MIP / MOF / COF hybrid material and preparation method and application thereof

Abstract

The invention belongs to the technical field of food safety sensing detection, adsorption and degradation, and particularly relates to an MIP / MOF / COF hybrid material and a preparation method and application thereof. Aiming at the defects and bottleneck problems of the existing patulin detection and removal technology, the preparation method comprises the following steps: firstly preparing an MOF / COF composite material, and then preparing an MIP / MOF / COF hybrid material by a sol-gel method, so that the photoelectrochemical sensor based on the MIP / MOF / COF hybrid material is constructed and is used for detecting patulin; meanwhile, based on the MIP / MOF / COF hybrid material, an attachment and degradation test platform is constructed. The prepared photoelectrochemical sensor can successfully detect trace patulin, and the hybrid material has good adsorption and degradation performance on patulin.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of food safety sensing detection, adsorption and degradation, and particularly relates to a MIP / MOF / COF hybrid material, a preparation method and application thereof, and is used for constructing a patulin detection, adsorption and catalytic degradation platform. BACKGROUND

[0002] Patulin (PAT), also known as clavatin, is a secondary metabolite produced by fungi such as Aspergillus and Penicillium, and widely exists in moldy fruits, especially apples and their products. PAT has serious carcinogenicity and teratogenicity, and can damage human health, and even show toxicity in genetics, immunity, skin, intestine, liver, kidney and the like. Current studies have shown that PAT also has some unknown potential toxicity. PAT often contaminates fruits and their products, especially apples, and can cause the apples to rot from the outside to the inside, thereby causing economic losses. Therefore, it is urgent to develop a method for ultra-sensitive and rapid detection of trace PAT and efficient removal of PAT.

[0003] Metal Organic Frameworks (MOF) is a kind of crystalline porous material formed by self-assembly of metal ions or metal clusters and organic ligands through coordination. Its core features include large specific surface area, adjustable pore structure, and functional diversification. With these advantages, MOF has shown great application prospects in gas storage, catalysis, adsorption, sensing, and drug delivery, becoming an ideal platform for multifunctional materials. Based on this, MOF has shown significant ability in the sensing detection, adsorption separation, and catalytic degradation of mycotoxins. Covalent Organic Frameworks (COF) is a kind of crystalline porous material constructed by carbon, hydrogen, oxygen, nitrogen, and other light elements through stable covalent bonds (such as imine bonds and triazine bonds). It has highly ordered pore structure, high specific surface area, and adjustable pore size, and its structure can be precisely controlled by designing different building units. Due to its unique properties, COF has been widely studied and applied in gas storage and separation, photocatalysis, photoelectric sensing, proton conduction, drug delivery, and energy storage and conversion in recent years. In recent years, COF has also shown significant ability in the sensing detection, adsorption separation, and catalytic degradation of mycotoxins. Although MOF has shown great potential in photocatalysis, its application still faces some challenges, such as weak light capture ability leading to insufficient electron excitation, high carrier recombination rate, low charge transfer efficiency, and poor stability of coordination bonds, which limit its performance in various aspects of photocatalytic applications. In addition, MOF is mainly prepared by hydrothermal synthesis, and the resulting material is usually in the form of microparticles, which is difficult to stabilize and fix on the electrode surface. Combined with its hydrolysis characteristics, its application in the sensing field is limited. To overcome these problems, researchers have begun to combine MOF with other functional materials. COF is a kind of organic porous material formed by light elements through covalent bonds, with unique advantages. However, the harsh synthesis conditions and poor crystallinity also limit the application of COF in certain fields. Therefore, it is considered to composite MOF and COF materials to obtain better MOF / COF hybrid materials. This hybrid material effectively overcomes the inherent defects of single MOF and COF through strong π-π stacking interactions and produces a synergistic effect. Through reasonable structure integration and functional modification, MOF / COF hybrid materials alleviate the problem of rapid recombination of photo-generated carriers, further improving the photocatalytic performance. So far, many researchers have prepared MOF / COF hybrid materials, which not only maintain the original advantages of MOF and COF, such as high specific surface area and abundance of active centers, but also solve the problem of insufficient catalytic activity. To date, MOF / COF hybrid materials have been applied in multiple fields and are becoming one of the core materials for building multifunctional platforms.With further research and optimization, MOFs and COFs are expected to play a key role in food safety monitoring, pollution control, and food quality control, providing innovative technical support for food safety protection. In addition, the synthesis of molecularly imprinted polymers (MIPs) on the surface of MOF / COF hybrid materials can achieve efficient and specific recognition and adsorption of target molecules.

[0004] Photoelectrochemical sensors (PEC) are a technology that generates an electrical signal through light excitation. It combines optical and electrochemical techniques, and the electron-hole pairs generated by light excitation react with target analytes to produce detectable electrical signals, providing an efficient and sensitive solution for the detection of mycotoxins. By combining light-sensitive materials with specific recognition elements, it can accurately identify mycotoxins in complex matrices, providing an efficient and reliable detection method for the food safety field. In addition, there is a close relationship between PEC sensing and catalytic degradation. Both are based on the reaction mechanism of light-sensitive materials generating electron-hole pairs under light, and both rely on light-sensitive materials absorbing photon energy under light, exciting electrons from the valence band to the conduction band to form electron-hole pairs. These electrons and holes then participate in redox reactions for target detection and degradation. PEC detection and catalytic degradation have significant commonalities in mechanism and application, providing a theoretical basis for using PEC active materials to build multifunctional platforms. In addition, PEC active materials are structurally adjustable and easy to modify, and these advantages enable them to be combined with nanomaterials, molecularly imprinted polymers, or biological recognition elements to further enhance the performance of multifunctional platforms. Therefore, the choice of PEC technology not only meets the detection needs, but also provides an efficient and sustainable technical path for applications in food safety, environmental remediation, and other fields. SUMMARY

[0005] In view of the shortcomings and bottleneck problems of the existing patulin detection and removal technologies, the application provides a MIP / MOF / COF hybrid material and a three-function platform based on the material for photoelectrochemical sensing detection, adsorption and catalytic degradation of patulin. The application first uses a one-step solvothermal method to prepare NH2-MIL-125, 2,3-Dha Tph and NH2-MIL-125 / 2,3-Dha Tph respectively, and then synthesizes the MIP / NH2-MIL-125 / 2,3-Dha Tph hybrid material through a surface imprinting method. Finally, the hybrid material is used for the construction of the three-function platform: 1) the hybrid material is modified on the surface of an ITO electrode to prepare a photoelectrochemical sensor; 2) the hybrid material and a mixed solution of patulin are magnetically stirred in the dark to test the adsorption performance; and 3) the hybrid material and the mixed solution of patulin are first magnetically stirred in the dark, and then the catalytic degradation performance is tested under the conditions of continuous light and magnetic stirring by using a xenon lamp configured by a photoelectric reaction analyzer as a light source. The three-function platform based on the hybrid material can be used for high-selectivity and high-sensitivity detection of patulin as well as excellent adsorption and degradation performance.

[0006] To achieve the above object, the application adopts the following technical scheme: The application provides a preparation method of a MIP / MOF / COF hybrid material, comprising the following steps: Step 1, 2-amino terephthalic acid, tetrabutyl titanate, methanol and N,N-dimethylformamide are added to a container, magnetic stirring is used, heating reaction is performed after the stirring is completed, the reaction is naturally cooled to room temperature after the reaction is completed, the suspension is centrifuged, the polymer is collected, and then washing, vacuum drying are performed to obtain NH2-MIL-125; Step 2, 2,3-dihydroxyterephthaldehyde, 5,10,15,20-tetra(4-aminophenyl)porphyrin, o-dichlorobenzene, n-butanol and an ice acetic acid aqueous solution are added to a container, ultrasonic treatment is performed, NH2-MIL-125 is added, ultrasonic treatment is performed, then heating reaction is performed, the reaction is naturally cooled to room temperature after the reaction is completed, the suspension is centrifuged, the polymer is collected, and then washing, vacuum drying are performed to obtain NH2-MIL-125 / 2,3-Dha Tph; Step 3, a virtual template molecule and 3-aminopropyl triethoxysilane are dispersed in a mixed solution of ethanol and water, magnetic stirring is used, then tetraethyl orthosilicate, NH2-MIL-125 / 2,3-Dha Tph and ammonia water are added to the mixed solution, magnetic stirring is used for reaction, the suspension is centrifuged after the reaction is completed, the polymer is collected, ultrasonic-assisted multiple centrifugal washing is performed, then the obtained precipitate is washed, vacuum dried to obtain MIP / NH2-MIL-125 / 2,3-Dha Tph.

[0007] Further, the ratio of 2-amino terephthalic acid, tetrabutyl titanate, methanol and N,N-dimethylformamide in step 1 is 6.6 mmol: 3 mmol: 25 mL: 25 mL; the temperature of heating reaction is 150 DEG C, and the time is 20 h; the centrifugal speed of the suspension is 4200 r / min, and the time is 5 min; the temperature of vacuum drying is 60 DEG C, and the time is 3 h.

[0008] Further, the ratio of 2,3-dihydroxyterephthaldehyde, 5,10,15,20-tetra(4-aminophenyl)porphyrin, o-dichlorobenzene, n-butanol, aqueous acetic acid and NH2-MIL-125 in step 2 is 0.3 mmol: 0.3 mmol: 9 mL: 9 mL: 1.2 mL: 50 mg, and the concentration of aqueous acetic acid is 6 M; the temperature of heating reaction is 120 DEG C, and the time is 72 h; the centrifugal speed of the suspension is 4200 r / min, and the time is 5 min; the temperature of vacuum drying is 60 DEG C, and the time is 5 h.

[0009] Further, the virtual template molecule in step 3 is a mixture of 2-indolone and 6-hydroxy nicotinic acid, and the mass ratio is 1:1; the ratio of virtual template molecule, 3-aminopropyl triethoxysilane, tetraethyl orthosilicate, NH2-MIL-125 / 2,3-DhaTph and ammonia is 5 mg: 0.175 mL: 0.5 mL: 11.25 mg: 2.0 mL; the reaction time is 12 h; the centrifugal speed of the suspension is 4200 r / min, and the time is 10 min; the temperature of vacuum drying is 50 DEG C, and the time is 3 h.

[0010] The application further provides a MIP / MOF / COF hybrid material prepared by the preparation method.

[0011] The application further provides an application of the MIP / MOF / COF hybrid material, which is used for constructing a penicillin detection, adsorption and catalytic degradation platform.

[0012] Further, the penicillin detection platform is a photoelectrochemical sensor, and specifically, The MIP / MOF / COF hybrid material is added into a to-be-detected penicillin sample, and incubated at room temperature to specifically recognize and adsorb the penicillin. The ITO electrode is immersed in anhydrous ethanol for ultrasonic treatment, and then washed with ultrapure water and dried; the hybrid material after the incubation in step 1 is dropped and coated on the surface of the treated ITO electrode, and dried to form a film, so that a working electrode is obtained, and a photoelectrochemical sensor is constructed, and photocurrent detection is performed.

[0013] Further, the penicillin adsorption platform, specifically: the MIP / MOF / COF hybrid material is added to the penicillin solution, the mixed solution is magnetically stirred in the dark, and the solution of different stirring time periods is sucked, and the absorbance change is determined by ultraviolet spectrophotometer after centrifugation.

[0014] Further, the penicillin catalytic degradation platform, specifically: The MIP / MOF / COF hybrid material is added to the penicillin solution, the mixed solution is magnetically stirred in the dark to achieve adsorption-desorption equilibrium; after reaching adsorption-desorption equilibrium, continuous light irradiation is carried out with magnetic stirring, and the solution of different light irradiation time periods is sucked, and the absorbance change is determined by ultraviolet spectrophotometer after centrifugation.

[0015] The application also provides a penicillin detection, adsorption and catalytic degradation platform based on the MIP / MOF / COF hybrid material.

[0016] Compared with the prior art, the application has the following advantages: (1) The MIP / MOF / COF multifunctional hybrid material is prepared for the first time, a three-function platform is constructed, PEC sensing detection, adsorption and catalytic degradation of PAT are provided, a new strategy for trace detection and adsorption removal of penicillin is provided, and the application has good application prospect in the fields of food safety and environmental monitoring.

[0017] (2) The MIP / MOF / COF hybrid material is prepared, a photoelectrochemical sensor based on the MIP / MOF / COF hybrid material is constructed, and it is applied to the detection of penicillin, which focuses on solving the problems of complicated sample pretreatment process, expensive instrument and complex operation in the current penicillin detection method based on chromatography, and provides a new idea and method for the construction of high-sensitivity and high-specificity molecularly imprinted electrochemical sensor.

[0018] (3) The MOF / COF (NH2-MIL-125 / 2,3-Dha Tph) is used as a carrier, then the computer simulation technology is used to screen out the substance Oxindle / 6-HNA which is most similar to PAT in structure, shape and size as a virtual template molecule, and the surface molecular imprinting is carried out by using sol-gel method, and the prepared MIP / MOF / COF material has specific recognition function for penicillin. The use of virtual template instead of target substance can solve the problems of high cost, strong toxicity and template leakage affecting analysis results caused by target substance. BRIEF DESCRIPTION OF DRAWINGS

[0019] Figure 1The photoelectric current response graph of the photoelectrochemical sensor based on MIP / MOF / COF hybrid materials in Example 3 for detecting different concentrations of patulin, a-i corresponds to the concentration of patulin solution of 0 mol / L, 1×10 -10 mol / L, 1×10 -9 mol / L, 1×10 - 8 mol / L, 1×10 -7 mol / L, 1×10 -6 mol / L, 1×10 -5 mol / L, 1×10 -4 mol / L, 1×10 -3 mol / L, respectively; Figure 2 The standard curve graph of the photoelectric current change value of the photoelectrochemical sensor based on MIP / MOF / COF hybrid materials in Example 3 for detecting different concentrations of patulin and the logarithmic value of the concentration of patulin in the range of 1×10 -10 mol / L to 1×10 -3 mol / L; Figure 3 The selectivity performance graph of the photoelectrochemical sensor based on MIP / MOF / COF hybrid materials in Example 4 for patulin, wherein the concentration of patulin is 1×10 -9 mol / L, and the concentration of structural analogues (aflatoxin B1 (AFB1), aflatoxin M1 (AFM1), ochratoxin A (OTA) and zearalenone (ZEN)) is 1×10 -9 mol / L; Figure 4 The anti-interference performance graph of the photoelectrochemical sensor based on MIP / MOF / COF hybrid materials in Example 4 for patulin, wherein the concentration of patulin is 1×10 -9 mol / L, and the concentration of structural analogues (aflatoxin B1 (AFB1), aflatoxin M1 (AFM1), ochratoxin A (OTA) and zearalenone (ZEN)) is 1×10 -8 mol / L; Figure 5 The reproducibility performance graph of the photoelectrochemical sensor based on MIP / MOF / COF hybrid materials in Example 5 for detecting patulin, wherein the concentration of patulin is 1×10 -9 mol / L; Figure 6 The stability performance graph of the photoelectrochemical sensor based on MIP / MOF / COF hybrid materials in Example 6 for detecting patulin, wherein the concentration of patulin is 1×10 -9 mol / L; Figure 7 Figure for the adsorption performance of patulin by the MIP / MOF / COF hybrid material and other materials in Example 7; Figure 8 Figure for the degradation performance of patulin by the MIP / MOF / COF hybrid material and other materials in Example 8. DETAILED DESCRIPTION

[0020] In order to further illustrate the technical scheme of the present application, the present application is further illustrated by the following examples. The following examples are only used to illustrate the present application and are not used to limit the scope of the present application. The various reagents, reaction conditions, detection methods, etc. used in the following examples are considered to be the reagents, reaction conditions and detection methods commonly used in the art, unless otherwise specified. Example 1

[0021] The preparation method of the MIP / MOF / COF hybrid material of the present embodiment comprises the following steps: Step 1, preparation of MOF by one-step solvothermal method: first, 2-amino terephthalic acid (H2BDC-NH2) (1.087 g, 6.6 mmol), tetrabutyl titanate (TBT) (1.021 g, 3 mmol), methanol (25 mL) and N,N-dimethylformamide (DMF) (25 mL) were added to a beaker, and the solution was stirred at room temperature for 30 min using a magnetic stirrer, then the solution was placed in a reaction kettle lined with polytetrafluoroethylene and reacted under the condition of heating at 150℃ for 20 h, after the reaction was completed, the suspension was naturally cooled to room temperature, and the suspension was centrifuged at a speed of 4200 r / min for 5 min, the polymer was collected, and the polymer was washed with DMF and methanol three times. Subsequently, the washed polymer was dried under vacuum at 60℃ for 3 h to obtain a yellow powder, i.e. NH2-MIL-125; Step 2, preparation of MOF / COF hybrid material by one-step solvothermal method: 2,3-dihydroxyterephthaldehyde (2,3-Dha) (49.8 mg, 0.3 mmol), 5,10,15,20-tetra(4-aminophenyl)porphyrin (Tph) (101.25 mg, 0.3 mmol), o-dichlorobenzene (o-DBC) (9 mL), n-butanol (9 mL) and aqueous acetic acid (6 M, 1.2 mL) were added into a beaker, and then the mixture was ultrasonically treated for 10 min. Then NH2-MIL-125 (50 mg) synthesized above was added into the mixture and ultrasonically treated for 10 min. Subsequently, the mixture was heated at 120 °C for 72 h. After the reaction, the mixture was naturally cooled to room temperature, and then centrifuged at 4200 r / min for 5 min. The polymer was collected and washed with ethanol for three times. Subsequently, the washed polymer was dried at 60 °C under vacuum for 5 h to obtain a black powder, i.e. NH2-MIL-125 / 2,3-Dha Tph.

[0022] Step 3, preparation of MIP / MOF / COF hybrid material: the virtual template molecule 2-indolone was dispersed in a solution of 6-hydroxy nicotinic acid (Oxindle / 6-HNA) (m / m, 1:1) (5 mg) and 3-aminopropyltriethoxysiloxane (APTES) (0.175 mL) with a volume ratio of 9:1 (3.0 mL). After stirring for 20 min using a magnetic stirrer, tetraethyl orthosilicate (TEOS) (0.5 mL), NH2-MIL-125 / 2,3-Dha Tph (11.25 mg) and aqueous ammonia (2.0 mL) were added into the above mixture, and the reaction was carried out at room temperature using a magnetic stirrer for 12 h. After the reaction, the mixture was centrifuged at 4200 r / min for 5 min, and the polymer was collected and washed with a mixture of acetic acid / methanol (V / V, 2 / 3) by ultrasonic-assisted washing (twice, each for 5 min). Then, the precipitated material was washed with ultrapure water and anhydrous ethanol alternately for four times. Subsequently, the washed polymer was dried at 50 °C under vacuum for 3 h to obtain MIP / NH2-MIL-125 / 2,3-Dha Tph. 乙醇 / 水 Example 2

[0023] The specific process of the photoelectrochemical sensor based on the MIP / MOF / COF hybrid material for detection of patulin is as follows: ​Step 1, 1-2 mg of the prepared MIP / NH2-MIL-125 / 2,3-Dha Tph hybrid material was added to 1-2 mL of the sample to be tested, and incubated at room temperature for 5-30 min to specifically recognize and adsorb the patulin; Step 2, pretreatment, adsorption and photocurrent detection of ITO electrode: the ITO electrode was immersed in anhydrous ethanol and ultrasonically treated for 10-30 min, then washed with ultrapure water and dried, 45 μL of the MIP / NH2-MIL-125 / 2,3-Dha Tph material after incubation in step 2 was dropped onto the surface of the treated ITO electrode and dried to form a film to obtain the working electrode MIP / NH2-MIL-125 / 2,3-Dha Tph / ITO, thereby constructing the photoelectrochemical sensor, and the photocurrent was detected in 0.1 mol / L Na2SO4 solution as the electrolyte, and the detection conditions were: constant potential of 0 V and light irradiation of 400-800 nm. Example 3

[0024] The standard curve of the patulin detected by the photoelectrochemical sensor based on the MIP / MOF / COF hybrid material was established, and the specific steps were as follows: The patulin solutions with concentrations of 0 mol / L, 1×10 -10 mol / L, 1×10 -9 mol / L, 1×10 -8 mol / L, 1×10 -7 mol / L, 1×10 -6 mol / L, 1×10 -5 mol / L, 1×10 -4 mol / L, 1×10 -3 mol / L were sequentially configured, 1 mL of each was taken, and 1 mg of the MIP / MOF / COF hybrid material prepared in Example 1 was added, and the photocurrent of each concentration of patulin was determined according to the method of Example 2. The change value of the photocurrent of the photoelectrochemical sensor was plotted against the logarithmic value of the patulin concentration in the range of 1×10 -10 mol / L to 1×10 -3 mol / L to obtain the standard curve.

[0025] Figure 1 The photocurrent response results of the photoelectrochemical sensor constructed for the patulin solutions with different concentrations showed that as the concentration of patulin gradually increased, more patulin was combined on the MIP / MOF / COF hybrid material, the imprint sites were blocked, the electron transfer on the electrode surface was hindered, and the photocurrent was continuously reduced. For example, Figure 2The constructed sensor showed a good linear relationship between the change value of photocurrent and the logarithm of patulin concentration in the range of 1×10 -10 mol / L to 1×10 -3 mol / L, and the linear equation was ΔI (μA) = 0.0222lgC (mol / L) + 0.2726, with a correlation coefficient R 2 = 0.9972. Example 4

[0026] Experiment on the selectivity and anti-interference performance of the photoelectrochemical sensor based on MIP / MOF / COF hybrid materials to patulin: The photocurrents of 1×10 -9 mol / L patulin solution and 1×10 -9 mol / L solutions of three structural analogues (aflatoxin B1 (AFB1), aflatoxin M1 (AFM1), ochratoxin A (OTA) and zearalenone (ZEN)) were determined by the method of Example 2, and the selectivity of the sensor was studied. The structural analogues of patulin were determined alone, and the results are shown in Figure 3 The change value of photocurrent was significantly different from that when patulin was determined alone. In the experiment, the selectivity of the sensor was evaluated by calculating the imprint factor (IF), which was defined as the ratio of the current response of the imprinted ΔI (MIP) and the non-imprinted ΔI (NIP) electrode (IF = ΔI (MIP) / ΔI (NIP)), where ΔI = I0-I, and I0 and I are the photocurrent responses of the MIP / NH2-MIL-125 / 2,3-Dha Tph / ITO electrode in the presence and absence of the target, respectively. Figure 3 It can be seen that the IF of the sensor to patulin, aflatoxin B1, aflatoxin M1, ochratoxin A and zearalenone was 3.83, 1.16, 1.25, 1.07 and 1.11, respectively, indicating that the sensor had good specific recognition performance to patulin. In the presence of patulin and interferents, the determination results are shown in Figure 4 The change value of photocurrent did not change significantly compared with that when patulin was determined alone, indicating that the constructed photoelectrochemical sensor had good selectivity and anti-interference ability to patulin. Example 5

[0027] Evaluation of the reproducibility of the photoelectrochemical sensor based on MIP / MOF / COF hybrid materials for detecting patulin: Six batches of MIP / NH2-MIL-125 / 2,3-Dha Tph / ITO were prepared by the same method as in Example 2, and the corresponding photoelectrochemical sensors were constructed according to the method of Example 2. Then, the reproducibility of the sensors for detecting 1×10 -9mol / L patulin solution. The results are shown in Fig. 6, which shows that the signal response of the photoelectrochemical sensors constructed in six batches has little difference, indicating that the prepared sensors have good reproducibility. Figure 5 As shown in Fig. 6, the signal response of the photoelectrochemical sensors constructed in six batches has little difference, indicating that the prepared sensors have good reproducibility. Example 6

[0028] Stability evaluation of the photoelectrochemical sensor for detecting patulin based on MIP / MOF / COF hybrid materials: A batch of MIP / NH2-MIL-125 / 2,3-Dha Tph / ITO was prepared under the same conditions, and the prepared sensor was used to detect 1×10 -9 mol / L patulin solution after 20 on / off irradiation cycles lasting for 400 s, and the results are shown in Fig. 9, which shows that the initial photocurrent signal of the photoelectrochemical sensor has little difference from the photocurrent signal at the end, indicating that the prepared sensor has good stability. Figure 6 As shown in Fig. 9, the initial photocurrent signal of the photoelectrochemical sensor has little difference from the photocurrent signal at the end, indicating that the prepared sensor has good stability. Example 7

[0029] Test of the adsorption performance of patulin based on MIP / MOF / COF hybrid materials: Patulin was prepared into a 1000 mg / L stock solution using ultrapure water, and then the stock solution was diluted with ultrapure water to obtain gradient solutions with concentrations of 10 mg / L, 15 mg / L, 30 mg / L and 50 mg / L, respectively. Then 20 mL of each gradient solution was added to 20 mg of MIP / NH2-MIL-125 / 2,3-Dha Tph and other materials (NH2-MIL-125, 2,3-Dha Tph, NH2-MIL-125 / 2,3-Dha Tph), and the mixed solution was magnetically stirred in the dark. Every 15 min, 2 mL of the solution was extracted and centrifuged to remove impurities. The change in absorbance at 276 nm was measured by a UV-visible spectrophotometer to determine the residual concentration of PAT. The results are shown in Fig. 8, which shows that the adsorption capacity of the above four materials in the same time is in the order of NH2-MIL-125>MIP / NH2-MIL-125 / 2,3-Dha Tph>NH2-MIL-125 / 2,3-Dha Tph>2,3-Dha Tph. This is because the adsorption capacity is related to the specific surface area, and the larger the specific surface area, the more adsorption sites are provided, and the stronger the adsorption performance is. Figure 7 As shown in Fig. 8, the adsorption capacity of the above four materials in the same time is in the order of NH2-MIL-125>MIP / NH2-MIL-125 / 2,3-Dha Tph>NH2-MIL-125 / 2,3-Dha Tph>2,3-Dha Tph. This is because the adsorption capacity is related to the specific surface area, and the larger the specific surface area, the more adsorption sites are provided, and the stronger the adsorption performance is. Example 8

[0030] Test of the degradation performance of patulin based on MIP / MOF / COF hybrid materials: A certain mass concentration of patulin solution 20 mL was added to 20 mg of MIP / NH2-MIL-125 / 2,3-Dha Tph and other materials (NH2-MIL-125, 2,3-Dha Tph, NH2-MIL-125 / 2,3-Dha Tph), and then the mixed solution was stirred in the dark environment for 30 min to reach adsorption-desorption equilibrium. Then light was applied, and under continuous light and stirring, 2 mL of solution sample was collected every 15 min, centrifuged to remove impurities, and the absorbance change at 276 nm was determined by ultraviolet visible spectrophotometer. The results are shown in Figure 8 As can be seen from the above, the degradation efficiency of the above materials is in the order of NH2-MIL-125 / 2,3-Dha Tph > MIP / NH2-MIL-125 / 2,3-Dha Tph > 2,3-Dha Tph > NH2-MIL-125. Considering that MIP / NH2-MIL-125 / 2,3-Dha Tph has better selectivity for the target PAT than NH2-MIL-125 / 2,3-Dha Tph, MIP / NH2-MIL-125 / 2,3-Dha Tph hybrid material is finally selected as the photocatalyst for degrading PAT.

[0031] The main features and advantages of the present application are shown and described above, and it is obvious to those skilled in the art that the present application is not limited to the details of the above exemplary embodiments, and can be implemented in other specific forms without departing from the spirit or essential characteristics of the present application. Therefore, the embodiments should be regarded as exemplary and non-limiting, and the scope of the present application is defined by the appended claims rather than the above description, and all changes falling within the meaning and scope of the equivalent elements of the claims are intended to be included in the present application.

[0032] In addition, it should be understood that although the present specification is described in terms of embodiments, not every embodiment contains only one independent technical solution, and the description of the specification is only for the sake of clarity, and those skilled in the art should consider the specification as a whole, and the technical solutions in each embodiment can also be appropriately combined to form other embodiments that those skilled in the art can understand.

Claims

1. A method for preparing a MIP / MOF / COF hybrid material, characterized in that, Comprising the following steps: Step 1, 2-amino terephthalic acid, tetrabutyl titanate, methanol and N, N-dimethylformamide are added into a container, magnetic stirring is used, after stirring is completed, heating reaction is carried out, after reaction is completed, natural cooling to room temperature is carried out, the suspension is centrifuged, the polymer is collected, washing, vacuum drying are carried out again, and NH2-MIL-125 is obtained; Step 2, 2, 3-dihydroxyterephthaldehyde, 5, 10, 15, 20-tetrakis (4-aminophenyl) porphyrin, o-dichlorobenzene, n-butanol and an ice acetic acid aqueous solution are added into a container, ultrasonic treatment is carried out, NH2-MIL-125 is added, ultrasonic treatment is carried out, then heating reaction is carried out, after reaction is completed, natural cooling to room temperature is carried out, the suspension is centrifuged, the polymer is collected, washing, vacuum drying are carried out again, and NH2-MIL-125 / 2, 3-Dha Tph is obtained; Step 3, the virtual template molecule and 3-aminopropyl triethoxysilane are dispersed in a mixed solution of ethanol and water, after magnetic stirring is used, tetraethyl orthosilicate, NH2-MIL-125 / 2, 3-Dha Tph and ammonia water are added into the mixed solution, and reaction is carried out using magnetic stirring, after reaction is completed, the suspension is centrifuged, the polymer is collected, ultrasonic-assisted multiple centrifugal washing is carried out, then the obtained precipitated substance is washed, vacuum dried, and MIP / NH2-MIL-125 / 2, 3-Dha Tph is obtained.

2. The method of claim 1, wherein the MIP / MOF / COF hybrid material is prepared by the steps of: In the step 1, the ratio of 2-amino terephthalic acid, tetrabutyl titanate, methanol and N, N-dimethylformamide is 6.6mmol:3mmol:25mL:25mL; the temperature of heating reaction is 150℃, and the time is 20h; the speed of centrifuging the suspension is 4200r / min, and the time is 5min; the temperature of vacuum drying is 60℃, and the time is 3h.

3. The method of claim 1, wherein the MIP / MOF / COF hybrid material is prepared by the steps of: In the step 2, the ratio of 2, 3-dihydroxyterephthaldehyde, 5, 10, 15, 20-tetrakis (4-aminophenyl) porphyrin, o-dichlorobenzene, n-butanol, an ice acetic acid aqueous solution and NH2-MIL-125 is 0.3mmol:0.3mmol:9mL:9mL:1.2mL:50mg, the concentration of the ice acetic acid aqueous solution is 6M; the temperature of heating reaction is 120℃, and the time is 72h; the speed of centrifuging the suspension is 4200r / min, and the time is 5min; the temperature of vacuum drying is 60℃, and the time is 5h.

4. The method of claim 1, wherein the MIP / MOF / COF hybrid material is prepared by the steps of: In the step 3, the virtual template molecule is a mixture of 2-indole ketone and 6-hydroxy nicotinic acid, and the mass ratio is 1:1; the ratio of the virtual template molecule, 3-aminopropyl triethoxysilane, tetraethyl orthosilicate, NH2-MIL-125 / 2, 3-Dha Tph and ammonia water is 5mg:0.175mL:0.5mL:11.25mg:2.0mL; the time of reaction is 12h; the speed of centrifuging the suspension is 4200r / min, and the time is 10min; the temperature of vacuum drying is 50℃, and the time is 3h.

5. The MIP / MOF / COF hybrid material prepared by the preparation method in any one of claims 1-2.

6. Use of the MIP / MOF / COF hybrid material according to claim 5, characterized in that, A penicillin detection, adsorption and catalytic degradation platform is constructed.

7. Use according to claim 6, characterized in that, The penicillin detection platform is a photoelectrochemical sensor, in particular: The MIP / MOF / COF hybrid material is added to the penicillin sample to be detected, and incubated at room temperature to specifically recognize and adsorb the penicillin. The ITO electrode is immersed in anhydrous ethanol for ultrasonic treatment, then washed with ultrapure water and dried, the hybrid material after incubation in step 1 is dropped on the surface of the treated ITO electrode, and dried to form a film to obtain a working electrode, and then a photoelectrochemical sensor is constructed for photocurrent detection.

8. Use according to claim 6, characterized in that, The penicillin adsorption platform, in particular, the MIP / MOF / COF hybrid material is added to the penicillin solution, the mixed solution is magnetically stirred in the dark, and the solution at different stirring time is taken, centrifuged and measured by ultraviolet spectrophotometer for absorbance change.

9. Use according to claim 6, characterized in that, The penicillin catalytic degradation platform, in particular: The MIP / MOF / COF hybrid material is added to the penicillin solution, the mixed solution is magnetically stirred in the dark to achieve adsorption-desorption equilibrium, and the solution is taken at different light time. After adsorption-desorption equilibrium, continuous light irradiation with magnetic stirring is carried out, the solution at different light time is taken, centrifuged and measured by ultraviolet spectrophotometer for absorbance change.

10. The penicillin detection, adsorption and catalytic degradation platform constructed based on the MIP / MOF / COF hybrid material of claim 5.

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