of 60 ℃ to obtain MIL-125-NH2/TiO2The composite material comprises a methanol-N, N-Dimethylformamide (DMF) with a volume ratio of 1: 9;
the specific preparation method of the uniform dispersion liquid in the step 2 is to mix-125-NH prepared in the step 12/TiO2Dispersing the composite material in deionized water, and ultrasonically obtaining uniform MIL-125-NH by an ultrasonic cleaner2/TiO2Dispersing liquid, wherein the ultrasonic time of the ultrasonic cleaning instrument is 30min, and the uniform MIL-125-NH2/TiO2The concentration of the dispersion is 0.5 mg/mL; the drying time under an infrared lamp in the step 2 is 30 min.
The scanning range of the electropolymerization method in the step 3 is 0-0.8V, and the scanning speed is as follows: 30mV/s, number of scan cycles: 10 circles; the concentration of the nitric acid solution is 5%, and the time for eluting the template molecule oxytetracycline is 5 min.
The molecularly imprinted polymer solution in the step 3 is prepared from template molecules: oxytetracycline (OTC), functional monomers: o-phenylenediamine and solvent: acetate buffer solution, wherein the pH of the acetate buffer solution is 5.2; and 3, dissolving Oxytetracycline (OTC) and o-phenylenediamine in an acetate buffer solution, introducing nitrogen to remove oxygen for 5min, and storing in a sealed and light-proof manner to obtain the molecularly imprinted polymer solution, wherein the concentration of the Oxytetracycline (OTC) is 0.09mg/mL, and the concentration of the o-phenylenediamine is 0.06 mg/mL.
Example 3
Based on MIL-125-NH2/TiO2The preparation method of the molecular imprinting photoelectric chemical sensor of the composite material comprises the following steps:
The hydrothermal synthesis method in the step 1 is used for preparing MIL-125-NH2/TiO2The specific method of the composite material is that 0.05moL/L of tetra-N-butyl titanate with the dosage of 0.18mL, 1moL/L of 2-amino terephthalic acid with the dosage of 0.16g, methanol, N-Dimethylformamide (DMF) with the concentration of 6moL/L and 0.16g of TiO are sequentially added into a 50mL hydrothermal reaction kettle2Sealing and reacting for 20h at 150 ℃; cooling the hydrothermal reaction kettle to 25 ℃, taking out the solution of the hydrothermal reaction kettle, centrifugally washing the solution by using N, N-Dimethylformamide (DMF) and methanol, putting the precipitate into a vacuum drying oven, and drying the precipitate at the drying temperature of 60 ℃ to obtain MIL-125-NH2/TiO2The composite material comprises a methanol-N, N-Dimethylformamide (DMF) with a volume ratio of 1: 9;
the specific preparation method of the uniform dispersion liquid in the step 2 is to mix-125-NH prepared in the step 12/TiO2Dispersing the composite material in deionized water, and ultrasonically obtaining uniform MIL-125-NH by an ultrasonic cleaner2/TiO2Dispersing liquid, wherein the ultrasonic time of the ultrasonic cleaning instrument is 50min, and the uniform MIL-125-NH2/TiO2The concentration of the dispersion is 1.5 mg/mL; the drying time under an infrared lamp in the step 2 is 60 min.
The scanning range of the electropolymerization method in the step 3 is 0-0.8V, and the scanning rate is as follows: 100mV/s, number of scan cycles: 20 circles; the concentration of the nitric acid solution is 5%, and the time for eluting the template molecule oxytetracycline is 10 min.
The molecularly imprinted polymer solution in the step 3 is prepared from template molecules: oxytetracycline (OTC), functional monomers: o-phenylenediamine and solvent: acetate buffer solution, wherein the pH of the acetate buffer solution is 5.2; and 3, dissolving Oxytetracycline (OTC) and o-phenylenediamine in an acetate buffer solution, introducing nitrogen to remove oxygen for 8min, sealing and storing in a dark place to obtain the molecularly imprinted polymer solution, wherein the concentration of the Oxytetracycline (OTC) is 0.15mg/mL, and the concentration of the o-phenylenediamine is 0.15 mg/mL.
Example 4
Based on MIL-125-NH2/TiO2Molecular imprinting of composite materialsThe preparation method of the photoelectrochemical sensor comprises the following steps:
The step 1 is a hydrothermal synthesis method for preparing MIL-125-NH2/TiO2The specific method of the composite material is that 0.05moL/L of tetra-N-butyl titanate with the dosage of 0.18mL, 1moL/L of tetra-N-butyl titanate with the dosage of 0.16g, methanol, N-Dimethylformamide (DMF) with the dosage of 6moL/L and the dosage of 2-aminoterephthalic acid with the dosage of 1moL/L are sequentially added into a 50mL hydrothermal reaction kettleTiO 0.16g2Sealing and reacting for 20h at 150 ℃; cooling the hydrothermal reaction kettle to 25 ℃, taking out the solution of the hydrothermal reaction kettle, centrifugally washing the solution by using N, N-Dimethylformamide (DMF) and methanol, putting the precipitate into a vacuum drying oven, and drying the precipitate at the drying temperature of 60 ℃ to obtain MIL-125-NH2/TiO2The composite material comprises a methanol-N, N-Dimethylformamide (DMF) with a volume ratio of 1: 9;
the specific preparation method of the uniform dispersion liquid in the step 2 is to mix-125-NH prepared in the step 12/TiO2Dispersing the composite material in deionized water, and ultrasonically obtaining uniform MIL-125-NH by an ultrasonic cleaner2/TiO2Dispersing liquid, wherein the ultrasonic time of the ultrasonic cleaning instrument is 40min, and the uniform MIL-125-NH2/TiO2The concentration of the dispersion is 1 mg/mL; the drying time under an infrared lamp in the step 2 is 45 min.
The scanning range of the electropolymerization method in the step 3 is 0-0.8V, and the scanning rate is as follows: 60mV/s, number of scan cycles: 15 circles; the concentration of the nitric acid solution is 5%, and the time for eluting the template molecule oxytetracycline is 8 min.
The molecularly imprinted polymer solution in the step 3 is prepared from template molecules: oxytetracycline (OTC), functional monomers: o-phenylenediamine and solvent: acetate buffer solution, wherein the pH of the acetate buffer solution is 5.2; and 3, dissolving Oxytetracycline (OTC) and o-phenylenediamine in an acetate buffer solution, introducing nitrogen to remove oxygen for 10min, and storing in a sealed and light-proof manner to obtain the molecularly imprinted polymer solution, wherein the concentration of the Oxytetracycline (OTC) is 0.12mg/mL, and the concentration of the o-phenylenediamine is 0.09 mg/mL.
Example 5
Based on MIL-125-NH2/TiO2The application of the molecular imprinting photoelectric chemical sensor of the composite material is used for detecting Oxytetracycline (OTC).
The molecular imprinting photoelectric chemical sensor is applied to the detection of oxytetracycline, and the specific detection method comprises the following steps:
step 1Establishing a terramycin detection standard curve: dripping 45 μ L of oxytetracycline standard solution with different concentrations on the surface of indium tin oxide electrode modified by molecularly imprinted polymer membrane, incubating for 15-45min for oxytetracycline adsorption, and placing the electrode adsorbed with oxytetracycline into Na2SO4And (3) accessing the aqueous solution into a photoelectrochemical sensing system, obtaining a photocurrent signal by adopting an amperometric method, and establishing an oxytetracycline detection standard curve with the abscissa as oxytetracycline concentration and the ordinate as the photocurrent signal.
Na in said step 1 and step 22SO4The concentration of the aqueous solution is 0.1 mmol/L; in the step 2, 45 μ L of sample solution with unknown concentration is sucked and dropped on the surface of the indium tin oxide electrode modified by the molecularly imprinted polymer membrane for incubation for 20min or 35 min.
The invention relates to a method based on MIL-125-NH2/TiO2The construction method and the detection principle of the molecular imprinting photoelectrochemical sensor of the composite material are shown in figure 1. Modifying MIL-125-NH on the surface of the ITO electrode2/TiO2Preparing a molecularly imprinted polymer film by an electropolymerization method, eluting template molecule oxytetracycline to obtain MIL-125-NH2/TiO2The ITO electrode modified by the composite material and the molecular imprinting material is connected into a photoelectrochemical sensing system to obtain the electrode based on MIL-125-NH2/TiO2A molecular imprinting photoelectric chemical sensor of composite material. During detection, oxytetracycline is recognized and adsorbed by the molecularly imprinted polymer film, so that the light current value of the sensor is reduced, and the oxytetracycline is detected.
MIL-125-NH-based compositions obtainable by the invention2/TiO2Composite materialThe molecular imprinting photoelectric chemical sensor of the material carries out sensitivity detection on OTC with different concentrations, as shown in figure 2, the concentration of OTC is 0.001, 0.01, 0.1, 1, 10 and 200 mu M from a to I in sequence, the response value of the sensor photocurrent is reduced along with the increase of the concentration of OTC, and the correlation linear relation is △ I-636.943 lgC (nM) +5149.190(△ I is the change value of photocurrent, C is the concentration of OTC), R is20.989, with a minimum detection limit of 0.621 nM.
The molecular imprinting photoelectrochemical sensor based on the MIL-125-NH2/TiO2 composite material has the following selective experiment on OTC, and the detection process is as follows:
the prepared molecular imprinting photoelectric chemical sensor based on the MIL-125-NH2/TiO2 composite material is subjected to a selectivity test, and an interference substance (tetracycline hydrochloride, ampicillin, chlortetracycline hydrochloride and doxycycline hydrochloride) and a mixed solution (sequentially represented by a, b, c and d) of OTC and an OTC solution (represented by e) are adsorbed to detect a photocurrent signal, wherein the concentration of the interference substance in the mixed solution is 0.1mM, and the concentration of OTC is 0.01mM, and the result is shown in figure 3.
The molecular imprinting photoelectrochemical sensor based on the MIL-125-NH2/TiO2 composite material provided by the invention has the following detection process for the repeatability of OTC:
5 MIP/MIL-125-NH are prepared simultaneously by adopting the same sensor preparation method2/TiO2ITO, photoelectric chemical sensing detection is carried out on 0.01mM OTC solution. The detection result is shown in fig. 4, the signal response difference of the sensor constructed by 5 modified electrodes is very small, and the prepared sensor has very good reproducibility.
In summary, the invention is based on MIL-125-NH2/TiO2The molecular imprinting photoelectrochemical sensor made of the composite material has good selectivity and anti-interference capability, and can be used for detecting oxytetracycline with high sensitivity and high selectivity. Therefore, the design thought and the preparation method provided by the invention can provide thought and method for developing the photoelectrochemical sensorThe method is carried out.
While there have been shown and described what are at present considered the fundamental principles and essential features of the invention and its advantages, it will be apparent to those skilled in the art that the invention is not limited to the details of the foregoing exemplary embodiments, but is capable of other specific forms without departing from the spirit or essential characteristics thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.
Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art should integrate the description, and the embodiments may be combined as appropriate to form other embodiments understood by those skilled in the art.
Claims (10)
1. A molecular imprinting photoelectric chemical sensor is characterized in that: comprises a working electrode and MIL-125-NH which is sequentially modified on the upper surface of the working electrode2/TiO2Photoelectric conversion layer and molecular imprinting rete, the working electrode is indium tin oxide electrode.
2. A preparation method of a molecular imprinting photoelectrochemical sensor is characterized by comprising the following steps: the method comprises the following steps:
step 1, preparing MIL-125-NH by adopting a hydrothermal synthesis method2/TiO2Compounding the material, and mixing MIL-125-NH2/TiO2The composite material is sealed and stored for later use after being dried in vacuum;
step 2, placing the indium tin oxide electrode in a cleaning solution, slightly scrubbing the surface by using a cotton ball, washing by using distilled water, placing in absolute ethyl alcohol for ultrasonic treatment for 5min, taking out the indium tin oxide electrode, washing by using distilled water, and drying by using nitrogen for later use;
step 3, preparing MIL-125-NH prepared in the step 12/TiO2Dispersing the composite material in ultrapure water to obtain uniform dispersion liquid, dropwise coating 30-70 mu L of the uniform dispersion liquid on the surface of the indium tin oxide electrode treated in the step 2, and drying under an infrared lamp to obtain MIL-125-NH2/TiO2Indium tin oxide electrode modified by photoelectric conversion layer;
step 4, the MIL-125-NH obtained in the step 3 is added2/TiO2Placing the indium tin oxide electrode modified by the photoelectric conversion layer into a molecularly imprinted polymer solution containing oxytetracycline, and preparing a molecularly imprinted polymer by an electropolymerization method to enable the molecularly imprinted polymer to be modified in MIL-125-NH in situ2/TiO2And eluting oxytetracycline by using a nitric acid solution on the surface of the indium tin oxide electrode modified by the photoelectric conversion layer to obtain the indium tin oxide electrode modified by the molecularly imprinted polymer film, and taking the indium tin oxide electrode modified by the molecularly imprinted polymer film as a working electrode to be connected into a photoelectrochemical sensing system to obtain the molecularly imprinted photoelectrochemical sensor based on the MIL-125-NH2/TiO2 composite material.
3. The method for preparing a molecularly imprinted photoelectrochemical sensor according to claim 2, characterized in that: the step 1 is a hydrothermal synthesis method for preparing MIL-125-NH2/TiO2The specific method of the composite material is that tetrabutyl titanate, 2-amino terephthalic acid, methanol, N-dimethylformamide and TiO are added in a 50mL hydrothermal reaction kettle in sequence2Sealing and reacting at 150 ℃; when the hydrothermal reaction kettle is cooled to 25 ℃, taking out the solution of the hydrothermal reaction kettle, centrifugally washing the solution by using N, N-dimethylformamide and methanol, and putting the precipitate into a vacuum drying oven to be dried to obtain MIL-125-NH2/TiO2A composite material.
4. A method for preparing a molecularly imprinted photoelectrochemical sensor according to claim 3, characterized in that: the concentration of the tetrabutyl titanate is 0.05moL/L, the dosage is 0.18mL, and the 2-amino-pairThe concentration of phthalic acid is 1moL/L, the dosage is 0.16g, and the TiO2The concentration is 6moL/L, the dosage is 0.16g, and the volume ratio of the methanol to the N, N-dimethylformamide is 1: 9; the reaction time is 20 hours when the mixture is sealed and placed at 150 ℃, and the drying temperature of the precipitate placed in a vacuum drying oven is 60 ℃.
5. The method for preparing a molecularly imprinted photoelectrochemical sensor according to claim 2, characterized in that: the specific preparation method of the uniform dispersion liquid in the step 3 is to mix-125-NH prepared in the step 12/TiO2Dispersing the composite material in deionized water, and ultrasonically obtaining uniform MIL-125-NH by an ultrasonic cleaner2/TiO2Dispersing liquid, wherein the ultrasonic time of the ultrasonic cleaning instrument is 30-50min, and the uniform MIL-125-NH2/TiO2The concentration of the dispersion liquid is 0.5-1.5 mg/mL; and the drying time under an infrared lamp in the step 3 is 30-60 min.
6. The method for preparing a molecularly imprinted photoelectrochemical sensor according to claim 2, wherein the method comprises the following steps: the scanning range of the electropolymerization method in the step 4 is 0-0.8V, and the scanning speed is as follows: 30-100mV/s, number of scan cycles: 10-20 circles; the concentration of the nitric acid solution is 5%, and the time for eluting the template molecule oxytetracycline is 5-10 min.
7. The method for preparing a molecularly imprinted photoelectrochemical sensor according to claim 2, characterized in that: the molecularly imprinted polymer solution in the step 4 is prepared from template molecules: oxytetracycline, functional monomers: o-phenylenediamine and solvent: acetate buffer solution, wherein the pH of the acetate buffer solution is 5.2; and 3, dissolving oxytetracycline and o-phenylenediamine in an acetate buffer solution, introducing nitrogen to remove oxygen for 5-10min, sealing and storing in a dark place to obtain the molecularly imprinted polymer solution, wherein the oxytetracycline concentration is 0.09-0.15mg/mL, and the o-phenylenediamine concentration is 0.06-0.15 mg/mL.
8. The application of the molecular imprinting photoelectrochemical sensor is characterized in that: the molecular imprinting photoelectric chemical sensor is applied to the detection of oxytetracycline.
9. Use of a molecularly imprinted photoelectrochemical sensor according to claim 8, characterized in that: the molecular imprinting photoelectric chemical sensor is applied to the detection of oxytetracycline, and the specific detection method comprises the following steps:
step 1, establishing a terramycin detection standard curve: dripping 45 μ L of oxytetracycline standard solution with different concentrations on the surface of indium tin oxide electrode modified by molecularly imprinted polymer membrane, incubating for 15-45min for oxytetracycline adsorption, and placing the electrode adsorbed with oxytetracycline into Na2SO4And (3) accessing the aqueous solution into a photoelectrochemical sensing system, obtaining a photocurrent signal by adopting an amperometric method, and establishing an oxytetracycline detection standard curve with the abscissa as oxytetracycline concentration and the ordinate as the photocurrent signal.
Step 2, sucking 45 mu L of sample solution with unknown concentration, dripping the sample solution on the surface of the indium tin oxide electrode modified by the molecularly imprinted polymer film, incubating for 15-45min for adsorption, and placing the indium tin oxide electrode modified by the molecularly imprinted polymer film of the adsorbed oxytetracycline into Na2SO4And (3) accessing the aqueous solution into a photoelectrochemical sensing system, obtaining a photocurrent signal by adopting a chronoamperometry method, and calculating the concentration of the oxytetracycline in the sample solution corresponding to the oxytetracycline detection standard curve in the step 1.
10. Use of a molecularly imprinted photoelectric electrochemical sensor according to claim 9, characterized in that: na in said step 1 and step 22SO4The concentration of the aqueous solution was 0.1 mmol/L.
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