Application of aminated MIL-101 (Fe) in piezoelectric catalytic degradation of ciprofloxacin

Abstract

The invention discloses an application of aminated MIL-101 (Fe) in piezoelectric catalytic degradation of ciprofloxacin, which comprises the following steps: adding aminated MIL-101 (Fe) into water containing ciprofloxacin, stirring to enable the adsorption of a ciprofloxacin solution to reach equilibrium, and then carrying out ultrasonic treatment. The process is simple, the prepared NH2-MIL-101 (Fe) catalyst has obvious piezoelectric catalysis performance, good stability and excellent catalysis performance, the separation efficiency of photo-induced electron hole pairs can be greatly improved, H2O2 does not need to be additionally added into the catalyst, hydrogen peroxide can be automatically generated through ultrasonic treatment under the piezoelectric catalysis condition, and the catalyst is suitable for industrial production. Then hydrogen peroxide generates singlet oxygen to degrade pollutants, the degradation rate of CIP reaches up to 86.11%, and the cytotoxicity of a degradation product is reduced. In addition, the catalyst disclosed by the invention can be recycled after reaction and is easy to recover, and is a green, non-toxic and pollution-free piezoelectric catalyst.

Description

Technical Field

[0001] The invention relates to the field of environmental pollution control, and in particular to an application of amino MIL-101 (Fe) in piezoelectric catalytic degradation of ciprofloxacin. Background Art

[0002] Ciprofloxacin (CIP), as the most common antibiotic among emerging pollutants, is widely used in various aspects of medical treatment, animal husbandry and aquaculture, causing serious persistent toxicity. In addition, CIP in water can induce bacteria to produce antibiotic resistance genes. As carriers of resistance genes, bacteria migrate along the food chain and ultimately threaten human health. Therefore, it is an urgent problem to study a method to degrade ciprofloxacin to reduce its toxicity. Traditional methods such as adsorption, membrane separation, and biodegradation are time-consuming, inefficient, and involve secondary pollution to remove compound pollution. Piezoelectric catalysis is an emerging and promising advanced oxidation technology that can use mechanical energy such as vibration, friction, natural wind, and tides to achieve clean energy conversion and pollutant treatment. Piezoelectric catalysts with ideal performance are the key to the promotion and application of piezoelectric catalysis technology. However, the limited specific surface area of ​​traditional piezoelectric catalysts and the long transmission distance of charge carriers greatly limit the practical application of piezoelectric catalysis technology.

[0003] Metal-organic frameworks (MOFs) are an emerging class of inorganic-organic composites with periodic structural arrangements that allow active sites to be evenly distributed throughout the framework. Their high porosity ensures good transport of reaction substrates and products throughout the framework, and their piezoelectric properties can be tuned by organic ligands and metal clusters as well as internal host-guest interactions. In addition, MOFs are often produced at low temperatures using simple procedures, which is a huge advantage over traditional oxide-based piezoelectrics / ferroelectrics. MOFs with excellent piezoelectric / ferroelectric properties show great promise in various energy harvesting technologies. The built-in electric field formed by the polarization of piezoelectric / ferroelectric materials serves as an intrinsic driving force for the separation of photoelectrons and holes, which can improve the separation efficiency of charge carriers and enhance catalytic activity. In addition, under the effect of electrostatic screening, the built-in electric field is very easy to exit, resulting in free carrier saturation, thereby reducing the separation efficiency of charge carriers due to polarization. Therefore, driven by mechanical force, the continuous enhancement of the built-in electric field formed by the piezoelectric catalyst will greatly promote the separation of charge carriers.

[0004] The Chinese patent application number 202410382370.X discloses a preparation method and application of a NH2-MIL-101(Fe)-derived Fe-Cu bimetallic catalyst, wherein the prepared bimetallic catalyst not only needs to be calcined at high temperature, and the preparation process is complicated, but also the catalyst needs to be additionally added with H2O2 when degrading CIP, and the degradation efficiency increases with the increase of the amount of H2O2 added, as described in paragraph

[0033] of the specification, "When studying the effect of H2O2 concentration ( Figure 3 ), and found that when the concentration increased from 0.05mM to 3mM, the CIP degradation efficiency increased significantly, from 61.5% to 93.8%. " Summary of the invention

[0005] In order to reduce the toxicity of ciprofloxacin and overcome the shortcomings and deficiencies of the above-mentioned prior art, the object of the present invention is to provide an application of amino MIL-101 (Fe) in piezoelectric catalytic degradation of ciprofloxacin.

[0006] The technical solution of the present invention is as follows: The application of aminated MIL-101(Fe) in the piezoelectric catalytic degradation of ciprofloxacin is as follows: the aminated MIL-101(Fe) is added to water containing ciprofloxacin, stirred to allow the adsorption of the ciprofloxacin solution to reach equilibrium, and then subjected to ultrasonic treatment.

[0007] Preferably, the power of the ultrasonic treatment is above 80 W, and the treatment time is above 45 min.

[0008] Preferably, the power of the ultrasonic treatment is 80-100 W, and the treatment time is more than 60 min.

[0009] Preferably, the concentration of the amino MIL-101(Fe) in water is 0.05-0.4 g / L.

[0010] Preferably, the concentration of the amino-MIL-101(Fe) in water is 0.2 g / L.

[0011] Preferably, the preparation method of aminated MIL-101(Fe) is as follows: ferric chloride hexahydrate and aminoterephthalic acid are dissolved in N,N-dimethylformamide to form a mixed solution, stirred evenly, subjected to hydrothermal reaction, cooled, washed and dried to obtain NH2-MIL-101(Fe).

[0012] Preferably, the molar ratio of the ferric chloride hexahydrate to aminoterephthalic acid is 2:1.

[0013] Preferably, the temperature of the hydrothermal reaction is 110±10° C. and the time is 20±2 h.

[0014] Preferably, the stirring time before the hydrothermal reaction is 60±30 minutes; the drying temperature is 60±20° C. and the drying time is 12±6 hours.

[0015] Preferably, the concentration of the NH2-MIL-101(Fe) catalyst in water is 0.5-1.0 g / L; and the power of the ultrasonic treatment is 20-100W.

[0016] Preferably, the ultrasonic treatment uses an ultrasonic cleaning machine.

[0017] The present invention utilizes -NH2 groups to modify MIL-101(Fe) to obtain NH2-MIL-101(Fe). In view of the excellent piezoelectric catalytic performance of NH2-MIL-101(Fe), under ultrasonic conditions, the continuous enhancement of the built-in electric field formed by NH2-MIL-101(Fe) will greatly promote the separation of charge carriers and the generation of hydrogen peroxide. The hydrogen peroxide then generates singlet oxygen to degrade ciprofloxacin, and the cytotoxicity of the degradation product is reduced.

[0018] Compared with the prior art, the present invention has the following advantages and beneficial effects: (1) The process of the present invention is simple. The prepared NH2-MIL-101(Fe) catalyst has obvious piezoelectric catalytic performance, good stability and excellent catalytic performance, which can greatly improve the separation efficiency of photogenerated electron-hole pairs. The catalyst does not need to add H2O2. Under piezoelectric catalytic conditions, ultrasonic treatment can generate hydrogen peroxide by itself, and then hydrogen peroxide generates singlet oxygen to degrade pollutants. The degradation rate of CIP is as high as 86.11%. At the same time, when a small amount of H2O2 (30μM) is added to the catalyst, the degradation rate of CIP can be increased to 99.77%.

[0019] (2) The catalyst of the present invention can not only greatly improve the efficiency of removing ciprofloxacin wastewater from water bodies but also reduce the cytotoxicity of degradation products; in addition, the catalyst of the present invention can be recycled and easily recovered after the reaction, and is a green, non-toxic and pollution-free piezoelectric catalyst. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] Figure 1 These are the SEM and FTIR images of NH2-MIL-101(Fe) prepared in Example 1 of the present invention.

[0022] Figure 2 This is a diagram showing the effect of piezoelectric catalysis of ciprofloxacin removal by NH2-MIL-101 (Fe) of different concentrations in Example 2 of the present invention.

[0023] Figure 3 This is a diagram showing the effect of piezoelectric catalysis of different samples in Example 3 of the present invention on the removal of ciprofloxacin.

[0024] Figure 4 This is a diagram showing the effect of piezoelectric catalysis of ciprofloxacin removal by NH2-MIL-101(Fe) at different ultrasonic powers in Example 4 of the present invention.

[0025] Figure 5 A diagram showing the removal effect of ciprofloxacin after adding hydrogen peroxide or a hydrogen peroxide quencher to NH2-MIL-101(Fe) piezoelectric catalysis in Example 5 of the present invention.

[0026] Figure 6 A test chart of the hydrogen peroxide content during the piezoelectric catalytic removal of ciprofloxacin by NH2-MIL-101(Fe) in Example 6 of the present invention.

[0027] Figure 7 This is a diagram of the quenching experiment of active species in the process of piezoelectric catalysis of ciprofloxacin removal by NH2-MIL-101(Fe) in Example 7 of the present invention.

[0028] Figure 8 This is a diagram showing the effect of piezoelectric catalytic removal of ciprofloxacin in real wastewater by NH2-MIL-101(Fe) in Example 8 of the present invention.

[0029] Fig. 9 This is a test diagram of the cycle performance of NH2-MIL-101 (Fe) piezoelectric catalysis for removing ciprofloxacin in Example 9 of the present invention.

[0030] Fig.10 This is a graph showing the toxicity study of the CCK-8 intermediate product of ciprofloxacin removed by piezoelectric catalysis by NH2-MIL-101(Fe) in Example 10 of the present invention.

[0031] Fig.11 This is a graph showing the toxicity study of the colony-forming intermediate product of ciprofloxacin removed by piezoelectric catalysis by NH2-MIL-101(Fe) in Example 11 of the present invention. DETAILED DESCRIPTION

[0032] The present invention is further described in detail below in conjunction with embodiments and drawings, but the embodiments of the present invention are not limited thereto.

[0033] Unless otherwise specified, the reagents used in the examples can be purchased from the market.

[0034] Example 1 This example provides a method for preparing NH2-MIL-101 (Fe) catalyst, and the specific steps are as follows: First, according to the reference (DOI: 10.1007 / s13738-019-01647-w), 0.670 g of ferric chloride hexahydrate and 0.226 g of aminoterephthalic acid were weighed and dissolved in 20 mL of N,N-dimethylformamide. After stirring for 60 minutes, the solution was transferred to the reactor and reacted at 120 °C for 20 hours. After the reactor was cooled to room temperature, the reactants were washed three times with 70 °C N,N-dimethylformamide and dried at 60 °C for 12 hours to finally obtain the product NH2-MIL-101(Fe).

[0035] The SEM and FTIR images of the NH2-MIL-101(Fe) catalyst prepared in the embodiment of the present invention are as follows: Figure 1 It is shown that the method described in the example successfully prepared NH2-MIL-101(Fe).

[0036] The application comprises the following steps: 1) Add NH2-MIL-101(Fe) catalyst into 30 mL, 5 mg / L ciprofloxacin solution and stir; the concentration of NH2-MIL-101(Fe) catalyst in water is 0.05-0.4 g / L; 2) subjecting the water to be treated obtained in step 1) to ultrasonic treatment; the power of the ultrasonic treatment is 20-100 W; 3) The water to be treated obtained in step 1) and the treated water obtained in step 2) are subjected to cell poisoning treatment; the cells are Hep-G2 cells.

[0037] Example 2 In this example, NH2-MIL-101(Fe) prepared in Example 1 was used, ciprofloxacin was selected as a representative of pollutants, and experiments were conducted on the piezoelectric catalytic removal of ciprofloxacin by NH2-MIL-101(Fe) of different concentrations.

[0038] The experimental steps are as follows: Prepare 30 mL of 5 mg / L ciprofloxacin solution in a beaker. Weigh 1.5, 3, 6, and 12 mg of NH2-MIL-101(Fe) powder respectively and add them to the ciprofloxacin solution. Stir for 30 min to allow the adsorption of the ciprofloxacin solution to reach equilibrium. Place the mixed solution in an ultrasonic cleaner to start the reaction.

[0039] The effect of different concentrations of NH2-MIL-101 (Fe) piezoelectric catalysis on the removal of ciprofloxacin in the embodiment of the present invention is shown in the figure. Figure 2As shown in the figure, as the concentration of NH2-MIL-101 (Fe) increases, the removal efficiency of ciprofloxacin is also increasing. When the concentration of NH2-MIL-101 (Fe) reaches 0.2 g / L, the removal efficiency of ciprofloxacin is 86.11%, and when the concentration of NH2-MIL-101 (Fe) reaches 0.4 g / L, the removal efficiency of ciprofloxacin is 81.35%. It may be that after the concentration of the catalyst reaches a certain level, the particles aggregate, the reaction area of ​​the catalyst surface decreases, and the degradation rate decreases. This result verifies that the preferred concentration of NH2-MIL-101 (Fe) for removing ciprofloxacin in the present invention is 0.2 g / L.

[0040] Example 3 In this example, NH2-MIL-101(Fe) prepared in Example 1 was used, ciprofloxacin was selected as a representative of pollutants, and experiments were conducted on the piezoelectric catalytic removal of ciprofloxacin by NH2-MIL-101(Fe) at different times.

[0041] The experimental steps are as follows: Prepare 30 mL of 50 mg / L ciprofloxacin solution in a beaker. Weigh 20 mg of NH2-MIL-101(Fe) powder and add it to the ciprofloxacin solution. Stir for 30 min to allow the adsorption of the ciprofloxacin solution to reach equilibrium. Place the mixed solution in an ultrasonic cleaner and start the reaction by ultrasound. The concentration of NH2-MIL-101(Fe) is 0.2 g / L.

[0042] The effect of NH2-MIL-101 (Fe) piezoelectric catalysis in removing ciprofloxacin in the present invention is as follows: Figure 3 As shown in the figure, it can be seen that NH2-MIL-101(Fe) has adsorption on ciprofloxacin, and the adsorption is 30% within 30 minutes. With ultrasound alone, almost no ciprofloxacin is reduced within 60 minutes. MIL-101(Fe) and NH2-MIL-101(Fe) can remove 43.57% and 47.79% of ciprofloxacin respectively within 60 minutes by stirring alone. MIL-101(Fe) piezoelectric catalysis can remove 57.21% of ciprofloxacin within 60 minutes. In contrast, NH2-MIL-101(Fe) piezoelectric catalysis shows excellent effect on the reduction and removal of ciprofloxacin, and the removal rate reaches 86.11% within 60 minutes. The results show that NH2-MIL-101(Fe) has excellent carrier separation efficiency and can significantly improve the reduction and removal efficiency of ciprofloxacin.

[0043] Example 4 In this example, NH2-MIL-101(Fe) prepared in Example 1 was used, ciprofloxacin was selected as a representative of pollutants, and an experiment on the piezoelectric catalytic removal of ciprofloxacin by NH2-MIL-101(Fe) under different ultrasonic powers was conducted.

[0044] The experimental steps are as follows: Prepare 30 mL of 5 mg / L ciprofloxacin solution in a beaker. Weigh 6 mg of NH2-MIL-101(Fe) powder and add it to the ciprofloxacin solution. Stir for 30 min to allow the adsorption of the ciprofloxacin solution to reach equilibrium. Place the mixed solution in an ultrasonic cleaner and adjust the power of the ultrasonic cleaner to 20, 40, 60, 80 and 100 W to start the reaction. The concentration of NH2-MIL-101(Fe) is 0.2 g / L.

[0045] The effect of NH2-MIL-101(Fe) piezoelectric catalysis on the removal of ciprofloxacin under different ultrasonic powers in the examples of the present invention is as follows: Figure 4 As shown, with the continuous increase of ultrasonic power, the performance of NH2-MIL-101 (Fe) piezoelectric catalytic removal of ciprofloxacin is also continuously improved. When the ultrasonic power is increased to 100 W, the removal efficiency of ciprofloxacin is 86.11%, so it is verified that the preferred power of the ultrasonic cleaning machine for removing ciprofloxacin by NH2-MIL-101 (Fe) in the present invention is 100 W.

[0046] Example 5 In this example, NH2-MIL-101(Fe) prepared in Example 1 was used, and ciprofloxacin was selected as a representative of the pollutants to conduct experiments.

[0047] The experimental steps are as follows: Prepare 30 mL of 5 mg / L ciprofloxacin solution in a beaker. Add 6 mg of NH2-MIL-101(Fe) powder and hydrogen peroxide or hydrogen peroxide quencher (catalase) to the ciprofloxacin solution and stir for 30 minutes to allow the adsorption of the ciprofloxacin solution to reach equilibrium. Place the mixed solution in an ultrasonic cleaner and treat it under 100 W ultrasound for 60 minutes.

[0048] Figure 5 This is a diagram of the removal effect of ciprofloxacin after adding hydrogen peroxide or hydrogen peroxide quencher to NH2-MIL-101 (Fe) piezoelectric catalysis in the embodiment of the present invention. The experiment shows that the introduction of catalase (CAT) has a strong inhibitory effect on CIP degradation, while the additional addition of 30μM hydrogen peroxide promotes CIP degradation. The removal rate of CIP reached 99.77% within 60 minutes, indicating that hydrogen peroxide plays a promoting role in the piezoelectric catalytic degradation of ciprofloxacin.

[0049] Example 6 In this example, NH2-MIL-101(Fe) prepared in Example 1 was used, and ciprofloxacin was selected as a representative of pollutants to test the hydrogen peroxide content in the process of piezoelectric catalytic removal of ciprofloxacin.

[0050] The experimental steps are as follows: Prepare 30 mL of 5 mg / L ciprofloxacin solution in a beaker. Weigh 6 mg of NH2-MIL-101(Fe) powder and add it to the ciprofloxacin solution. Stir for 30 min to allow the adsorption of the ciprofloxacin solution to reach equilibrium. Place the mixed solution in an ultrasonic cleaner and treat it under 100 W ultrasound for 60 min. Take samples at the corresponding time points to determine the hydrogen peroxide content.

[0051] Figure 6 This is a test diagram of the hydrogen peroxide content in the process of removing ciprofloxacin by piezoelectric catalysis of NH2-MIL-101(Fe) in the embodiment of the present invention. The experiment shows that under ultrasonic conditions, the amount of hydrogen peroxide generated by NH2-MIL-101(Fe) in water is the highest. The presence of NH2-MIL-101(Fe) significantly increases the production of hydrogen peroxide, which may be due to the amino group promoting the production of hydrogen peroxide. The amount of hydrogen peroxide generated by NH2-MIL-101(Fe) in the ciprofloxacin solution is relatively low, which may be due to the fact that CIP consumes a certain amount of hydrogen peroxide during the degradation process.

[0052] Example 7 In this example, NH2-MIL-101(Fe) prepared in Example 1 was used, and ciprofloxacin was selected as a representative of pollutants to conduct an active species quenching experiment.

[0053] The experimental steps are as follows: Prepare 30 mL of 5 mg / L ciprofloxacin solution in a beaker. Weigh 6 mg of NH2-MIL-101(Fe) powder and quenchers (ammonium oxalate, furfuryl alcohol, silver nitrate, isopropanol and p-benzoquinone) and add them to the ciprofloxacin solution. Stir for 30 minutes to allow the adsorption of the ciprofloxacin solution to reach equilibrium. Place the mixed solution in an ultrasonic cleaner and treat it under 100 W ultrasound for 60 minutes.

[0054] Figure 7 This is a diagram of the quenching experiment of active species in the process of piezoelectric catalytic removal of ciprofloxacin by NH2-MIL-101(Fe) in the embodiment of the present invention. The experiment shows that singlet oxygen plays a major role in the process of piezoelectric catalytic degradation of ciprofloxacin by NH2-MIL-101(Fe).

[0055] Example 8 This example uses the NH2-MIL-101(Fe) prepared in Example 1, selects ciprofloxacin as a representative of pollutants, and conducts an experiment on the piezoelectric catalytic removal of ciprofloxacin in real water using NH2-MIL-101(Fe).

[0056] The experimental steps are as follows: Prepare 30 mL of 5 mg / L ciprofloxacin solution in 5 beakers with deionized water, tap water, lake water, rainwater and seawater. Weigh 5 portions of 6 mg NH2-MIL-101(Fe) powder and add them to the ciprofloxacin solution. Stir for 30 min to allow the adsorption of ciprofloxacin to reach equilibrium and start the reaction. The concentration of NH2-MIL-101(Fe) is 0.2 g / L.

[0057] Figure 8 This is a diagram showing the effect of piezoelectric catalytic removal of ciprofloxacin by NH2-MIL-101(Fe) in real water bodies in an embodiment of the present invention. Experiments show that ciprofloxacin can be effectively removed from deionized water, tap water, lake water, rainwater and seawater in 60 minutes. This example shows that NH2-MIL-101(Fe) can efficiently remove ciprofloxacin by piezoelectric catalysis in different water environments, which provides a feasible solution for industrial control of ciprofloxacin pollution.

[0058] Example 9 In this example, NH2-MIL-101(Fe) prepared in Example 1 was used, and ciprofloxacin was selected as a representative of pollutants to conduct an experiment on catalyst recycling.

[0059] The experimental steps are as follows: Prepare 30 mL of 5 mg / L ciprofloxacin solution in a beaker. Weigh 6 mg of NH2-MIL-101(Fe) powder and add it to the ciprofloxacin solution. Stir until the adsorption of the ciprofloxacin solution reaches equilibrium. Place the mixed solution in an ultrasonic cleaner and treat it under 100 W ultrasound for 60 min. After the reaction is completed, use a suction filtration device to recover the catalyst from the remaining solution, then add the catalyst to a 30 mL beaker of 5 mg / L ciprofloxacin solution, and repeat the above ciprofloxacin removal steps. Repeat this experiment five times.

[0060] Fig. 9 This is a rendering of the recycling of the catalyst in the piezoelectric catalytic removal of ciprofloxacin by NH2-MIL-101(Fe) in an embodiment of the present invention. The experiment shows that after NH2-MIL-101(Fe) has been recycled for five times, the removal efficiency of ciprofloxacin in 60 minutes has dropped from 86.11% to 79.76%, and the performance has only decreased by about 7%. This example shows that the piezoelectric catalytic removal of ciprofloxacin by NH2-MIL-101(Fe) has recyclability and property stability in practical applications.

[0061] Example 10 In this example, NH2-MIL-101(Fe) prepared in Example 1 was used, and ciprofloxacin was selected as a representative of pollutants to conduct a CCK-8 cytotoxicity experiment.

[0062] The experimental steps are as follows: Hep-G2 cells in the logarithmic growth phase were seeded in a 96-well plate (5000 cells / well) for 24 hours, and then infected with the solutions before and after the reaction and cultured for 48 hours. 10μl of CCK-8 solution was added to each well, and the culture plate was gently shaken to help mix. The culture plate was placed in an incubator and incubated for 1-4 hours, and the absorbance (OD) at 450 nm was measured with a microplate reader.

[0063] Fig.10 This is a diagram showing the toxicity effect of the NH2-MIL-101 (Fe) piezoelectric catalytic removal of the intermediate product CCK-8 of ciprofloxacin in an embodiment of the present invention. The experiment shows that the cell viability of the solution culture before the reaction is low, while the cell viability of the solution culture after the reaction is high. This example shows that the toxicity of the intermediate product to the cells after the reaction is reduced.

[0064] Embodiment 11 In this example, NH2-MIL-101(Fe) prepared in Example 1 was used, and ciprofloxacin was selected as a representative of pollutants to conduct a cytotoxicity experiment on colony formation.

[0065] The experimental steps are as follows: Collect the cells in the logarithmic growth phase of the subculture, add the culture medium to make a cell suspension; inoculate the cells in a 6-well plate at a cell density of 200-400 cells / well per well, place the 6-well plate in a cell culture incubator at 37°C and 5% CO2 for 24 hours, and then add the drug after the cells adhere to the wall. Add 2 mL of the drug before and after the reaction for an appropriate time, set up 3 replicates for each group, and set up a blank control, and place it in a cell culture incubator at 37°C and 5% CO2 for culture. After that, replace the medium containing the drug before and after the reaction every 2 days, and continue to culture in the cell incubator for 10 days. When the time is up, wash it twice with cold PBS solution, fix it with 4% paraformaldehyde for 15-30 min, wash it twice with cold PBS after fixation, and then stain it with crystal violet stain.

[0066] Fig.11 This is a toxicity study effect diagram of the colony formation experiment of NH2-MIL-101 (Fe) piezoelectric catalysis to remove the intermediate product of ciprofloxacin in the embodiment of the present invention. The experiment shows that the cell colonies cultured in the solution before the reaction are relatively small, while the cell colonies cultured in the solution after the reaction are relatively large, indicating that the toxicity of the intermediate product to the cells after the reaction is reduced.

[0067] The above embodiments are preferred implementation modes of the present invention, but the implementation modes of the present invention are not limited to the above embodiments. Any other changes, modifications, substitutions, combinations, and simplifications that do not deviate from the spirit and principles of the present invention should be equivalent replacement methods and are included in the protection scope of the present invention.

Claims

1. Application of amino-modified MIL-101(Fe) in piezoelectric catalytic degradation of ciprofloxacin.

2. The use according to claim 1, characterized in that: The aminated MIL-101(Fe) was added to water containing ciprofloxacin, stirred to allow the adsorption of the ciprofloxacin solution to reach equilibrium, and then subjected to ultrasonic treatment.

3. The use according to claim 2, characterized in that: The power of the ultrasonic treatment is above 80 W, and the treatment time is above 45 min.

4. The use according to claim 3, characterized in that: The power of the ultrasonic treatment is 80-100 W, and the treatment time is more than 60 min.

5. The use according to claim 3, characterized in that: The concentration of the amino MIL-101 (Fe) in water is 0.05-0.4 g / L.

6. The use according to claim 5, characterized in that: The concentration of the amino-modified MIL-101(Fe) in water is 0.2 g / L.

7. The use according to any one of claims 1 to 6, characterized in that: The preparation method of aminated MIL-101 (Fe) is as follows: ferric chloride hexahydrate and aminoterephthalic acid are dissolved in N, N-dimethylformamide to form a mixed solution, and after stirring evenly, a hydrothermal reaction is carried out, and the solution is cooled, washed and dried to obtain NH2-MIL-101 (Fe).

8. The use according to claim 7, characterized in that: The molar ratio of the ferric chloride hexahydrate to aminoterephthalic acid is 2:

1.

9. The use according to claim 8, characterized in that: The temperature of the hydrothermal reaction is 110±10° C. and the time is 20±2 h.

10. The use according to claim 9, characterized in that: The stirring time before the hydrothermal reaction is 60±30 minutes; the drying temperature is 60±20° C. and the drying time is 12±6 hours.

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