Preparation of cyclodextrin-loaded sulfur-modified zero-valent iron catalyst and method for removing antibiotics and antibiotic resistance genes in water by using cyclodextrin-loaded sulfur-modified zero-valent iron catalyst to activate persulfate

Abstract

The invention discloses a method for degrading antibiotics and antibiotic resistance genes in water by activating persulfate with a cyclodextrin-loaded sulfurized zero-valent iron catalyst. The cyclodextrin loaded sulfurized zero-valent iron catalyst (S-nZVI at CD) with a core-shell structure can be prepared through one-step synthesis. Sulfur doping realizes cyclic utilization and rapid electron transfer of iron, and external shell cyclodextrin promotes controlled release of active substances. The constructed S-nZVI CD / PMS system can realize efficient removal of antibiotics such as norfloxacin and ARGs within 40 minutes, and has a relatively wide pH application range (pH is 3-9). The catalytic efficiency of the catalyst is still higher than 91.2% after 11 cycles, and the removal rate of 95% or above is still maintained after the catalyst is exposed in air for 60 days. The preparation process is simple, the problems that a traditional catalyst is prone to inactivation, depends on a high-concentration oxidizing agent, is difficult to recover and the like are solved, and an efficient and stable technical scheme is provided for long-acting treatment of antibiotic and resistance gene pollution.

Description

Technical Field

[0001] This invention relates to the field of water treatment technology, specifically to a method for preparing cyclodextrin-loaded sulfur-modified zero-valent iron particles and removing antibiotics and antibiotic resistance genes by persulfate activation. Background Technology

[0002] In recent years, antibiotics have received widespread attention as a new type of pollutant. These compounds are widely used to prevent and treat bacterial diseases in humans and animals, and are characterized by strong environmental mobility and complex transformation pathways. Antibiotics can be directly exposed to the environment and accumulate continuously in different environmental media. Besides their own harmful effects, such as interfering with the immune system, they easily induce the emergence and rapid reproduction of antibiotic-resistant bacteria and antibiotic resistance genes in the environment, posing a long-term threat to the ecological environment and human health. Furthermore, antibiotic resistance genes have low biodegradability and persistent antibacterial activity, making them difficult to remove effectively using conventional water treatment technologies. Therefore, developing novel, safe, efficient, and sustainable water treatment technologies is a key means to solve the problem of antibiotic pollutants and their resistance pollutants in the aquatic environment.

[0003] Advanced oxidation techniques based on sulfate radicals (SRs-AOPs) are an effective way to degrade recalcitrant organic pollutants due to their high redox potential, excellent oxidation efficiency, and wider pH adaptability. Transition metal-based catalysts, as ideal PMS activation materials, can break peroxy bonds in PMS molecules through electron transfer mechanisms, generating highly oxidizing active substances to degrade target pollutants. Gao Boqiang et al. invented a non-metallic heteroatom-coordinated diatomic catalyst to activate persulfate for the degradation of aromatic organic pollutants in water. Compared with traditional single-atom catalysts, it has advantages such as uniform active sites, atomic-level dispersion, and excellent catalytic effect, making it a key technology for eliminating organic pollution in aquatic environments (patent number 119841434A). However, the catalyst has problems such as short catalytic lifetime and ineffective recovery, which can increase the operating cost of treatment. Nano-zero-valent iron-based materials activating persulfate for advanced oxidation is one of the effective pathways for efficiently degrading organic pollutants, with advantages such as recyclability and long catalytic lifetime. However, in practical applications, these materials still face bottlenecks such as easy agglomeration and passivation, and rapid deactivation of active substances, which seriously restrict their pollutant degradation effect and make sustainable use difficult. Zhu Xueqiang et al. invented a method for activating persulfate degradation of naphthalene in water using modified biochar-loaded nano-zero-valent iron. By loading nano-zero-valent iron onto modified biochar, this method solves the problem of easy agglomeration and oxidation of nano-zero-valent iron, significantly improving the activation efficiency of persulfate and the degradation effect of naphthalene (Patent No. 115025759A). However, its process is highly complex, and the rapid release of iron ions causes self-quenching of persulfate, posing secondary environmental risks and potentially limiting its application in low-dosage scenarios. Chen Yun et al. invented a method for treating phenol-containing wastewater using biochar-loaded sulfided zero-valent iron to activate persulfate. This method prepares biochar through high-temperature pyrolysis of straw, combines polyethylene glycol dispersant and external magnetic field technology to load sulfided zero-valent iron (S / Fe molar ratio 0.05:1), effectively solving the problems of easy agglomeration, sedimentation, and poor degradation effect of traditional sulfided nano-zero-valent iron (S-nZVI) on monophenols (Patent No. CN118084176 A). However, biochar has a porous, sheet-like or blocky structure with uneven structure. A large loading may prevent free radicals from fully contacting pollutants, and the increased mass transfer distance limits the effectiveness and long-term effect of degradation. Therefore, existing persulfate-activated catalysts still have the following disadvantages: (1) rapid dissolution of active ions leads to rapid catalyst deactivation, causing secondary harm to the environment; (2) free radicals generated by PMS activation are localized on the catalyst surface, leading to rapid decomposition and quenching, which prevents them from fully contacting pollutants and reduces catalytic efficiency; (3) catalysts are difficult to recover effectively, increasing application costs.

[0004] Therefore, constructing catalysts to achieve efficient degradation and long-term release of active substances, reduce preparation costs, and extend catalyst lifespan are crucial for the efficient removal of antibiotics and antibiotic resistance genes from water. Summary of the Invention

[0005] To address the aforementioned problems of advanced oxidation in removing antibiotics and antibiotic resistance gene contamination, this invention provides a method for preparing and activating a core-shell structured cyclodextrin-supported sulfur-modified nano-zero-valent iron catalyst (S-nZVI@CD) for persulfate degradation of antibiotics and antibiotic resistance genes. This invention features a simple preparation method, high catalyst efficiency, long-term sustained release of active substances, and magnetically controlled recovery. 80% degradation of antibiotics and nearly 100% degradation of antibiotic resistance genes can be achieved within 20 minutes, without the need for additional reagents; complete degradation of antibiotics and antibiotic resistance genes is achieved within 120 minutes. The catalyst designed in this invention has a core-shell structure. The internal zero-valent iron undergoes sulfidation treatment, forming the active species ferrous iron, which is recycled and rapidly transfers electrons. The external cyclodextrin has an amphiphilic structure similar to a "molecular bowl" (hydrophobic inner surface and hydrophilic outer surface), forming a confinement effect through host-guest inclusion, effectively promoting the controlled release of active substances and facilitating the efficient binding and degradation of free radicals and pollutants. The cyclodextrin-supported sulfur-modified nano-zero-valent iron catalyst designed in this invention has a simple preparation method and can achieve efficient removal of antibiotics and effective control of antibiotic resistance genes, reducing the environmental risk of pollutants. The catalyst can also be improved by magnetic field regulation to enhance PMS activation effect and can be recycled and reused, extending the catalyst's service life.

[0006] To achieve the above objectives, the present invention adopts the following technical solution: a method for activating persulfate degradation of antibiotics and antibiotic resistance genes in water using a cyclodextrin-supported zero-valent iron sulfide catalyst, wherein the cyclodextrin-supported zero-valent iron sulfide catalyst is characterized by having a core-shell structure, enabling efficient and sustained release of active substances to degrade antibiotics and antibiotic resistance genes, comprising the following steps:

[0007] (1) Dissolve a certain mass fraction of β-cyclodextrin in 40 mL of sulfur-modified nano-zero-valent iron suspension with a mass fraction of 0.1-1 wt%;

[0008] (2) Mix and stir under an inert atmosphere with a vacuum degree of 10-50 kPa;

[0009] (3) The reaction products were washed with deionized water that had been deoxygenated and the solid was recovered by magnetic separation of solid and liquid.

[0010] (4) The washed solid was dried in a freeze dryer at -40 to -60°C to obtain a black powdered catalyst S-nZVI@CD.

[0011] Preferably, the composite products of S-nZVI and β-CD in different ratios are 1:1 to 1:10.

[0012] Preferably, the concentration of persulfate (PMS) is 0.02–0.2 mmol / L.

[0013] Preferably, the pH of the antibiotic and antibiotic resistance gene wastewater is 3.0 to 9.0.

[0014] Optionally, the concentration of the antibiotic wastewater is 1–20 mg·L⁻¹. -1 The concentration of antibiotic resistance genes is 1–5 ng / μL. -1 .

[0015] Optionally, the antibiotic in the antibiotic wastewater is norfloxacin, and the antibiotic resistance gene is aac(6')-Ib, bla TEM One or more of tetQ, sulI-2, vanA, qnrb, qnrA, and qepA.

[0016] Optionally, the catalyst activation rate can be adjusted by setting an external magnetic field with a magnetic field strength of 0-106 mT. When the magnetic field strength is greater than 58 mT, the catalyst can be recovered.

[0017] The present invention has the following advantages and outstanding technical effects.

[0018] (1) To address the problems of easy deactivation and difficult cycling of active species in existing catalysts, green and inexpensive cyclodextrin was selected as the host for modifying zero-valent iron sulfide. The presence of sulfur accelerates the activation of PMS and the ion cycling on the nZVI surface. The cavity structure of β-CD provides reaction sites for PMS activation and iron ion cycling. In addition, the external loading of β-CD provides antioxidant protection for nZVI, effectively prolonging the catalyst lifetime and improving electron cycling to promote efficient and long-lasting activation of PMS.

[0019] (2) This invention provides a method for synthesizing a cyclodextrin-supported zero-valent iron sulfide catalyst. The resulting catalyst exhibits good stability, high catalytic performance, wide environmental applicability, and low energy consumption. This preparation method is simple and convenient, requires few types of raw materials, has low cost, and high yield, making it suitable for large-scale preparation.

[0020] (3) The catalyst with a core-shell structure obtained by the preparation method of the present invention is magnetic and the reaction process can be adjusted by controlling the magnetic field strength, and the material can be efficiently recovered and reused.

[0021] (4) Compared with existing technologies for removing antibiotics and antibiotic resistance gene pollutants, the core of the catalytic enhancement method provided by this invention lies in the cyclic regulation and in-situ activation of iron ions. When the catalyst comes into contact with the solution, zero-valent iron is first oxidized to release Fe. 2+The catalyst activates persulfate via electron transfer to generate highly oxidizing sulfate radicals, which further react with water to form hydroxyl radicals. During norfloxacin removal, these radicals primarily attack the C3 and C4 sites of the quinolone ring. During antibiotic resistance gene removal, they primarily attack the C10, C12, N9, and N11 sites. The catalyst exhibits highly efficient degradation of antibiotics and antibiotic resistance genes, achieving complete removal of both without premixing. Furthermore, the catalyst demonstrates high stability and can be recycled multiple times. After 11 cycles, the removal efficiency for norfloxacin remains above 91.2%. Even after 60 days of air exposure, the S-nZVI@CD catalyst maintains high levels of degradation for norfloxacin and antibiotic resistance genes, with degradation efficiencies of 95.4% and 98.7%, respectively. In particular, the system of this invention uses low amounts of persulfate and has high utilization rates. Only 0.2 mmol / L of persulfate needs to be added to achieve the simultaneous removal of antibiotics and antibiotic resistance genes. It can be widely used for the rapid and continuous treatment of water environments polluted by antibiotics and antibiotic resistance genes. It is suitable for water environments with different drug resistance, such as medical wastewater, aquaculture wastewater, reclaimed water and other water environments with combined antibiotic and antibiotic resistance gene pollution. Attached Figure Description

[0022] To make the technical solutions and performance advantages of the embodiments of the present invention clearer, the accompanying drawings of the scenarios described in the embodiments will be briefly introduced below.

[0023] Figure 1 Scanning electron microscope image of a cyclodextrin-supported sulfur-modified nano-zero-valent iron (CD:S-nZVI=6:1) catalyst;

[0024] Figure 2 Transmission electron microscopy image of a cyclodextrin-supported sulfur-modified nano-zero-valent iron (CD:S-nZVI=6:1) catalyst;

[0025] Figure 3 This is a graph showing the degradation efficiency of antibiotics removed by persulfate using sulfur-modified cyclodextrin-loaded nanoparticles at different pH conditions. (The S-nZVI@CD / PMS system under different pH conditions for norfloxacin) Figure 3 a) and antibiotic resistance genes ( Figure 3 b) Removal rate;

[0026] Figure 4 This is a graph showing the degradation efficiency of S-nZVI@CD on norfloxacin after 60 days of air exposure using sulfur-modified cyclodextrin-loaded nanoparticles to remove antibiotics and antibiotic resistance genes. (S-nZVI@CD degradation efficiency on norfloxacin after air exposure) Figure 4 a) and antibiotic resistance genes ( Figure 4 b) Degradation effects;

[0027] Figure 5 This is a graph showing the degradation efficiency of antibiotics and antibiotic resistance genes removed by activating persulfate with sulfur-modified cyclodextrin-loaded nanoparticles through controlled magnetic field strength. (Treatment of norfloxacin under different magnetic field strengths) Figure 5 a) and antibiotic resistance genes ( Figure 5 b) Removal rate;

[0028] Figure 6 The degradation efficiency of the prepared cyclodextrin-loaded sulfur-modified nano-zero-valent iron activated sodium persulfate for removing antibiotics and antibiotic resistance genes from actual reclaimed water is shown in the figure. (Degradation concentrations of norfloxacin and 8 types of antibiotic resistance genes in the S-nZVI@CD / PMS system under actual reclaimed water conditions are shown in the figure.) Figure 6 a) and removal rate ( Figure 6 b)). Detailed Implementation

[0029] The following describes in detail a method for activating persulfate degradation of antibiotics and antibiotic resistance genes in water using a cyclodextrin-supported zero-valent iron sulfide catalyst, with reference to the accompanying drawings and specific preferred embodiments. Obviously, the following scenario descriptions are some embodiments of the present invention. For those skilled in the art, other performance examples of the catalyst can be obtained based on these scenarios without creative effort.

[0030] Example 1

[0031] A method for preparing a cyclodextrin-supported sulfur-modified zero-valent iron catalyst and its activated persulfate-based composite material for removing antibiotics and antibiotic resistance genes from water, the specific steps of which are as follows:

[0032] First, sulfur-modified nano-zero-valent iron catalyst was prepared by sodium borohydride reduction. The catalyst was then washed three times with deionized water and ethanol alternately to remove surface impurities. After separation using a magnet, it was freeze-dried at -50°C using a freeze dryer.

[0033] S-nZVI@CD catalysts were prepared using a two-step method. The prepared S-nZVI was combined with β-CD in specific ratios (e.g., Fe:CD = 1:1, 1:2, 1:6, 1:10). Taking a [Fe] / [CD] ratio of 1:6 as an example, 1.2 g of β-CD was dissolved in 20 mL of S-nZVI suspension (10 g·L⁻¹). -1In this process, nitrogen gas was continuously introduced into the system at room temperature to maintain an oxygen-free environment. The mixture was stirred at 1000 rpm for 18 hours using a mechanical stirrer. The solid separator was then washed five times with deoxygenated deionized water and ethanol, and the black powder was freeze-dried. Finally, a core-shell structured cyclodextrin-supported sulfurized nano-zero-valent iron (S-nZVI@CD) catalyst with low cost, simple preparation, high stability, and strong continuous activation ability was obtained.

[0034] Figure 1 and Figure 2 The images show SEM and TEM images of the cyclodextrin-supported sulfur-modified zero-valent iron catalyst obtained by the above preparation method.

[0035] Example 2

[0036] The specific steps for applying cyclodextrin-loaded sulfur-modified zero-valent iron particles to activate persulfate for antibiotic and antibiotic resistance gene removal at different pH conditions are as follows:

[0037] Water quality conditions: Norfloxacin concentration 5 mg / L -1 The concentration of the antibiotic resistance gene was 2 ng / μL. -1 The PMS concentration was 16 μmol·L⁻¹. -1 The initial pH of the solution was adjusted to 3.0, 5.0, 7.0 and 9.0, and the temperature was 25℃.

[0038] The main process parameters are as follows: water volume treated: 100 mL; catalyst prepared using the method in Application Example 1; reaction time: 120 min. Other process parameters required for the degradation process are the same as in Example 1.

[0039] Figure 3 The effects of different solution pH values ​​on the degradation of norfloxacin and antibiotic resistance genes in the S-nZVI@CD / PMS system were investigated. Experimental results showed that the system achieved complete degradation of norfloxacin (100% removal rate) within 120 min in the pH range of 3-7. At pH=9, the removal rate decreased significantly for the same reaction time, but still met the degradation efficiency of 81.9%. Under the same conditions, the effect of initial pH value on the removal efficiency of antibiotic resistance genes was tested. When the system pH value transitioned from alkaline (pH=9) to acidic (pH=3), the removal rate of the same antibiotic resistance genes showed a significant increasing trend, increasing from 84.8% to complete removal (100%), indicating that an acidic environment is more conducive to the oxidative degradation of antibiotic resistance genes. The different pH response characteristics of the catalyst indicate that the prepared catalyst has a wide pH application range.

[0040] Example 3

[0041] The specific steps for applying cyclodextrin-loaded sulfur-modified zero-valent iron particles activated by persulfate to remove antibiotics and antibiotic resistance genes after 60 days of air exposure are as follows:

[0042] Water quality conditions: Norfloxacin concentration 5 mg / L -1 The concentration of the antibiotic resistance gene was 2 ng / μL. -1 The PMS concentration was 16 μmol·L⁻¹. -1 The initial pH of the solution was adjusted to 7.0, and the temperature was set to 25°C.

[0043] The main process parameters are as follows: 100 mL of water was treated; the catalyst prepared using the method in Application Example 1 was tested after air exposure for 0, 15, 30, and 60 days; and the reaction time was 120 min. The process parameters required for other degradation processes are the same as in Example 1.

[0044] Figure 4 Air exposure tests showed that under 60 days of natural oxidation, the catalyst still achieved simultaneous removal of 95.4% of norfloxacin and 98.7% of antibiotic resistance genes, demonstrating significantly superior antioxidant performance compared to conventional nano-iron materials. Experimental data indicated that surface sulfidation treatment, by constructing a protective layer, formed a synergistic protective effect with the stereocoating of β-CD, resulting in enhanced activity of the active component Fe. 0 It remains stable during long-term storage. These characteristics give the S-nZVI@CD / PMS system a unique advantage in the treatment of complex water environments: it not only has excellent broad-spectrum removal capabilities for pollutants, but also breaks through the technical bottleneck of easy deactivation of traditional iron-based catalysts through innovative structural design, providing a reliable technical solution for the long-term treatment of wastewater containing antibiotics and resistance genes.

[0045] Example 4

[0046] A method for activating persulfate degradation of antibiotics and antibiotic resistance genes in water using a cyclodextrin-supported zero-valent iron sulfide catalyst, specifically using the cyclodextrin-supported zero-valent iron sulfide catalyst prepared in Example 1, investigates the removal effect of the S-nZVI@CD / PMS system on norfloxacin and antibiotic resistance genes under controlled external magnetic field strength, including the following steps:

[0047] Water quality conditions: Norfloxacin concentration 5 mg / L -1 The concentration of the antibiotic resistance gene was 2 ng / μL. -1 The PMS concentration was 16 μmol·L⁻¹. -1 The initial pH of the solution was adjusted to 7.0, and the temperature was set to 25°C.

[0048] The main process parameters are as follows: 100 mL of water was treated; the catalyst prepared using the method in Application Example 1 was tested under magnetic field strengths of 0, 27, 58, 77, and 106 mT; and the reaction time was 20 min. The process parameters required for other degradation processes are the same as in Example 2.

[0049] Figure 5 The results showed that when a 58 mT magnetic field was applied to the system, the continuous-flow degradation efficiency of norfloxacin significantly increased from 89.8% under no magnetic field conditions to 100%, and the degradation kinetic constant increased by approximately 1.12 times. Simultaneously, the degradation efficiency of antibiotic resistance genes increased from 92.0% to complete degradation (100%). This enhanced effect may be related to the accelerated activation mechanism of nZVI surface induced by a weak magnetic field: the magnetic field promotes Fe... 0 The efficiency of electron transfer in the nucleus enhances the amount of ROS generated during PMS activation. When the magnetic field strength exceeds 58 mT, the degradation efficiency of norfloxacin and antibiotic resistance genes shows a decreasing trend. Within the experimental setup, significant catalyst particle aggregation was observed in the reaction system. Excessively high magnetic field strength leads to enhanced magnetic dipole interactions between nZVI particles, thereby reducing the catalyst's specific surface area and the accessibility of surface active sites. Catalyst recovery can be achieved under high magnetic field strength, with recovery efficiency approaching 100%. Therefore, by applying an external magnetic field, an appropriate magnetic field strength (<58 mT) can enhance the catalyst's catalytic efficiency, and catalyst recovery can be achieved under a high magnetic field (106 mT).

[0050] Example 5

[0051] The specific steps for applying cyclodextrin-loaded sulfur-modified zero-valent iron particles to activate persulfate in reclaimed water to remove antibiotics and antibiotic resistance genes are as follows:

[0052] Water quality conditions: Norfloxacin concentration 5 mg / L -1 The concentration of antibiotic resistance genes was 1.5 × 10⁻⁶. 7 copies·mL -1 The PMS concentration was 16 μmol·L⁻¹. -1 The initial pH of the solution was adjusted to 7.0, and the temperature was set to 25°C.

[0053] The main process parameters are as follows: the water volume is 100 mL, the catalyst prepared by the method in Application Example 1 is used in the experiment, and the reaction time is 120 min.

[0054] Figure 6The S-nZVI@CD / PMS system exhibited excellent degradation performance, with a total ARG removal rate exceeding 97.4%. During the study, intI1, a key factor in the horizontal transfer and proliferation of antibiotic resistance genes, was analyzed by comparing changes in the abundance of transfer elements before and after the reaction to assess the catalyst's potential for controlling the environmental migration and transformation risks of antibiotic resistance genes. Results showed that the S-nZVI@CD / PMS system significantly reduced the relative abundance of the intI1 gene, achieving a removal efficiency of 98.2%, demonstrating its significant role in inhibiting the spread and diffusion of antibiotic resistance genes. The S-nZVI@CD / PMS system achieved a 97.3% removal efficiency for the 16S rDNA gene. This further demonstrates that the S-nZVI@CD / PMS system not only effectively removes harmful substances from water bodies but also significantly inhibits bacterial proliferation and the spread of antibiotic resistance genes. Therefore, the S-nZVI@CD / PMS system can effectively reduce the horizontal transfer of ARGs and the increase in bacterial abundance in the treatment of antibiotic resistance gene pollution in natural water bodies, thereby helping to reduce the risk of antibiotic-resistant microorganism pollution in water bodies.

[0055] The above content is merely illustrative of the technical concept of this invention, and the examples given are only preferred embodiments of the invention. They should not be construed as limiting the scope of protection of this invention. Any modifications, equivalent substitutions, or improvements made in accordance with the technical concept and specification of this invention should be included within the scope of protection of this invention. Content not described in detail in this invention refers to conventional technical content.

Claims

1. A method for activating persulfate degradation of antibiotics and antibiotic resistance genes in water using a cyclodextrin-supported zero-valent iron sulfide catalyst, wherein the cyclodextrin-supported zero-valent iron sulfide catalyst is characterized in that... This catalyst has a core-shell structure and can efficiently and sustainably release active substances to degrade antibiotics and antibiotic resistance genes, including the following steps: (1) Dissolve a certain mass fraction of β-cyclodextrin in 40 mL of sulfur-modified nano-zero-valent iron suspension with a mass fraction of 0.1-1 wt%; (2) Mix and stir under an inert atmosphere with a vacuum degree of 10-50 kPa; (3) The reaction products were washed with deionized water that had been deoxygenated and the solid was recovered by magnetic separation of solid and liquid. (4) The washed solid was dried in a freeze dryer at -40 to -60°C to obtain a black powdered catalyst S-nZVI@CD; (5) Add S-nZVI@CD and persulfate to the water environment containing pollutants to oxidize and degrade antibiotics and antibiotic resistance genes in the water.

2. The method for activating persulfate degradation of antibiotics and antibiotic resistance genes in water using a cyclodextrin-supported zero-valent iron sulfide catalyst as described in claim 1, characterized in that: The catalyst contains S-nZVI and β-CD in different composite ratios ranging from 1:1 to 1:

10.

3. The method for activating persulfate degradation of antibiotics and antibiotic resistance genes in water using a cyclodextrin-supported zero-valent iron sulfide catalyst as described in claim 1, characterized in that: Cyclodextrin and sulfur-modified nano-zero-valent iron were mixed and stirred at 20–30°C for 8–20 hours.

4. The method for activating persulfate degradation of antibiotics and antibiotic resistance genes in water using a cyclodextrin-supported zero-valent iron sulfide catalyst as described in claim 1, characterized in that: The persulfate is permonosulfate (PMS).

5. The method for activating persulfate degradation of antibiotics and antibiotic resistance genes in water using a cyclodextrin-supported zero-valent iron sulfide catalyst as described in claim 1, characterized in that: The concentration of sodium persulfate added is 0.02–0.2 mmol / L, and the amount of catalyst added is 0.01–0.15 g·L. -1 .

6. The method for activating persulfate degradation of antibiotics and antibiotic resistance genes in water using a cyclodextrin-supported zero-valent iron sulfide catalyst as described in claim 1, characterized in that: The initial pH value of the water containing antibiotics and antibiotic resistance genes is 3-11, and the temperature range is 15-35℃.

7. The method for activating persulfate degradation of antibiotics and antibiotic resistance genes in water using a cyclodextrin-supported zero-valent iron sulfide catalyst as described in claim 1, characterized in that: The antibiotic resistance genes are detectable antibiotic resistance subtype genes in the environment, including aac(6')-Ib (aminoglycoside resistance), bla TEM One or more of the following genes: (β-lactam resistance), tetQ (tetracycline resistance gene), sulI-2 (sulfonamide resistance gene), vanA (vancomycin resistance), qnrb, qnrA, and qepA (quinolone resistance).

8. The method for activating persulfate degradation of antibiotics and antibiotic resistance genes in water using a cyclodextrin-supported zero-valent iron sulfide catalyst as described in claim 1, characterized in that... The controlled release of active species of the catalyst can be adjusted by regulating the dosage of cyclodextrin, with the release of dissolved iron ranging from 0.05 to 0.25 mmol·L⁻¹. -1 .

9. The method for activating persulfate degradation of antibiotics and antibiotic resistance genes in water using a cyclodextrin-supported zero-valent iron sulfide catalyst as described in claim 1, characterized in that... The activation rate of the catalyst can be adjusted by setting an external magnetic field with a magnetic field strength of 0-106 mT. When the magnetic field strength is greater than 58 mT, the catalyst can be recovered.

Images