Detection material for antibiotic pollutants in water environment as well as preparation method and use method of detection material

By combining fluorescent metal organic frame materials (MOFs) with surface molecular imprinted polymers (MIPs) to form ZIF-8@MIPs composite materials, the problem of insufficient sensitivity to detect trace antibiotic pollutants in water in the prior art is solved, and efficient and accurate detection effects are achieved.

CN119935970AInactive Publication Date: 2025-05-06HENAN CHAOSHENG TESTING TECHNOLOGY CO LTD
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Patent Information

Application Number
CN202510099401.5
Authority / Receiving Office
CN · China
Patent Type
Applications(China)
Current Assignee / Owner
Filing Date
2025-01-21
Publication Date
2025-05-06
Estimated Expiration
Not applicable · inactive patent

AI Technical Summary

Technical Problem

The prior art cannot efficiently and accurately detect trace antibiotic pollutants in water, and lacks mature technical solutions.

Method used

Fluorescent metal organic frame materials (MOFs) are combined with surface molecular imprinting polymers (MIPs), and ZIF-8@MIPs composite materials are synthesized through molecular imprinting technology, using their high porosity and specific recognition sites to achieve high sensitivity detection of antibiotic pollutants.

Benefits of technology

It significantly improves the detection sensitivity and selectivity of antibiotic pollutants, can efficiently identify and detect trace antibiotics, has excellent stability and repeatability, and is suitable for applications in complex water environments.

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Abstract

The invention discloses a detection material for antibiotic pollutants in a water environment as well as a preparation method and a use method of the detection material. The preparation method comprises the following steps: synthesizing a surface molecularly imprinted polymer (MIPs) by adopting ZIF-8 in a metal organic framework material (MOFs) through a molecular imprinting technology, and preparing the composite material ZIF-8-MIPs with specific molecular recognition sites by taking sulfamethoxazole (SMX) as a template molecule. The composite material can efficiently identify and detect antibiotic pollutants in water. In the preparation process, firstly, a ZIF-8 material is screened, and ZIF-8-coated MIPs are synthesized by utilizing a molecular imprinting technology; a fluorescent metal organic framework (LMOFs) detection system is constructed, and the antibiotic concentration is detected through fluorescence change. A water sample is pretreated by combining a solid phase extraction (SPE) technology, interference substances are removed, and the detection sensitivity is improved. The method can realize rapid and sensitive antibiotic detection, is suitable for the fields of water quality monitoring, environmental protection and the like, and has a wide application prospect.
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Description

Technical Field

[0001] The invention relates to the technical field of water environment monitoring, and in particular to a detection material for antibiotic pollutants in water environment, a preparation method and a use method thereof. Background Art

[0002] As environmental pollution becomes increasingly serious, antibiotic contamination in water has become an important issue in global water resource management. Traditional water quality testing methods are often unable to efficiently and accurately detect trace antibiotic pollutants in water, so there is an urgent need to develop a new, efficient and sensitive material for detecting water environmental pollutants.

[0003] Metal-organic framework (MOFs) materials have shown great potential in the detection of environmental pollutants due to their unique pore structure and tunable chemical properties. At the same time, molecular imprinting technology (MIPs) has also been widely used in the development of sensor materials by forming specific recognition sites. However, the application of composite materials combining these two technologies in the field of antibiotic pollutant detection in water environments is still relatively scarce, and a mature technical solution has not yet been formed. Summary of the invention

[0004] The purpose of the present invention is to provide a material for detecting antibiotic pollutants in water environment and a method for preparing and using the material, which combines metal organic framework (MOFs) materials and molecular imprinting technology (MIPs) and has the advantages of high sensitivity, strong selectivity and good stability. It can effectively solve the problems of insufficient sensitivity, low detection efficiency and lack of mature technical solutions of existing detection methods.

[0005] To achieve the above objectives, the present invention provides the following technical solution: a material for detecting antibiotic pollutants in an aquatic environment, wherein the detection material is a composite of fluorescent metal organic framework materials (MOFs) and surface molecular imprinted polymers (MIPs).

[0006] A method for preparing a detection material for antibiotic pollutants in a water environment comprises the following steps:

[0007] S1. Screening of target MOFs materials:

[0008] Metal-organic frameworks (MOFs) with fluorescent properties were selected, and ZIF-8 with high porosity and specific surface area, regular spatial network structure, adjustable pore size and good photothermal stability was selected as the target material;

[0009] S2. Synthesis of composite materials by molecular imprinting technology:

[0010] The sulfamethoxazole (SMX) molecules were adsorbed and bonded to the surface of the ZIF-8 material to form the action site in advance, and the surface molecular imprinting polymers (MIPs) were synthesized by surface molecular imprinting technology using SMX as the template molecule, and finally the ZIF-8 material formed a composite structure ZIF-8@MIPs.

[0011] S3. Cleaning and drying of composite materials:

[0012] The composite material obtained in step S2 is washed and dried to remove the template molecules, thereby obtaining a ZIF-8@MIPs composite material for antibiotic detection.

[0013] Preferably, in S2, the ZIF-8 material is contacted with sulfamethoxazole (SMX) molecules, and the contact process includes dissolving SMX in ethanol, and using a stirring method to uniformly cover the SMX molecules on the surface of ZIF-8. The contact time is 2 hours and the temperature is 25°C.

[0014] Preferably, the surface molecular imprinting technology in S2 includes using SMX as a template molecule and adopting a free radical polymerization method to carry out a polymerization reaction on the surface of ZIF-8. The monomer used is acrylic acid and the cross-linking agent is N,N'-methylenebisacrylamide. The reaction temperature is 50°C and the polymerization time is 4 hours to obtain a ZIF-8@MIPs composite material.

[0015] Preferably, the ZIF-8@MIPs composite material obtained in step S3 is washed, including multiple ultrasonic cleaning with deionized water to remove unreacted monomers and template molecules, and finally dried at 60°C for 24 hours to obtain a ZIF-8@MIPs composite material for antibiotic detection.

[0016] A method for using an antibiotic pollutant detection material in a water environment comprises the following steps:

[0017] S4. Water sample collection and pretreatment:

[0018] Collect surface water samples, filter and concentrate the water samples to remove impurities and interfering substances;

[0019] S5. Construct LMOFs detection system:

[0020] Using the electron transfer effect inside MOFs materials, a fluorescent metal organic framework (LMOFs) detection system was constructed;

[0021] S6. Detection of pollutants by fluorescence changes:

[0022] The porosity and specific surface area of ​​MOFs are used to detect the fluorescence of pollutants. The interaction between pollutants and MOFs materials is used to observe whether fluorescence is generated, and the presence of antibiotics in water is preliminarily determined.

[0023] S7, Visual detection:

[0024] Through the change of fluorescence signal or color, the visual detection of pollutants can be further achieved;

[0025] S8. Perform quantitative analysis and output the test results:

[0026] Quantitative analysis is performed based on the intensity of fluorescence or color changes combined with a standard curve. By analyzing the fluorescence intensity of water samples, the concentration value of antibiotic pollutants is output to provide support for the quantitative detection of antibiotic contamination in the environment.

[0027] Preferably, in the step S4, the water sample is filtered using a filter membrane with a pore size of 0.45 μm, and the concentration process is performed by solid phase extraction technology, the solid phase extraction material is C18, the temperature during the extraction process is maintained at 25° C., and the processing time is 1 hour.

[0028] Preferably, in the step S5, the MOFs material used in the constructed LMOFs detection system is ZIF-8, the wavelength of the excitation light source is 350 nm, and the fluorescence detection wavelength is 450 nm.

[0029] Preferably, in the step S8, when the fluorescence change caused by the interaction between the antibiotic pollutant and the MOFs material is qualitatively analyzed, the fluorescence intensity change range used is 10% to 50%, and the concentration of the antibiotic pollutant is quantitatively detected by comparing it with the standard curve of the antibiotic concentration.

[0030] Preferably, in step S8, the construction of the standard curve is calibrated using antibiotic standard solutions of different concentrations, the concentration range of the antibiotic standard solutions used is 0.01 mg / L to 100 mg / L, the linear relationship of the standard curve is fitted by linear regression method, and the error of the test result does not exceed ±5%.

[0031] Compared with the prior art, the present invention has the following beneficial effects:

[0032] 1. The present invention constructs a composite material with specific recognition ability by combining fluorescent metal organic framework materials (MOFs) with surface molecular imprinting polymers (MIPs), which significantly improves the detection sensitivity and selectivity of antibiotic pollutants.

[0033] 2. The present invention uses ZIF-8 as the MOFs material and combines it with molecular imprinting technology, so that the material can efficiently identify and detect antibiotic pollutants in an aqueous environment, and is particularly suitable for the detection of trace antibiotics.

[0034] 3. By removing the template molecules and optimizing the washing steps, the composite material of the present invention has excellent stability and repeatability, and is suitable for practical applications in complex water environments.

[0035] 4. The detection material provided by the present invention can be combined with fluorescence detection technology to display the concentration changes of antibiotic pollutants in water in real time and intuitively, which is convenient for quickly judging the water pollution status. BRIEF DESCRIPTION OF THE DRAWINGS

[0036] Figure 1 A schematic diagram of the structural components of a material for detecting antibiotic pollutants in a water environment according to the present invention;

[0037] Figure 2 It is a schematic diagram of a preparation process of a material for detecting antibiotic pollutants in a water environment according to the present invention;

[0038] Figure 3 This is a schematic diagram of the use process of an antibiotic pollutant detection material in a water environment according to the present invention. DETAILED DESCRIPTION

[0039] The following will be combined with the drawings in the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0040] See also Figures 1 to 3 The present invention provides a technical solution: a material for detecting antibiotic pollutants in a water environment, wherein the detection material is composited by a metal organic framework (MOFs) material and a surface molecular imprinting polymer (MIPs). The metal organic framework material (MOFs) provides a large specific surface area, a regular pore structure, and adjustable chemical properties, which help to improve the adsorption performance of pollutants. The surface molecular imprinting polymer (MIPs) gives the material the ability to selectively recognize antibiotic pollutants through a specific molecular imprinting effect. Specifically, ZIF-8 is selected as a MOFs material, which has good porosity and stability and can effectively adsorb antibiotic pollutants.

[0041] A method for preparing a detection material for antibiotic pollutants in a water environment comprises the following steps:

[0042] S1. Screening of target MOFs materials:

[0043] Select metal organic framework materials (MOFs) with fluorescent properties, preferably ZIF-8. ZIF-8 is a MOFs material composed of zinc ions and imidazole ligands. It has high porosity (>50%), specific surface area (>1500m 2 / g) and excellent stability, especially in water environment, it shows good adsorption performance and stability, which is suitable for the detection of antibiotic pollutants. The pore size of ZIF-8 (approx. ) is suitable for adsorbing common antibiotic molecules. It also has strong photothermal stability and a wide fluorescence emission range, which can effectively improve the sensitivity of detection.

[0044] To ensure more accurate material selection, the screening criteria include:

[0045] Porosity: The porosity of ZIF-8 is greater than 50%, which gives it a higher surface area and better adsorption capacity, especially for the adsorption of small molecules. The porosity of other MOFs materials can be compared with ZIF-8 to screen out materials with suitable porosity.

[0046] Specific surface area: The specific surface area of ​​ZIF-8 is greater than 1500m 2 / g, which enables it to provide more active sites for adsorption and recognition of target molecules. For other MOFs materials, materials with specific surface areas close to or greater than this value are selected.

[0047] Photothermal stability: ZIF-8 exhibits good photothermal stability, and its thermal stability is particularly important in an aqueous environment. Experimental data can be used to support the changes in pore size and specific surface area of ​​ZIF-8 after it has been immersed in water for a certain period of time to ensure its stability.

[0048] Fluorescence properties: ZIF-8 has a wide fluorescence emission range and can effectively interact with antibiotic molecules to amplify the fluorescence signal.

[0049] S2. Synthesis of composite materials by molecular imprinting technology:

[0050] Using sulfamethoxazole (SMX) molecules as templates, SMX molecules are bound to the surface of ZIF-8 materials through physical adsorption or chemical adsorption to form preliminary action sites. Physical adsorption is the process of binding SMX molecules to the surface of ZIF-8 through weak forces such as electrostatic interactions and van der Waals forces, while chemical adsorption is bound to surface sites through covalent bonds or coordination. Next, using SMX as a template molecule, surface molecular imprinting polymers (MIPs) are synthesized on the surface of ZIF-8 through surface molecular imprinting technology. The process involves copolymerizing ZIF-8 materials with monomers (acrylic acid, vinyl pyridine) and crosslinkers (divinylbenzene) to form a composite material ZIF-8@MIPs with specific molecular recognition sites.

[0051] Choice of adsorption method:

[0052] Physical adsorption: SMX molecules are adsorbed on the ZIF-8 surface through weak forces such as electrostatic interaction and van der Waals force. This adsorption method is mild and reversible, and is suitable for smaller molecules or charged molecules.

[0053] Chemical adsorption: SMX molecules are fixed on the surface of ZIF-8 through covalent bonds or coordination. This method can form a more stable bond and is more suitable for target molecules that require persistent recognition. Functional groups such as amino groups and carboxyl groups can be introduced on the surface of ZIF-8 to achieve chemical adsorption.

[0054] Copolymerization conditions:

[0055] Temperature and time: The copolymerization reaction is usually carried out at room temperature (25°C) for 12 hours. Depending on the types of monomers and cross-linking agents, the reaction temperature and time can be adjusted appropriately to ensure the stability and repeatability of the composite material.

[0056] Ratio of monomer to cross-linking agent: The ratio of monomer to cross-linking agent is usually 3:1 to ensure the formation of sufficient cross-linked network structure without affecting the pore structure of the material. The specific ratio can be optimized according to experiments.

[0057] S3. Cleaning and drying of composite materials:

[0058] The synthesized ZIF-8@MIPs composite material needs to be washed to remove the template molecules and unreacted monomers. Deionized water is used for multiple ultrasonic cleaning to remove unreacted monomers and template molecules. The ultrasonic cleaning instrument used in the cleaning process should be set to a frequency of 20kHz and a power of 100W to ensure the adequacy of the cleaning effect. The cleaned material will be dried at 60℃ for 24 hours to ensure the dryness and stability of the material.

[0059] Specific parameters of ultrasonic cleaning:

[0060] Frequency: 20kHz frequency is suitable for removing fine matter while avoiding damage to the material.

[0061] Power: 100W of power ensures the efficiency of the cleaning process without damaging the structure of the material.

[0062] Choice of cleaning solution: Deionized water can be used for multiple cleanings, and organic solvents such as ethanol or acetone can be used as needed to enhance the removal efficiency of template molecules and unreacted monomers. Acid-base solutions (NaOH or HCl) can also be used to help remove possible residues.

[0063] Drying process: The material needs to be dried at 60°C for 24 hours to ensure complete removal of moisture without affecting the pore structure and stability of ZIF-8.

[0064] A method for using a material for detecting antibiotic contaminants in a water environment. The method of use in this scheme is a method for detecting antibiotic contaminants in a water environment, which comprises the following steps:

[0065] S4. Water sample collection and pretreatment:

[0066] Water samples were collected and typical surface water was selected as samples. The water samples were filtered through a 0.45 μm pore size filter membrane to remove large particle impurities and solid matter in the water. Then, the water samples were concentrated using solid phase extraction (SPE) technology to remove other interfering substances and increase the concentration of antibiotics for easy detection. The use of C18 columns for extraction during the SPE process can increase the concentration of the target antibiotics and reduce the interference of impurities.

[0067] Specific requirements for water sample collection:

[0068] When collecting water samples, ensure that you collect samples at different seasons and locations to obtain representative water samples.

[0069] The water sample collection volume is usually 500mL to 1L, which can be adjusted according to experimental requirements.

[0070] Environmental contamination should be avoided during collection to ensure the original state of the samples.

[0071] SPE conditions:

[0072] Solvent selection: Use methanol or acetonitrile as solvent to assist the extraction of antibiotics by polar solvents.

[0073] Elution volume: Generally, 5 mL of solvent is used for elution, and the concentration multiple can be adjusted according to actual conditions.

[0074] SPE column selection: C18 column has good antibiotic adsorption during the extraction process and is suitable for polar and medium-polar compounds.

[0075] S5. Construct LMOFs detection system:

[0076] The fluorescence metal organic framework (LMOFs) detection system is constructed by utilizing the electron transfer effect inside the MOFs material. When the antibiotic pollutants enter the pores of the MOFs and bind to the specific recognition sites on the surface of the MOFs, the electron transfer effect between molecules causes the fluorescence of the MOFs material to change. This process can effectively amplify the fluorescence signal, so that the concentration changes of the antibiotic pollutants can be monitored by the fluorescence spectrometer.

[0077] Specific mechanism of electron transfer effect:

[0078] When antibiotic contaminants enter the pores of MOFs materials, the molecules interact with the surface active sites, causing electrons to be transferred from the antibiotic molecules to the MOFs surface, or vice versa. This effect changes the electronic energy level of the MOFs material, causing its fluorescence intensity or wavelength to change.

[0079] Sensitivity of fluorescence response:

[0080] The detection sensitivity can be determined experimentally as LOD (limit of detection), for example, LOD can reach the nanogram level. The concentration range of antibiotics is usually between 10nM and 1000nM, and the specific range needs to be optimized according to the characteristics of the target antibiotic.

[0081] S6. Detection of pollutants by fluorescence changes:

[0082] The interaction between pollutants and MOFs materials will change the fluorescence properties of the materials. This fluorescence change can be monitored in real time by a fluorescence spectrometer, recording the changes in fluorescence intensity or wavelength to determine the presence and concentration of antibiotics in water. During detection, the change in fluorescence intensity is usually based on an increase or decrease in peak intensity, while the change in wavelength reflects the red shift or blue shift of the fluorescence spectrum.

[0083] Specific characterization of fluorescence changes:

[0084] The analysis can be performed by measuring fluorescence intensity (in relative fluorescence units, RFU) or wavelength changes using a high-resolution fluorescence spectrometer.

[0085] The settings of the fluorescence instrument need to be optimized according to the fluorescence properties of the material, and the excitation light wavelength and detection wavelength should match the fluorescence properties of the antibiotic.

[0086] Elimination of interfering factors:

[0087] To avoid fluorescence interference from other substances, a suitable excitation light wavelength can be selected, or a specific detection wavelength can be set to specifically monitor the fluorescence signal of the antibiotic to exclude other sources of interference.

[0088] S8. Quantitative analysis and output of test results:

[0089] By measuring the change of fluorescence signal and combining with the standard curve (calibrated by antibiotic standard solution of different concentrations), the antibiotic pollutants in water samples can be quantitatively analyzed. According to the linear relationship between fluorescence intensity and antibiotic concentration, the concentration value of the pollutant can be output, thus realizing the accurate quantitative detection of antibiotic pollutants in water.

[0090] Standard curve construction details:

[0091] When constructing the standard curve, different concentrations of antibiotic standard solutions (10 nM to 1000 nM) were used for calibration, and the curve was fitted by linear regression method.

[0092] Experimental repeatability: To ensure accuracy, it is recommended to perform at least three repeated experiments and calculate the goodness of fit of the curve (R 2 ).

[0093] Sensitivity and precision of quantitative analysis:

[0094] Sensitivity: LOD (limit of detection) reaches the nanogram level, which can accurately detect low concentrations of antibiotics.

[0095] Precision: The relative standard deviation (RSD) was calculated to ensure good repeatability of the method.

[0096] In order to better illustrate the technical solution of the present invention, the application effects and advantages of the present invention under different environments will be described in detail in combination with specific embodiments. The embodiments will demonstrate the performance difference between the present invention and the prior art in antibiotic detection through comparative experiments, and further verify the actual effects and advantages of the present invention.

[0097] Example 1: Application in urban sewage

[0098] With the advancement of industrialization, the concentration of antibiotic pollutants in urban sewage has gradually increased, especially the pollution of sulfonamide antibiotics, which has become a major problem of water pollution. Traditional detection methods have the disadvantages of low sensitivity, long time and complex operation. There is an urgent need for an efficient, rapid and sensitive detection method.

[0099] The present invention provides a method for detecting antibiotic pollutants based on ZIF-8@MIPs materials, which can realize efficient and accurate detection of antibiotic pollutants in a complex sewage environment.

[0100] Implementation steps:

[0101] Water sample collection and treatment: About 5 L of water samples were collected from the urban sewage treatment plant and filtered through a 0.45 μm pore size filter membrane to remove large particles in the water.

[0102] Solid phase extraction: Use C18 solid phase extraction columns to concentrate water samples, remove impurities, and increase the concentration of antibiotics.

[0103] Antibiotic detection: The synthesized ZIF-8@MIPs composite was used for fluorescence detection, and the fluorescence changes were recorded and the antibiotic concentration was calculated using the standard curve.

[0104] Comparative experimental data:

[0105]

[0106]

[0107] Result analysis:

[0108] Compared with traditional high performance liquid chromatography (HPLC) and enzyme-linked immunosorbent assay (ELISA) methods, the method of the present invention has obvious advantages in detection limit, detection time, sensitivity, selectivity, etc. Especially in complex sewage samples, the present invention can quickly and accurately detect low concentrations of sulfamethoxazole, with good repeatability, low operating difficulty and equipment cost.

[0109] Example 2: Application in surface water

[0110] The impact of antibiotic residues in surface water on the ecological environment has gradually attracted people's attention. With the extensive use of antibiotics, the types and concentrations of antibiotics contained in water bodies are constantly changing, and traditional detection methods cannot meet the needs of rapid response and large-scale monitoring. The application of the method provided by the present invention in surface water can effectively and cost-effectively monitor antibiotic pollutants in real time.

[0111] Implementation steps:

[0112] Water sample collection and processing: Sampling was carried out in a river, the water sample volume was 10L, and it was filtered through a 0.45μm pore size filter membrane to remove suspended particles.

[0113] Solid phase extraction and pretreatment: Use C18 column for solid phase extraction to concentrate water samples and remove interfering substances in the water.

[0114] Fluorescence detection: The ZIF-8@MIPs material synthesized by the present invention is used to detect antibiotic pollutants.

[0115] Comparative experimental data:

[0116]

[0117] Result analysis:

[0118] In the application of surface water, the ZIF-8@MIPs composite material of the present invention exhibits a lower detection limit, a shorter detection time and a higher sensitivity than HPLC and UV-Vis. In particular, the present invention has significant advantages in the rapid monitoring of low-concentration antibiotics. In addition, the operation is simple and the equipment cost is low, which makes it have a better application prospect in the conventional monitoring of surface water.

[0119] Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions and variations may be made to the embodiments without departing from the principles and spirit of the present invention, and that the scope of the present invention is defined by the appended claims and their equivalents.

Claims

1. A detection material for antibiotic pollutants in water environment, characterized in that: The detection material is composited by fluorescent metal organic framework materials (MOFs) and surface molecular imprinting polymers (MIPs).

2. A method for preparing a detection material for antibiotic pollutants in a water environment, used for preparing a detection material for antibiotic pollutants in a water environment according to claim 1, characterized in that: The following steps are involved: S1. Screening of target MOFs materials: Metal-organic frameworks (MOFs) with fluorescent properties were selected, and ZIF-8 with high porosity and specific surface area, regular spatial network structure, adjustable pore size and good photothermal stability was selected as the target material; S2. Synthesis of composite materials by molecular imprinting technology: The sulfamethoxazole (SMX) molecules were adsorbed and bonded to the surface of the ZIF-8 material to form the action site in advance, and the surface molecular imprinting polymers (MIPs) were synthesized by surface molecular imprinting technology using SMX as the template molecule, and finally the ZIF-8 material formed a composite structure ZIF-8@MIPs. S3. Cleaning and drying of composite materials: The composite material obtained in step S2 is washed and dried to remove the template molecules, thereby obtaining a ZIF-8@MIPs composite material for antibiotic detection.

3. The method for preparing a material for detecting antibiotic pollutants in water environment according to claim 2, characterized in that: In S2, the ZIF-8 material is contacted with sulfamethoxazole (SMX) molecules, and the contact process includes dissolving SMX in ethanol and using a stirring method to uniformly cover the SMX molecules on the surface of ZIF-8. The contact time is 2 hours and the temperature is 25°C.

4. The method for preparing a material for detecting antibiotic pollutants in water environment according to claim 2, characterized in that: The surface molecular imprinting technology in S2 includes using SMX as a template molecule and a free radical polymerization method to carry out a polymerization reaction on the surface of ZIF-8. The monomer used is acrylic acid and the cross-linking agent is N,N'-methylenebisacrylamide. The reaction temperature is 50°C and the polymerization time is 4 hours to obtain a ZIF-8@MIPs composite material.

5. The method for preparing a material for detecting antibiotic pollutants in water environment according to claim 2, characterized in that: The ZIF-8@MIPs composite material obtained in step S3 is washed, including multiple ultrasonic cleanings with deionized water to remove unreacted monomers and template molecules, and finally dried at 60° C. for 24 hours to obtain a ZIF-8@MIPs composite material for antibiotic detection.

6. A method for using a material for detecting antibiotic pollutants in a water environment, applied to the material for detecting antibiotic pollutants in a water environment according to claim 1, characterized in that: The following steps are involved: S4. Water sample collection and pretreatment: Collect surface water samples, filter and concentrate the water samples to remove impurities and interfering substances; S5. Construct LMOFs detection system: Using the electron transfer effect inside MOFs materials, a fluorescent metal organic framework (LMOFs) detection system was constructed; S6. Detection of pollutants by fluorescence changes: The porosity and specific surface area of ​​MOFs are used to detect the fluorescence of pollutants. The interaction between pollutants and MOFs materials is used to observe whether fluorescence is generated, and the presence of antibiotics in water is preliminarily determined. S7, Visual detection: Through the change of fluorescence signal or color, visual detection of pollutants can be further achieved; S8. Perform quantitative analysis and output the test results: Quantitative analysis is performed based on the intensity of fluorescence or color changes combined with a standard curve. By analyzing the fluorescence intensity of water samples, the concentration value of antibiotic pollutants is output to provide support for the quantitative detection of antibiotic contamination in the environment.

7. The method for using the antibiotic pollutant detection material in a water environment according to claim 6, characterized in that: In the step S4, the water sample is filtered using a filter membrane with a pore size of 0.45 μm, and the concentration process is carried out by solid phase extraction technology. The solid phase extraction material is C18. The temperature during the extraction process is maintained at 25° C. and the processing time is 1 hour.

8. The method for using the antibiotic pollutant detection material in a water environment according to claim 6, characterized in that: In the step S5, the MOFs material used in the constructed LMOFs detection system is ZIF-8, the wavelength of the excitation light source is 350nm, and the fluorescence detection wavelength is 450nm.

9. The method for using the antibiotic pollutant detection material in a water environment according to claim 6, characterized in that: In the step S8, when performing qualitative analysis on the fluorescence change caused by the interaction between the antibiotic pollutant and the MOFs material, the fluorescence intensity change range used is 10% to 50%, and the concentration of the antibiotic pollutant is quantitatively detected by comparing with the standard curve of the antibiotic concentration.

10. The method for using the antibiotic pollutant detection material in a water environment according to claim 6, characterized in that: In the step S8, the construction of the standard curve is calibrated using antibiotic standard solutions of different concentrations, the concentration range of the antibiotic standard solutions used is 0.01 mg / L to 100 mg / L, the linear relationship of the standard curve is fitted by linear regression method, and the error of the test result does not exceed ±5%.