Co-MoS2@PTFE ozone catalytic membrane, its preparation method and application

Abstract

The application belongs to the technical field of catalytic membrane, and particularly relates to a Co-MoS2@PTFE ozone catalytic membrane, a preparation method thereof and application thereof in removal of pollutants in water. The surface of a PTFE hollow fiber membrane is treated by plasma to obtain a functionalized carrier p-PTFE; then MoS2 nanosheets are grown in situ on the surface of the p-PTFE to form a MoS2@PTFE composite membrane; finally, the Co-MoS2@PTFE ozone catalytic membrane is prepared by hydrothermal reaction in a cobalt source and a reducing agent to realize Co atom doping. A stable interface is constructed on the substrate by plasma treatment, so that the MoS2 nanosheets are firmly grown on the surface and the pores of the PTFE; the Co doping forms a heterojunction catalyst to enhance the catalytic activity. The catalytic membrane can synergize with ozone to efficiently degrade organic pollutants in water, realize efficient synergy of membrane separation and catalytic oxidation, and solve the problem that the active components of the traditional catalytic membrane are prone to fall off.

Description

Technical Field

[0001] This invention belongs to the field of catalytic membrane technology, specifically relating to a Co-MoS2@PTFE ozone catalytic membrane and its preparation method, as well as its application in synergy with ozone in high-efficiency water treatment. Background Technology

[0002] Rapid industrial development has exacerbated environmental pollution, with various organic pollutants (such as antibiotics, dyes, phenolic compounds, fluorinated compounds, and endocrine disruptors) detected in industrial wastewater, medical wastewater, and domestic sewage. Ozone technology can effectively remove these pollutants from water, but its application faces limitations such as low mineralization capacity and low oxygen utilization. Ozone catalysts can promote the decomposition of ozone molecules, generating more reactive oxygen species that are environmentally friendly and have stronger oxidizing capabilities, thus improving ozone utilization efficiency. However, current ozone catalysts also suffer from drawbacks such as easy catalyst loss, poor mass transfer efficiency, unreasonable reactor structure, and poor stability.

[0003] Ozone catalytic oxidation and membrane separation integration technology is a novel coupling technology. Assembling or embedding the catalyst into the membrane matrix not only mitigates the loss of active ingredients but also accelerates mass transfer efficiency through water flow. Chinese patent document CN115487869A discloses a method for preparing a ceramic membrane for catalytic ozone formation, fixing manganese dioxide onto the membrane surface and in the pores through surface grafting. Chinese patent document CN116808839A discloses a method for preparing and applying an ozone catalyst-modified ceramic membrane. This catalytic membrane is formed by uniformly adding an ozone catalyst to ceramic aggregate and calcining it at high temperature. Chinese patent document CN116832624A discloses a functional ceramic membrane for catalytic ozone formation, achieving uniform catalyst loading in ceramic powder through high-temperature sintering, and in-situ modification of the ceramic membrane to obtain the water permeability of the ozone catalyst ceramic membrane. Although ceramic membranes can improve catalyst stability, their low surface area and pore size inhomogeneity limit their effective application in ozone-oxidation systems. In addition, ceramic membranes increase application costs and are less economical.

[0004] Polytetrafluoroethylene (PTFE) is often used as a supported catalyst in the preparation of polymer materials due to its chemical inertness, high mechanical strength, and resistance to degradation by oxidants. However, its stable surface properties and lack of microspaces that can stably anchor the catalyst limit its degradation performance, affecting its degradation performance in practical applications. Summary of the Invention

[0005] One of the objectives of this invention is to provide a method for preparing a Co-MoS2@PTFE ozone catalytic membrane. The prepared catalytic membrane exhibits high efficiency in degrading organic pollutants in water, achieving efficient synergy between membrane separation and catalytic oxidation, and solving the problem of easy detachment of active components in traditional catalytic membranes.

[0006] To achieve the above objectives, the present invention adopts the following technical solution: a method for preparing a Co-MoS2@PTFE ozone catalytic membrane, comprising the following steps:

[0007] S1. Take a PTFE hollow fiber membrane and perform surface plasma treatment to obtain a p-PTFE membrane;

[0008] S2, Take ammonium molybdate tetrahydrate (NH4)6Mo7O 24 Ammonium molybdate tetrahydrate or sodium molybdate dihydrate Na2MoO4·2H2O, together with thiourea (CH4N2S), are dissolved in water with the pH adjusted to 1-2 to form a mixture. The concentration of ammonium molybdate tetrahydrate or sodium molybdate dihydrate in the mixture is 5-15 mmol / L, and the concentration of thiourea is 1-4 mmol / L.

[0009] S3. Immerse the p-PTFE membrane from step S1 into the mixture from step S2 and sonicate it. Then transfer it to a high-pressure reactor and heat it at 180~210℃ for 6~24h. After cooling to room temperature, collect the product, wash and dry it to obtain the MoS2@PTFE membrane.

[0010] S4. Immerse the MoS2@PTFE membrane in a Co(NO3)2·6H2O solution, then add reducing agent hydrazine hydrate N2H4·H2O or hydroxylamine NH2OH or ammonia water NH3·H2O, react at 60~65℃ for 6~8h, remove, wash and dry to obtain Co-MoS2@PTFE ozone catalytic membrane;

[0011] Steps S1 and S2 are not in any particular order.

[0012] Further improvements to the preparation method of Co-MoS2@PTFE ozone catalytic membrane:

[0013] Preferably, the PTFE hollow fiber membrane has a length of 10~20cm, an inner and outer diameter of 0.5~0.8 / 1.0~1.5mm respectively, a pore size of 0.1~1.0μm, and a porosity of ≥80%.

[0014] Preferably, in step S1, the current for surface plasma treatment is alternating current with an output frequency of 1~3GHz, a treatment pressure of 100~500Pa, a treatment temperature of 200~250℃, and a treatment time of 1~2h.

[0015] Preferably, in step S4, the concentration of the Co(NO3)2·6H2O solution is 1~5 wt%; the mass ratio of the MoS2@PTFE membrane added to the Co(NO3)2·6H2O solution is 1%~10%; and the mass ratio of the reducing agent added to the Co(NO3)2·6H2O solution is 1%~5%.

[0016] Preferably, in step S2, hydrochloric acid or sulfuric acid is used to adjust the pH of the water to 1-2.

[0017] Preferably, in step S3, the collected product is washed several times in distilled water and ethanol, and then dried at 60-70°C for 24-48 hours.

[0018] Preferably, in step S3, the p-PTFE membrane from step S1 is immersed in the mixture from step S2 and ultrasonically treated for 1-2 hours.

[0019] The second objective of this invention is to provide a Co-MoS2@PTFE ozone catalytic membrane prepared by any of the above-mentioned methods.

[0020] The third objective of this invention is to provide an application of the above-mentioned Co-MoS2@PTFE ozone catalytic membrane in the removal of pollutants in water.

[0021] Further improvements to the application of the aforementioned Co-MoS2@PTFE ozone catalytic membrane in the removal of pollutants from water:

[0022] Preferably, the Co-MoS2@PTFE ozone catalytic membrane is applied in the ozone reactor via a cross-flow internal circulation method to remove pollutants from water. The ozone dosage is 10-50 mg / L, and the membrane flux of the cross-flow internal circulation system is 10-80 L / (m²). 2 The internal circulation reflux ratio is 1:1, the reaction time is 0.5~1h, and the operating throughput is 10~20LMH.

[0023] The advantages of this invention compared to the prior art are as follows:

[0024] (1) This technology uses PTFE to make a microfiltration membrane as a carrier. Through plasma surface treatment, catalyst nanosheets can be uniformly grown on its surface and in its pores. In the ozone oxidation system, a cross-flow internal circulation method is creatively proposed to combine membrane separation and ozone catalytic oxidation. The prepared catalytic membrane is different from traditional ozone catalysts, has high stability, and has the dual functions of ozone catalytic oxidation and filtration, thereby promoting the improvement of pollutant decomposition efficiency. This invention provides a method for preparing a Co-MoS2@PTFE ozone catalytic membrane, the steps of which are as follows:

[0025] 1.1 Surface Treatment: The surface of a raw PTFE membrane is highly inert, hydrophobic, and lacks active functional groups. Its surface is stable and cannot be composited with metals, making it difficult to treat with conventional acids and alkalis. This invention employs plasma treatment to introduce active groups such as hydroxyl groups and structural defects into the PTFE surface, thereby obtaining a p-PTFE membrane.

[0026] 1.2 Functional modification: The p-PTFE membrane after surface plasma treatment was immersed in a solution containing molybdenum salt and thiourea. Molybdate was used as the molybdenum source and thiourea as the sulfur source and reducing agent. Through hydrothermal reaction, MoS2 nanomaterials were generated in situ on the surface and pores of the p-PTFE membrane in a strongly acidic hydrothermal environment.

[0027] The hydroxyl, carboxyl, and defect groups on the p-PTFE membrane surface can serve as nucleation sites, binding with molybdate ions from the hydrothermal reaction via electrostatic or coordination interactions. This allows MoS2 to grow firmly in situ on the substrate, rather than through physical adsorption. Ultrasound utilizes the cavitation effect to thoroughly penetrate the precursor solution into the porous structure of the PTFE membrane and allow it to adhere to the fiber surface, laying the foundation for subsequent in-situ growth. Ammonium molybdate tetrahydrate or sodium molybdate dihydrate dissociates in water to provide MoO4. 2- Under strongly acidic conditions (pH=1~2), molybdate ions will polymerize into various molybdate ions (such as [Mo7O]). 24 ] 6- These polymeric ions are more readily vulcanized. The ultra-high molybdenum concentration ensures sufficient molybdenum source for nucleation and growth on the PTFE fiber surface, forming a dense MoS2 capping layer. Thiourea slowly decomposes under hydrothermal conditions, releasing H2S / S. 2- It provides a reducing environment, partially reducing Mo(VI) to Mo(IV), thereby generating MoS2. Low thiourea (low sulfur) concentrations favor the formation of defect-rich MoS2 with more exposed edge sites. The molybdenum source precursor in solution attaches to the active sites of the p-PTFE membrane through interactions, subsequently... 2- It reacts with the fiber to directly generate MoS2 nanosheets on the fiber surface.

[0028] 1.3 Cobalt Modification: A wet chemical method was used to introduce high-performance Co active centers into the MoS2 structure. The introduction of cobalt significantly increased the number of highly active sites per unit area. This solved the problems of low active sites and low intrinsic conductivity in pure MoS2 catalysts, ultimately yielding an advanced catalytic electrode material that integrates flexibility, self-support, high performance, and high stability. Hydrazine hydrate is a strong reducing agent that can remove Co adsorbed on the MoS2 surface. 2+ Ions reduced to metallic cobalt (Co) 0The nanoparticles are composed of hydrazine hydrate. The aqueous solution of hydrazine hydrate is alkaline and can form complexes with metal ions. This helps to control the rate of the reduction reaction, resulting in cobalt nanoparticles that are fine and uniformly dispersed on the MoS2 substrate, rather than agglomerating into large particles.

[0029] (2) The Co-MoS2@PTFE ozone catalytic membrane prepared in this invention can be combined with ozone oxidation to help ozone oxidation technology efficiently remove new pollutants in water, achieving the purpose of in-situ ozone activation and targeted adsorption of pollutants, thus overcoming the inefficiency of traditional ozone technology. The hydrophobicity of the PTFE membrane forces ozone to accumulate at the gas-liquid interface, increasing the local concentration of ozone molecules. Pollutants are adsorbed into the pores by the PTFE membrane, and Co / Mo catalysis promotes the decomposition of ozone into ·OH and ·O2. Free radicals promote the in-situ oxidation and decomposition of pollutants. This invention cleverly combines an easily recyclable catalytic membrane with ozone catalytic oxidation, exhibiting long-lasting stability. It solves the problem of reactor blockage caused by the easy peeling and accumulation of traditional catalyst substrates, resulting in lower fluctuations in catalytic degradation performance. In addition, the PTFE substrate has the advantage of easy recycling.

[0030] (3) The present invention uses an internal circulation method in the ozone reaction device to remove pollutants in water, enhance the contact and mass transfer between pollutants and catalyst, control the mass transfer efficiency of ozone molecules and catalyst based on the internal reflux of membrane filtration, enhance the mineralization capacity of pollutants, and achieve a TOC removal rate of 85%~90% for industrial wastewater. Attached Figure Description

[0031] Figure 1 This is a schematic diagram of a cross-flow internal circulation device used by ozone catalytic membranes in wastewater treatment.

[0032] Figure 2 This is an electron microscope image of the MoS2@PTFE membrane prepared in Example 1 of the present invention. Detailed Implementation

[0033] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to the embodiments. All other embodiments obtained by those skilled in the art based on the embodiments of this invention without creative effort are within the scope of protection of this invention.

[0034] Example 1

[0035] This embodiment provides a method for preparing a Co-MoS2@PTFE ozone catalytic membrane, which specifically includes the following steps:

[0036] S1. Take a 10cm long PTFE hollow fiber membrane (inner and outer diameters are 0.8 / 1.5mm, pore size is 0.1μm, porosity is 85%) and perform surface plasma treatment on it to generate active groups on the surface, thus obtaining a p-PTFE membrane; the surface plasma treatment current is alternating current, the output frequency is 1 GHz, the treatment pressure is 500 Pa, the treatment temperature is 200 ℃, and the treatment time is 2h.

[0037] S2, Ammonium molybdate tetrahydrate (NH4)6Mo7O 24 • 4H2O and thiourea (CH4N2S) were dissolved in 100 mL of water with the pH adjusted to 2.0 to form a mixture. The concentration of ammonium molybdate tetrahydrate in the mixture was 5 mmol / L and the concentration of thiourea was 1 mmol / L.

[0038] S3. Immerse the p-PTFE membrane from step S1 into the mixture from step S2 and sonicate it for 1 hour. Then transfer it to a stainless steel high-pressure reactor and hydrothermally react it at 180°C for 24 hours. After cooling to room temperature, collect the product and wash it several times in distilled water and ethanol. Dry it at 70°C for 24 hours to obtain the MoS2@PTFE membrane.

[0039] S4. Immerse 1g of MoS2@PTFE membrane in 100g of 1% Co(NO3)2·6H2O solution (containing 1g Co(NO3)2·6H2O), then add 1g of ammonia water, react at 65℃ for 6 h, remove, wash and dry to obtain Co-MoS2@PTFE ozone catalytic membrane 1.

[0040] The Co-MoS2@PTFE ozone catalytic membrane 1 prepared above is applied in an ozone reaction device (such as...) via a cross-flow internal circulation method. Figure 1 As shown), this was used to treat a tetracycline solution with an initial concentration of 100 mg / L. During the treatment, the ozone dosage was 10 mg / L, and the membrane flux of the cross-flow internal circulation system was 10 L / (m²). 2 The reaction time was 30 min, with an internal circulation reflux ratio of 1:1 and an operating flux of 10 LMH. Tests showed a tetracycline removal rate of 99.2% and a TOC mineralization rate of 89.5%.

[0041] Figure 2 These are SEM images of the MoS2@PTFE membrane prepared in Example 1 above. Figure 2 It can be seen that MoS2 has a distinct lamellar distribution, and its surface functional groups are more likely to combine with PTFE, providing a wider support space for Co loading.

[0042] Example 2

[0043] This embodiment provides a method for preparing a Co-MoS2@PTFE ozone catalytic membrane, which specifically includes the following steps:

[0044] S1. Take a 10cm long PTFE hollow fiber membrane (inner and outer diameters are 0.8 / 1.5mm, pore size is 0.5μm, porosity is 88%) and perform surface plasma treatment on it to generate active groups on the surface, thus obtaining a p-PTFE membrane; the surface plasma treatment current is AC, the output frequency is 2 GHz, the treatment pressure is 200 Pa, the treatment temperature is 220 ℃, and the treatment time is 1.5h;

[0045] S2. Dissolve Na2MoO4·2H2O and thiourea (CH4N2S) in 100mL of water with pH adjusted to 1.5 to form a mixture. The concentration of ammonium molybdate tetrahydrate or sodium molybdate dihydrate in the mixture is 10mmol / L, and the concentration of thiourea is 2mmol / L.

[0046] S3. Immerse the p-PTFE membrane from step S1 into the mixture from step S2 and sonicate it for 1 hour. Then transfer it to a stainless steel high-pressure reactor and hydrothermally react it at 210°C for 6 hours. After cooling to room temperature, collect the product and wash it several times in distilled water and ethanol. Dry it at 65°C for 30 hours to obtain the MoS2@PTFE membrane.

[0047] S4. Immerse 5 g of MoS2@PTFE membrane in 100 g of 2.5% Co(NO3)2·6H2O solution (containing 2.5 g Co(NO3)2·6H2O), then add 3 g of hydrazine hydrate, react at 60℃ for 8 h, remove, wash and dry to obtain Co-MoS2@PTFE ozone catalytic membrane 2.

[0048] The Co-MoS2@PTFE ozone catalytic membrane 2 prepared above is applied in an ozone reaction device (such as...) via a cross-flow internal circulation method. Figure 1 The sample (shown) is used to treat reverse osmosis concentrate from coal chemical processing. The concentrate's characteristics are as follows: TOC 25 mg / L, COD 180 mg / L, sulfate ion 3500 mg / L, chloride ion 5000 mg / L, pH 7.5, and ammonia nitrogen concentration 18 mg / L. During treatment, ozone dosage is 20 mg / L, and the membrane flux of the cross-flow internal circulation system is 15 L / (m²). 2 The reaction time was 30 min, with an internal circulation reflux ratio of 1:1 and an operating flux of 15 LMH. Tests showed that the effluent TOC concentration was 4.43 mg / L, with a TOC mineralization rate of 82.3%; the effluent COD was 45 mg / L, with a COD removal rate of 75%; and the effluent ammonia nitrogen was 15.5 mg / L.

[0049] Example 3

[0050] This embodiment provides a method for preparing a Co-MoS2@PTFE ozone catalytic membrane, which specifically includes the following steps:

[0051] S1. Take 10 PTFE hollow fiber membranes with a length of 10 cm (inner and outer diameters of 0.8 / 1.5 mm, pore size of 0.1 μm, and porosity of 85%) and perform surface plasma treatment on them to generate active groups on the surface, thus obtaining p-PTFE membranes. The surface plasma treatment current is AC, the output frequency is 3 GHz, the treatment pressure is 100 Pa, the treatment temperature is 250 ℃, and the treatment time is 1 h.

[0052] S2. Dissolve Na2MoO4·2H2O and thiourea (CH4N2S) in 100mL of water with pH adjusted to 1.0 to form a mixture. The concentration of ammonium molybdate tetrahydrate or sodium molybdate dihydrate in the mixture is 15mmol / L, and the concentration of thiourea is 4mmol / L.

[0053] S3. Immerse the p-PTFE membrane from step S1 into the mixture from step S2 and sonicate it for 1 hour. Then transfer it to a stainless steel high-pressure reactor and hydrothermally react it at 200°C for 10 hours. After cooling to room temperature, collect the product and wash it several times in distilled water and ethanol. Dry it at 60°C for 48 hours to obtain the MoS2@PTFE membrane.

[0054] S4. Immerse 10 g of MoS2@PTFE membrane in 100 g of 5% Co(NO3)2·6H2O solution (containing 5.0 g Co(NO3)2·6H2O), then add 5.0 g of hydrazine hydrate, react at 63℃ for 7 h, remove, wash and dry to obtain Co-MoS2@PTFE ozone catalytic membrane 3.

[0055] The Co-MoS2@PTFE ozone catalytic membrane 3 prepared above is applied in an ozone reaction device (such as...) via a cross-flow internal circulation method. Figure 1 The wastewater (as shown) was used to treat dyeing and printing wastewater from a certain enterprise. The wastewater had the following characteristics: TOC concentration 1250 mg / L, COD 2850 mg / L, ammonia nitrogen 28 mg / L, color 1000 times, SS 300 mg / L, and pH 10.0. During the treatment process, the ozone dosage was 50 mg / L, and the membrane flux of the cross-flow internal circulation system was 80 L / (m²). 2 The reaction time was 30 min, with an internal circulation reflux ratio of 1:1 and an operating flux of 20 LMH. Tests showed a TOC mineralization rate of 85.8%, a COD of 625 mg / L (removal rate of 78.1%), and an ammonia nitrogen concentration of 20.6 mg / L (removal rate of 26.4%).

[0056] Comparative Example 1

[0057] Traditional ozone catalyst 1: ALO series ozone catalyst from Shandong Aoxiangrun Environmental Protection Technology Co., Ltd., with filler material in the form of spherical shape with a diameter of 3~5mm.

[0058] Traditional ozone catalyst 2: Carbon-based ozone catalyst from Shandong Longantai Environmental Protection Technology Co., Ltd., with a rod-shaped structure of 2-3cm in length.

[0059] The two conventional ozone catalysts described above were used to treat a tetracycline solution with an initial concentration of 100 mg / L. The ozone catalyst loading rate was 60%, the ozone concentration was 10 mg / L, and the reaction time was 30 min. Testing showed a TOC removal rate of 81.5%, lower than that of Example 1, indicating that the Co-MoS2@PTFE catalytic membrane prepared in this application, combined with a cross-flow internal circulation method, is beneficial for improving the efficiency of ozone catalytic oxidation.

[0060] Comparative Example 2

[0061] This comparative example provides a method for preparing a common ozone catalytic membrane. The specific steps are the same as in Example 1, except that the surface plasma treatment in step S1 is not performed, and the ozone catalytic membrane is finally obtained.

[0062] The ozone catalytic membrane prepared above is applied to an ozone reaction device (such as...) via a cross-flow internal circulation method. Figure 1 As shown in Example 1), this method was used to treat a tetracycline solution with an initial concentration of 100 mg / L. The treatment parameters were the same as in Example 1. Tests showed that after a reaction time of 30 min, the average TOC removal rate was 72.4%. After 24 h of operation, the MoS2 shedding rate reached over 20%, and the removal rate decreased to 51%, demonstrating that plasma treatment of the PTFE membrane is crucial for maintaining stable catalyst loading in this technology.

[0063] Comparative Example 3

[0064] This comparative example provides a method for preparing an ozone catalytic membrane. The specific steps are the same as in Example 1, except that step S4 is not performed to obtain the MoS2@PTFE membrane.

[0065] The MoS2@PTFE membrane prepared above was applied in an ozone reactor (e.g., using a cross-flow internal circulation method). Figure 1 (As shown), it was used to treat a tetracycline solution with an initial concentration of 100 mg / L. The treatment parameters were the same as in Example 1. After a reaction time of 30 min, the average TOC removal rate was 70.5%, demonstrating that the Co-MoS2 heterojunction formed by the transition metal Co support is key to maintaining the catalytic activity of the catalyst.

[0066] Those skilled in the art should understand that the above descriptions are merely several specific embodiments of the present invention, and not all embodiments. It should be noted that many modifications and improvements can be made by those skilled in the art, and all modifications or improvements not exceeding the scope of the claims should be considered within the protection scope of the present invention.

Claims

1. A method for preparing a Co-MoS2@PTFE ozone catalytic membrane, characterized in that, Includes the following steps: S1. Take a PTFE hollow fiber membrane and perform surface plasma treatment to obtain a p-PTFE membrane; S2. Take ammonium molybdate tetrahydrate or sodium molybdate dihydrate and dissolve it together with thiourea in water with pH adjusted to 1-2 to form a mixture. The concentration of ammonium molybdate tetrahydrate or sodium molybdate dihydrate in the mixture is 5-15 mmol / L and the concentration of thiourea is 1-4 mmol / L. S3. Immerse the p-PTFE membrane from step S1 into the mixture from step S2 and sonicate it. Then transfer it to a high-pressure reactor and heat it at 180~210℃ for 6~24h. After cooling to room temperature, collect the product, wash and dry it to obtain the MoS2@PTFE membrane. S4. Immerse the MoS2@PTFE membrane in a Co(NO3)2·6H2O solution, then add reducing agent hydrazine hydrate N2H4·H2O or hydroxylamine NH2OH or ammonia water NH3·H2O, react at 60~65℃ for 6~8h, remove, wash and dry to obtain Co-MoS2@PTFE ozone catalytic membrane; Steps S1 and S2 are not in any particular order.

2. The method for preparing the Co-MoS2@PTFE ozone catalytic membrane according to claim 1, characterized in that, The PTFE hollow fiber membrane has a length of 10~20cm, an inner and outer diameter of 0.5~0.8 / 1.0~1.5mm respectively, a pore size of 0.1~1.0μm, and a porosity of ≥80%.

3. The method for preparing the Co-MoS2@PTFE ozone catalytic membrane according to claim 1, characterized in that, In step S1, the surface plasma treatment uses alternating current with an output frequency of 1~3GHz, a treatment pressure of 100~500Pa, a treatment temperature of 200~250℃, and a treatment time of 1~2h.

4. The method for preparing the Co-MoS2@PTFE ozone catalytic membrane according to claim 1, 2, or 3, characterized in that, In step S4, the concentration of the Co(NO3)2·6H2O solution is 1~5 wt%; the mass ratio of the MoS2@PTFE membrane added to the Co(NO3)2·6H2O solution is 1~10%; and the mass ratio of the reducing agent added to the Co(NO3)2·6H2O solution is 1~5%.

5. The method for preparing the Co-MoS2@PTFE ozone catalytic membrane according to claim 1, characterized in that, In step S2, hydrochloric acid or sulfuric acid is used to adjust the pH of the water to 1-2.

6. The method for preparing the Co-MoS2@PTFE ozone catalytic membrane according to claim 1, characterized in that, In step S3, the collected product is washed several times in distilled water and ethanol, and then dried at 60-70°C for 24-48 hours.

7. The method for preparing the Co-MoS2@PTFE ozone catalytic membrane according to claim 1, characterized in that, In step S3, the p-PTFE membrane from step S1 is immersed in the mixture from step S2 and ultrasonically treated for 1-2 hours.

8. A Co-MoS2@PTFE ozone catalytic membrane prepared by the method of any one of claims 1-7.

9. The application of the Co-MoS2@PTFE ozone catalytic membrane according to claim 8 in the removal of pollutants in water.

10. The application of the Co-MoS2@PTFE ozone catalytic membrane according to claim 9 in the removal of pollutants in water, characterized in that, A Co-MoS2@PTFE ozone catalytic membrane was applied in an ozone reactor via a cross-flow internal circulation system to remove pollutants from water. The ozone dosage was 10-50 mg / L, and the membrane flux of the cross-flow internal circulation system was 10-80 L / (m²). 2 The internal circulation reflux ratio is 1:1, the reaction time is 0.5~1h, and the operating throughput is 10~20LMH.

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