Electrode material for purification and disinfection of drinking water and preparation and use thereof

Abstract

The application discloses an electrode material for drinking water purification and disinfection and preparation and application thereof, and belongs to the technical field of drinking water purification. The electrode material is endowed with excellent antibacterial and catalytic performance by sequentially constructing Ag nanostructure and Au nanostructure on a plastic base material. Acid treatment and precursor solution immersion form Ag nanostructure, which endows the electrode material with preliminary antibacterial performance. Microemulsion immersion enhances the antibacterial effect. Microemulsion A and solution B are mixed to prepare a spraying liquid, and stable Au nanostructure is formed after spraying, which promotes electrochemical oxygen reduction reaction, improves H2O2 generation efficiency, and forms a micro honeycomb structure by using hydroxyethyl ethylenediamine triacetate and acrylamide in combination, adjusting the amount of Au and the complexing temperature, and significantly improving the H2O2 concentration. The electrode material has antibacterial performance, excellent conductivity and catalytic activity, stable purification effect before and after use, can be repeatedly used, and has a wide application prospect in the field of drinking water purification.

Description

Technical Field

[0001] This invention relates to the technical field of electrochemical advanced oxidation electrode material design and application, and particularly to an electrode material for drinking water purification and disinfection, its preparation and application. Background Technology

[0002] In recent years, with the improvement of people's living standards and the enhancement of health awareness, the requirements for drinking water quality have become increasingly stringent. As a key link in ensuring drinking water safety, drinking water purification technology has made significant progress in recent years, with an increasing number of purification technologies and in-depth research on filtration and purification materials, powerfully promoting the development of the drinking water treatment industry. Currently, there are three main types of purification technologies: 1) Activated carbon filtration technology. Due to its high decontamination efficiency and ease of use, activated carbon technology is widely used in water treatment plants and household water purification equipment. However, the adsorption range of activated carbon is limited, directly affecting the water purification effect and making it difficult to completely remove various pollutants from the water. In addition, the surface of activated carbon has large pores, which can easily become a breeding ground for bacteria and microorganisms during long-term operation, leading to secondary pollution of drinking water. 2) Membrane separation technology. Membrane separation technology is widely used in the field of drinking water purification, covering technologies such as microfiltration, ultrafiltration, nanofiltration, and reverse osmosis. However, in drinking water purification, membrane fouling is a significant problem when using membrane separation technology. This significantly reduces the filtration performance of the membrane and affects the purification effect. Simultaneously, membrane regeneration technology is not mature enough, requiring the replacement of membrane modules every certain period, which not only increases operational difficulty but also leads to a substantial increase in treatment costs. 3. Chlorine disinfection and ozone disinfection technologies are important methods for sterilizing and disinfecting drinking water. These technologies can effectively kill bacterial and viral microorganisms in drinking water, thereby preventing the spread of waterborne diseases. However, the effectiveness of these disinfection methods is affected by many factors, such as water temperature, turbidity and pH value, chlorine dosage, and the types of microorganisms, making it difficult to consistently control the disinfection effect. Furthermore, the application of chlorine disinfection technology can easily generate byproducts, which pose potential health hazards and increase the safety risks of drinking water.

[0003] Hydrogen peroxide (H2O2), as an environmentally friendly strong oxidant, has shown great application potential in disinfection, water treatment, chemical industry, and even energy. Its reaction products are only H2O and O2, without introducing new pollutants, aligning with the concept of green and environmentally friendly development. In drinking water treatment, electrochemical oxygen reduction to produce H2O2 is a product of the reduction reaction at the cathode. When it reaches a high concentration, it can effectively oxidize and degrade organic matter in water, demonstrating good drinking water treatment capabilities. Furthermore, the electrochemical oxygen reduction to H2O2 process also generates various oxygen-active species, which are beneficial for removing viruses, microorganisms, and other organic matter from drinking water, providing a new and effective approach to drinking water purification. Although electrochemical hydrogen peroxide production technology has made some research progress, existing electrode materials still have serious defects, restricting its further development in the field of drinking water purification. Currently, carbon-based materials such as carbon felt, activated carbon fiber, and graphite felt are often used as electrode materials for H2O2 production due to their good conductivity, ease of availability, and commercialization. However, the low oxygen reduction reactivity of these materials results in a limited concentration of hydrogen peroxide produced, restricting their application in electrochemical drinking water treatment. Furthermore, existing electrode materials generally have poor antibacterial properties, making it difficult to effectively kill microorganisms in water, further limiting their application in electrochemical drinking water treatment. Therefore, developing a novel electrochemical oxygen reduction electrode material to produce H₂O₂ is of great significance for promoting its application in electrochemical drinking water purification technology. Summary of the Invention

[0004] To address the limitations of existing electrochemical oxygen reduction (OR) electrode materials for producing H2O2 in drinking water purification, which suffer from low OR reaction activity leading to limited H2O2 concentration and poor antibacterial properties, hindering their effectiveness and widespread application, this invention provides an electrode material for drinking water purification and disinfection, along with its preparation and application. This invention solves the problems of insufficient activity and poor antibacterial properties in OR-generated hydrogen peroxide electrodes, effectively improving the performance of drinking water treatment technology based on electrochemical hydrogen peroxide production.

[0005] To achieve the above objectives, the present invention employs the following technical solution:

[0006] This invention provides a method for preparing an electrode material for drinking water purification and disinfection, comprising:

[0007] S1, the plastic substrate is immersed in an acid solution by heating and then dried to obtain a pretreated substrate;

[0008] The plastic substrate is any one of engineering plastics (ABS), PP, PV and PE;

[0009] S2, the pretreated substrate is immersed in the precursor mixture solution and then vacuum dried to obtain a dried substrate; the precursor mixture solution is obtained by vacuum heating and stirring reaction of a metallic silver salt, an organic solvent, isopropanol, and a dispersant; the metallic silver salt is any one of silver nitrate, silver sulfate, and silver chloride; the organic solvent is any one or a combination of two of dichloropropane, dichloromethane, and trichloroethane; the dispersant is any one of polycarboxylate, ethylene oxalate, or isopropanolamine.

[0010] S3, add the dried substrate to the microemulsion, soak, and vacuum dry to obtain the antibacterial substrate; the microemulsion is obtained by ultrasonic vibration of a mixed solution of glucose, tartaric acid and precursor.

[0011] S4, Microemulsion A is mixed with solution B to prepare a spraying liquid;

[0012] The microemulsion A is obtained by heating and stirring a gold salt, a metal complexing agent, and citric acid; the gold salt is any one of chloroauric acid, gold chloride, and potassium chloroaurate; the metal complexing agent is any one or a combination of two of isopropanol, diethyl phthalate, hydroxyethyl ethylenediamine triacetic acid, dihydroxyethyl glycine, and ethylenediaminetetraacetic acid.

[0013] Solution B is obtained by dissolving sodium nitrite, acrylamide, and Nafion solution in deionized water;

[0014] S5. The coating liquid is sprayed onto the antibacterial substrate, microwave-dried, and freeze-dried to obtain an electrode material for drinking water purification and disinfection.

[0015] In S1, the heating temperature is 40 ℃~80 ℃, and the soaking time is 10 min~30 min.

[0016] In S2, the mass ratio of the silver salt to the organic solvent, isopropanol and dispersant is 1~3:1~10:3~5:2~6.

[0017] Furthermore, the dispersant is ethylene oxalate.

[0018] In S3, the mass ratio of the glucose, tartaric acid and precursor mixed solution is 1~6:1~3:2~12.

[0019] In S4, the mass ratio of the metal gold salt, the metal complexing agent and the citric acid is 10~15:1~6:3~6; the mass ratio of the sodium nitrite, acrylamide and Nafion solution is 1~3:1~10:3~6.

[0020] In S4, the mass ratio of microemulsion A to solution B is 1:140~150.

[0021] Furthermore, the Nafion solution has a concentration of 5% and uses perfluorosulfonic acid as the solvent.

[0022] In S5, the microwave drying is carried out for 0.5 h to 2 h under the conditions of Ar gas flow rate of 5 L / min to 20 L / min, microwave power of 500 W to 1500 W, and temperature of 80 ℃ to 150 ℃.

[0023] In S5, the freeze drying is carried out under the conditions of 500 W to 1200 W power and -20℃ to -10℃ for 10 min to 30 min.

[0024] Electrode materials for drinking water purification and disinfection were prepared using the above-described method.

[0025] The electrode material used for drinking water purification and disinfection has a specific surface area of ​​1800 m². 2 / g~3200 m 2 / g, hydrophilic angle 60°~80°, porosity 75%~90%, average pore size 0.14 μm~3.5 μm, pore volume 0.15 cm³. 3 / g~0.65cm 3 / g.

[0026] The above-mentioned electrode material for drinking water purification and disinfection is used in drinking water purification, wherein the electrode material for drinking water purification and disinfection is used as a cathode.

[0027] Compared with the prior art, the present invention achieves the following technical effects:

[0028] This invention provides a novel method for preparing electrode materials for drinking water purification and disinfection. This method involves a series of carefully designed steps to sequentially construct Ag and Au nanostructures on a plastic substrate, thereby endowing the electrode material with excellent antibacterial and catalytic properties. Through acid treatment and immersion in a precursor solution, Ag ions are uniformly dispersed on the substrate surface to form Ag nanostructures, imparting initial antibacterial properties to the electrode material. The dried substrate is then immersed in a microemulsion obtained by ultrasonic vibration of a mixed solution of glucose, tartaric acid, and the precursor. The glucose and tartaric acid synergistically interact with the Ag nanostructures to enhance the electrode material's ability to kill microorganisms and improve the purification and disinfection effect of drinking water. A spraying solution is prepared by mixing microemulsion A (containing gold salt, metal complexing agent, and citric acid) and solution B (containing sodium nitrite, acrylamide, and Nafion solution). After being sprayed onto the antibacterial substrate, a stable Au nanostructure is formed. The Au nanostructure exhibits good catalytic activity, promoting the electrochemical oxygen reduction reaction and improving the in-situ generation efficiency of H2O2. The metal complexing agent and acrylamide... The method utilizes Au nanostructures to facilitate the formation of a stable crystalline phase structure, preventing the aggregation and shedding of Au nanoparticles and increasing the stability of the catalytic layer. Ag nanostructures effectively kill microorganisms in drinking water, while Au nanostructures promote electrochemical oxygen reduction reactions, generating highly oxidizing hydrogen peroxide in situ, further oxidizing and decomposing organic pollutants, thus providing a foundation for drinking water purification and disinfection. The nanoscale active catalytic layer is uniformly loaded in a porous structure, improving oxygen adsorption and conductivity, which is beneficial for efficient H2O2 production. The combination of microwave and freeze-drying increases the material's reaction interface and microchannel structure, enhancing the active sites for the catalytic reaction, improving the efficiency of oxygen reduction to H2O2 production, and strengthening the drinking water purification effect. The entire preparation method has clear steps, is relatively simple to operate, does not require complex equipment or harsh reaction conditions, is easy to implement for industrial production, and has broad application prospects.

[0029] Furthermore, by using hydroxyethyl ethylenediamine triacetic acid and acrylamide in combination and adjusting the amount of Au, a complexation reaction was achieved to allow Au to form a stable crystal form and create a micro-honeycomb structure. Simultaneously, by adjusting the complexation temperature, the prepared electrode material achieved a hydrogen peroxide concentration of 1335 mg / L within 1 hour. This electrode material also possesses antibacterial properties; after immersing in Staphylococcus aureus culture medium for 60 min, the average reduction in the number of regenerating bacteria per milliliter reached 99.9%, demonstrating excellent antibacterial and bactericidal performance, achieving bacterial elimination during drinking water purification.

[0030] The electrode material for drinking water purification and disinfection provided by this invention utilizes the high-temperature solvent swelling effect of a plastic substrate to retain Ag ions on the plastic surface. The penetrated portion is embedded in the plastic surface like a rivet, resulting in a dense inner layer structure. The outer layer forms an Au nano-electrocatalytic active layer through a complexation reduction reaction. This material not only has excellent conductivity and catalytic activity, but also provides more electron transfer space and electrocatalytic active sites through the high dispersion and spatiality of metal nanomaterials. This significantly improves the efficiency of electrocatalytic oxygen reduction to produce H2O2, providing highly efficient drinking water disinfection and purification functions. The purification effect is stable before and after use, which is conducive to repeated use and reduces the cost of use.

[0031] The electrode material for drinking water purification and disinfection provided by this invention has the ability to efficiently produce H2O2 and purify and disinfect drinking water. Moreover, the removal effect is stable before and after use, which is conducive to repeated use. This provides a broad application prospect for the material in the fields of drinking water purification, environmental protection, and energy. Attached Figure Description

[0032] Figure 1 This is a surface electron microscope scan of the electrode material prepared in Example 1 of the present invention;

[0033] Figure 2 This is a photograph of the electrode material prepared in Example 2 of the present invention;

[0034] Figure 3 This is a comparison diagram of hydrogen peroxide production between the electrode material prepared in Example 3 of the present invention and commercially available conventional carbon-based materials;

[0035] Figure 4 This is a diagram showing the effect of the electrode material prepared in Example 3 of the present invention on drinking water treatment;

[0036] Figure 5 Comparison chart of continuous operation capability test of electrode materials prepared in Example 3 of this invention. Detailed Implementation

[0037] To enable those skilled in the art to better understand the present invention, the technical solutions of the present invention will be clearly and completely described below with reference to the accompanying drawings of the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort should fall within the scope of protection of the present invention.

[0038] For experiments not specifically described in the examples, the procedures or conditions should be followed according to the conventional experimental procedures described in the literature in this field. Reagents or instruments whose manufacturers are not specified are all commercially available conventional reagent products.

[0039] Unless otherwise specified, all experimental materials used in this invention are commercially available products well known to those skilled in the art.

[0040] Specific surface area: refers to the total surface area per unit mass of a substance. The commonly used detection method is the BET method.

[0041] Porosity refers to the percentage of pore volume in a material's total volume, and can be measured using mercury porosimetry or gas adsorption methods combined with relevant models. Mercury porosimetry measures the volume of mercury entering the pores under different pressures to obtain the pore diameter distribution, and then calculates the porosity.

[0042] Pore ​​volume refers to the total volume of pores per unit mass of material, and can be detected using mercury porosimetry or gas adsorption methods. Mercury porosimetry: In mercury porosimetry, the pore volume is obtained by measuring the total volume of mercury entering the pores of the sample and then dividing it by the mass of the sample.

[0043] I. Specific Implementation Cases

[0044] Example 1

[0045] This embodiment provides an electrode material for drinking water purification and disinfection, and the specific preparation process is as follows:

[0046] The ABS substrate was placed in a concentrated sulfuric acid solution, heated at 40 ℃ for 10 min, and dried at 80 ℃ to obtain the pretreated substrate.

[0047] 2 g silver nitrate, 2 g dichloropropane, 9 mL isopropanol and 4 g ethylene oxalate were mixed and heated and stirred at 70 °C for 2 h to obtain a mixture. The mixture was placed in a reaction vessel and reacted at 300 °C for 1 h under a pressure of 2 MPa to obtain a precursor mixture solution. The pretreated substrate was immersed in the precursor mixture solution for 1 h and then vacuum dried at 80 °C for 30 min to obtain a dried substrate.

[0048] Weigh 4 g of glucose and 4 g of tartaric acid, add them to 14 mL of precursor mixture solution, and ultrasonically vibrate to obtain microemulsion; immerse the dried substrate in the microemulsion for 1.5 h, and then vacuum dry at 80 ℃ for 2 h to obtain antibacterial substrate.

[0049] Weigh 5 g potassium chloroaurate, 0.5 g hydroxyethyl ethylenediamine triacetic acid and 1.5 g citric acid, mix them and ultrasonically stir at 70 ℃ for 0.5 h to obtain microemulsion A; weigh 4 g sodium nitrite, 4 g acrylamide and 12 mL Nafion solution (5% fluorosulfonic acid by mass), dissolve them in deionized water and bring the volume to 1 L to obtain solution B; slowly add microemulsion A to solution B and stir evenly to obtain the spraying liquid.

[0050] The coating liquid was sprayed onto the antibacterial substrate, and then subjected to microwave drying and freeze drying in sequence. The microwave drying conditions were: 500W, 80 ℃, Ar gas flow rate of 5 L / min for 0.5 h; the freeze drying conditions were: 500W, -20 ℃ for 10 min, to obtain electrode materials for drinking water purification and disinfection.

[0051] See appendix Figure 1 The microstructure of the electrode material for drinking water purification and disinfection prepared in this embodiment was tested using scanning electron microscopy. Figure 1 As can be seen, the electrode material for drinking water purification and disinfection prepared in this embodiment has a unique micro-honeycomb structure. This honeycomb structure has obvious differences between the inner and outer layers. The inner layer has a dense structure, which provides a stable skeleton support for the entire electrode material and ensures the structural integrity of the material during the electrochemical reaction process. The outer layer forms an Au nano-electrocatalytic active layer through a complexation reduction reaction. This active layer is tightly combined with the inner layer to jointly construct a stable porous network. The honeycomb structure surface is uniformly loaded with a large number of particles with a diameter of 200 nm. The presence of these particles further increases the surface roughness of the material and the number of active sites, providing more channels for oxygen transport, enabling oxygen to reach the reaction site faster and more effectively, thereby facilitating the electrochemical reaction and significantly improving the electrochemical H2O2 production performance of the material.

[0052] The specific surface area of ​​the electrode material prepared in this embodiment for drinking water purification and disinfection, as measured by a specific surface area analyzer, is 2000 m². 2 The porosity of the electrode material, measured by mercury porosimetry, was 75%, the hydrophilic angle was 70°, the average pore size was 0.24 μm, and the pore volume was 0.45 cm³. 3 / g.

[0053] In summary, this embodiment successfully prepared an electrode material with excellent H2O2 production performance for drinking water purification and disinfection. This electrode material exhibits good hydrophilicity, electron transport properties, and dielectric transport properties in drinking water treatment. Good hydrophilicity allows the material to better contact with water, improving the adsorption and catalytic efficiency of pollutants in the water. Excellent electron transport properties ensure the efficient conduction of the electrochemical reaction, rapidly converting electrical energy into chemical energy to generate sufficient H2O2 for disinfection and purification. Dielectric transport properties ensure the smooth transport of reactants and products within the material, improving the overall efficiency of the reaction. This electrode material with excellent H2O2 production performance provides new ideas and methods for the development of the drinking water treatment field.

[0054] Example 2

[0055] This embodiment provides an electrode material for drinking water purification and disinfection, and the specific preparation process is as follows:

[0056] The PP substrate was placed in a concentrated sulfuric acid solution, heated at 80 ℃ for 30 min, and dried at 80 ℃ to obtain the pretreated substrate.

[0057] 5 g silver nitrate, 5 g dichloropropane, 15 mL isopropanol and 10 g ethylene oxalate were mixed and heated and stirred at 120 °C for 5 h to obtain a mixture. The mixture was placed in a reaction vessel and reacted at 500 °C under a pressure of 6 MPa for 3 h to obtain a precursor mixture solution. The pretreated substrate was immersed in the precursor mixture solution for 1 h and then vacuum dried at 80 °C for 30 min to obtain a dried substrate.

[0058] Weigh 3 g of glucose and 4 g of tartaric acid, add them to 10 mL of precursor mixture solution, and ultrasonically vibrate to obtain microemulsion; immerse the dried substrate in the microemulsion for 0.5 h, and then vacuum dry at 80 ℃ for 2 h to obtain antibacterial substrate;

[0059] Weigh 15 g potassium chloroaurate, 3 g hydroxyethyl ethylenediamine triacetic acid and 3 g citric acid, mix them, heat to 120 ℃ and sonicate for 2 h to obtain microemulsion A; weigh 3 g sodium nitrite, 10 g acrylamide and 15 mL Nafion solution (5% fluorosulfonic acid by mass) and dissolve them in deionized water to a final volume of 1 L to obtain solution B; slowly add microemulsion A to solution B and stir evenly to obtain the spray coating.

[0060] The coating liquid was sprayed onto the antibacterial substrate, and then subjected to microwave drying and freeze drying sequentially. The microwave drying conditions were: 1500 W, 150 ℃, and Ar gas flow rate of 20 L / min for 2 h. The freeze drying conditions were: 1200 W, -10 ℃ for 30 min, to obtain electrode materials for drinking water purification and disinfection.

[0061] See appendix Figure 2 The image shown is a physical photograph of the electrode material prepared for drinking water purification and disinfection in this embodiment. (See attached image.) Figure 2 It is known that the electrode material used for drinking water purification and disinfection has a uniformly rough surface. The uniformly distributed rough structure on the material surface increases its surface area, providing more adsorption sites for oxygen molecules. Oxygen molecules are more likely to stay on the material surface and be adsorbed. This adsorption is crucial for electrocatalytic reactions because it can promote effective contact between oxygen molecules and the active sites of the catalyst, thereby improving the H2O2 production performance. The rough surface structure also helps to improve the stability of the catalyst, which can reduce the shedding and aggregation of the catalyst during the reaction process.

[0062] Further testing revealed that the specific surface area of ​​the electrode material prepared in this embodiment for drinking water purification and disinfection was 1800 m². 2 / g, hydrophilic angle 75°, porosity 88%, average pore size 0.16 μm, pore volume 0.25 cm³. 3 / g.

[0063] In summary, the electrode material prepared in this embodiment for drinking water purification and disinfection possesses a uniformly rough surface structure and specific properties such as specific surface area, hydrophilic angle, porosity, average pore size, and pore volume, exhibiting good performance and stability in the electrocatalytic H₂O₂ production reaction. Its surface structure increases the adsorption sites for oxygen molecules, promoting effective contact between oxygen molecules and the catalyst's active sites; its hydrophilicity facilitates the wetting and diffusion of reactants; and its porous structure provides channels and more active sites for the reaction, while simultaneously improving the material's stability. These characteristics make this electrocatalyst potentially valuable in related electrocatalysis fields.

[0064] Example 3

[0065] This embodiment provides an electrode material for drinking water purification and disinfection, and the specific preparation process is as follows:

[0066] The PE substrate was placed in a concentrated sulfuric acid solution, heated at 50 °C for 20 min, and dried at 80 °C to obtain the pretreated substrate.

[0067] 10 g silver nitrate, 12 g dichloropropane, 30 mL isopropanol and 20 g ethylene oxalate were mixed and added, and the mixture was heated and stirred at 80 °C for 3 h to obtain a mixture. The mixture was placed in a reaction vessel and reacted at 250 °C under a pressure of 4 MPa for 1.5 h to obtain a precursor mixture solution. The pretreated substrate was immersed in the precursor mixture solution for 1 h and then vacuum dried at 80 °C for 30 min to obtain the dried substrate.

[0068] Weigh 6 g glucose and 8 g tartaric acid, add them to 18 mL precursor mixed solution, and ultrasonically vibrate to obtain microemulsion. Soak the dried substrate in the microemulsion for 1 h, and then vacuum dry at 80 ℃ for 2 h to obtain antibacterial substrate.

[0069] Weigh 30 g potassium chloroaurate, 5 g hydroxyethyl ethylenediamine triacetic acid and 10 g citric acid, mix them, heat to 120 ℃ and ultrasonically stir for 2 h to obtain microemulsion A; weigh 12 g sodium nitrite, 12 g acrylamide and 40 mL Nafion solution (5% fluorosulfonic acid by mass) and dissolve them in deionized water to a final volume of 1 L to obtain solution B; slowly add microemulsion A to solution B and stir evenly to obtain the spray coating.

[0070] The coating liquid was sprayed onto an antibacterial substrate, and then subjected to microwave drying and freeze drying sequentially. The microwave drying conditions were: 550 W, 100 ℃, and Ar gas flow rate of 12 L / min for 1.6 h. The freeze drying conditions were: 600 W, -15 ℃ for 12 min, to obtain electrode materials for drinking water purification and disinfection.

[0071] Further testing revealed that the specific surface area of ​​the electrode material prepared in this embodiment for drinking water purification and disinfection was 2800 m². 2 / g, hydrophilic angle 63°, porosity 79%, average pore size 0.16 μm, pore volume 0.55 cm³. 3 / g.

[0072] The electrode material prepared in this embodiment for drinking water purification and disinfection and the traditional carbon-based electrode materials (commercial carbon felt, commercial activated carbon fiber, and commercial graphite felt, purchased from Shanghai Qijie Carbon Co., Ltd.) were used as cathodes (electrode area 10 cm²). 2 Titanium plates are commonly used as anodes in the market (electrode area 10 cm²). 2 The electrode material (purchased from Shaanxi Baoji Taisheng Metal Technology Co., Ltd.) had an electrode spacing of 0.5 cm and a potential set to 5 V. The electrode material prepared according to this invention for drinking water purification and disinfection was compared with commercially available carbon-based materials (including carbon felt, activated carbon fiber, and graphite felt). A two-hour in-situ oxygen reduction (ORR) experiment to produce H2O2 was conducted, and the H2O2 production was observed and recorded. Specific results are shown in the appendix. Figure 3 .

[0073] From the appendix Figure 3Data shows that during the two-hour oxygen reduction reaction, the H2O2 yield of the electrode material prepared by this invention reached 1335 mg / L, while the H2O2 yields of the other three traditional carbon-based materials were 65 mg / L, 108 mg / L, and 138 mg / L, respectively. The H2O2 yield of the electrode material of this invention is 10-20 times higher than that of traditional materials. This significant difference indicates that the electrode material prepared by this invention has an absolute advantage in in-situ H2O2 production during oxygen reduction. This is mainly attributed to the unique catalytic performance and optimized structure of the electrode material prepared by this invention. The unique structure provides more active sites, which is beneficial to electron transport and the stability of reaction intermediates, thereby improving the efficiency of the oxygen reduction reaction and thus significantly increasing the yield of H2O2.

[0074] The electrode material for drinking water purification and disinfection prepared in Example 3 of this invention and the traditional carbon-based electrocatalyst materials (commercial carbon felt material, commercial activated carbon fiber, and commercial graphite felt, purchased from Shanghai Qijie Carbon Co., Ltd.) are respectively the cathodes (electrode area 15 cm²). 2 The most common metal electrode on the market is a titanium plate as the anode (electrode area 15 cm²). 2 The sample (purchased from Shaanxi Baoji Taisheng Metal Technology Co., Ltd.) was 0.03 g of sodium sulfate added to 500 mL of water from a reservoir in Shaanxi Province. The prepared cathode and anode were installed in the electrochemical reaction apparatus with an electrode spacing of 1 cm. The power supply was connected to form a closed circuit between the electrodes and the power supply. The potential was set to 5 V. The experiment was started, and the experimental conditions were kept stable for 60 min. The total organic carbon (TOC) content of the water sample was determined using a total organic carbon (TOC) analyzer. The TOC removal rate was calculated using the formula: TOC removal rate (%) = (initial TOC value - post-reaction TOC value) / initial TOC value × 100%. The TOC removal rate was observed and recorded. See Appendix for details. Figure 4 As shown.

[0075] From the appendix Figure 4 Data shows that the electrode material prepared in this invention achieved a TOC removal rate of 99% when treating drinking water. In comparison, the TOC removal rates of commercial cathodes (carbon felt, activated carbon fiber, and graphite felt, purchased from Shanghai Qijie Carbon Co., Ltd.) were only 14.6%, 16.5%, and 18.9%, respectively. This indicates that the electrode material prepared in this invention has a significant advantage as a cathode material in removing total organic carbon (TOC) from drinking water, with a treatment efficiency far exceeding that of commercial cathode materials. This demonstrates the high efficiency of the electrode material prepared in this invention in treating drinking water and shows broad application prospects in the field of drinking water treatment.

[0076] The reusability test was conducted on the electrode material for drinking water purification and disinfection prepared according to the present invention. The electrode material prepared in Example 3 of the present invention and the commercial graphite felt material were used as cathodes (electrode area 10 cm²). 2 (Purchased from Shanghai Qijie Carbon Co., Ltd.) A common metal electrode on the market is a titanium mesh anode (electrode area 10 cm²). 2 The sample was purchased from Shaanxi Baoji Yongji Metal Technology Co., Ltd. The electrode spacing was 0.4 cm. 0.02 g of sodium sulfate was added to 500 mL of water from a reservoir in Shaanxi. The potential was 5 V. The TOC removal experiment was repeated 9 times.

[0077] From the appendix Figure 5 The data shows that the TOC removal rate of the electrode material prepared in Example 3 of this invention is relatively stable and remains at a high level in 9 repeated experiments. This indicates that the electrode material has good reusability and durability, and can continuously and efficiently carry out drinking water purification treatment during long-term use. It can maintain stable performance in 9 consecutive treatment experiments.

[0078] The electrode material for drinking water purification and disinfection prepared in Example 3 of this invention, along with commercially available carbon-based materials [commercially available carbon felt material (Comparative Example 4), commercially available activated carbon fiber (Comparative Example 5), and commercially available graphite felt (Comparative Example 6), purchased from Shanghai Qijie Carbon Co., Ltd.] and ABS substrate (Comparative Example 7), were subjected to bactericidal performance tests. The initial inoculum concentration was 1.0 × 10⁻⁶. 5 CFU / mL - 1.0×10 6 Within the CFU / mL range, Staphylococcus aureus was used as the inoculum. The prepared electrode material was immersed in a bacterial culture dish. The growth of the inoculum stopped during the immersion time, and the average reduction in the number of bacteria recovering growth per milliliter was recorded at 5 min, 15 min, 30 min, and 60 min.

[0079] Table 1: Antibacterial performance tests of Example 3 and Comparative Examples 4-7

[0080]

[0081] As shown in Table 1, the sterilization effect of the electrode material prepared in Example 3 of this invention is far superior to that of the comparative materials as time progresses. At 5 min, the electrode material of Example 3 reduced the average number of Staphylococcus aureus bacteria regenerating per milliliter by 95.6, while the reduction values ​​of Comparative Examples 4-6 were between 10-17.4, and Comparative Example 7 (ABS substrate) showed almost no sterilization effect, with a reduction value of 0. As time progressed to 15 min, 30 min, and 60 min, the sterilization effect of the electrode material of Example 3 further improved, reaching significant levels at 30 min and 60 min. At min, the reduction value reached 99.9, while the bactericidal effect of the comparative material was not significantly improved and remained at a low level. Comparison of Example 3 with Comparative Examples 4-6: The electrode material prepared by the present invention showed significantly better bactericidal performance than commercially available carbon-based materials at various time points, indicating that the electrode material of the present invention introduced components or structures with highly efficient antibacterial properties during the preparation process, giving it a stronger killing ability against Staphylococcus aureus. Comparison of Example 3 with Comparative Example 7: The ABS substrate had almost no antibacterial properties, while the electrode material of Example 3 had excellent antibacterial properties, indicating that a series of modifications to the ABS substrate (such as the addition of organic solvents and Ag, the formation of Au nanolayers, etc.) played a key role in improving the antibacterial properties of the material.

[0082] Antibacterial Mechanism Analysis: The addition of organic solvents and Ag significantly affects the antibacterial properties of the electrode material. The use of non-polar organic solvents causes swelling of the plastic surface, allowing silver ions to penetrate more effectively into the plastic surface layer. After the low-boiling-point solvent evaporates, the silver ions remain on the plastic surface, with the penetrated portion embedded in the plastic surface like rivets. A reduction reaction then modifies the ABS substrate surface with elemental silver. This rivet-like structure increases the bonding strength with the plastic, reduces the difficulty of Au loading, and enhances catalytic activity by forming an Au nanolayer on the outer layer. The use of elemental silver improves the antibacterial properties of the substrate and enhances the drinking water treatment performance of the electrode material.

[0083] In summary, the electrode material prepared by this invention for drinking water purification and disinfection exhibits excellent bactericidal performance, effectively killing Staphylococcus aureus in a short time, and is significantly superior to commercially available carbon-based materials and ABS substrates. The treatment effect can be effectively improved by increasing H2O2 production, and it can operate efficiently and stably. The electrode material prepared by this invention is simple to prepare and can be industrialized and applied.

[0084] The above content is only for illustrating the technical concept of the present invention and should not be construed as limiting the scope of protection of the present invention. Any modifications made to the technical solution based on the technical concept proposed in this invention shall fall within the scope of protection of the claims of this invention.

Claims

1. A method for preparing an electrode material for drinking water purification and disinfection, characterized in that, include: S1, immerse the plastic substrate in an acid solution heated to 40 ℃~80 ℃ for 10 min~30 min, and then dry to obtain the pretreated substrate; The plastic substrate is any one of ABS, PP, PV and PE; S2, the pretreated substrate is immersed in the precursor mixture solution and then vacuum dried to obtain a dried substrate; the precursor mixture solution is obtained by vacuum heating and stirring reaction of a metallic silver salt, an organic solvent, isopropanol, and a dispersant; the metallic silver salt is any one of silver nitrate, silver sulfate, and silver chloride; the organic solvent is any one or a combination of two of dichloropropane, dichloromethane, and trichloroethane; the dispersant is any one of polycarboxylate, ethylene glycol monophosphate, and isopropanolamine. S3, add the dried substrate to the microemulsion, soak, and vacuum dry to obtain the antibacterial substrate; the microemulsion is obtained by ultrasonic vibration of a mixed solution of glucose, tartaric acid and precursor. S4, Microemulsion A is mixed with solution B to prepare a spraying liquid; The microemulsion A is obtained by heating and stirring a gold salt, a metal complexing agent, and citric acid; the gold salt is any one of chloroauric acid, gold chloride, and potassium chloroaurate; the metal complexing agent is any one or a combination of two of isopropanol, diethyl phthalate, hydroxyethyl ethylenediamine triacetic acid, dihydroxyethyl glycine, and ethylenediaminetetraacetic acid. Solution B is obtained by dissolving sodium nitrite, acrylamide, and Nafion solution in deionized water; S5. The coating liquid is sprayed onto the antibacterial substrate, microwave-dried, and freeze-dried to obtain an electrode material for drinking water purification and disinfection.

2. The method for preparing an electrode material for drinking water purification and disinfection according to claim 1, characterized in that, In S2, the mass ratio of the silver salt to the organic solvent, isopropanol and dispersant is 1~3:1~10:3~5:2~6.

3. The method for preparing an electrode material for drinking water purification and disinfection according to claim 1, characterized in that, In S3, the mass ratio of the glucose, tartaric acid and precursor mixed solution is 1~6:1~3:2~12.

4. The method for preparing an electrode material for drinking water purification and disinfection according to claim 1, characterized in that, In S4, the mass ratio of the metal gold salt, the metal complexing agent and the citric acid is 10~15:1~6:3~6; the mass ratio of the sodium nitrite, acrylamide and Nafion solution is 1~3:1~10:3~6.

5. The method for preparing an electrode material for drinking water purification and disinfection according to claim 1, characterized in that, In S4, the mass ratio of microemulsion A to solution B is 1:140~150.

6. The method for preparing an electrode material for drinking water purification and disinfection according to claim 1, characterized in that, In S5, the microwave drying is carried out for 0.5 h to 2 h under the conditions of Ar gas flow rate of 5 L / min to 20 L / min, microwave power of 500 W to 1500 W, and temperature of 80 ℃ to 150 ℃.

7. The method for preparing an electrode material for drinking water purification and disinfection according to claim 1, characterized in that, In S5, the freeze drying is carried out under the conditions of 500 W to 1200 W power and -20℃ to -10℃ for 10 min to 30 min.

8. An electrode material for drinking water purification and disinfection prepared by the preparation method according to any one of claims 1 to 7, characterized in that, The electrode material used for drinking water purification and disinfection has a specific surface area of ​​1800 m². 2 / g~3200 m 2 / g, hydrophilic angle 60°~80°, porosity 75%~90%, average pore size 0.14 μm~3.5 μm, pore volume 0.15 cm³. 3 / g~0.65 cm 3 / g.

9. The application of the electrode material for drinking water purification and disinfection according to claim 8 in drinking water purification, characterized in that, The electrode material used for drinking water purification and disinfection serves as the cathode.

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