A thorn-shaped photothermal anode material and its application in sterilization in an electro-Fenton system

Abstract

The present invention belongs to the technical field of photothermal materials, and specifically relates to a thorn-shaped photothermal anode material and its application in sterilization in an electro-Fenton system. The thorn-shaped photothermal anode material provided by the present invention has a nano-thorn-like structure, which has a capture and puncture effect on cells, and can assist the free radicals generated by the electro-Fenton sterilization system to enter the microbial cells and react with cellular substances, thereby improving the utilization efficiency of hydroxyl radicals and enhancing the sterilization and disinfection effect; further, the thorn-shaped photothermal anode material has oxygen vacancies, which can serve as active centers to activate hydrogen peroxide to produce hydroxyl radicals, reduce the amount of reagent added, reduce iron sludge formation, and improve the operating efficiency of the system. The application of the thorn-shaped photothermal anode material to the construction of an electro-Fenton sterilization system can significantly improve the sterilization efficiency.

Description

Technical Field

[0001] The present invention belongs to the technical field of photothermal materials. More specifically, it relates to a thorn-shaped photothermal anode material and its application in sterilization in an electro-Fenton system. Background Art

[0002] Disinfection is a necessary step in water treatment to eliminate the hazards and spread of microorganisms such as bacteria and viruses. Traditional water disinfection technologies, including chlorine disinfection, ozone disinfection, and ultraviolet disinfection, have certain limitations. For example, the chlorine disinfection process produces a large number of disinfection by-products and bacterial resistance. In recent years, advanced oxidation technologies have gradually replaced conventional disinfection and sterilization technologies, and have made significant progress in the research of pathogenic microorganism killing in water and sewage. For example, through the effects of light, electricity, and ultrasound, catalysts are induced to produce active substances. The generated active substances can quickly oxidize organic pollutants and microorganisms in water, thereby achieving water purification and disinfection. However, the sterilization and disinfection effect still needs to be improved.

[0003] The electro-Fenton process is an electrochemical advanced oxidation technology that can directly generate OH through electrolysis and simultaneously achieve Fe 2+ with Fe 3+ To complete the cycle, just add an appropriate amount of Fe 2+ It can continuously produce a large amount of ·OH by combining with H2O2, and has the advantages of simple technology, easy operation and low cost. It is mainly used in the removal of organic matter. For example, Chinese patent application CN114988631A discloses a dual oxidation-electrochemical oxidation combined process for deep treatment of landfill leachate, which uses the electro-Fenton method to remove organic matter, but it is rarely used in sterilization and disinfection. This is because, in the process of oxidizing microorganisms in the electro-Fenton reaction system, the existence time of ·OH is very short, and it is easy to react with other substances in the water and be quenched; while bacteria have cell membranes and cell walls, and it is difficult for ·OH to react directly and quickly with intracellular substances. Therefore, during the disinfection process, the utilization rate of the generated ·OH is low, which directly reduces the efficiency of electro-Fenton disinfection and sterilization. In addition, the conventional electro-Fenton system requires the additional addition of Fe 2+ The agent produces ·OH, and the iron sludge produced is also prone to cause secondary pollution, which greatly limits the application of electro-Fenton method in sterilization and disinfection. Summary of the Invention

[0004] The technical problem to be solved by the present invention is to overcome the defects and shortcomings of the existing electro-Fenton method, which has a poor sterilization and disinfection effect, and to provide a thorn-shaped photothermal anode material, which can significantly improve the sterilization and disinfection effect of the electro-Fenton method.

[0005] The purpose of the present invention is to provide a method for preparing the thorn-shaped photothermal anode material.

[0006] Another object of the present invention is to provide the application of the thorn-shaped photothermal anode material for sterilization in an electro-Fenton system.

[0007] The present invention also provides an electro-Fenton sterilization system.

[0008] The above object of the present invention is achieved by the following technical solutions:

[0009] A spiky photothermal anode material, the spiky photothermal anode material is TiO with a nano-spiky structure 2-x , MnO 2-x or MoS 2-x , where 0 ≤ x < 2.

[0010] Furthermore, the length of the nano-spiky structure is 50 - 200 nm; preferably 200 nm. It can cause a perforation effect on the microbial cell membrane, increasing the cell membrane permeability and accelerating the entry of ·OH into the cell, thus enhancing the sterilization effect.

[0011] Preferably, 0 < x < 2. With oxygen vacancies, it can further catalyze H2O2 to generate ·OH, improving the sterilization efficiency.

[0012] In addition, the present invention also provides a preparation method of the spiky photothermal anode material. When the spiky photothermal anode material is TiO with a nano-spiky structure 2-x , it specifically includes the following steps:

[0013] Mix K2TiO(C2O4)2 and Escherichia coli cells evenly in a water - diethylene glycol mixed solution, perform hydrothermal reaction at 150 - 250 °C for 8 - 24 h, wash and dry the product, calcine at 500 °C for 1 - 3 h to remove Escherichia coli cells, anneal, wash and dry to obtain.

[0014] Among them, the mass ratio of K2TiO(C2O4)2 to Escherichia coli cells is 0.35:(0.1 - 1).

[0015] Preferably, the volume ratio of water to diethylene glycol in the water - diethylene glycol mixed solution is 1:(1 - 5).

[0016] Furthermore, when the spiky photothermal anode material is MnO with a nano-spiky structure 2-x , it specifically includes the following steps:

[0017] Add manganese salt and potassium chlorate into nitric acid solution, heat in a water bath until the solution color changes from brown to black, then perform hydrothermal reaction at 80 - 130 °C for 4 - 12 h, wash and dry the product, anneal, wash and dry to obtain.

[0018] Preferably, the manganese salt is selected from one or more of manganese sulfate, manganese chloride, and manganese nitrate; the concentration of the nitric acid solution is 8 - 16 mol L -1The molar ratio of the manganese salt and potassium chlorate is 1:5 to 20; the water bath heating temperature is 50 to 100°C and the time is 10 to 60 minutes; the washing is performed with deionized water and ethanol respectively.

[0019] Preferably, the annealing is performed under vacuum conditions at 300-400° C. at a heating rate of 5-20° C. / min for 2-8 hours. The formation of oxygen vacancies is controlled by changing the annealing atmosphere and annealing time.

[0020] Furthermore, the thorn-shaped photothermal anode material is MoS with a nano-thorn-shaped structure. 2-x The specific steps include:

[0021] Na2Mo4 and thioacetamide are placed in an ethanol-oleic acid mixed solution and mixed evenly, and hydrothermally reacted at 180-300°C for 4-24 hours. The intermediate product is washed (ethanol and water), dried, placed in ethanol and mixed evenly, and NaBH4 solution is added for ultrasonication, washed, and dried to obtain the product;

[0022] The mass ratio of the intermediate product to NaBH4 is 10:1 to (11.5 to 115). The formation of sulfur vacancies in the material can be controlled by changing the amount of NaBH4 added.

[0023] Preferably, the molar ratio of Na2Mo4 to thioacetamide is 4:(10-20); and the volume ratio of ethanol to oleic acid in the ethanol-oleic acid mixed solution is 1:(1-3).

[0024] Specifically, the drying is performed at 60-80° C. for 6-12 hours.

[0025] In addition, the present invention also claims protection for the application of the thorn-shaped photothermal anode material for sterilization in an electro-Fenton system.

[0026] Furthermore, the thorn-shaped photothermal anode material is sterilized under light and oxygen conditions.

[0027] The principle is as follows: under light irradiation conditions, the thorny photothermal anode material generates hot electrons and holes due to the photothermal effect. The holes can oxidize water to generate hydroxyl radicals. At the same time, the hot electrons transfer to the cathode and undergo a two-electron reduction reaction with oxygen molecules to generate hydrogen peroxide. The hydrogen peroxide is further activated by the vacancies in the photoanode to generate hydroxyl radicals. In addition, the thorny photothermal anode material with a tip thermal effect has a perforating effect on the microbial cell membrane, causing the cell membrane permeability to increase, accelerating the entry of OH into the cell, and reacting with cellular substances, thereby enhancing the bactericidal effect.

[0028] Preferably, the bacteria may be Escherichia coli (E. coli K-12), Staphylococcus aureus (S. aureus), Salmonella, Enterococcus faecalis (E. faecalis) and the like.

[0029] Based on the above application, the present invention also provides an electro-Fenton sterilization system, using the thorn-shaped photothermal anode material as the anode.

[0030] Furthermore, the electro-Fenton sterilization system includes an energy cathode, an anode made of the thorny photothermal anode material, a power supply, a reaction cell, an electrolyte and an oxygen supply pump.

[0031] Furthermore, the cathode is a platinum electrode, an activated carbon fiber electrode or a graphite electrode.

[0032] Furthermore, the anode is prepared by placing the thorn-shaped photothermal anode material in isopropyl alcohol, adding Nafion solution, ultrasonically dispersing, dripping the obtained dispersion on the front and back of the dried carbon felt, and air-drying.

[0033] Preferably, the concentration of the thorn-shaped photothermal anode material in isopropanol is 5-20 mg / mL, the volume ratio of isopropanol to Nafion solution is 1000:30-1000:50; the ultrasonic dispersion time is 0.5-1.5 h; 50-110 μL of dispersion liquid is added per square centimeter on the front and back of the carbon felt.

[0034] The present invention has the following beneficial effects:

[0035] The thorn-shaped photothermal anode material provided by the present invention has a nano-thorn-like structure, which has a capture and puncture effect on cells, can assist the free radicals generated by the electro-Fenton sterilization system to enter microbial cells and react with cellular substances, improve the utilization efficiency of hydroxyl free radicals, and enhance the sterilization and disinfection effect; further, the thorn-shaped photothermal anode material has oxygen vacancies, which can serve as active centers to activate hydrogen peroxide to produce hydroxyl free radicals, reduce the amount of reagent added, alleviate iron sludge formation, and improve the operating efficiency of the system.

[0036] The thorn-shaped photothermal anode material is used to construct an electro-Fenton sterilization system. The anode generates photothermal electrons and holes through the photothermal effect, which increases the yield of hydroxyl radicals at the anode and hydrogen peroxide at the cathode, and reduces power consumption. Compared with traditional disinfection and sterilization methods, the electro-Fenton sterilization system constructed by the present invention is used for water treatment, with less secondary pollution, higher free radical oxidizing properties, no microbial resistance, and higher sterilization efficiency. Moreover, due to the high oxidizing properties of free radicals, the present invention can also achieve a considerable treatment effect on difficult-to-degrade pollutants while sterilizing and disinfecting. In addition, the electro-Fenton sterilization system of the present invention is technologically advanced, simple to operate, and stable in operation. It has strong practicality and economy, and the equipment is small in size, making it suitable for a variety of sites with limited space. BRIEF DESCRIPTION OF THE DRAWINGS

[0037] Figure 1 The thorn-shaped TiO prepared in Example 1 2-x Scanning electron microscope (SEM) image of the photothermal anode material.

[0038] Figure 2 The thorn-shaped MnO prepared in Example 11 2-x Scanning electron microscope (SEM) image of the photothermal anode material.

[0039] Figure 3 Schematic diagram of the photoanode-electro-Fenton sterilization system with tip piercing effect and photothermal catalytic effect in the application example. DETAILED DESCRIPTION

[0040] The present invention will be further described below with reference to the accompanying drawings and specific examples, but the examples do not limit the present invention in any way. Unless otherwise specified, the reagents, methods and equipment used in the present invention are conventional reagents, methods and equipment in the art.

[0041] Unless otherwise specified, all reagents and materials used in the following examples were commercially available.

[0042] Example 1 A thorn-shaped TiO 2-x Photothermal anode materials

[0043] The preparation method of the material is as follows:

[0044] Weigh 2.1 g of LB broth powder into a conical flask, dissolve it in 100 mL of ultrapure water, and sterilize it under high temperature and high pressure (121°C, 30 min); after cooling to room temperature, use an inoculation loop to pick a single colony of Escherichia coli K-12 and inoculate it into the sterilized LB broth, place it in a constant temperature shaker (37°C, 140 rpm) and culture it for 24 h; after the culture is completed, remove the bacterial liquid from the shaker, centrifuge (5000 rpm, 5 min) to separate the remaining LB broth, and collect the bacteria.

[0045] 0.35 g of K2TiO(C2O4)2 and 1 g of Escherichia coli K-12 cells were added to a mixture of 10 mL of deionized water and 30 mL of diethylene glycol and stirred vigorously. After 1 hour, the solution was transferred to an autoclave and maintained at 180°C for 12 hours. The mixture was cooled to room temperature, and the precipitate was collected by centrifugation. After being washed three times with ultrapure water by filtration, the precipitate was dried in an oven at 80°C overnight. The obtained solid powder was calcined at 500°C in a muffle furnace for 2 hours to burn off the residual Escherichia coli cells at high temperature to form a hollow Escherichia coli-like shell structure. After cooling to room temperature, the dried sample was annealed at 350°C in vacuum at a heating rate of 10°C / min for 5 hours, washed with pure water, and dried at 80°C for 6 hours. The obtained material has a thorn-like structure with a length of about 200 nm. The scanning electron microscope (SEM) image is shown in FIG. Figure 1 .

[0046] Example 2 A thorn-shaped TiO2 photothermal anode material

[0047] The preparation method of the material is as follows:

[0048] Weigh 2.1 g of LB broth powder into a conical flask, dissolve it in 100 mL of ultrapure water, and sterilize it under high temperature and high pressure (121°C, 30 min); after cooling to room temperature, use an inoculation loop to pick a single colony of Escherichia coli K-12 and inoculate it into the sterilized LB broth, place it in a constant temperature shaker (37°C, 140 rpm) and culture it for 24 h; after the culture is completed, remove the bacterial liquid from the shaker, centrifuge (5000 rpm, 5 min) to separate the remaining LB broth, and collect the bacteria.

[0049] 0.35g K2TiO(C2O4)2 and 1g Escherichia coli K-12 cells were added to a mixture of 10mL deionized water and 30mL diethylene glycol and stirred vigorously. After 1 hour, the solution was transferred to a high-pressure reactor, maintained at 180°C for 12 hours, cooled to room temperature, and the precipitate was collected by centrifugation. After being filtered and washed three times with ultrapure water, it was placed in an 80°C oven and dried overnight; the obtained solid powder was placed in a muffle furnace and calcined at 500°C for 2 hours to burn off the residual Escherichia coli cells at high temperature to form a hollow Escherichia coli-like shell structure. After cooling to room temperature, the dried sample was annealed in air at 350°C at a heating rate of 10°C / min for 5 hours, washed with pure water, and dried at 80°C for 6 hours.

[0050] Example 3 A thorn-shaped TiO 2-x Photothermal anode materials

[0051] The preparation method of the material is as follows:

[0052] Weigh 2.1 g of LB broth powder into a conical flask, dissolve it in 100 mL of ultrapure water, and sterilize it under high temperature and high pressure (121°C, 30 min); after cooling to room temperature, use an inoculation loop to pick a single colony of Escherichia coli K-12 and inoculate it into the sterilized LB broth, place it in a constant temperature shaker (37°C, 140 rpm) and culture it for 24 h; after the culture is completed, remove the bacterial liquid from the shaker, centrifuge (5000 rpm, 5 min) to separate the remaining LB broth, and collect the bacteria.

[0053] 0.35g K2TiO(C2O4)2 and 1g Escherichia coli K-12 cells were added to a mixture of 10mL deionized water and 30mL diethylene glycol and stirred vigorously. After 1 hour, the solution was transferred to a high-pressure reactor, maintained at 150°C for 12 hours, cooled to room temperature, and the precipitate was collected by centrifugation. After being filtered and washed three times with ultrapure water, it was placed in an 80°C oven and dried overnight; the obtained solid powder was placed in a muffle furnace and calcined at 500°C for 2 hours to burn off the residual Escherichia coli cells at high temperature to form a hollow Escherichia coli-like shell structure. After cooling to room temperature, the dried sample was annealed at 350°C in a vacuum at a heating rate of 10°C / min for 5 hours, washed with pure water, and dried at 80°C for 6 hours.

[0054] Example 4 A thorn-shaped TiO 2-x Photothermal anode materials

[0055] The preparation method of the material is as follows:

[0056] Weigh 2.1 g of LB broth powder into a conical flask, dissolve it in 100 mL of ultrapure water, and sterilize it under high temperature and high pressure (121°C, 30 min); after cooling to room temperature, use an inoculation loop to pick a single colony of Escherichia coli K-12 and inoculate it into the sterilized LB broth, place it in a constant temperature shaker (37°C, 140 rpm) and culture it for 24 h; after the culture is completed, remove the bacterial liquid from the shaker, centrifuge (5000 rpm, 5 min) to separate the remaining LB broth, and collect the bacteria.

[0057] 0.35g K2TiO(C2O4)2 and 1g Escherichia coli K-12 cells were added to a mixture of 10mL deionized water and 30mL diethylene glycol and stirred vigorously. After 1 hour, the solution was transferred to a high-pressure reactor, maintained at 250°C for 12 hours, cooled to room temperature, and the precipitate was collected by centrifugation. After being filtered and washed three times with ultrapure water, it was placed in an 80°C oven and dried overnight; the obtained solid powder was placed in a muffle furnace and calcined at 500°C for 2 hours to burn off the residual Escherichia coli cells at high temperature to form a hollow Escherichia coli-like shell structure. After cooling to room temperature, the dried sample was annealed at 350°C in a vacuum at a heating rate of 10°C / min for 5 hours, washed with pure water, and dried at 80°C for 6 hours.

[0058] Example 5 A thorn-shaped TiO 2-x Photothermal anode materials

[0059] The preparation method of the material is as follows:

[0060] Weigh 2.1 g of LB broth powder into a conical flask, dissolve it in 100 mL of ultrapure water, and sterilize it under high temperature and high pressure (121°C, 30 min); after cooling to room temperature, use an inoculation loop to pick a single colony of Escherichia coli K-12 and inoculate it into the sterilized LB broth, place it in a constant temperature shaker (37°C, 140 rpm) and culture it for 24 h; after the culture is completed, remove the bacterial liquid from the shaker, centrifuge (5000 rpm, 5 min) to separate the remaining LB broth, and collect the bacteria.

[0061] 0.35g K2TiO(C2O4)2 and 1g Escherichia coli K-12 cells were added to a mixture of 10mL deionized water and 30mL diethylene glycol and stirred vigorously. After 1 hour, the solution was transferred to a high-pressure reactor, maintained at 180°C for 8 hours, cooled to room temperature, and the precipitate was collected by centrifugation. After being filtered and washed three times with ultrapure water, it was placed in an 80°C oven and dried overnight; the obtained solid powder was placed in a muffle furnace and calcined at 500°C for 2 hours to burn off the residual Escherichia coli cells at high temperature to form a hollow Escherichia coli-like shell structure. After cooling to room temperature, the dried sample was annealed at 350°C in a vacuum at a heating rate of 10°C / min for 5 hours, washed with pure water, and dried at 80°C for 6 hours. The obtained material has a thorn-like structure length of about 50nm.

[0062] Example 6 A thorn-shaped TiO 2-x Photothermal anode materials

[0063] The preparation method of the material is as follows:

[0064] Weigh 2.1 g of LB broth powder into a conical flask, dissolve it in 100 mL of ultrapure water, and sterilize it under high temperature and high pressure (121°C, 30 min); after cooling to room temperature, use an inoculation loop to pick a single colony of Escherichia coli K-12 and inoculate it into the sterilized LB broth, place it in a constant temperature shaker (37°C, 140 rpm) and culture it for 24 h; after the culture is completed, remove the bacterial liquid from the shaker, centrifuge (5000 rpm, 5 min) to separate the remaining LB broth, and collect the bacteria.

[0065] 0.35g K2TiO(C2O4)2 and 1g Escherichia coli K-12 cells were added to a mixture of 10mL deionized water and 30mL diethylene glycol and stirred vigorously. After 1 hour, the solution was transferred to a high-pressure reactor, maintained at 180°C for 24 hours, cooled to room temperature, and the precipitate was collected by centrifugation. After being filtered and washed three times with ultrapure water, it was placed in an 80°C oven and dried overnight; the obtained solid powder was placed in a muffle furnace and calcined at 500°C for 2 hours to burn off the residual Escherichia coli cells at high temperature to form a hollow Escherichia coli-like shell structure. After cooling to room temperature, the dried sample was annealed at 350°C in a vacuum at a heating rate of 10°C / min for 5 hours, washed with pure water, and dried at 80°C for 6 hours. The obtained material has a thorn-like structure length of about 150nm.

[0066] Example 7 A thorn-shaped TiO 2-x Photothermal anode materials

[0067] The preparation method of the material is as follows:

[0068] Weigh 2.1 g of LB broth powder into a conical flask, dissolve it in 100 mL of ultrapure water, and sterilize it under high temperature and high pressure (121°C, 30 min); after cooling to room temperature, use an inoculation loop to pick a single colony of Escherichia coli K-12 and inoculate it into the sterilized LB broth, place it in a constant temperature shaker (37°C, 140 rpm) and culture it for 24 h; after the culture is completed, remove the bacterial liquid from the shaker, centrifuge (5000 rpm, 5 min) to separate the remaining LB broth, and collect the bacteria.

[0069] 0.35g K2TiO(C2O4)2 and 1g Escherichia coli K-12 cells were added to a mixture of 10mL deionized water and 30mL diethylene glycol and stirred vigorously. After 1 hour, the solution was transferred to a high-pressure reactor, maintained at 180°C for 12 hours, cooled to room temperature, and the precipitate was collected by centrifugation. After being filtered and washed three times with ultrapure water, it was placed in an 80°C oven and dried overnight; the obtained solid powder was placed in a muffle furnace and calcined at 500°C for 2 hours to burn off the residual Escherichia coli cells at high temperature to form a hollow Escherichia coli-like shell structure. After cooling to room temperature, the dried sample was annealed at 300°C in a vacuum at a heating rate of 10°C / min for 5 hours, washed with pure water, and dried at 80°C for 6 hours.

[0070] Example 8 A thorn-shaped TiO 2-x Photothermal anode materials

[0071] The preparation method of the material is as follows:

[0072] Weigh 2.1 g of LB broth powder into a conical flask, dissolve it in 100 mL of ultrapure water, and sterilize it under high temperature and high pressure (121°C, 30 min); after cooling to room temperature, use an inoculation loop to pick a single colony of Escherichia coli K-12 and inoculate it into the sterilized LB broth, place it in a constant temperature shaker (37°C, 140 rpm) and culture it for 24 h; after the culture is completed, remove the bacterial liquid from the shaker, centrifuge (5000 rpm, 5 min) to separate the remaining LB broth, and collect the bacteria.

[0073] 0.35g K2TiO(C2O4)2 and 1g Escherichia coli K-12 cells were added to a mixture of 10mL deionized water and 30mL diethylene glycol and stirred vigorously. After 1 hour, the solution was transferred to a high-pressure reactor, maintained at 180°C for 12 hours, cooled to room temperature, and the precipitate was collected by centrifugation. After being filtered and washed three times with ultrapure water, it was placed in an 80°C oven and dried overnight; the obtained solid powder was placed in a muffle furnace and calcined at 500°C for 2 hours to burn off the residual Escherichia coli cells at high temperature to form a hollow Escherichia coli-like shell structure. After cooling to room temperature, the dried sample was annealed at 400°C in a vacuum at a heating rate of 10°C / min for 5 hours, washed with pure water, and dried at 80°C for 6 hours.

[0074] Example 9 A thorn-shaped TiO 2-x Photothermal anode materials

[0075] The preparation method of the material is as follows:

[0076] Weigh 2.1 g of LB broth powder into a conical flask, dissolve it in 100 mL of ultrapure water, and sterilize it under high temperature and high pressure (121°C, 30 min); after cooling to room temperature, use an inoculation loop to pick a single colony of Escherichia coli K-12 and inoculate it into the sterilized LB broth, place it in a constant temperature shaker (37°C, 140 rpm) and culture it for 24 h; after the culture is completed, remove the bacterial liquid from the shaker, centrifuge (5000 rpm, 5 min) to separate the remaining LB broth, and collect the bacteria.

[0077] 0.35g K2TiO(C2O4)2 and 1g Escherichia coli K-12 cells were added to a mixture of 10mL deionized water and 30mL diethylene glycol and stirred vigorously. After 1h, the solution was transferred to a high-pressure reactor, maintained at 180℃ for 12h, cooled to room temperature, and the precipitate was collected by centrifugation. After being filtered and washed three times with ultrapure water, it was placed in an 80℃ oven and dried overnight; the obtained solid powder was placed in a muffle furnace and calcined at 500℃ for 2h to burn off the residual Escherichia coli cells at high temperature to form a hollow Escherichia coli-like shell structure. After cooling to room temperature, the dried sample was annealed at 350℃ in a vacuum at a heating rate of 10℃ / min for 2h, washed with pure water, and dried at 80℃ for 6h. The obtained material has a thorn-like structure length of about 200nm.

[0078] Example 10 A thorn-shaped TiO 2-x Photothermal anode materials

[0079] The preparation method of the material is as follows:

[0080] Weigh 2.1 g of LB broth powder into a conical flask, dissolve it in 100 mL of ultrapure water, and sterilize it under high temperature and high pressure (121°C, 30 min); after cooling to room temperature, use an inoculation loop to pick a single colony of Escherichia coli K-12 and inoculate it into the sterilized LB broth, place it in a constant temperature shaker (37°C, 140 rpm) and culture it for 24 h; after the culture is completed, remove the bacterial liquid from the shaker, centrifuge (5000 rpm, 5 min) to separate the remaining LB broth, and collect the bacteria.

[0081] 0.35g K2TiO(C2O4)2 and 1g Escherichia coli K-12 cells were added to a mixture of 10mL deionized water and 30mL diethylene glycol and stirred vigorously. After 1 hour, the solution was transferred to a high-pressure reactor, maintained at 180°C for 12 hours, cooled to room temperature, and the precipitate was collected by centrifugation. After being filtered and washed three times with ultrapure water, it was placed in an 80°C oven and dried overnight; the obtained solid powder was placed in a muffle furnace and calcined at 500°C for 2 hours to burn off the residual Escherichia coli cells at high temperature to form a hollow Escherichia coli-like shell structure. After cooling to room temperature, the dried sample was annealed at 350°C in a vacuum at a heating rate of 10°C / min for 8 hours, washed with pure water, and dried at 80°C for 6 hours.

[0082] Example 11 A thorn-shaped MnO 2-x Photothermal anode materials

[0083] The preparation method of the material is as follows:

[0084] 60 mL of 16 mol L -1 Nitric acid, 0.01 mol manganese sulfate solid, and 0.015 mol potassium chlorate solid were added to a 150 mL three-necked round-bottom flask equipped with a reflux condenser and a magnetic stirrer. The mixture was heated to 80°C in a water bath and maintained for 30 min. The color of the solution was observed to change from brown to black. The black mixture was transferred to a 100 mL polytetrafluoroethylene-lined hydrothermal reactor and subjected to a hydrothermal reaction at 110°C for 6 h. After the reaction, the precipitate was collected, washed with deionized water and ethanol, respectively, and dried in an oven at 80°C. The dried sample was annealed at 350°C in a vacuum at a heating rate of 10°C / min for 5 h, washed with pure water, and dried at 80°C for 6 h. The SEM image is shown in FIG. Figure 2 .

[0085] Example 12: A thorn-shaped MnO2 photothermal anode material

[0086] The preparation method of the material is as follows:

[0087] 60 mL of 16 mol L -1 Nitric acid, 0.01 mol manganese sulfate solid and 0.015 mol potassium chlorate solid were added to a 150 mL three-necked round-bottom flask equipped with a reflux condenser and a magnetic stirrer, heated to 80°C in a water bath and maintained for 30 min. It was observed that the color of the solution changed from brown to black. The black mixture was transferred to a 100 mL polytetrafluoroethylene-lined hydrothermal autoclave and subjected to a hydrothermal reaction at 110°C for 6 h. After the reaction, the generated precipitates were collected, washed with deionized water and ethanol, respectively, and dried in an oven at 80°C. The dried sample was annealed at 350°C in air at a heating rate of 10°C / min for 5 h, washed with pure water, and dried at 80°C for 6 h.

[0088] Example 13 A thorn-shaped MnO 2-x Photothermal anode materials

[0089] The preparation method of the material is as follows:

[0090] 60 mL of 16 mol L -1 Nitric acid, 0.01 mol manganese sulfate solid and 0.015 mol potassium chlorate solid were added to a 150 mL three-necked round-bottom flask equipped with a reflux condenser and a magnetic stirrer, heated to 80°C in a water bath and maintained for 30 min. It was observed that the color of the solution changed from brown to black. The black mixture was transferred to a 100 mL polytetrafluoroethylene-lined hydrothermal autoclave and subjected to a hydrothermal reaction at 110°C for 4 h. After the reaction, the generated precipitates were collected, washed with deionized water and ethanol, respectively, and dried in an oven at 80°C. The dried sample was annealed at 350°C in a vacuum at a heating rate of 10°C / min for 5 h, washed with pure water, and dried at 80°C for 6 h.

[0091] Example 14 A thorn-shaped MnO 2-x Photothermal anode materials

[0092] The preparation method of the material is as follows:

[0093] 60 mL of 16 mol L -1Nitric acid, 0.01 mol manganese sulfate solid and 0.015 mol potassium chlorate solid were added to a 150 mL three-necked round-bottom flask equipped with a reflux condenser and a magnetic stirrer, heated to 80°C in a water bath and maintained for 30 min. It was observed that the color of the solution changed from brown to black. The black mixture was transferred to a 100 mL polytetrafluoroethylene-lined hydrothermal autoclave and subjected to a hydrothermal reaction at 110°C for 12 h. After the reaction, the generated precipitates were collected, washed with deionized water and ethanol, respectively, and dried in an oven at 80°C. The dried sample was annealed at 350°C in a vacuum at a heating rate of 10°C / min for 5 h, washed with pure water, and dried at 80°C for 6 h.

[0094] Example 15 A thorn-shaped MnO 2-x Photothermal anode materials

[0095] The preparation method of the material is as follows:

[0096] 60 mL of 16 mol L -1 Nitric acid, 0.01 mol manganese sulfate solid and 0.015 mol potassium chlorate solid were added to a 150 mL three-necked round-bottom flask equipped with a reflux condenser and a magnetic stirrer, heated to 80°C in a water bath and maintained for 30 min. It was observed that the color of the solution changed from brown to black. The black mixture was transferred to a 100 mL polytetrafluoroethylene-lined hydrothermal autoclave and subjected to a hydrothermal reaction at 80°C for 6 h. After the reaction, the generated precipitate was collected, washed with deionized water and ethanol, respectively, and dried in an oven at 80°C. The dried sample was annealed at 350°C in a vacuum at a heating rate of 10°C / min for 5 h, washed with pure water, and dried at 80°C for 6 h.

[0097] Example 16 A thorn-shaped MnO 2-x Photothermal anode materials

[0098] The preparation method of the material is as follows:

[0099] 60 mL of 16 mol L -1 Nitric acid, 0.01 mol manganese sulfate solid and 0.015 mol potassium chlorate solid were added to a 150 mL three-necked round-bottom flask equipped with a reflux condenser and a magnetic stirrer, heated to 80°C in a water bath and maintained for 30 min. It was observed that the color of the solution changed from brown to black. The black mixture was transferred to a 100 mL polytetrafluoroethylene-lined hydrothermal autoclave and subjected to a hydrothermal reaction at 130°C for 6 h. After the reaction, the generated precipitate was collected, washed with deionized water and ethanol, respectively, and dried in an oven at 80°C. The dried sample was annealed at 350°C in a vacuum at a heating rate of 10°C / min for 5 h, washed with pure water, and dried at 80°C for 6 h.

[0100] Example 17 A thorn-shaped MnO 2-xPhotothermal anode materials

[0101] The preparation method of the material is as follows:

[0102] 60 mL of 16 mol L -1 Nitric acid, 0.01 mol manganese sulfate solid and 0.015 mol potassium chlorate solid were added to a 150 mL three-necked round-bottom flask equipped with a reflux condenser and a magnetic stirrer, heated to 80°C in a water bath and maintained for 30 min. It was observed that the color of the solution changed from brown to black. The black mixture was transferred to a 100 mL polytetrafluoroethylene-lined hydrothermal autoclave and subjected to a hydrothermal reaction at 110°C for 6 h. After the reaction, the generated precipitates were collected, washed with deionized water and ethanol, respectively, and dried in an oven at 80°C. The dried sample was annealed at 350°C in a vacuum at a heating rate of 10°C / min for 2 h, washed with pure water, and dried at 80°C for 6 h.

[0103] Example 18 A thorn-shaped MnO 2-x Photothermal anode materials

[0104] The preparation method of the material is as follows:

[0105] 60 mL of 16 mol L -1 Nitric acid, 0.01 mol manganese sulfate solid and 0.015 mol potassium chlorate solid were added to a 150 mL three-necked round-bottom flask equipped with a reflux condenser and a magnetic stirrer, heated to 80°C in a water bath and maintained for 30 min. It was observed that the color of the solution changed from brown to black. The black mixture was transferred to a 100 mL polytetrafluoroethylene-lined hydrothermal autoclave and subjected to a hydrothermal reaction at 110°C for 6 h. After the reaction, the generated precipitates were collected, washed with deionized water and ethanol, respectively, and dried in an oven at 80°C. The dried sample was annealed at 350°C in a vacuum at a heating rate of 10°C / min for 8 h, washed with pure water, and dried at 80°C for 6 h.

[0106] Example 19: A thorn-shaped MoS 2-x Photothermal anode materials

[0107] The preparation method of the material is as follows:

[0108] 4mmol Na2Mo4 and 15mmol thioacetamide (CH3CSNH2) were added to 10mL ethanol (C2H6O) and 20ml oleic acid (C 18 H 34O2) mixture, stirred for 30 min, the solution was transferred to a 40 mL polytetrafluoroethylene tube, sealed in an autoclave, heated to 240 ° C for 24 h; after cooling to room temperature, the obtained product was washed with ethanol and water several times, and dried at 60 ° C for 12 h to obtain MoS2; 10 mg of the obtained MoS2 was added to 4 ml of ethanol and ultrasonicated for 30 min to obtain a uniform suspension, and 6 mL of 0.1 mol L -1 NaBH4, further ultrasonically treated for 2 h, cooled to room temperature, and the resulting product was washed with ethanol and water several times, and dried at 60 °C for 12 h.

[0109] Example 20 A thorn-shaped MoS2 photothermal anode material

[0110] The preparation method of the material is as follows:

[0111] 4mmol Na2Mo4 and 15mmol thioacetamide (CH3CSNH2) were added to 10mL ethanol (C2H6O) and 20ml oleic acid (C 18 H 34 O2) and stirred for 30 minutes. The solution was transferred to a 40 mL polytetrafluoroethylene tube and sealed in an autoclave, heated to 240 ° C for reaction for 24 hours; after cooling to room temperature, the resulting product was washed with ethanol and water several times, and dried at 60 ° C for 12 hours to obtain MoS2; 10 mg of the obtained MoS2 was added to 4 ml of ethanol and ultrasonically treated for 30 minutes to obtain a uniform suspension, 6 mL of deionized water was added, and further ultrasonically treated for 2 hours. After cooling to room temperature, the resulting product was washed with ethanol and water several times, and dried at 60 ° C for 12 hours.

[0112] Example 21 A thorn-shaped MoS 2-x Photothermal anode materials

[0113] The preparation method of the material is as follows:

[0114] 4mmol Na2Mo4 and 15mmol thioacetamide (CH3CSNH2) were added to 10mL ethanol (C2H6O) and 20ml oleic acid (C 18 H 34 O2) mixture, stirred for 30 min, the solution was transferred to a 40 mL polytetrafluoroethylene tube, sealed in an autoclave, heated to 240 ° C for 4 h; after cooling to room temperature, the obtained product was washed with ethanol and water several times, and dried at 60 ° C for 12 h to obtain MoS2; 10 mg of the obtained MoS2 was added to 4 ml of ethanol and ultrasonicated for 30 min to obtain a uniform suspension, and 6 mL of 0.1 mol L -1NaBH4, further ultrasonically treated for 2 h, cooled to room temperature, and the resulting product was washed with ethanol and water several times, and dried at 60 °C for 12 h.

[0115] Example 22 A thorn-shaped MoS 2-x Photothermal anode materials

[0116] The preparation method of the material is as follows:

[0117] 4mmol Na2Mo4 and 15mmol thioacetamide (CH3CSNH2) were added to 10mL ethanol (C2H6O) and 20ml oleic acid (C 18 H 34 O2) mixture, stirred for 30 min, the solution was transferred to a 40 mL polytetrafluoroethylene tube, sealed in an autoclave, heated to 240 ° C for 12 h; after cooling to room temperature, the obtained product was washed with ethanol and water several times, and dried at 60 ° C for 12 h to obtain MoS2; 10 mg of the obtained MoS2 was added to 4 ml of ethanol and ultrasonicated for 30 min to obtain a uniform suspension, and 6 mL of 0.1 mol L -1 NaBH4, further ultrasonically treated for 2 h, cooled to room temperature, and the resulting product was washed with ethanol and water several times, and dried at 60 °C for 12 h.

[0118] Example 23: A thorn-shaped MoS 2-x Photothermal anode materials

[0119] The preparation method of the material is as follows:

[0120] 4mmol Na2Mo4 and 15mmol thioacetamide (CH3CSNH2) were added to 10mL ethanol (C2H6O) and 20ml oleic acid (C 18 H 34 O2) mixture, stirred for 30 min, the solution was transferred to a 40 mL polytetrafluoroethylene tube, sealed in an autoclave, heated to 240 ° C for 24 h; after cooling to room temperature, the obtained product was washed with ethanol and water several times, and dried at 60 ° C for 12 h to obtain MoS2; 10 mg of the obtained MoS2 was added to 4 ml of ethanol, ultrasonicated for 30 min to obtain a uniform suspension, and 6 mL of 0.05 mol L -1 NaBH4, further ultrasonically treated for 2 h, cooled to room temperature, and the resulting product was washed with ethanol and water several times, and dried at 60 °C for 12 h.

[0121] Example 24: A thorn-shaped MoS 2-x Photothermal anode materials

[0122] The preparation method of the material is as follows:

[0123] 4mmol Na2Mo4 and 15mmol thioacetamide (CH3CSNH2) were added to 10mL ethanol (C2H6O) and 20ml oleic acid (C 18 H 34 O2) mixture, stirred for 30 min, the solution was transferred to a 40 mL polytetrafluoroethylene tube, sealed in an autoclave, heated to 240 ° C for 24 h; after cooling to room temperature, the obtained product was washed with ethanol and water several times, and dried at 60 ° C for 12 h to obtain MoS2; 10 mg of the obtained MoS2 was added to 4 ml of ethanol, ultrasonicated for 30 min to obtain a uniform suspension, and 6 mL of 0.5 mol L -1 NaBH4, further ultrasonically treated for 2 h, cooled to room temperature, and the resulting product was washed with ethanol and water several times, and dried at 60 °C for 12 h.

[0124] Application Examples 1-24 Construction of a Photoanode-Electro-Fenton Sterilization System with Tip Piercing Effect and Photothermal Catalytic Effect

[0125] The system includes: a cathode capable of in-situ generation of hydrogen peroxide, a photoanode with a tip-piercing effect and a photothermal catalytic effect, a DC regulated power supply, a reaction cell (with a water inlet and outlet), an electrolyte (0.01M Na2SO4 solution), and an oxygen pump (providing oxygen). The reaction proceeds under oxygenation and light irradiation (λ≥420nm). For a schematic structural diagram, see Figure 3 .

[0126] Among them, an activated carbon fiber ACF (ACF was immersed in a 3M nitric acid solution, activated for 13 hours, rinsed with a large amount of water until neutral, and dried) electrode was used as the cathode, and the anode materials prepared in Examples 1 to 24 were loaded onto the surface of the carbon felt electrode by the Nafion coating method as the photoanode. The contact area of ​​the electrode plate was 10 cm 2 The plates are arranged vertically in the reaction tank with a spacing of 3 cm between them. The anode plate is connected to the positive pole of the DC regulated power supply, and the cathode plate is connected to the negative pole of the DC regulated power supply.

[0127] The specific steps of the Nafion coating method for loading the carbon felt electrode surface are as follows: adding the anode material powder to isopropanol to make the concentration of the anode material powder 10 mg / mL, adding Nafion solution at a volume ratio of 1000:50, and ultrasonically dispersing for 1.5 hours to obtain a dispersion; adding the dispersion dropwise to the front and back surfaces of the dried carbon felt, adding 100 μL of the dispersion dropwise per square centimeter to both the front and back surfaces of the carbon felt, and air-drying to obtain a photoanode.

[0128] Construction of sterilization systems of comparative examples 1 to 6

[0129] Commercially available TiO2 powder, MnO2 powder, and MoS2 powder (purchased from Aladdin) were used as comparisons, replacing the anode materials in the application examples. The remaining parameters and operations were referred to the application examples to construct a sterilization system, and comparative examples 1 to 3 were obtained.

[0130] Connect the oxygen supply pump in the application example to the air, and refer to the application example for other parameters and operations to construct a sterilization system to obtain Comparative Example 4.

[0131] Remove the lighting conditions in the application example, and refer to the application example for other parameters and operations to construct a sterilization system to obtain Comparative Example 5.

[0132] Turn off the power supply in the application example, and refer to the application example for other parameters and operations to build a sterilization system to obtain Comparative Example 6.

[0133] Sterilization effect of experimental system

[0134] Water containing Escherichia coli (E. coli K12) or Staphylococcus aureus (S. aureus) at a concentration of 6.5 log10 cfu / mL was sterilized using the sterilization systems of Application Examples 1 to 24 or Comparative Examples 1 to 6. After 30 minutes of reaction, 50 μL of the sample was evenly spread on the culture medium and incubated in a constant temperature incubator at 37°C for 12 hours. The number of colonies on the culture medium was recorded, and the concentration of E. coli remaining in the sample was calculated. The results are shown in Table 1.

[0135] Table 1 Sterilization effect of sterilization system

[0136]

[0137]

[0138] As can be seen from the table:

[0139] Using spiny TiO 2-x The bactericidal performance of the system using the material as the anode (Application Example 1) is better than that of the thorn-shaped TiO2 material system (Application Example 2). This is because the oxygen vacancies have an electron-rich effect, which can enhance the separation of photothermal electrons and holes, strengthen the generation of hydroxyl radicals at the anode and the generation efficiency of cathodic hydrogen peroxide. At the same time, it can act as an active center to further activate the hydrogen peroxide produced by the system to produce a large number of hydroxyl radicals and other free radicals. The bactericidal effect of the thorn-shaped TiO2 material (Application Example 2) is better than that of the commercial titanium dioxide material (Comparative Example 1). This is because the thorn-shaped material can have a perforating effect on the cell membrane of microorganisms, causing the permeability of the cell membrane to increase, accelerating the entry of ·OH into the cell to enhance the bactericidal effect. From the above, it can be seen that the thorn-shaped TiO 2-x The photoanode can enhance the effect of the electro-Fenton system in inactivating pathogenic microorganisms. The photothermal effect and thorn-like structure are conducive to improving the catalytic bactericidal performance of this system.

[0140] Application examples 3 to 6 investigated the effects of different conditions (time and temperature of hydrothermal reaction) of anode material preparation process on the TiO 2-x Influence of the anode thorn structure: When the time is short and the temperature is low, the thorn structure does not grow obviously, and the sterilization effect is somewhat reduced compared with Application Example 1; when the time is long and the temperature is high, the thorn structure is too long and easily damaged, and the sterilization effect is somewhat reduced compared with Application Example 1, but the degree of reduction is not obvious. Under the preferred process conditions of the present invention, a good and stable thorn structure can be better generated. Application Examples 7 to 10 use annealing time and temperature to control the growth of thorn-shaped TiO 2-x The oxygen vacancies in the material are compared with those in Application Example 1. The annealing time and temperature affect the distribution and generation of vacancies. Too much or too little will affect the generation of hydroxyl groups. A better sterilization effect can be achieved under the preferred time of the present invention, among which 5 hours at 350°C is the most preferred.

[0141] Application Examples 11 to 18 use spiny MnO 2-x The material is used as a photoanode. As in Application Examples 1 to 10, the electro-Fenton-photothermal coupling effect and the tip piercing effect of the material are also illustrated. Different process conditions have a certain influence on the thorn length and oxygen vacancies, which in turn affects the sterilization effect. Application Examples 19 to 24 use thorn-shaped MoS 2-x The material is used as an anode. By comparing with commercial materials, the photothermal effect of the thorn-like structure and vacancies is better in MoS 2-x The material can still be formed, and different process conditions have different degrees of influence on the sterilization effect. Unlike the first two materials, MoS 2-x The sulfur vacancy content of the material is controlled by controlling the concentration of the added NaBH4 solution.

[0142] Comparison of the bactericidal performance of Application Example 1 and Comparative Example 4 shows that oxygen significantly impacts the bactericidal efficacy of this system. After connecting the oxygen pump in Application Example 1 to air, the system's bactericidal capacity dropped to 3.2 log10 cfu / mL (30 min). This suggests that an adequate oxygen supply can enhance the system's cathode hydrogen peroxide production reaction and improve its bactericidal capacity.

[0143] The comparison of the bactericidal performance of Application Example 1 and Comparative Example 5 shows that visible light (λ≥420nm) has a significant improvement in the bactericidal effect of this system; under light irradiation conditions, the spiny TiO 2-x The anode and the ACF cathode can kill 4.9 log10 cfu / mL of E. coli (Application Example 1). Under lightless conditions (Comparative Example 5), the bactericidal ability of the system decreases by about 0.3 log10 cfu / mL (30 min). This shows that visible light can activate photosensitive materials such as titanium dioxide, promote the activation of photocurrent, and generate hydroxyl groups at the anode, thereby improving the reaction system's ability to inactivate E. coli.

[0144] Application Example 1 and Comparative Example 6 confirmed through different reaction conditions that, without power supply, the sterilization effect achieved by the system solely through the photothermal effect is very unsatisfactory, so the generation of hydrogen peroxide is one of the key steps of this system.

[0145] The system undergoes water electrolysis and oxygen reduction reactions. When the photoanode photocatalytically produces hydroxyl radicals, the cathode in situ produces hydrogen peroxide through the photoelectric effect. Vacancies act as active centers to promote the further production of ·OH radicals from the hydrogen peroxide produced at the cathode. The photoanode used has a thorn-like structure that can achieve a tip piercing effect that pierces the cell membrane. The hydroxyl radicals produced at the two poles undergo an oxidation reaction with the intracellular substances of the microorganisms pierced by the anode material, synergistically achieving the effect of inactivating the microorganisms.

[0146] The above embodiments are preferred implementation modes of the present invention, but the implementation modes of the present invention are not limited to the above embodiments. Any other changes, modifications, substitutions, combinations, and simplifications that do not deviate from the spirit and principles of the present invention should be considered as equivalent replacement methods and are included in the scope of protection of the present invention.

Claims

1. A thorn-shaped photothermal anode material, characterized in that: The thorn-shaped photothermal anode material is TiO with a nano-thorn-shaped structure. 2-x or MoS 2-x , where 0≤x<2; The thorn-shaped photothermal anode material is TiO with a nano-thorn-shaped structure. 2-x The specific steps include: The K2TiO(C2O4)2 and Escherichia coli cells are placed in a water-diethylene glycol mixed solution and mixed evenly, and hydrothermally reacted at 150-250°C for 8-24 hours. The product is washed and dried, and calcined at 450-550°C to remove the Escherichia coli cells, annealed, washed, and dried to obtain the product. The thorn-shaped photothermal anode material is MoS with a nano-thorn-shaped structure. 2-x The specific steps include: Na2MoO4 and thioacetamide are placed in an ethanol-oleic acid mixed solution and mixed evenly, and hydrothermally reacted at 180-300°C for 4-24 hours. The intermediate product is washed and dried, placed in ethanol and mixed evenly, and NaBH4 solution is added for ultrasonication, washed, and dried to obtain the product; Wherein, the mass ratio of the intermediate product to NaBH4 is 10:(11.5~115).

2. The thorn-shaped photothermal anode material according to claim 1, characterized in that: The length of the thorn-like structure is 50 to 200 nm.

3. The thorn-shaped photothermal anode material according to claim 1, characterized in that: The annealing is carried out at 300-400° C. under vacuum conditions at a heating rate of 5-20° C. / min for 2-8 hours.

4. A thorn-shaped photothermal anode material, characterized in that: The thorn-shaped photothermal anode material is MnO with a nano-thorn-shaped structure. 2-x , where 0<x<2; The thorn-shaped photothermal anode material is MnO with a nano-thorn-shaped structure. 2-x The specific steps include: Add manganese salt and potassium chlorate to nitric acid solution, heat in a water bath until the solution changes from brown to black, and then hydrothermally react at 80-130°C for 4-12 hours. Wash and dry the product, anneal, wash, and dry it to obtain the product. The annealing is carried out at 300-400° C. under vacuum conditions at a heating rate of 5-20° C. / min for 2-8 hours.

5. The thorn-shaped photothermal anode material according to claim 4, characterized in that: The length of the thorn-like structure is 50 to 200 nm.

6. Use of the thorn-shaped photothermal anode material according to any one of claims 1 to 5 for sterilization in an electro-Fenton system.

7. The application according to claim 6, characterized in that The thorn-shaped photothermal anode material is sterilized under light and oxygen conditions.

8. An electro-Fenton sterilization system, characterized in that: The thorn-shaped photothermal anode material according to any one of claims 1 to 5 is used as the anode.

9. The electro-Fenton sterilization system according to claim 8, characterized in that: The electro-Fenton sterilization system further comprises a cathode, a power supply, a reaction cell, an electrolyte and an oxygen supply pump.

Images