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

Abstract

The application discloses application of aminated MIL-101(Fe) in piezoelectric catalytic degradation of ciprofloxacin, and the aminated MIL-101(Fe) is added into water containing ciprofloxacin, stirring is carried out to make adsorption of the ciprofloxacin solution reach equilibrium, and then ultrasonic treatment is carried out.The process is simple, the prepared NH2-MIL-101(Fe) catalyst has obvious piezoelectric catalytic performance, good stability and excellent catalytic performance, can greatly improve separation efficiency of photo-generated electron-hole pairs, the catalyst does not need to add H2O2 additionally, hydrogen peroxide can be generated under piezoelectric catalytic conditions through ultrasonic treatment, then the hydrogen peroxide generates singlet oxygen to degrade pollutants, the degradation rate of CIP is as high as 86.11%, and cytotoxicity of degradation products is reduced.In addition, the catalyst 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] This invention relates to the field of environmental pollution control, and in particular to the application of an aminated MIL-101(Fe) piezoelectric catalytic degradation of ciprofloxacin. Background Technology

[0002] Ciprofloxacin (CIP), one of the most common antibiotics among emerging pollutants, is widely used in various aspects of medicine, animal husbandry, and aquaculture, causing serious and persistent toxicity. Furthermore, CIP in water can induce bacteria to produce antibiotic resistance genes, which, acting as carriers of these genes, migrate along the food chain, ultimately threatening human health. Therefore, researching methods to degrade ciprofloxacin and reduce its toxicity is an urgent problem to be solved. Traditional methods for removing compound pollutants, such as adsorption, membrane separation, and biodegradation, are time-consuming, inefficient, and involve secondary pollution. Piezoelectric catalysis, on the other hand, is a promising emerging advanced oxidation technology that can utilize mechanical energy such as vibration, friction, natural wind, and tides to achieve clean energy conversion and pollutant treatment. Ideal piezoelectric catalysts are key to the widespread application of piezoelectric catalysis technology. However, the limited specific surface area and long charge carrier transport distance of traditional piezoelectric catalysts greatly limit the practical application of piezoelectric catalysis technology.

[0003] Metal-organic frameworks (MOFs) are an emerging type of inorganic-organic composite material with a periodic structural arrangement that allows active sites to be uniformly distributed throughout the framework. Their high porosity ensures good transport of reaction substrates and products within the framework, and their piezoelectric properties can be tuned through organic ligands and metal clusters, as well as internal host-guest interactions. Furthermore, MOFs are often produced at low temperatures using simple processes, offering a significant advantage over traditional oxide-based piezoelectrics / ferroelectrics. MOFs, with their superior piezoelectric / ferroelectric properties, show great promise in various energy harvesting technologies. The built-in electric field formed by the polarization of electroelectric / ferroelectric materials acts as an intrinsic driving force for the separation of photoelectrons and holes, improving carrier separation efficiency and enhancing catalytic activity. However, under electrostatic shielding, the built-in electric field easily dissipates, leading to free carrier saturation and reducing the polarization-based carrier separation efficiency. Therefore, the continuous enhancement of the built-in electric field formed by the piezoelectric catalyst under mechanical force will greatly promote charge carrier separation.

[0004] Chinese Patent Application No. 202410382370.X discloses a method for preparing and applying an NH2-MIL-101(Fe)-derived Fe-Cu bimetallic catalyst. The prepared bimetallic catalyst not only requires high-temperature calcination, making the preparation process complex, but also requires the addition of H2O2 during CIP degradation, and the degradation efficiency increases with the amount of H2O2 added. As stated in paragraph

[0033] of the specification, "When studying the effect of H2O2 concentration (… Figure 3 The study found that increasing the concentration from 0.05 mM to 3 mM significantly improved the CIP degradation efficiency, raising it 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 prior art, the present invention aims to provide an application of aminated MIL-101(Fe) piezoelectric catalytic degradation of ciprofloxacin.

[0006] The technical solution of the present invention is as follows:

[0007] The application of ammoniated MIL-101(Fe) piezoelectric catalytic degradation of ciprofloxacin involves adding ammoniated MIL-101(Fe) to water containing ciprofloxacin, stirring to allow the adsorption of the ciprofloxacin solution to reach equilibrium, and then subjecting it to ultrasonic treatment.

[0008] Preferably, the ultrasonic treatment has a power of 80 W or more and a treatment time of 45 min or more.

[0009] Preferably, the ultrasonic treatment power is 80~100 W and the treatment time is 60 minutes or more.

[0010] Preferably, the concentration of the aminated MIL-101(Fe) in water is 0.05~0.4 g / L.

[0011] Preferably, the concentration of the aminated MIL-101(Fe) in water is 0.2 g / L.

[0012] 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. After stirring evenly, a hydrothermal reaction is carried out, followed by cooling, washing, and drying to obtain NH2-MIL-101(Fe).

[0013] Preferably, the molar ratio of ferric chloride hexahydrate to aminoterephthalic acid is 2:1.

[0014] Preferably, the hydrothermal reaction is carried out at a temperature of 110±10℃ for a time of 20±2h.

[0015] Preferably, the stirring time before the hydrothermal reaction is 60±30 minutes; the drying temperature is 60±20℃ and the time is 12±6h.

[0016] 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.

[0017] Preferably, the ultrasonic treatment uses an ultrasonic cleaner.

[0018] This invention utilizes the -NH2 group to modify MIL-101(Fe) to obtain NH2-MIL-101(Fe). Taking advantage 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 promote the generation of hydrogen peroxide. The hydrogen peroxide then generates singlet oxygen to degrade ciprofloxacin and reduces the cytotoxicity of the degradation products.

[0019] Compared with the prior art, the present invention has the following advantages and beneficial effects:

[0020] (1) The process of this invention is simple, and the NH2-MIL-101(Fe) catalyst prepared has obvious piezoelectric catalytic performance, good stability and excellent catalytic performance, which can greatly improve the separation efficiency of photogenerated electron-hole pairs. This catalyst does not require the addition of H2O2. Under piezoelectric catalytic conditions, ultrasonic treatment can generate hydrogen peroxide on its own, and then the 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, the degradation rate of CIP can be increased to 99.77%.

[0021] (2) The catalyst of the present invention can not only greatly improve the efficiency of ciprofloxacin removal from water bodies, but also reduce the cytotoxicity of degradation products; in addition, the catalyst of the present invention can be recycled and is easy to recover after the reaction, and is a green, non-toxic and pollution-free piezoelectric catalyst. Attached Figure Description

[0022] Figure 1 These are the SEM and FTIR images of NH2-MIL-101(Fe) prepared in Example 1 of this invention.

[0023] Figure 2 This is a graph showing the effect of piezoelectric catalysis of NH2-MIL-101(Fe) at different concentrations in Example 2 of the present invention to remove ciprofloxacin.

[0024] Figure 3 This is a graph showing the effect of piezoelectric catalysis on the removal of hexacycloprofloxacin from different samples in Example 3 of the present invention.

[0025] Figure 4 This is a graph showing the effect of NH2-MIL-101(Fe) piezoelectric catalysis on the removal of ciprofloxacin under different ultrasonic powers in Example 4 of the present invention.

[0026] Figure 5 The effect of ciprofloxacin removal after adding hydrogen peroxide or hydrogen peroxide quencher to NH2-MIL-101(Fe) piezoelectric catalysis in Example 5 of this invention is shown in the figure.

[0027] Figure 6 The test diagram of hydrogen peroxide content during the NH2-MIL-101(Fe) piezoelectric catalytic removal of ciprofloxacin in Example 6 of this invention.

[0028] Figure 7 This is an experimental diagram of the quenching of active species during the piezoelectric catalytic removal of ciprofloxacin by NH2-MIL-101(Fe) in Example 7 of the present invention.

[0029] Figure 8 This is a diagram showing the effect of NH2-MIL-101(Fe) in the piezoelectric catalytic removal of ciprofloxacin in real wastewater in Example 8 of this invention.

[0030] Figure 9 This is a cycle performance test diagram of NH2-MIL-101(Fe) piezoelectric catalysis for the removal of ciprofloxacin in Example 9 of the present invention.

[0031] Figure 10 This is a toxicity study diagram of the CCK-8 intermediate product for the piezoelectric catalytic removal of ciprofloxacin by NH2-MIL-101(Fe) in Example 10 of this invention.

[0032] Figure 11 This is a graph showing the toxicity study of the colony-forming intermediate products of ciprofloxacin removal by NH2-MIL-101(Fe) piezoelectric catalysis in Example 11 of this invention. Detailed Implementation

[0033] The present invention will be further described in detail below with reference to the embodiments and accompanying drawings, but the embodiments of the present invention are not limited thereto.

[0034] Unless otherwise specified, all reagents used in the examples are commercially available.

[0035] Example 1

[0036] This example provides a method for preparing NH2-MIL-101(Fe) catalyst, and the specific steps are as follows:

[0037] First, following the instructions in 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 a reaction vessel and reacted at 120 °C for 20 hours. Then, after the reaction vessel cooled to room temperature, the reactants were washed three times with N,N-dimethylformamide at 70 °C and dried at 60 °C for 12 hours to finally obtain the product NH2-MIL-101(Fe).

[0038] The SEM and FTIR images of the NH2-MIL-101(Fe) catalyst prepared in the embodiments of the present invention are as follows: Figure 1 As shown in the figure. This demonstrates that the method described in the examples successfully prepared NH2-MIL-101(Fe).

[0039] The application includes the following steps:

[0040] 1) Add the NH2-MIL-101(Fe) catalyst to 30 mL of 5 mg / L ciprofloxacin solution and stir; the concentration of the NH2-MIL-101(Fe) catalyst in water is 0.05~0.4 g / L;

[0041] 2) The water to be treated obtained in step 1) is subjected to ultrasonic treatment; the power of the ultrasonic treatment is 20~100 W;

[0042] 3) The water to be treated obtained in step 1) and the water to be treated obtained in step 2) are subjected to cell poisoning treatment; the cells are Hep-G2 cells.

[0043] Example 2

[0044] In this embodiment, NH2-MIL-101(Fe) prepared in Example 1 was used, and ciprofloxacin was selected as a representative pollutant to conduct experiments on the piezoelectric catalytic removal of ciprofloxacin by NH2-MIL-101(Fe) at different concentrations.

[0045] The experimental steps are as follows:

[0046] Prepare 30 mL of a 5 mg / L ciprofloxacin solution in a beaker. Weigh out 1.5, 3, 6, and 12 mg of NH2-MIL-101(Fe) powder and add them to the ciprofloxacin solution, stirring for 30 min to allow the adsorption of ciprofloxacin to reach equilibrium. Place the mixture in an ultrasonic cleaner and initiate the ultrasonic reaction.

[0047] The effect of different concentrations of NH2-MIL-101(Fe) piezoelectric catalysis on the removal of ciprofloxacin in the embodiments of the present invention are shown in the figure. Figure 2As shown in the figure, the removal efficiency of ciprofloxacin increases with the continuous increase of NH2-MIL-101(Fe) concentration. When the NH2-MIL-101(Fe) concentration reaches 0.2 g / L, the removal efficiency of ciprofloxacin is 86.11%, while when the NH2-MIL-101(Fe) concentration reaches 0.4 g / L, the removal efficiency of ciprofloxacin is 81.35%. This may be because when the catalyst concentration reaches a certain level, particles aggregate, reducing the catalyst surface reaction area and leading to a decrease in degradation rate. This result verifies that the preferred concentration of NH2-MIL-101(Fe) for removing ciprofloxacin in this invention is 0.2 g / L.

[0048] Example 3

[0049] In this embodiment, NH2-MIL-101(Fe) prepared in Example 1 was used, and ciprofloxacin was selected as a representative pollutant. Experiments were conducted on the piezoelectric catalytic removal of ciprofloxacin by NH2-MIL-101(Fe) at different times.

[0050] The experimental steps are as follows:

[0051] Prepare 30 mL of a 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 ciprofloxacin to reach equilibrium. Place the mixture in an ultrasonic cleaner and initiate the ultrasonic reaction. The concentration of NH2-MIL-101(Fe) is 0.2 g / L.

[0052] The effect of NH2-MIL-101(Fe) piezoelectric catalysis on the removal of ciprofloxacin in the examples of this invention is as follows: Figure 3 As shown in the figure, NH2-MIL-101(Fe) adsorbs ciprofloxacin, reaching 30% adsorption within 30 minutes. Ultrasonication alone resulted in almost no reduction of ciprofloxacin within 60 minutes. Stirring MIL-101(Fe) and NH2-MIL-101(Fe) alone removed 43.57% and 47.79% of ciprofloxacin, respectively, within 60 minutes. Piezoelectric catalysis with MIL-101(Fe) removed 57.21% of ciprofloxacin within 60 minutes. In comparison, NH2-MIL-101(Fe) piezoelectric catalysis showed superior reduction and removal of ciprofloxacin, achieving a removal rate of 86.11% within 60 minutes. These results indicate that NH2-MIL-101(Fe) possesses excellent carrier separation efficiency and can significantly improve the reduction and removal efficiency of ciprofloxacin.

[0053] Example 4

[0054] In this embodiment, NH2-MIL-101(Fe) prepared in Example 1 was used, and ciprofloxacin was selected as a representative pollutant. Experiments were conducted on the piezoelectric catalytic removal of ciprofloxacin by NH2-MIL-101(Fe) under different ultrasonic powers.

[0055] The experimental steps are as follows:

[0056] Prepare 30 mL of a 5 mg / L ciprofloxacin solution in a beaker. Weigh 6 mg of NH2-MIL-101(Fe) powder and add it to the ciprofloxacin solution, stirring for 30 min to allow the adsorption of ciprofloxacin to reach equilibrium. Place the mixture in an ultrasonic cleaner, adjusting the power to 20, 40, 60, 80, and 100 W to initiate the reaction. The concentration of NH2-MIL-101(Fe) is 0.2 g / L.

[0057] The effects of NH2-MIL-101(Fe) piezoelectric catalysis on the removal of ciprofloxacin under different ultrasonic powers in the examples of this invention are as follows: Figure 4 As shown, the performance of NH2-MIL-101(Fe) piezoelectric catalysis in removing ciprofloxacin continuously improves with increasing ultrasonic power. When the ultrasonic power increases to 100 W, the removal efficiency of ciprofloxacin is 86.11%. Therefore, it is verified that the preferred ultrasonic cleaner for removing ciprofloxacin with NH2-MIL-101(Fe) in this invention has a power of 100 W.

[0058] Example 5

[0059] In this embodiment, NH2-MIL-101(Fe) prepared in Example 1 was used, and ciprofloxacin was selected as a representative pollutant for the experiment.

[0060] The experimental steps are as follows:

[0061] Prepare 30 mL of a 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 min to allow the adsorption of ciprofloxacin to reach equilibrium. Place the mixture in an ultrasonic cleaner and treat it at 100 W for 60 min.

[0062] Figure 5This diagram illustrates the removal efficiency of ciprofloxacin after the addition of hydrogen peroxide or a hydrogen peroxide quencher to the NH2-MIL-101(Fe) piezoelectric catalysis in this invention. Experiments show that the introduction of catalase (CAT) strongly inhibits CIP degradation, while the addition of 30 μM hydrogen peroxide promotes CIP degradation, achieving a CIP removal rate of 99.77% within 60 minutes. This indicates that hydrogen peroxide plays a promoting role in the piezoelectric catalytic degradation of ciprofloxacin.

[0063] Example 6

[0064] In this embodiment, NH2-MIL-101(Fe) prepared in Example 1 was used, and ciprofloxacin was selected as a representative pollutant to test the hydrogen peroxide content during the piezoelectric catalytic removal of ciprofloxacin.

[0065] The experimental steps are as follows:

[0066] Prepare 30 mL of a 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 ciprofloxacin to reach equilibrium. Place the mixture in an ultrasonic cleaner and treat it under ultrasonication at 100 W for 60 min. Take samples at the corresponding time points to determine the hydrogen peroxide content.

[0067] Figure 6 This is a test graph showing the hydrogen peroxide content during the piezoelectric catalytic removal of ciprofloxacin using NH2-MIL-101(Fe) in this embodiment of the invention. Experiments show that under ultrasonic conditions, NH2-MIL-101(Fe) produces the highest amount of hydrogen peroxide in water. The presence of NH2-MIL-101(Fe) significantly increases hydrogen peroxide production, possibly because the amino groups promote its generation. The lower hydrogen peroxide production in the ciprofloxacin solution using NH2-MIL-101(Fe) is likely due to CIP consuming a certain amount of hydrogen peroxide during the degradation process.

[0068] Example 7

[0069] In this embodiment, NH2-MIL-101(Fe) prepared in Example 1 was used, and ciprofloxacin was selected as a representative pollutant for quenching experiments of active species.

[0070] The experimental steps are as follows:

[0071] Prepare 30 mL of a 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 min to allow the ciprofloxacin adsorption to reach equilibrium. Place the mixture in an ultrasonic cleaner and treat it at 100 W for 60 min.

[0072] Figure 7 This is an experimental diagram illustrating the quenching of active species during the piezoelectric catalytic removal of ciprofloxacin using NH2-MIL-101(Fe) in an embodiment of the present invention. The experiment shows that singlet oxygen plays a major role in the piezoelectric catalytic degradation of ciprofloxacin by NH2-MIL-101(Fe).

[0073] Example 8

[0074] This embodiment uses NH2-MIL-101(Fe) prepared in Example 1, and selects ciprofloxacin as a representative pollutant. The experiment demonstrates the piezoelectric catalytic removal of ciprofloxacin from real water bodies by NH2-MIL-101(Fe).

[0075] The experimental steps are as follows:

[0076] Five 5 mg / L ciprofloxacin solutions (30 mL each) were prepared in five beakers using deionized water, tap water, lake water, rainwater, and seawater, respectively. Five 6 mg portions of NH2-MIL-101(Fe) powder were weighed and added to the ciprofloxacin solutions. The mixtures were stirred for 30 min to allow the adsorption of ciprofloxacin to reach equilibrium and initiate the reaction. The concentration of NH2-MIL-101(Fe) was 0.2 g / L.

[0077] Figure 8 This image shows the effect of NH2-MIL-101(Fe) in the piezoelectric catalytic removal of ciprofloxacin in real water bodies, as described in this invention embodiment. Experiments show that ciprofloxacin can be effectively removed from deionized water, tap water, lake water, rainwater, and seawater within 60 minutes. This example demonstrates that NH2-MIL-101(Fe) can efficiently remove ciprofloxacin using piezoelectric catalytic methods under various water conditions, providing a feasible solution for the industrial treatment of ciprofloxacin pollution.

[0078] Example 9

[0079] In this embodiment, NH2-MIL-101(Fe) prepared in Example 1 was used, and ciprofloxacin was selected as a representative pollutant to conduct an experiment on catalyst recycling.

[0080] The experimental steps are as follows:

[0081] Prepare 30 mL of a 5 mg / L ciprofloxacin solution in a beaker. Weigh 6 mg of NH2-MIL-101(Fe) powder and add it to the ciprofloxacin solution, stirring until the adsorption of ciprofloxacin reaches equilibrium. Place the mixture in an ultrasonic cleaner and treat it at 100 W for 60 min. After the reaction is complete, recover the catalyst from the remaining solution using a vacuum filtration device. Add this catalyst back to the 30 mL beaker of the 5 mg / L ciprofloxacin solution and repeat the above steps for ciprofloxacin removal five times.

[0082] Figure 9 This diagram illustrates the effect of recycling the catalyst in the piezoelectric catalytic removal of ciprofloxacin using NH2-MIL-101(Fe) in this embodiment of the invention. Experiments show that after five cycles, the removal efficiency of NH2-MIL-101(Fe) for ciprofloxacin decreased from 86.11% to 79.76% within 60 minutes, a performance reduction of only about 7%. This example demonstrates that the piezoelectric catalytic removal of ciprofloxacin using NH2-MIL-101(Fe) exhibits recyclability and property stability in practical applications.

[0083] Example 10

[0084] In this embodiment, NH2-MIL-101(Fe) prepared in Example 1 was used, and ciprofloxacin was selected as a representative pollutant for CCK-8 cytotoxicity experiments.

[0085] The experimental steps are as follows:

[0086] After seeding Hep-G2 cells in the logarithmic growth phase into 96-well plates (5000 cells / well) for 24 hours, the cells were exposed to pre- and post-reaction solutions and cultured for 48 hours. 10 μl of CCK-8 solution was added to each well, and the culture plate was gently shaken to help mix. The culture plate was then placed in an incubator and incubated for 1-4 hours. The absorbance (OD) at 450 nm was measured using a microplate reader.

[0087] Figure 10 This is a toxicity effect diagram of the piezoelectric catalytic removal of ciprofloxacin intermediate CCK-8 by NH2-MIL-101(Fe) in an embodiment of the present invention. The experiment shows that the cell viability of the solution cultured before the reaction is low, while the cell viability of the solution cultured after the reaction is high. This example illustrates that the toxicity of the intermediate product to cells is reduced after the reaction.

[0088] Example 11

[0089] In this embodiment, NH2-MIL-101(Fe) prepared in Example 1 was used, and ciprofloxacin was selected as a representative pollutant to conduct a colony formation cytotoxicity experiment.

[0090] The experimental steps are as follows:

[0091] Collect passaged cells in the logarithmic growth phase and prepare a cell suspension by adding culture medium. Seed the cells at a density of 200-400 cells / well in 6-well plates and incubate at 37°C with 5% CO2 for 24 hours. After cell adhesion, add 2 mL of the pre- and post-reaction drug and incubate for an appropriate time. Set up 3 replicates per group and a blank control. Incubate at 37°C with 5% CO2. Change the medium every 2 days with the pre- and post-reaction drug and continue incubation for 10 days. After 10 days, wash twice with cold PBS, fix with 4% paraformaldehyde for 15-30 min, wash twice with cold PBS, and then stain with crystal violet.

[0092] Figure 11 This is a toxicity study diagram of the colony formation experiment for the piezoelectric catalytic removal of ciprofloxacin intermediates using NH2-MIL-101(Fe) in an embodiment of the present invention. The experiment shows that there are fewer cell colonies in the solution culture before the reaction, while there are more cell colonies in the solution culture after the reaction, indicating that the intermediates have reduced toxicity to cells after the reaction.

[0093] The above embodiments are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above embodiments. Any changes, modifications, substitutions, combinations, or simplifications made without departing from the spirit and principle of the present invention shall be considered equivalent substitutions and shall be included within the protection scope of the present invention.

Claims

1. The application of amination-modified MIL-101(Fe) piezoelectric catalytic degradation of ciprofloxacin, characterized in that, Aminated MIL-101(Fe) was added to water containing ciprofloxacin, and the mixture was stirred until the adsorption of the ciprofloxacin solution reached equilibrium. Then, the solution was subjected to ultrasonic treatment.

2. The application according to claim 1, characterized in that, The ultrasonic treatment has a power of 80 W or more and a treatment time of 45 minutes or more.

3. The application according to claim 2, characterized in that, The ultrasonic treatment power is 80~100 W, and the treatment time is more than 60 minutes.

4. The application according to claim 1, characterized in that, The concentration of the aminated MIL-101(Fe) in water is 0.05~0.4 g / L.

5. The application according to claim 4, characterized in that, The concentration of the aminated MIL-101(Fe) in water is 0.2 g / L.

6. The application according to any one of claims 1 to 5, characterized in that, Preparation method of aminated MIL-101(Fe): Ferric chloride hexahydrate and aminoterephthalic acid are dissolved in N,N-dimethylformamide to form a mixed solution. After stirring evenly, a hydrothermal reaction is carried out. After cooling, washing and drying, NH2-MIL-101(Fe) is obtained.

7. The application according to claim 6, characterized in that, The molar ratio of ferric chloride hexahydrate to aminoterephthalic acid is 2:

1.

8. The application according to claim 6, characterized in that, The hydrothermal reaction was carried out at a temperature of 110±10℃ for a time of 20±2h.

9. The application according to claim 8, characterized in that, The stirring time before the hydrothermal reaction is 60±30 minutes; the drying temperature is 60±20℃ and the time is 12±6 hours.

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