BiMn-coated CPAN composite material as well as preparation method and application thereof

Abstract

The invention belongs to the technical field of photocatalytic environment purification, discloses a BiMn-coated CPAN composite material as well as a preparation method and application thereof, and aims to solve the technical problems that the catalytic degradation rate of antibiotics is low and catalytic materials are difficult to recycle. The preparation method comprises the following steps: preparing a BiMn catalyst by taking sodium bismuthate dehydrate and manganese chloride tetrahydrate as raw materials through an in-situ loading method, and obtaining BiMn suspension liquid by adopting an ultrasonic dispersion method; and uniformly spraying the BiMn suspension onto the surface of the CPAN fiber to obtain the BiMn-coated CPAN composite material. The composite material can form a synergistic system with Fe < 3 + >, realizes efficient degradation of SMT in water under visible light irradiation, and has very strong anti-interference ability to the environment. The catalyst is simple to synthesize, low in cost, environment-friendly, capable of purifying environmental pollutants and good in stability.

Description

Technical Field

[0001] The present invention relates to the technical field of photocatalytic environmental purification, and particularly relates to a photocatalytic material. Background Art

[0002] Sulfonamide antibiotics are a broad-spectrum class of antibiotics used for the prevention and treatment of bacterial infections in humans and animals. Due to their poor biodegradability, sulfonamide drugs can accumulate in the environment, resulting in the frequent detection of these antibiotics in various water bodies, thus seriously threatening human health and the ecosystem and causing bacterial drug resistance. Researchers have developed a variety of techniques for removing antibiotics from water, which are generally divided into two main methods: non-destructive methods and destructive methods. Non-destructive methods include physical methods such as adsorption, liquid extraction, and membrane separation, while destructive methods mainly employ chemical oxidation and biodegradation techniques. Due to the sludge formation of pollutants, the pollutant removal rate of physicochemical methods is low, and from a sustainable perspective, biodegradation technology has good prospects, but it is difficult to completely and efficiently remove antibiotics from water. Therefore, the development of new methods for removing sulfonamide drugs has become a research hotspot in environmental science and water treatment. Advanced oxidation processes (AOPs) can generate highly reactive active species such as hydroxyl radicals (·OH), superoxide radicals (·O 2 ) and singlet oxygen ( 1 O 2 ) to achieve efficient degradation of antibiotics.

[0003] In recent years, photocatalytic technology has received increasing attention due to its high reaction rate, strong oxidation ability, and environmental friendliness, as well as its potential in degrading antibiotic pollutants. Photocatalysis generates electron-hole pairs by utilizing light energy, and these electron-hole pairs can interact with surface-adsorbed oxygen and water molecules to produce reactive oxygen species, thereby oxidizing and degrading organic pollutants into molecules with lower molecular weights and less harm. For example, in the prior art, CN118751260A discloses a photocatalyst, its preparation method, and its application in removing sulfonamide antibiotics from water, which is prepared by hydrothermal and calcination methods. Although the degradation efficiency of this material for sulfamethoxazole can reach 89%, the preparation method of its composite material is complex, and it still faces the technical problem of being difficult to recycle after one-time degradation. Summary of the Invention

[0004] Aiming at the technical problems of low catalytic degradation rate and difficult recycling of sulfonamide antibiotics, a BiMn@CPAN composite material, its preparation method and application are proposed. Carboxyl-modified polyacrylonitrile fiber (CPAN) is a commonly used fiber in the textile industry. Compared with other types of fibers, CPAN is reasonably priced and has strong chemical stability, and can stably exist in a highly saline and alkaline environment, becoming a promising carrier material. Most importantly, CPAN fibers contain abundant carboxylic acid groups, which results in strong covalent, electrostatic, hydrogen bond and other binding interactions between CPAN and the loaded catalyst. In the present invention, a BiMn@CPAN composite material is prepared, which has good stability and recyclability and can be used in the Fe 3+ synergistic photocatalytic system to achieve efficient degradation of sulfamethazine (SMT) in water bodies.

[0005] To achieve the above object, the technical solution of the present invention is realized as follows:

[0006] A preparation method of a BiMn@CPAN composite material, the steps are as follows:

[0007] (1) Dispersing sodium bismuthate dihydrate and manganese chloride tetrahydrate in deionized water, adding an alkali solution to adjust the pH to 9-11, stirring evenly to obtain a suspension; filtering, washing, drying and grinding the obtained suspension to obtain the catalyst BiMn;

[0008] (2) Dispersing the catalyst BiMn obtained in step (1) in ethanol to obtain a suspension;

[0009] (3) Spraying the suspension obtained in step (2) onto carboxyl-modified polyacrylonitrile fiber (CPAN) in small amounts and multiple times, and drying to obtain the BiMn@CPAN composite material.

[0010] In the above step (1), the molar ratio of sodium bismuthate dihydrate to manganese chloride tetrahydrate is 1:(1-100)×10 -5 .

[0011] In the above step (1), the addition amount (concentration) of sodium bismuthate dihydrate is 0.01-0.1 mol / L.

[0012] In the above step (1), the stirring temperature is 20-25 °C and the time is 30-40 min.

[0013] In the above step (2), the concentration of the catalyst BiMn in the suspension is 0.5-5 g / L.

[0014] Further, the carboxyl-modified polyacrylonitrile fiber in the above step (3) needs to be pretreated by washing, and the carboxyl content of the carboxyl-modified polyacrylonitrile fiber is 5-10 mmol / g.

[0015] In the above step (3), the spraying amount of the catalyst BiMn is 2 - 2.5 mg / cm 2 .

[0016] The BiMn@CPAN composite material prepared by the above method for preparing the BiMn@CPAN composite material.

[0017] The above BiMn@CPAN composite material in Fe 3+ Application in the synergistic photocatalytic degradation of antibiotics.

[0018] A method for the synergistic photocatalytic degradation of sulfonamide antibiotics, the steps are as follows: adding the above BiMn@CPAN composite material into a solution containing antibiotics and FeCl 3+ ·6H 3 O, after reaching the adsorption equilibrium through the dark reaction, carry out photocatalytic degradation under the irradiation of LED white light. 2 O.

[0019] Furthermore, the above antibiotics are any one of sulfamethazine, ciprofloxacin and tetracycline, and 6.25 μmol of FeCl 2 is required for each cm 3 ·6H 2 O of the BiMn@CPAN composite material.

[0020] Furthermore, the above antibiotic is sulfamethazine.

[0021] Taking the degradation of sulfamethazine as an example, the specific method is as follows: add 12.5 mL of 0.05 mmol / L sulfamethazine solution into the photocatalytic reaction flask, cut 1×1 cm 2 of the BiMn@CPAN composite material and add it to the reaction flask, add 625 μL of 10 mM FeCl 3 ·6H 2 O solution, carry out a 1-hour dark reaction adsorption under dark conditions and reach the adsorption equilibrium, then turn on the light source, and place the mixed solution under the irradiation of 5w LED white light to start photocatalytic degradation.

[0022] The beneficial effects of the present invention are as follows:

[0023] (1) The preparation of the BiMn@CPAN composite material disclosed in the present invention can be carried out by spraying at room temperature, and the preparation method is simple, easy to operate and low in cost.

[0024] (2) The BiMn@CPAN composite material prepared by the present invention and Fe 3+A photocatalytic synergistic system is formed to achieve efficient degradation of SMT in polluted water. That is, the degradation rate of SMT can reach as high as 97.49% after 1 h of adsorption and 6 h of photocatalytic reaction. This system has strong anti-interference ability and high catalytic activity in a wide pH range of 5 - 10. It has strong anti-interference ability against most impurity ions in water, and the degradation efficiency still remains above 65% after five cycle experiments, showing excellent reusability and stability. It has broad application prospects in the field of treating water organic pollutants. Brief Description of the Drawings

[0025] In order to more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the following will briefly introduce the drawings required for use in the description of the embodiments or the prior art. Obviously, the following drawings are only some embodiments of the present invention. For those of ordinary skill in the art, without creative efforts, other drawings can be obtained based on these drawings.

[0026] Figure 1 SEM images of the BiMn@CPAN composite material (left) and CPAN (right) prepared by the present invention.

[0027] Figure 2 Electrochemical impedance diagrams of the BiMn@CPAN composite material and CPAN prepared by the present invention.

[0028] Figure 3 Transient photocurrent diagrams of the BiMn@CPAN composite material and CPAN prepared by the present invention.

[0029] Figure 4 UV-Vis diffuse reflection diagrams of the BiMn@CPAN composite material and CPAN prepared by the present invention.

[0030] Figure 5 Photocatalytic degradation performance diagram of the BiMn@CPAN composite material prepared by the present invention.

[0031] Figure 6 Photocatalytic degradation performance diagrams of the BiMn@CPAN composite material prepared by the present invention at different pH values.

[0032] Figure 7 Photocatalytic degradation performance diagram of the BiMn@CPAN composite material prepared by the present invention after five cycles. Detailed Embodiments

[0033] Next, the technical solutions in the embodiments of the present invention will be clearly and completely described in conjunction with the accompanying drawings in the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without creative efforts shall fall within the protection scope of the present invention.

[0034] A preparation method of a BiMn@CPAN composite material is as follows:

[0035] (1) Dispersed sodium bismuthate dihydrate and manganese chloride tetrahydrate in deionized water, added an alkali solution to adjust the pH to 9-11, stirred evenly to obtain a suspension; the obtained suspension was filtered, washed, dried and ground to obtain the catalyst BiMn;

[0036] (2) Dispersed the catalyst BiMn obtained in step (1) in ethanol to obtain a suspension;

[0037] (3) Sprayed the suspension obtained in step (2) onto carboxyl-modified polyacrylonitrile fibers (CPAN) in small amounts and multiple times, and obtained the BiMn@CPAN composite material after drying.

[0038] In the above step (1), the molar ratio of sodium bismuthate dihydrate to manganese chloride tetrahydrate is 1:(1-100)×10 -5 .

[0039] In the above step (1), the addition amount of sodium bismuthate dihydrate is 0.01-0.1 mol / L.

[0040] In the above step (1), the stirring temperature is 20-25 °C and the time is 30-40 min.

[0041] In the above step (2), the concentration of the catalyst BiMn in the suspension is 0.5-5 g / L.

[0042] Furthermore, the carboxyl-modified polyacrylonitrile fibers in the above step (3) need to be pretreated by washing.

[0043] In the above step (3), the carboxyl content of the carboxyl-modified polyacrylonitrile fibers is 5-10 mmol / g, and the spraying amount of the catalyst BiMn is 2-2.5 mg / cm 2 .

[0044] A BiMn@CPAN composite material prepared by using the above preparation method of the BiMn@CPAN composite material.

[0045] Example 1

[0046] A preparation method of a BiMn@CPAN composite material in this example is as follows:

[0047] (1) Weigh 0.316 g of sodium bismuthate dihydrate and 30 μL of 1 mM manganese chloride tetrahydrate, disperse them in 30 mL of deionized water, and stir at 25 °C for 0.5 h to form a homogeneous suspension; adjust the pH of the suspension to 9 using 1 mM sodium hydroxide solution, and continue stirring at 25 °C for 0.5 h. Filter and wash the suspension, rinse it repeatedly with deionized water 3 - 5 times, put the filter cake in an oven at 60 °C and dry it completely, then grind it evenly to obtain the BiMn catalyst.

[0048] (2) Cut the carboxyl - modified polyacrylonitrile fiber (CPAN fiber, hydroxyl content is 7.5 mmol / g) into 2×2 cm 2 blocks, ultrasonically clean them with absolute ethanol and ultrapure water for 1 h respectively, and then put them in an oven and dry at 60 °C for 4 h.

[0049] (3) Weigh 10 mg of BiMn and disperse it in 5 mL of ethanol solution by ultrasonic dispersion for 1 h to obtain a brown suspension. Spray the suspension onto the CPAN in small amounts and multiple times using a Max airbrush gun (the spraying amount of the catalyst BiMn on the polyacrylonitrile fiber is 2.2 mg / cm 2 ), and dry it in an oven at 50 °C to finally obtain the BiMn@CPAN composite material.

[0050] Figure 1 SEM spectra of a BiMn@CPAN composite material (a) and CPAN (b) prepared in this example. The surface of the pure CPAN fiber is relatively smooth and flat, showing a strip - like structure. After loading the catalyst BiMn, obvious particle protrusions appear on the surface of CPAN, which confirms the successful preparation of the BiMn@CPAN composite material.

[0051] Example 2

[0052] A preparation method of a BiMn@CPAN composite material in this example is as follows:

[0053] (1) Weigh 0.316 g of sodium bismuthate dihydrate and 30 μL of 1 mM manganese chloride tetrahydrate, disperse them in 30 mL of deionized water, and stir at 25 °C for 0.5 h to form a homogeneous suspension; adjust the pH of the suspension to 11 using 1 mM sodium hydroxide solution, and continue stirring at 25 °C for 0.5 h. Filter and wash the suspension, rinse it repeatedly with deionized water 3 - 5 times, put the filter cake in an oven at 60 °C and dry it completely, then grind it evenly to obtain the BiMn catalyst.

[0054] (2) Cut the carboxyl - modified polyacrylonitrile fiber (CPAN fiber, hydroxyl content is 5 mmol / g) into 2×2 cm 2The blocks were ultrasonically cleaned with absolute ethanol and ultrapure water for 1 h respectively, then placed in an oven and dried at 60 °C for 4 h.

[0055] (3) Weigh 10 mg of BiMn and disperse it in 5 mL of ethanol solution by ultrasonic dispersion for 1 h to obtain a brown suspension. The suspension was sprayed onto CPAN (the spraying amount of the catalyst BiMn on the polyacrylonitrile fiber is 2 mg / cm 2 ) in small amounts and multiple times with a Max airbrush gun, and then dried in an oven at 50 °C to finally obtain the BiMn@CPAN composite material.

[0056] Example 3

[0057] A preparation method of the BiMn@CPAN composite material in this example is as follows:

[0058] (1) Weigh 0.316 g of sodium bismuthate dihydrate and 30 μL of 1 mM manganese chloride tetrahydrate and disperse them in 30 mL of deionized water, and stir at 20 °C for 40 min to form a homogeneous suspension; use 1 mM sodium hydroxide solution to adjust the pH of the suspension to 10, and continue to stir at 25 °C for 0.5 h. The suspension was filtered and washed, rinsed repeatedly with deionized water for 3 - 5 times, and the filter cake was placed in an oven at 60 °C and dried completely, then ground evenly to obtain the BiMn catalyst.

[0059] (2) Cut the carboxyl - modified polyacrylonitrile fiber (CPAN fiber, with a hydroxyl content of 5 mmol / g) into 2×2 cm 2 The blocks were ultrasonically cleaned with absolute ethanol and ultrapure water for 1 h respectively, then placed in an oven and dried at 60 °C for 4 h.

[0060] (3) Weigh 10 mg of BiMn and disperse it in 20 mL of ethanol solution by ultrasonic dispersion for 1 h to obtain a brown suspension. The suspension was sprayed onto CPAN (the spraying amount of the catalyst BiMn on the polyacrylonitrile fiber is 2.5 mg / cm 2 ) in small amounts and multiple times with a Max airbrush gun, and then dried in an oven at 50 °C to finally obtain the BiMn@CPAN composite material.

[0061] Example 4

[0062] A preparation method of the BiMn@CPAN composite material in this example is as follows:

[0063] (1) Weigh 0.316 g of sodium bismuthate dihydrate and 10 μL of 1 mM manganese chloride tetrahydrate, disperse them in 10 mL of deionized water, and stir at 25 °C for 0.5 h to form a homogeneous suspension; adjust the pH of the suspension to 9 using 1 mM sodium hydroxide solution, and continue stirring at 25 °C for 0.5 h. Filter and wash the suspension, rinse it repeatedly with deionized water 3 - 5 times, put the filter cake in an oven at 60 °C and dry it completely, then grind it evenly to obtain the BiMn catalyst.

[0064] (2) Cut the carboxyl - modified polyacrylonitrile fiber (CPAN fiber, hydroxyl content is 10 mmol / g) into blocks of 2×2 cm 2 , ultrasonically clean it with anhydrous ethanol and ultrapure water for 1 h respectively, put it in an oven, and dry it at 60 °C for 4 h.

[0065] (3) Weigh 10 mg of BiMn and disperse it in 5 mL of ethanol solution, ultrasonically disperse for 1 h to obtain a brown suspension. Spray the suspension onto CPAN in small amounts and multiple times using a Max airbrush gun (the spraying amount of the catalyst BiMn on the polyacrylonitrile fiber is 2.2 mg / cm 2 ), and dry it in an oven at 50 °C to finally obtain the BiMn@CPAN composite material.

[0066] Example 5

[0067] A preparation method of a BiMn@CPAN composite material in this example is as follows:

[0068] (1) Weigh 0.316 g of sodium bismuthate dihydrate and 10 μL of 100 mM manganese chloride tetrahydrate, disperse them in 30 mL of deionized water, and stir at 25 °C for 0.5 h to form a homogeneous suspension; adjust the pH of the suspension to 9 using 1 mM sodium hydroxide solution, and continue stirring at 25 °C for 0.5 h. Filter and wash the suspension, rinse it repeatedly with deionized water 3 - 5 times, put the filter cake in an oven at 60 °C and dry it completely, then grind it evenly to obtain the BiMn catalyst.

[0069] (2) Cut the carboxyl - modified polyacrylonitrile fiber (CPAN fiber, hydroxyl content is 10 mmol / g) into blocks of 2×2 cm 2 , ultrasonically clean it with anhydrous ethanol and ultrapure water for 1 h respectively, put it in an oven, and dry it at 60 °C for 4 h.

[0070] (3) Weigh 10 mg of BiMn and disperse it in 5 mL of ethanol solution, ultrasonically disperse for 1 h to obtain a brown suspension. Spray the suspension onto CPAN in small amounts and multiple times using a Max airbrush gun (the spraying amount of the catalyst BiMn on the polyacrylonitrile fiber is 2 mg / cm 2 ), and dry it in an oven at 50 °C to finally obtain the BiMn@CPAN composite material.

[0071] Example 6

[0072] A preparation method of a BiMn@CPAN composite material in this example is as follows:

[0073] (1) Weigh 0.316 g of sodium bismuthate dihydrate and 30 μL of 1 mM manganese chloride tetrahydrate and disperse them in 100 mL of deionized water. Stir at 25 °C for 0.5 h to form a homogeneous suspension; adjust the pH of the suspension to 9 using 1 mM sodium hydroxide solution, and continue to stir at 25 °C for 0.5 h. Filter and wash the suspension, rinse it repeatedly with deionized water 3 - 5 times, put the filter cake into an oven at 60 °C and dry it completely, and grind it evenly to obtain the BiMn catalyst.

[0074] (2) Cut the carboxyl - modified polyacrylonitrile fiber (CPAN fiber, with a hydroxyl content of 10 mmol / g) into blocks of 2×2 cm 2 , ultrasonically clean it with absolute ethanol and ultrapure water for 1 h respectively, and put it into an oven and dry it at 60 °C for 4 h.

[0075] (3) Weigh 10 mg of BiMn and disperse it in 2 mL of ethanol solution by ultrasonic dispersion for 1 h to obtain a brown suspension. Use a Max airbrush gun to spray the suspension onto CPAN in small amounts and multiple times (the spraying amount of the catalyst BiMn on the polyacrylonitrile fiber is 2.5 mg / cm 2 ), and dry it in an oven at 50 °C to finally obtain the BiMn@CPAN composite material.

[0076] Example of implementation effect

[0077] Figure 2 The electrochemical impedance spectra of a BiMn@CPAN composite material and CPAN prepared in Example 1 of the present invention. It can be seen from the Nyquist plot that, compared with CPAN, BiMn@CPAN has a smaller Nyquist arc radius, indicating that the composite material has a lower charge transfer resistance and a higher charge transfer rate.

[0078] Figure 3 The transient photocurrent diagrams of a BiMn@CPAN composite material and CPAN prepared in Example 1 of the present invention. When the two materials are irradiated by an LED lamp, the photoelectric signal stability during the on - off cycle is very good, and the photocurrent signal intensity of BiMn@CPAN is much higher than that of CPAN, proving that the loading of the catalyst BiMn on the fiber surface is beneficial to improving the light absorption ability of CPAN.

[0079] Figure 4The UV-Vis diffuse reflectance spectra of a BiMn@CPAN composite material and CPAN prepared in Example 1 of the present invention. Compared with CPAN, the light absorption intensity of the BiMn@CPAN composite material is significantly enhanced, the light absorption range is increased, and the light absorption ability is enhanced.

[0080] Application Example

[0081] The BiMn@CPAN composite material prepared by the present invention is used for Fe 3+ Synergistic photocatalytic degradation of SMT. The specific application method is as follows: Add 12.5 mL of a 0.05 mmol / L sulfamethazine solution to a photocatalytic reaction flask, cut a 1×1 cm 2 piece of the BiMn@CPAN composite material and add it to the reaction flask, add 625 μL of a 10 mM FeCl 3 ·6H 2 O solution. After carrying out a 1-hour dark reaction adsorption under dark conditions and reaching the adsorption equilibrium, turn on the light source, and place the mixed solution under 5W LED white light irradiation to start photocatalytic degradation.

[0082] Figure 5 The photocatalytic degradation performance diagram of a BiMn@CPAN composite material prepared by the present invention. The degradation rates of SMT by materials CPAN, BiMn@CPAN, and BiMn@CPAN / Fe 3+ after 1 hour of adsorption and 6 hours of photocatalytic reaction are 1.1%, 88.9%, and 97.49% respectively, which confirms that the degradation performance of BiMn@CPAN is greatly improved under the synergistic photocatalysis of Fe 3+ synergistic photocatalysis.

[0083] Figure 6 The photocatalytic degradation performance diagram of the BiMn@CPAN composite material prepared by the present invention at different pH values. Compared with the acidic environment, the BiMn@CPAN composite material is more suitable for a neutral to slightly alkaline environment, and the degradation efficiency of SMT in the solution can reach more than 90% at this time.

[0084] Figure 7 The photocatalytic degradation performance diagram of a BiMn@CPAN composite material prepared by the present invention after five cycles. After five cycles, the efficiency of the BiMn@CPAN / Fe 3+ synergistic photocatalytic degradation of SMT can still reach 65.21%, showing excellent stability and reusability.

[0085] The above are only the preferred embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A method for preparing a BiMn@CPAN composite material, characterized in that: Here are the steps: (1) dispersing sodium bismuthate dihydrate and manganese chloride tetrahydrate in deionized water, adding an alkaline solution to adjust the pH to 9-11, and stirring evenly to obtain a suspension; filtering, washing, drying and grinding the obtained suspension to obtain a catalyst BiMn; (2) dispersing the catalyst BiMn obtained in step (1) in ethanol to obtain a suspension; (3) The suspension obtained in step (2) is sprayed onto the carboxyl-modified polyacrylonitrile fiber in small amounts and multiple times, and the BiMn@CPAN composite material is obtained after drying.

2. The method for preparing the BiMn@CPAN composite material according to claim 1, characterized in that: The mass ratio of sodium bismuthate dihydrate to manganese chloride tetrahydrate in step (1) is 1:(1-100)×10 -5 .

3. The method for preparing the BiMn@CPAN composite material according to claim 2, characterized in that: The concentration of sodium bismuthate dihydrate in step (1) is 0.01-0.1 mol / L.

4. The method for preparing the BiMn@CPAN composite material according to claim 3, characterized in that: The stirring temperature in step (1) is 20-25° C. and the stirring time is 30-40 min.

5. The method for preparing the BiMn@CPAN composite material according to claim 4, characterized in that: The concentration of the catalyst BiMn in the suspension of step (2) is 0.5-5 g / L.

6. The method for preparing the BiMn@CPAN composite material according to claim 5, characterized in that: In the step (3), the carboxyl content of the carboxyl-modified polyacrylonitrile fiber is 5-10 mmol / g, and the spraying amount of the catalyst BiMn is 2-2.5 mg / cm 2 .

7. A BiMn@CPAN composite material prepared by the method for preparing a BiMn@CPAN composite material according to any one of claims 1 to 6.

8. The BiMn@CPAN composite material according to claim 7 is 3+ Application in synergistic photocatalytic degradation of antibiotics.

9. A kind of Fe 3+ The method for collaborative photocatalytic degradation of antibiotics is characterized by: The steps are: adding the BiMn@CPAN composite material described in claim 7 into a solution containing antibiotics and FeCl3·6H2O, and after reaching adsorption equilibrium through dark reaction, photocatalytic degradation is performed under LED white light irradiation.

10. The method according to claim 9, characterized in that The antibiotic is any one of sulfamethoxazole, ciprofloxacin and tetracycline.

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