Catalytic material for degrading fluoroquinolone antibiotics by activating persulfate

Abstract

The invention discloses a catalytic material for degrading fluoroquinolone antibiotics by activating persulfate, Fe2O3 nanoparticles and CeO2 nanoparticles are introduced into a carbon nanotube channel, and Fe / Ce nano metal particles are assembled in the carbon nanotube channel, so that the catalytic material is obtained; the catalytic material can degrade fluoroquinolone antibiotics in a water body at room temperature. According to the invention, the nanometer confinement catalyst is successfully constructed: Fe2O3 and CeO2 nanoparticles are introduced into a carbon nanotube (CNTs) channel so as to construct the nanometer confinement catalyst; according to the catalytic material, the degradation rate of fluoroquinolone antibiotics is greatly increased, the inner cavity structure and unique electronic regulation and control characteristics of the CNTs are fully utilized, the physical adsorption effect and advanced oxidation advantages of the CNTs are comprehensively utilized, and an efficient degradation mode of suction and oxidation is constructed.

Description

Technical Field

[0001] This invention relates to the field of environmental pollutant treatment technology, specifically to a catalytic material for activating persulfate to degrade fluoroquinolone antibiotics. This patent application is a divisional application of the patent application filed on July 30, 2024, with application number 2024110316729, entitled "A Catalytic Material for Activating Persulfate to Degrade Fluoroquinolone Antibiotics". Background Technology

[0002] In recent years, the presence of emerging pollutants (ECs) in water bodies has become an increasingly serious environmental problem worldwide, with irreversible impacts on human health and ecosystems. Among these emerging pollutants, antibiotics are the most worrying because they can cause drug resistance and have long-term effects on ecological sustainability.

[0003] Fluoroquinolones (FQs) are a class of synthetic, amphiphilic, broad-spectrum antibacterial drugs, and are typical antibiotics. They are widely used to treat bacterial infections, prevent diseases, and generally improve human health, as well as in fisheries and agriculture. Although FQs can be absorbed to some extent, large quantities are still released into the aquatic environment due to human and livestock metabolism and incomplete removal during wastewater treatment. The accumulation of large amounts of antibiotics in the environment can disrupt native microbial communities, interfere with the material cycle and energy flow of aquatic ecosystems, and cause significant ecological and environmental risks. Simultaneously, antibiotics accumulated in the environment can enter the human body through the food chain, threatening human life. Furthermore, large amounts of antibiotics entering the environment may induce antibiotic resistance genes, increasing the risk of "superbugs." In recent years, the overuse of antibiotics has led to the large-scale release of antibiotics into the environment, becoming a difficult-to-manage emerging environmental pollutant. Antibiotic pollution in the aquatic environment is considered a serious pollution problem. Therefore, there is an urgent need for an environmentally friendly and efficient method to remove FQs from various aquatic environments.

[0004] Currently, existing technologies for the degradation of quinolone antibiotics mainly include physical treatment, biological treatment, phytoremediation, and chemical treatment. However, many of these methods either have low degradation rates, are uneconomical, or require stringent operating conditions. For example, physical adsorption has advantages such as simple operation and low cost, but it only transfers the antibiotics without fundamentally degrading them. Furthermore, antibiotics adsorbed on the adsorbent surface are difficult to desorb from the adsorbent, making adsorbent regeneration challenging. Summary of the Invention

[0005] In view of the above-mentioned shortcomings of the existing technology, the purpose of the present invention is to provide a catalytic material for the degradation of fluoroquinolone antibiotics by activated persulfate, so as to solve the problems of low degradation rate of quinolone antibiotics, high processing cost, harsh operating conditions, and difficulty in desorbing antibiotics adsorbed on the adsorbent, which leads to difficulty in adsorbent regeneration.

[0006] To solve the above-mentioned technical problems, the present invention adopts the following technical solution:

[0007] A catalytic material for activating persulfate to degrade fluoroquinolone antibiotics is obtained by introducing Fe2O3 nanoparticles and CeO2 nanoparticles into carbon nanotube channels; the catalytic material can activate persulfate to degrade fluoroquinolone antibiotics in water at room temperature.

[0008] Preferably, the catalytic material is prepared by the following steps:

[0009] Step 1: Dissolve ferric nitrate and cerium nitrate in water and stir until homogeneous. Then add multi-walled carbon nanotube powder, stir, and sonicate to obtain a mixed solution. The mass ratio of ferric nitrate to cerium nitrate is (0.5~2):1.

[0010] Step 2: Stir and evaporate the mixed solution obtained in Step 1 at 70°C until dry, and then perform a drying process;

[0011] Step 3: Calcine the product after step 2 at 500~700℃ for 2~4h, and then cool it to obtain the catalyst material.

[0012] Preferably, in step 1, after adding multi-walled carbon nanotube powder, the mixture is stirred for 1-2 hours and then ultrasonically treated for 10-20 minutes.

[0013] Preferably, in step 2, the product after evaporation of the mixed solution is placed in an oven and dried for 12-24 hours.

[0014] Preferably, in water containing fluoroquinolone antibiotics, persulfate is added to the water first, followed by the catalytic material; or persulfate and the catalytic material are added to the water simultaneously; or the catalytic material is added to the water first, followed by the persulfate.

[0015] Preferably, the pH value of the water body is 1 to 11.

[0016] The present invention also provides a catalyst, wherein the above-mentioned catalytic material is reduced to zero-valent iron by a reducing agent to obtain the catalyst; the catalyst can activate persulfate to degrade fluoroquinolone antibiotics in water at room temperature.

[0017] Preferably, in water containing fluoroquinolone antibiotics, persulfate is added to the water first, followed by the catalyst, or persulfate and the catalyst are added to the water simultaneously; or the catalyst is added to the water first, followed by the persulfate.

[0018] Preferably, the pH value of the water body is 1 to 11.

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

[0020] 1. This invention successfully constructs a nano-confined catalyst: Fe2O3 and CeO2 nanoparticles are introduced into carbon nanotube (CNT) channels, and Fe or Ce nano-metal particles are assembled in the CNT channels to construct a nano-confined catalyst; the catalytic material of this invention significantly improves the degradation rate of fluoroquinolone antibiotics by persulfate, making full use of the internal cavity structure and unique electronic regulation characteristics of CNTs, and comprehensively utilizing the physical adsorption and advanced oxidation advantages of CNTs to construct a highly efficient degradation mode of "absorption + oxidation".

[0021] 2. The preparation method of the catalytic material described in this invention is simple, convenient, and easy to operate and control. At the same time, it does not have high requirements for the activation conditions of persulfate, and the activation of persulfate can be achieved at room temperature. Moreover, the activated persulfate has an excellent degradation effect on fluoroquinolone antibiotics, with a degradation rate of up to 99%. It also has a wide pH adaptability, which enables the catalytic material to better complete the activation of persulfate in complex environments, thereby achieving the degradation of fluoroquinolone antibiotics, and has a good application prospect. Attached Figure Description

[0022] Figure 1 For CNTs and Fe2O3 / CeO prepared in Example 1 x XRD diffraction pattern of CNTs.

[0023] Figure 2 The Raman spectrum of Fe2O3-CeO2 / CNTs prepared in Example 1.

[0024] Figure 3 In the diagram, a represents the N2 adsorption-desorption isotherm of the Fe2O3-CeO2 / CNTs prepared in Example 1; b represents the pore size distribution curve of the catalytic material prepared in Example 1.

[0025] Figure 4ab is the SEM image of Fe2O3-CeO2 / CNTs prepared in Example 1; ce is the TEM image of Fe2O3-CeO2 / CNTs prepared in Example 1; fg is the HRTEM image of Fe2O3-CeO2 / CNTs prepared in Example 1; h is the HADDF-STEM image of Fe2O3-CeO2 / CNTs prepared in Example 1; i, j, k, and l are the EDX mapping images of C, Fe, Ce, and O of Fe2O3-CeO2 / CNTs prepared in Example 1, respectively.

[0026] Figure 5 The graphs show the catalytic degradation curves of ciprofloxacin, ofloxacin, and norfloxacin by Fe2O3-CeO2 / CNTs / sodium persulfate prepared in Example 1.

[0027] Figure 6 The effect of pH on the degradation of ciprofloxacin by Fe2O3-CeO2 / CNTs / sodium persulfate prepared in Example 1.

[0028] Figure 7 Photographs of mung bean plants grown in untreated ciprofloxacin solution, ciprofloxacin solution treated with Fe2O3-CeO2 / CNTs / sodium persulfate, and pure water.

[0029] Figure 8 Fe prepared in Example 2 0 -CeO2 / CNTs / sodium persulfate catalytic degradation curves of ciprofloxacin, ofloxacin and norfloxacin respectively.

[0030] Figure 9 The graphs show the catalytic degradation of ciprofloxacin by Fe2O3-CeO2 / CNTs / sodium persulfate, CNTs / sodium persulfate, and sodium persulfate alone in Example 1, respectively. Detailed Implementation

[0031] The technical solutions of the present invention will be clearly and completely described in conjunction with the accompanying drawings of the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. All other embodiments obtained by those skilled in the art based on the present invention are within the scope of protection of the present invention.

[0032] Unless otherwise specified in the specific circumstances, the numerical ranges listed herein include upper and lower limits, as well as all integers and fractions within that range, but are not limited to the specific values ​​listed when the range is defined.

[0033] I. A catalytic material for activating persulfate degradation of fluoroquinolone antibiotics

[0034] Fe2O3 nanoparticles and CeO2 nanoparticles are introduced into carbon nanotube channels and assembled into Fe or Ce nanometal particles in the carbon nanotube channels to obtain the catalytic material; the catalytic material can activate persulfate to degrade fluoroquinolone antibiotics in water at room temperature.

[0035] In researching the degradation technology of fluoroquinolone antibiotics, this invention investigated and screened various catalytic materials in existing technologies. Among existing technologies, advanced oxidation processes (AOPs) based on persulfate have been extensively studied for eliminating recalcitrant organic pollutants in water, with research ranging from laboratory to pilot-scale. Although persulfate itself can degrade certain electron-rich pollutants (such as sulfonamides and β-lactams), its degradation effect is very poor without activation. This invention attempted to use persulfate directly for the degradation of fluoroquinolone antibiotics, but found the degradation rate to be very low. Therefore, when using persulfate to treat emerging recalcitrant pollutants, activation is necessary. Alternatively, magnetic nanomaterials are widely used due to their good recyclability, but they still have drawbacks such as small particle size, easy aggregation due to magnetism, poor dispersibility, and poor degradation effect. Therefore, this invention conceives of constructing a nano-confined catalyst that utilizes the physical adsorption of carbon nanotubes (CNTs) combined with the advantages of advanced oxidation to create a highly efficient "inhalation + oxidation" degradation mode. This activates persulfate and ultimately enhances its degradation efficiency against fluoroquinolone antibiotics. Thus, this invention introduces Fe₂O₃ and CeO₂ nanoparticles into carbon nanotube (CNT) channels and assembles Fe / Ce nanoparticles within these channels, successfully constructing a nano-confined catalyst. The catalytic material described in this invention significantly improves the degradation rate of fluoroquinolone antibiotics by persulfate, fully utilizing the internal cavity structure and unique electronic regulation characteristics of CNTs. By comprehensively leveraging the physical adsorption of CNTs and the advantages of advanced oxidation, a highly efficient "inhalation + oxidation" degradation mode is constructed.

[0036] In some embodiments, the catalytic material is prepared by the following steps:

[0037] Step 1: Dissolve ferric nitrate and cerium nitrate in water and stir until homogeneous. Then add multi-walled carbon nanotube powder, stir, and sonicate to obtain a mixed solution. The mass ratio of ferric nitrate to cerium nitrate is (0.5~2):1.

[0038] Step 2: Evaporate the mixed solution obtained in Step 1 to dryness, and then perform a drying process;

[0039] Step 3: Calcine the product after step 2 at 500~700℃ for 2~4h, and then cool it to obtain the catalyst material.

[0040] In some embodiments, in step 1, after adding multi-walled carbon nanotube powder, the mixture is stirred for 1-2 hours, followed by ultrasonic treatment for 10-20 minutes. The mass ratio of ferric nitrate to cerium nitrate is controlled at (0.5-2):1. This mass ratio should not exceed this range, as excess of either raw material will prevent the multi-walled carbon nanotubes from containing the excess material, leading to blockage and agglomeration of the excess material near the nanotubes, thus affecting the activation effect of the catalytic material on persulfate. Similarly, insufficient amounts of either raw material will also adversely affect the activation effect. Therefore, the mass ratio of ferric nitrate to cerium nitrate can be 0.5:1, 0.7:1, 1:1, 1.5:1, 2:1, etc., as well as all ranges and sub-ranges between these values. It should be understood that, in embodiments, any of the above ranges can be combined with any other range.

[0041] In some embodiments, in step 2, the product after evaporation of the mixed solution is placed in an oven and dried for 12-24 hours.

[0042] In some embodiments, in water containing fluoroquinolone antibiotics, a catalytic material is added to the water first, followed by persulfate; or persulfate and catalytic material are added simultaneously; or the catalytic material is added first, followed by persulfate. The order of addition of the catalytic material does not affect the activation effect of persulfate. In specific implementations, the catalytic material can be added in advance, simultaneously with persulfate, or first followed by persulfate. All these methods can achieve activation of persulfate and give it a high degradation rate for fluoroquinolone antibiotics. After adding it to the water for at least 50 minutes, and then treating the fluoroquinolone antibiotics in the water for 50 minutes, the degradation rate of ciprofloxacin, norfloxacin, and ofloxacin is all above 95%.

[0043] In some embodiments, the pH value of the water body is 1-11. The catalytic material of the present invention has a good activation effect in different pH environments, which effectively solves the problem that some catalytic materials for activating persulfate in the prior art have poor activation effects in acidic or alkaline environments. This allows the catalytic material of the present invention to adapt to more diverse and complex environments, ensuring that the activation of persulfate can be completed in these environments, thereby achieving the degradation of fluoroquinolone antibiotics.

[0044] II. A catalyst

[0045] After in-depth research on the catalytic material, this invention also discovered that the catalytic material, through reduction, reduces iron to zero-valent iron, which can activate persulfate at room temperature to rapidly degrade fluoroquinolone antibiotics in water.

[0046] Specifically, the catalytic material is reduced to zero-valent iron by H2 reduction at 400°C for 1 hour. However, this invention does not limit the reduction method; any reducing agent capable of achieving this process is acceptable.

[0047] In some embodiments, in water containing fluoroquinolone antibiotics, a catalyst is added to the water first, followed by persulfate; or persulfate and catalyst are added simultaneously; or the catalyst is added first, followed by persulfate. The order of catalyst addition does not affect the activation effect of persulfate. In specific implementations, the catalyst can be added in advance, simultaneously with persulfate, or the catalyst can be added first, followed by persulfate. All these methods can activate persulfate and give it a high degradation rate for fluoroquinolone antibiotics. Within 10 minutes of adding it to the water, fluoroquinolone antibiotics can be rapidly degraded (approximately 80%). After treating the water with fluoroquinolone antibiotics for 50 minutes, the degradation rate of ciprofloxacin, norfloxacin, and ofloxacin is all above 95%.

[0048] In some embodiments, the pH of the water body is 1-11. The zero-valent iron catalyst obtained after reduction treatment of the catalytic material of this invention can also adapt to different pH environments and exhibits good activation effects in various pH environments. This effectively solves the problem in the prior art where some catalytic materials for activating persulfate have poor activation effects in acidic or alkaline environments. This allows the catalyst of this invention to adapt to more diverse and complex environments, ensuring the activation of persulfate can be completed under these conditions, thereby achieving the degradation of fluoroquinolone antibiotics.

[0049] III. Examples and Comparative Examples

[0050] Example 1

[0051] Preparation of Fe2O3 / CeO2-CNTs composite materials:

[0052] 0.721 g of ferric nitrate was dissolved in 10 ml of distilled water and stirred until dissolved. 0.77 g of cerium nitrate was added and stirred until dissolved. Then 0.9 g of multi-walled carbon nanotube powder was added. The mixture was allowed to stand at room temperature and stirred for 1 h. It was then sonicated for 15 min and transferred to a water bath at 70 °C to evaporate to dryness. The mixture was then dried in an oven overnight and calcined in a muffle furnace at 600 °C for 3 h. After the temperature dropped to 100 °C, the mixture was removed to obtain the material.

[0053] Example 2

[0054] The composite material prepared in Example 1 was subjected to reduction with H2 at 400°C for 1 hour to reduce the iron in it to zero-valent iron, yielding Fe. 0 / CeO2-CNTs catalyst.

[0055] Comparative Example 1

[0056] Sodium persulfate is used to directly degrade fluoroquinolone antibiotics.

[0057] Comparative Example 2

[0058] Using CNTs / sodium persulfate as comparative example 2, CNTs were added to activate the persulfate, which was then used to degrade fluoroquinolone antibiotics.

[0059] III. Performance Analysis

[0060] 1. Structural characterization of Fe2O3 / CeO2-CNTs

[0061] 1) XRD analysis

[0062] Taking the product prepared in Example 1 as an example, the surface crystal phase composition of CNTs and Fe2O3 / CeO2-CNTs nanocomposites was characterized by XRD. Figure 1 As shown, a broad diffraction peak appears near 2θ = 25.9° (JCPDS 75-1621), which is attributed to the (002) crystal plane structure of graphite in CNTs and Fe2O3 / CeO2-CNTs nanocomposites. Diffraction peaks for CeO2 (JCPDS 34-0394) and Fe2O3 (JCPDS 72-0469) were observed in the Fe2O3 / CeO2-CNTs sample. This indicates that Fe2O3 and CeO2 nanoparticles were successfully encapsulated by carbon nanotubes.

[0063] 2) Raman spectroscopy

[0064] Taking the product prepared in Example 1 as an example, the structural defects of the nanocomposite material were further studied using Raman spectroscopy. Figure 2 As shown, in Fe2O3-CeO2 / CNTs, 1342.9 cm -1 1580.7 cm -1 and 2693.1 cm -1 Three distinct characteristic peaks appear, corresponding to the D peak, G peak, and 2D peak, respectively, where I D / I G= 0.74, proving that the Fe2O3-CeO2 / CNTs nanocomposite material possesses a graphite-rich carbon structure. The D peak is related to defective carbon or amorphous carbon, the G peak is related to graphitic carbon, and the 2D peak is related to sp... 2 The number of layers in the hybrid carbon is relevant. The sp... 2 The hybridization of carbon layers leads to the transfer of π electrons from the inner (concave) carbon layer to the outer (convex) carbon layer, further resulting in a change in electron density from the outside to the inside. Under confined conditions, due to the interaction between Fe2O3 or CeO2 and CNTs, the d orbitals of the metal particles hybridize with the p orbitals of the carbon layer, and the electron transfer in the graphitized structure is the cause of the generation of non-radicals.

[0065] 3) BET Analysis

[0066] Taking the product prepared in Example 1 as an example, such as Figure 3 As shown, the BET surface area of ​​Fe2O3-CeO2 / CNTs is 90.61 m². 2 / g, pore volume is 0.66 cm³ 3 / g, pore size is 28.39 nm. For example... Figure 3 (b) As shown in the pore size distribution diagram of the composite material, the mesopores of Fe2O3-CeO2 / CNTs are mainly concentrated in the range of 2-10 nm, which further confirms that the prepared nanocomposite material has a good mesoporous structure.

[0067] 4) SEM and TEM image analysis

[0068] Taking the product prepared in Example 1 as an example, the morphology and structure of Fe2O3-CeO2 / CNTs were observed by SEM and TEM, respectively. Figure 4 As can be seen from (a) and (b), Fe2O3-CeO2 / CNTs exhibit a nanotube structure, with no obvious aggregation observed, indicating good dispersion of the material on the surface.

[0069] Depend on Figure 4 (c)-(g) show that the Fe2O3-CeO2 / CNTs nanocomposite material exhibits a nanotubular structure, with some Fe2O3 and CeO2 nanoparticles encapsulated within the CNTs. For example... Figure 4As shown in (f) and (g), the Fe2O3-CeO2 / CNTs nanocomposite contains Fe2O3(104) and CeO2(111) crystals with lattice distances of 0.25 nm and 0.31 nm, respectively. C(002) crystal planes appear in the external regions of the Fe2O3 and CeO2, further verifying that some Fe2O3 and CeO2 nanoparticles are encapsulated within the CNTs. The encapsulation of some Fe2O3 and CeO2 nanoparticles by CNTs helps to suppress nanoparticle aggregation and limit grain size growth, thereby significantly improving the stability and catalytic activity of the nanocomposite.

[0070] 2. The degradation effect of catalysts on fluoroquinolone antibiotics

[0071] 1) Prepare 20 mg / L solutions of ciprofloxacin, norfloxacin, and ofloxacin respectively, measure the absorbance, and record it as the initial absorbance A0.

[0072] 2) Weigh 80 mg (0.08 g) of the catalyst material prepared in Example 1 and dissolve it in 80 ml of the ciprofloxacin, norfloxacin, and ofloxacin solutions prepared above. Then, add 0.02 g of sodium persulfate directly to each solution, stir, and measure the absorbance every 0-5-10-20-30-50-70-90 seconds, and record it as A. x Do three parallel sets for each group.

[0073] 3) Then, the experimental process in step 2) is repeated under different pH conditions, where the pH values ​​are 1, 3, 5, 7, 9 and 11 respectively.

[0074] 4) Calculate the degradation rate using Equation 1:

[0075] Formula 1: Degradation rate (%) = (A0 - A x ) ÷ A0 × 100%

[0076] 5) Catalytic activity of Fe2O3 / CeO2-CNTs and the effect of pH

[0077] The degradation rates for ciprofloxacin, norfloxacin, and ofloxacin are all above 95%, with ciprofloxacin reaching up to 99%. It also exhibits a wide pH range, demonstrating good activation of persulfate even in harsh environments such as pH 1 or 11. Furthermore, as... Figure 9 As shown, the Fe2O3-CeO2 / CNTs system can effectively neutralize the biotoxicity of CIP to mung bean plants, and the growth of mung bean sprouts in the treated solution is not hindered. Therefore, the Fe2O3-CeO2 / CNTs system is an environmentally friendly method for CIP degradation and toxicity attenuation.

[0078] 6) Catalytic activity in Example 2

[0079] Depend on Figure 8 It can be seen that, compared with Comparative Example 1, the Fe obtained after reduction is 0 The / CeO2-CNTs catalyst enables rapid degradation of ciprofloxacin, norfloxacin, and ofloxacin, achieving nearly 80% degradation within 10 minutes, with a final degradation efficiency comparable to that of Example 1. Furthermore, the catalyst further enhances the activation rate of persulfate. Compared to Example 1, where the degradation rate of fluoroquinolone antibiotics only reaches over 95% after 50 minutes of persulfate activation, Example 2 achieves over 80% degradation after only 10 minutes of persulfate activation.

[0080] 7) Catalytic activity of Comparative Example 1 and Comparative Example 2

[0081] In Comparative Example 1, without any catalyst, the degradation rate of ciprofloxacin was only 3.29% when only sodium persulfate was added as an oxidant, indicating that sodium persulfate cannot effectively activate the generation of free radicals without a catalyst. Meanwhile, in Comparative Example 2, the degradation efficiency of ciprofloxacin by CNTs / sodium persulfate was 45.00%. However, the degradation rate of ciprofloxacin by Fe2O3 / CeO2-CNTs / sodium persulfate reached as high as 97.6%. Therefore, in confined carbon nanotubes, the increased contact between active sites significantly enhances the interaction between the catalyst and the substrate, thereby improving catalytic efficiency. Under confined conditions, strong electronic interactions occur between carbon nanotubes and the concave surfaces of Fe2O3 or CeO2.

[0082] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and not to limit the technical solutions. Those skilled in the art should understand that any modifications or equivalent substitutions to the technical solutions of the present invention without departing from the spirit and scope of the present invention should be covered within the scope of the claims of the present invention.

Claims

1. A method for degrading fluoroquinolone antibiotics in water, characterized in that, At room temperature, persulfate and a catalyst are added to water containing fluoroquinolone antibiotics; the catalyst is obtained by reducing a catalytic material with a reducing agent; wherein the catalytic material is obtained through the following steps: Step 1: Dissolve ferric nitrate and cerium nitrate in water and stir until homogeneous. Then add multi-walled carbon nanotube powder, stir, and sonicate to obtain a mixed solution. The mass ratio of ferric nitrate to cerium nitrate is (0.5~2):

1. Step 2: Stir and evaporate the mixed solution obtained in Step 1 at 70°C until dry, and then perform a drying process; Step 3: Calcine the product after step 2 at 500~700℃ for 2~4h, and then cool it to obtain the catalyst material.

2. The method according to claim 1, characterized in that, Persulfate was added to the water body first, followed by the catalyst.

3. The method according to claim 1, characterized in that, Persulfate and a catalyst were added to the water body simultaneously.

4. The method according to claim 1, characterized in that, A catalyst is added to the water, followed by persulfate.

5. The method according to claim 1, characterized in that, The pH value of the water containing fluoroquinolone antibiotics is 1 to 11.

6. The method according to claim 1, characterized in that, The catalyst is obtained through the following steps: The catalyst is obtained by reducing the iron in the catalytic material to zero-valent iron after being reduced by H2 at 400°C for 1 hour.

7. The method according to claim 1, characterized in that, The fluoroquinolone antibiotics mentioned are ciprofloxacin, norfloxacin, and ofloxacin.

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