Dual-channel oxygen supply floating cathode electro-fenton system, and preparation method and application thereof

Abstract

The application discloses a double-channel oxygen supply floating cathode electro-Fenton system and a preparation method and application thereof. The floating cathode electro-Fenton system comprises a floating cathode and an anode which constitutes a horizontal reaction system with the floating cathode. The floating cathode comprises carbonized wood with ordered vertical channels, and phenolic resin and hydrophobic organic polymer loaded in the carbonized wood. In the floating cathode electro-Fenton system, the floating cathode and the anode constitute a horizontal reactor. The design enables oxygen generated by the anode and oxygen in air to be better transmitted in a directional manner through the ordered vertical channels in the floating cathode. Therefore, the floating cathode can utilize oxygen from the upper and lower sides simultaneously. In addition, the structure enables H2O2 to be diffused out of the electrode in a timely manner, reduces loss caused by a side reaction, and thus builds a high-efficiency electro-Fenton device without aeration.

Description

Technical Field

[0001] This invention relates to the field of electrocatalysis technology, and in particular to a dual-channel oxygen-supplying floating cathode electro-Fenton system, its preparation method, and its application. Background Technology

[0002] With the increasing prevalence of antibiotics in the natural environment, their degradation has become more challenging. This has led to the introduction of persistent antibiotic genes into pathogens, making the development of efficient antibiotic removal technologies for water a pressing need. Over the past few decades, various advanced oxidation processes have been developed to remove organic pollutants from wastewater. Of particular note is the Fenton reaction process, which generates hydroxyl radicals through solution chemistry or electrochemistry, attracting widespread attention. Compared to traditional solution-chemical Fenton reactions, the electro-Fenton process offers the advantage of in-situ generation and activation of H₂O₂, and is therefore considered a safe, green, and efficient process.

[0003] In the electro-Fenton system, key factors for achieving efficient H2O2 production include catalyst selectivity, oxygen mass transfer, and electron transfer at the cathode reaction interface. To this end, many electrocatalysts with high reduction selectivity, such as carbon-based materials like carbon black, carbon cloth, and graphite felt, have been widely developed and applied. These materials are favored due to their excellent conductivity, large specific surface area, good selectivity, and affordable price. However, under natural conditions, the dissolved oxygen concentration in the aqueous phase is low (only 1 × 10⁻⁶). -3 mol·dm -3 Therefore, the reaction is limited by low oxygen mass transfer, making it difficult to effectively increase the H2O2 concentration. Traditional electro-Fenton reaction systems require additional aeration devices to ensure sufficient oxygen supply to the cathode to sustain the reaction. However, this results in significant energy consumption, limiting the system's large-scale application prospects. In this context, designing an efficient oxygen-supplying catalytic cathode and a suitable reactor becomes crucial.

[0004] Gas diffusion electrodes are currently the most widely used method. This electrode consists of a catalyst layer, a current collector layer, and a gas diffusion layer. Through the gas diffusion layer, oxygen can be directly supplied to the catalyst layer from the outside without dissolving in the electrolyte. This is because the concentration of oxygen in the air (approximately 45 × 10⁻⁶) is high. -3 mol·dm -3 The dissolved oxygen concentration is much higher than that in the aqueous phase, thus this innovative design overcomes the limitation of low dissolved oxygen concentration and effectively improves the electrosynthesis efficiency of H2O2. For many years, many researchers have been working to improve the catalytic layer of gas diffusion electrodes to increase hydrogen peroxide production, but research on gas diffusion layers has been relatively limited.

[0005] During the reaction, the gas diffusion layer is crucial for maintaining the three-phase reaction interface of oxygen, catalyst, and electrolyte. However, the disordered and tortuous diffusion channels within the layer hinder the effective transfer of gas and liquid, affecting reaction kinetics and causing the generated products to have difficulty diffusing out of the reaction interface, leading to side reactions and ultimately the decomposition of H₂O₂. Furthermore, since gas diffusion electrodes are mostly used in vertical reactors, overflow occurs after prolonged reactions, making long-term stable operation impossible. Additionally, the varying water pressure experienced in a vertical position leads to uneven current distribution, affecting cathode performance and hindering the application of the electrode in large-scale wastewater treatment. Summary of the Invention

[0006] The purpose of this invention is to achieve effective oxygen mass transfer and promote the efficient production of H2O2 by optimizing the transport channel structure inside the electrode in the floating cathode electro-Fenton system.

[0007] The first aspect of the present invention is:

[0008] A floating cathode electro-Fenton system is provided.

[0009] The second aspect of the present invention is:

[0010] A method for preparing a floating cathode electro-Fenton system is provided.

[0011] The third aspect of the present invention is:

[0012] Application of the floating cathode electro-Fenton system.

[0013] Specifically, the technical solution adopted according to the first aspect of the present invention is as follows:

[0014] A floating cathode electro-Fenton system includes a floating cathode and an anode that forms a transverse reaction system with the floating cathode;

[0015] The floating cathode comprises carbonized wood with ordered vertical channels, and phenolic resin and hydrophobic organic polymer loaded in the carbonized wood.

[0016] According to embodiments of the present invention, one of the technical solutions has at least one of the following advantages or beneficial effects:

[0017] The floating cathode electro-Fenton system of this invention uses carbonized wood loaded with phenolic resin and a hydrophobic organic polymer as the floating cathode, wherein the phenolic resin serves as the active material providing active sites. To improve the yield of H₂O₂, the hydrophobic organic polymer is introduced into the floating cathode, endowing it with hydrophobic properties. Since the 2e-ORR reaction is a three-phase reaction, the electrode's hydrophobicity is beneficial for forming the three-phase reaction interface.

[0018] The floating cathode electro-Fenton system of this invention utilizes the orderly arranged vertical channels in a wooden substrate as transport channels, enabling unobstructed directional transport of substances within the channels. This structure not only better utilizes oxygen from both above and below simultaneously, but also allows the generated H2O2 to diffuse out of the electrode interior in a timely manner, reducing losses caused by side reactions, thereby constructing a highly efficient electro-Fenton device that does not require aeration.

[0019] In the floating cathode electro-Fenton system of this invention, the floating cathode and anode together constitute a transverse reactor. This design allows for better directional transport of oxygen generated at the anode and oxygen from the air through the orderly arranged vertical channels inside the floating cathode. Therefore, the floating cathode can utilize oxygen from both above and below, thereby achieving a high yield of H2O2. Furthermore, this structure allows the generated H2O2 to diffuse out of the electrode interior in a timely manner, reducing losses caused by side reactions, thus constructing a highly efficient electro-Fenton device that does not require aeration.

[0020] According to one embodiment of the present invention, the floating cathode floats above the solution to be treated, and the anode is placed below the solution to be treated, thereby forming a horizontal reactor. This allows the oxygen generated at the lower anode to be more easily delivered to the upper cathode. Ultimately, this enables the upper cathode to more effectively utilize both the oxygen from below and the oxygen from the air above.

[0021] According to one embodiment of the present invention, the mass ratio of the phenolic resin and the hydrophobic organic polymer loaded in the carbonized wood is 16-110:391-780.

[0022] According to one embodiment of the present invention, the mass ratio of the phenolic resin and the hydrophobic organic polymer loaded in the carbonized wood is 41-110:391-780.

[0023] According to one embodiment of the present invention, the mass ratio of the phenolic resin and the hydrophobic organic polymer loaded in the carbonized wood is 16-110:524-780.

[0024] The amount of hydrophobic organic polymer loaded in the carbonized wood determines the hydrophobicity of the floating cathode. Although the hydrophobic design can enhance O2 diffusion and achieve a rich three-phase interface, thereby synergistically improving performance, excessive use of the hydrophobic organic polymer coating may hinder electron transport, thus negating its potential advantages. Therefore, finding the optimal hydrophobic organic polymer loading is crucial for optimizing electrocatalytic efficiency.

[0025] The amount of phenolic resin loaded in the carbonized wood affected the reactivity of the floating cathode.

[0026] According to one embodiment of the present invention, the hydrophobic organic polymer includes polytetrafluoroethylene.

[0027] According to one embodiment of the present invention, the carbonized wood comprises carbonized pine.

[0028] According to one embodiment of the present invention, the thickness of the carbonized wood is 2-6 mm.

[0029] According to one embodiment of the present invention, the thickness of the carbonized wood is 2-4 mm.

[0030] According to one embodiment of the present invention, the thickness of the carbonized wood is 4-6 mm.

[0031] According to one embodiment of the present invention, in the floating cathode electro-Fenton system, a metal oxide electrode is used as the counter electrode.

[0032] Specifically, the technical solution adopted according to the second aspect of the present invention is as follows:

[0033] A method for preparing the floating cathode electro-Fenton system includes the following steps:

[0034] After carbonizing the wood, it is immersed in a phenolic resin precursor solution. Through hydrothermal reaction, the phenolic resin is formed in situ in the wood pores to obtain RF-CW.

[0035] The RF-CW was immersed in a hydrophobic organic polymer solution, removed, dried, and then heat-treated to obtain a floating cathode.

[0036] The floating cathode and coupled anode form a transverse reaction system to obtain the floating cathode electro-Fenton system.

[0037] According to embodiments of the present invention, one of the technical solutions has at least one of the following advantages or beneficial effects:

[0038] This invention carbonizes wood to create naturally ordered wood pores, and through a hydrothermal reaction, allows phenolic resin to be evenly distributed inside the wood pores without damaging the wood pore structure.

[0039] It should be noted that if phenolic resin is not loaded into carbonized pine wood using the in-situ hydrothermal method, but instead is loaded directly into carbonized pine wood by impregnation, the phenolic resin is difficult to dissolve in water and often requires stirring. After stirring, the internal pore structure of the wood will be damaged, making it difficult for the phenolic resin to be evenly distributed inside the pores.

[0040] According to one embodiment of the present invention, the carbonization of wood further includes the following steps: cutting the wood into wood chips perpendicular to its growth direction, placing them in a protective atmosphere, and heating them at 800-850°C to obtain carbonized wood with ordered vertical channels.

[0041] At high temperatures, the organic matter in wood gradually decomposes and volatilizes, leaving carbonaceous residue. In the presence of a porous structure, this process causes the woody parts around the pores to be filled and wrapped with the residue. However, because the pores are vertically arranged, the carbonized residue fills and forms along the direction of the pores, resulting in the final carbonized pine wood having an orderly arrangement of vertical pores.

[0042] According to one embodiment of the present invention, the wood is carbonized for 6-6.5 hours.

[0043] According to one embodiment of the present invention, the raw material for the carbonized wood is pine. During its growth, pine wood naturally forms a porous structure perpendicular to the trunk axis, used for transporting moisture and nutrients. After the pine wood is cut into thin slices perpendicular to its growth direction, these porous structures remain perpendicular to the surface of the slices. Through prolonged heat treatment at high temperature (800-850℃) and under a protective atmosphere, the organic matter in the wood is decomposed and volatilized, leaving carbonaceous residue to fill the porous structures. Because the porous structures are vertically arranged, the carbonized residue fills and forms along the direction of the porous structures, ultimately forming a carbonized pine wood material with an ordered vertical porous structure.

[0044] According to one embodiment of the present invention, the raw materials of the phenolic resin precursor solution include the following components: resorcinol, formaldehyde and ammonia.

[0045] According to one embodiment of the present invention, the temperature is maintained at 250-260°C during the hydrothermal reaction.

[0046] According to one embodiment of the present invention, the hydrothermal reaction takes 24-26 hours.

[0047] According to one embodiment of the present invention, the heat treatment is performed at a temperature of 300-310°C.

[0048] According to one embodiment of the present invention, the heat treatment lasts for 2-2.5 hours.

[0049] Another aspect of the present invention provides a method for degrading tetracycline in solution using a floating cathode electro-Fenton system, comprising the following steps:

[0050] A solution containing tetracycline and a catalyst are added to the floating cathode Fenton system to obtain a mixed solution, which is then electrolyzed to degrade the tetracycline in the solution.

[0051] According to one embodiment of the present invention, the catalyst comprises Fe 2+ The compound in which Fe 2+ The concentration in the mixed solution is 0.2-0.4 mol / L.

[0052] According to one embodiment of the present invention, the pH of the mixed solution is 1-5.

[0053] According to one embodiment of the present invention, the pH of the mixed solution is 1-3.

[0054] According to one embodiment of the present invention, the pH of the mixed solution is 3-5.

[0055] According to one embodiment of the present invention, the current density during electrolysis is 10-20 mA·cm⁻¹. -2 .

[0056] According to one embodiment of the present invention, the current density during electrolysis is 10-15 mA·cm⁻¹. -2 .

[0057] According to one embodiment of the present invention, the current density during electrolysis is 15-20 mA·cm⁻¹. -2 .

[0058] Other features and advantages of the invention will be set forth in the description which follows, and will be apparent in part from the description, or may be learned by practicing the invention. Attached Figure Description

[0059] The above and / or additional aspects and advantages of the present invention will become apparent and readily understood from the description of the embodiments taken in conjunction with the following drawings, in which:

[0060] Figure 1 This is a schematic diagram of the floating cathode electro-Fenton system in Example 1.

[0061] Figure 2 This is a schematic diagram of the cathode preparation process in Example 1.

[0062] Figure 3 The graphs show the H2O2 yield test results for Examples 1-3.

[0063] Figure 4 The graphs show the H2O2 yield test results for Examples 1 and 4-5.

[0064] Figure 5 The graphs show the H2O2 yield test results for Examples 1 and 6-7.

[0065] Figure 6 The figures are contact angle test diagrams for Examples 1 and 6-7.

[0066] Figure 7 The graphs show the H2O2 yield test results for Examples 1 and 10-11.

[0067] Figure 8 The graphs show the H2O2 yield test results for Examples 1 and 12-13.

[0068] Figure 9 The graphs show the H2O2 yield test results for Examples 1 and 14-15.

[0069] Figure 10 The graphs show the H2O2 yield test results for Examples 1, 16, and Comparative Example 4.

[0070] Figure 11 The graphs show the H2O2 yield test results for Example 1 and Comparative Examples 1-3.

[0071] Figure 12 The image shows a SEM image of the P / RF-CW prepared in Example 1.

[0072] Figure 13 SEM image of the P / RF-CW prepared in Example 17.

[0073] Figure 14 The graphs show the H2O2 yield test results of the P / RF-CW prepared in Examples 1 and 17.

[0074] Figure 15 The figure shows the experimental test results of the cyclic stability of the electric Fenton system in Example 1. Detailed Implementation

[0075] In the description of this invention, it should be understood that the orientation descriptions, such as up, down, etc., are based on the orientation or positional relationship shown in the embodiments, and are only for the purpose of facilitating the description of this invention and simplifying the description, and are not intended to indicate or imply that the device or element referred to must have a specific orientation, or be constructed and operated in a specific orientation, and therefore should not be construed as a limitation of this invention.

[0076] When a numerical range is disclosed herein, the range is considered continuous and includes the minimum and maximum values ​​of the range, as well as every value between the minimum and maximum values. Furthermore, when the range refers to integers, it includes every integer between the minimum and maximum values ​​of the range. Additionally, when multiple ranges are provided to describe a feature or characteristic, the ranges may be combined. In other words, unless otherwise specified, all ranges disclosed herein should be understood to include any and all subranges to which they are incorporated.

[0077] The technical solutions of the present invention will be clearly and completely described below with reference to 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 of ordinary skill in the art without creative effort are within the scope of the present invention.

[0078] Unless otherwise specified, the reagents, methods and equipment used in this invention are all conventional reagents, methods and equipment in this technical field.

[0079] In the examples and comparative examples, the electrolyte in the electro-Fenton system was a 50 mM Na2SO4 solution.

[0080] Example 1

[0081] A floating cathode electro-Fenton system, schematic diagram as follows: Figure 1 As shown, specifically, it includes a floating cathode and an anode that forms a transverse reaction system with the aforementioned floating cathode;

[0082] The aforementioned floating cathode comprises carbonized pine wood with ordered vertical channels, and phenolic resin and polytetrafluoroethylene loaded in the aforementioned carbonized pine wood.

[0083] The thickness of the carbonized pine wood is 2mm.

[0084] The phenolic resin loading in the carbonized pine wood was 223 mg.

[0085] The polytetrafluoroethylene loading in the carbonized pine wood was 524 mg.

[0086] In the above-mentioned floating cathode electro-Fenton system, an MMO (metal oxide) electrode is used as the counter electrode, and silver / silver chloride is used as the reference electrode.

[0087] The method for preparing the above-mentioned floating cathode electro-Fenton system includes the following steps:

[0088] Natural pine wood measuring 4cm × 8cm was selected and cut into 2mm thick pine chips perpendicular to its growth direction. The pine chips were placed in a tube furnace and heat-treated under an argon atmosphere. After 6 hours of high-temperature treatment at 800℃, carbonization was achieved. The carbonized pine wood was then immersed in a mixed solution containing resorcinol, formaldehyde, ammonia, and pure water. The reaction was carried out in a high-temperature reactor at 250℃ for 24 hours, allowing phenolic resin to form in situ in the wood pores. Free phenolic resin and excess precursors were removed by washing with acetone to obtain RF-CW.

[0089] The above-mentioned RF-CW was immersed in a polytetrafluoroethylene solution, removed and dried, and then placed in a muffle furnace at 300°C for 2 hours for heat treatment to obtain the cathode; a schematic diagram of the above cathode preparation process is shown below. Figure 2 As shown.

[0090] By merging the cathode and anode into a transverse reaction system, the above-mentioned floating cathode electro-Fenton system is obtained.

[0091] A method for degrading tetracycline in solution using the above-mentioned floating cathode electro-Fenton system includes the following steps:

[0092] A solution containing tetracycline and a catalyst were added to the above-mentioned floating cathode Fenton system to obtain a mixed solution with a pH of 3. The solution was then electrolyzed to degrade the tetracycline in the solution.

[0093] The above catalyst contains Fe 2+ The compound in which Fe 2+ The concentration in the mixed solution is 0.4 mol / L.

[0094] During the electrolysis process described above, the applied current was 200 mA and the current density was 20 mA cm⁻¹. -2 .

[0095] Example 2

[0096] The difference between Example 2 and Example 1 is that the thickness of the carbonized pine wood is different. In Example 2, the thickness of the carbonized pine wood is 4 mm.

[0097] A floating cathode electro-Fenton system includes a floating cathode and an anode that forms a transverse reaction system with the floating cathode.

[0098] The cathode comprises carbonized pine wood having ordered vertical channels, and phenolic resin and polytetrafluoroethylene loaded in the carbonized pine wood.

[0099] The thickness of the carbonized pine wood is 4mm.

[0100] The phenolic resin loading in the carbonized pine wood was 223 mg.

[0101] The polytetrafluoroethylene loading in the carbonized pine wood was 524 mg.

[0102] In the above-mentioned floating cathode electro-Fenton system, an MMO (metal oxide) electrode is used as the counter electrode, and silver / silver chloride is used as the reference electrode.

[0103] The method for preparing the above-mentioned floating cathode electro-Fenton system includes the following steps:

[0104] Natural pine wood measuring 4cm × 8cm was selected and cut into 2mm thick pine chips perpendicular to its growth direction. The pine chips were placed in a tube furnace and heat-treated under an argon atmosphere. After 6 hours of high-temperature treatment at 800℃, carbonization was achieved. The carbonized pine wood was then immersed in a mixed solution containing resorcinol, formaldehyde, ammonia, and pure water. The reaction was carried out in a high-temperature reactor at 250℃ for 24 hours, allowing phenolic resin to form in situ in the wood pores. Free phenolic resin and excess precursors were removed by washing with acetone to obtain RF-CW.

[0105] The above-mentioned RF-CW was immersed in a polytetrafluoroethylene solution, removed and dried, and then placed in a muffle furnace at 300°C for 2 hours of heat treatment to obtain a cathode;

[0106] By merging the cathode and anode into a transverse reaction system, the above-mentioned floating cathode electro-Fenton system is obtained.

[0107] A method for degrading tetracycline in solution using the above-mentioned floating cathode electro-Fenton system includes the following steps:

[0108] A solution containing tetracycline and a catalyst were added to the above-mentioned floating cathode Fenton system to obtain a mixed solution with a pH of 3. The solution was then electrolyzed to degrade the tetracycline in the solution.

[0109] The above catalyst contains Fe 2+ The compound in which Fe 2+ The concentration in the mixed solution is 0.4 mol / L.

[0110] During the electrolysis process described above, the applied current was 200 mA and the current density was 20 mA cm⁻¹. -2 .

[0111] Example 3

[0112] The difference between Example 3 and Example 1 is that the thickness of the carbonized pine wood is different. In Example 3, the thickness of the carbonized pine wood is 6 mm.

[0113] A floating cathode electro-Fenton system includes a floating cathode and an anode that forms a transverse reaction system with the floating cathode.

[0114] The cathode comprises carbonized pine wood having ordered vertical channels, and phenolic resin and polytetrafluoroethylene loaded in the carbonized pine wood.

[0115] The thickness of the carbonized pine wood is 6mm.

[0116] The phenolic resin loading in the carbonized pine wood was 223 mg.

[0117] The polytetrafluoroethylene loading in the carbonized pine wood was 524 mg.

[0118] In the above-mentioned floating cathode electro-Fenton system, an MMO (metal oxide) electrode is used as the counter electrode, and silver / silver chloride is used as the reference electrode.

[0119] The method for preparing the above-mentioned floating cathode electro-Fenton system includes the following steps:

[0120] Natural pine wood measuring 4cm × 8cm was selected and cut into 2mm thick pine chips perpendicular to its growth direction. The pine chips were placed in a tube furnace and heat-treated under an argon atmosphere. After 6 hours of high-temperature treatment at 800℃, carbonization was achieved. The carbonized pine wood was then immersed in a mixed solution containing resorcinol, formaldehyde, ammonia, and pure water. The reaction was carried out in a high-temperature reactor at 250℃ for 24 hours, allowing phenolic resin to form in situ in the wood pores. Free phenolic resin and excess precursors were removed by washing with acetone to obtain RF-CW.

[0121] The above-mentioned RF-CW was immersed in a polytetrafluoroethylene solution, removed and dried, and then placed in a muffle furnace at 300°C for 2 hours of heat treatment to obtain a cathode;

[0122] By merging the cathode and anode into a transverse reaction system, the above-mentioned floating cathode electro-Fenton system is obtained.

[0123] A method for degrading tetracycline in solution using the above-mentioned floating cathode electro-Fenton system includes the following steps:

[0124] A solution containing tetracycline and a catalyst were added to the above-mentioned floating cathode Fenton system to obtain a mixed solution with a pH of 3. The solution was then electrolyzed to degrade the tetracycline in the solution.

[0125] The above catalyst contains Fe 2+ The compound in which Fe 2+ The concentration in the mixed solution is 0.4 mol / L.

[0126] During the electrolysis process described above, the applied current was 200 mA and the current density was 20 mA cm⁻¹. -2 .

[0127] Example 4

[0128] The difference between Example 4 and Example 1 lies in the loading of phenolic resin in the carbonized pine wood. In Example 4, the loading of phenolic resin in the carbonized pine wood was 94 mg.

[0129] A floating cathode electro-Fenton system includes a floating cathode and an anode that forms a transverse reaction system with the floating cathode.

[0130] The cathode comprises carbonized pine wood having ordered vertical channels, and phenolic resin and polytetrafluoroethylene loaded in the carbonized pine wood.

[0131] The thickness of the carbonized pine wood is 2mm.

[0132] The phenolic resin loading in the carbonized pine wood was 94 mg.

[0133] The polytetrafluoroethylene loading in the carbonized pine wood was 524 mg.

[0134] In the above-mentioned floating cathode electro-Fenton system, an MMO (metal oxide) electrode is used as the counter electrode, and silver / silver chloride is used as the reference electrode.

[0135] The method for preparing the above-mentioned floating cathode electro-Fenton system includes the following steps:

[0136] Natural pine wood measuring 4cm × 8cm was selected and cut into 2mm thick pine chips perpendicular to its growth direction. The pine chips were placed in a tube furnace and heat-treated under an argon atmosphere. After 6 hours of high-temperature treatment at 800℃, carbonization was achieved. The carbonized pine wood was then immersed in a mixed solution containing resorcinol, formaldehyde, ammonia, and pure water. The reaction was carried out in a high-temperature reactor at 250℃ for 24 hours, allowing phenolic resin to form in situ in the wood pores. Free phenolic resin and excess precursors were removed by washing with acetone to obtain RF-CW.

[0137] The above-mentioned RF-CW was immersed in a polytetrafluoroethylene solution, removed and dried, and then placed in a muffle furnace at 300°C for 2 hours of heat treatment to obtain a cathode;

[0138] By merging the cathode and anode into a transverse reaction system, the above-mentioned floating cathode electro-Fenton system is obtained.

[0139] A method for degrading tetracycline in solution using the above-mentioned floating cathode electro-Fenton system includes the following steps:

[0140] A solution containing tetracycline and a catalyst were added to the above-mentioned floating cathode Fenton system to obtain a mixed solution with a pH of 3. The solution was then electrolyzed to degrade the tetracycline in the solution.

[0141] The above catalyst contains Fe 2+ The compound in which Fe 2+ The concentration in the mixed solution is 0.4 mol / L.

[0142] During the electrolysis process described above, the applied current was 200 mA and the current density was 20 mA cm⁻¹. -2 .

[0143] Example 5

[0144] The difference between Example 5 and Example 1 lies in the loading of phenolic resin in the carbonized pine wood. In Example 5, the loading of phenolic resin in the carbonized pine wood was 146 mg.

[0145] A floating cathode electro-Fenton system includes a floating cathode and an anode that forms a transverse reaction system with the floating cathode.

[0146] The cathode comprises carbonized pine wood having ordered vertical channels, and phenolic resin and polytetrafluoroethylene loaded in the carbonized pine wood.

[0147] The thickness of the carbonized pine wood is 2mm.

[0148] The phenolic resin loading in the carbonized pine wood was 146 mg.

[0149] The polytetrafluoroethylene loading in the carbonized pine wood was 524 mg.

[0150] In the above-mentioned floating cathode electro-Fenton system, an MMO (metal oxide) electrode is used as the counter electrode, and silver / silver chloride is used as the reference electrode.

[0151] The method for preparing the above-mentioned floating cathode electro-Fenton system includes the following steps:

[0152] Natural pine wood measuring 4cm × 8cm was selected and cut into 2mm thick pine chips perpendicular to its growth direction. The pine chips were placed in a tube furnace and heat-treated under an argon atmosphere. After 6 hours of high-temperature treatment at 800℃, carbonization was achieved. The carbonized pine wood was then immersed in a mixed solution containing resorcinol, formaldehyde, ammonia, and pure water. The reaction was carried out in a high-temperature reactor at 250℃ for 24 hours, allowing phenolic resin to form in situ in the wood pores. Free phenolic resin and excess precursors were removed by washing with acetone to obtain RF-CW.

[0153] The above-mentioned RF-CW was immersed in a polytetrafluoroethylene solution, removed and dried, and then placed in a muffle furnace at 300°C for 2 hours of heat treatment to obtain a cathode;

[0154] By merging the cathode and anode into a transverse reaction system, the above-mentioned floating cathode electro-Fenton system is obtained.

[0155] A method for degrading tetracycline in solution using the above-mentioned floating cathode electro-Fenton system includes the following steps:

[0156] A solution containing tetracycline and a catalyst were added to the above-mentioned floating cathode Fenton system to obtain a mixed solution with a pH of 3. The solution was then electrolyzed to degrade the tetracycline in the solution.

[0157] The above catalyst contains Fe 2+ The compound in which Fe 2+ The concentration in the mixed solution is 0.4 mol / L.

[0158] During the electrolysis process described above, the applied current was 200 mA and the current density was 20 mA cm⁻¹. -2 .

[0159] Example 6

[0160] The difference between Example 6 and Example 1 is that the polytetrafluoroethylene (PTFE) loading in the carbonized pine wood is different. In Example 6, the PTFE loading in the carbonized pine wood is 391 mg.

[0161] A floating cathode electro-Fenton system includes a floating cathode and an anode that forms a transverse reaction system with the floating cathode.

[0162] The cathode comprises carbonized pine wood having ordered vertical channels, and phenolic resin and polytetrafluoroethylene loaded in the carbonized pine wood.

[0163] The thickness of the carbonized pine wood is 2mm.

[0164] The phenolic resin loading in the carbonized pine wood was 223 mg.

[0165] The polytetrafluoroethylene loading in the carbonized pine wood was 391 mg.

[0166] In the above-mentioned floating cathode electro-Fenton system, an MMO (metal oxide) electrode is used as the counter electrode, and silver / silver chloride is used as the reference electrode.

[0167] The method for preparing the above-mentioned floating cathode electro-Fenton system includes the following steps:

[0168] Natural pine wood measuring 4cm × 8cm was selected and cut into 2mm thick pine chips perpendicular to its growth direction. The pine chips were placed in a tube furnace and heat-treated under an argon atmosphere. After 6 hours of high-temperature treatment at 800℃, carbonization was achieved. The carbonized pine wood was then immersed in a mixed solution containing resorcinol, formaldehyde, ammonia, and pure water. The reaction was carried out in a high-temperature reactor at 250℃ for 24 hours, allowing phenolic resin to form in situ in the wood pores. Free phenolic resin and excess precursors were removed by washing with acetone to obtain RF-CW.

[0169] The above-mentioned RF-CW was immersed in a polytetrafluoroethylene solution, removed and dried, and then placed in a muffle furnace at 300°C for 2 hours of heat treatment to obtain a cathode;

[0170] By merging the cathode and anode into a transverse reaction system, the above-mentioned floating cathode electro-Fenton system is obtained.

[0171] A method for degrading tetracycline in solution using the above-mentioned floating cathode electro-Fenton system includes the following steps:

[0172] A solution containing tetracycline and a catalyst were added to the above-mentioned floating cathode Fenton system to obtain a mixed solution with a pH of 3. The solution was then electrolyzed to degrade the tetracycline in the solution.

[0173] The above catalyst contains Fe 2+ The compound in which Fe 2+ The concentration in the mixed solution is 0.4 mol / L.

[0174] During the electrolysis process described above, the applied current was 200 mA and the current density was 20 mA cm⁻¹. -2 .

[0175] Example 7

[0176] The difference between Example 7 and Example 1 is that the polytetrafluoroethylene (PTFE) loading in the carbonized pine wood is different. In Example 7, the PTFE loading in the carbonized pine wood is 780 mg.

[0177] A floating cathode electro-Fenton system includes a floating cathode and an anode that forms a transverse reaction system with the floating cathode.

[0178] The cathode comprises carbonized pine wood having ordered vertical channels, and phenolic resin and polytetrafluoroethylene loaded in the carbonized pine wood.

[0179] The thickness of the carbonized pine wood is 2mm.

[0180] The phenolic resin loading in the carbonized pine wood was 223 mg.

[0181] The polytetrafluoroethylene loading in the carbonized pine wood was 780 mg.

[0182] In the above-mentioned floating cathode electro-Fenton system, an MMO (metal oxide) electrode is used as the counter electrode, and silver / silver chloride is used as the reference electrode.

[0183] The method for preparing the above-mentioned floating cathode electro-Fenton system includes the following steps:

[0184] Natural pine wood measuring 4cm × 8cm was selected and cut into 2mm thick pine chips perpendicular to its growth direction. The pine chips were placed in a tube furnace and heat-treated under an argon atmosphere. After 6 hours of high-temperature treatment at 800℃, carbonization was achieved. The carbonized pine wood was then immersed in a mixed solution containing resorcinol, formaldehyde, ammonia, and pure water. The reaction was carried out in a high-temperature reactor at 250℃ for 24 hours, allowing phenolic resin to form in situ in the wood pores. Free phenolic resin and excess precursors were removed by washing with acetone to obtain RF-CW.

[0185] The above-mentioned RF-CW was immersed in a polytetrafluoroethylene solution, removed and dried, and then placed in a muffle furnace at 300°C for 2 hours of heat treatment to obtain a cathode;

[0186] By merging the cathode and anode into a transverse reaction system, the above-mentioned floating cathode electro-Fenton system is obtained.

[0187] A method for degrading tetracycline in solution using the above-mentioned floating cathode electro-Fenton system includes the following steps:

[0188] A solution containing tetracycline and a catalyst were added to the above-mentioned floating cathode Fenton system to obtain a mixed solution with a pH of 3. The solution was then electrolyzed to degrade the tetracycline in the solution.

[0189] The above catalyst contains Fe 2+ The compound in which Fe 2+ The concentration in the mixed solution is 0.4 mol / L.

[0190] During the electrolysis process described above, the applied current was 200 mA and the current density was 20 mA cm⁻¹. -2 .

[0191] Example 8

[0192] The difference between Example 8 and Example 1 lies in the current density during electrolysis. Specifically, the current density in Example 8 is 10 mA cm⁻¹. -2 .

[0193] A floating cathode electro-Fenton system includes a floating cathode and an anode that forms a transverse reaction system with the floating cathode.

[0194] The cathode comprises carbonized pine wood having ordered vertical channels, and phenolic resin and polytetrafluoroethylene loaded in the carbonized pine wood.

[0195] The thickness of the carbonized pine wood is 2mm.

[0196] The phenolic resin loading in the carbonized pine wood was 223 mg.

[0197] The polytetrafluoroethylene loading in the carbonized pine wood was 524 mg.

[0198] In the above-mentioned floating cathode electro-Fenton system, an MMO (metal oxide) electrode is used as the counter electrode, and silver / silver chloride is used as the reference electrode.

[0199] The method for preparing the above-mentioned floating cathode electro-Fenton system includes the following steps:

[0200] Natural pine wood measuring 4cm × 8cm was selected and cut into 2mm thick pine chips perpendicular to its growth direction. The pine chips were placed in a tube furnace and heat-treated under an argon atmosphere. After 6 hours of high-temperature treatment at 800℃, carbonization was achieved. The carbonized pine wood was then immersed in a mixed solution containing resorcinol, formaldehyde, ammonia, and pure water. The reaction was carried out in a high-temperature reactor at 250℃ for 24 hours, allowing phenolic resin to form in situ in the wood pores. Free phenolic resin and excess precursors were removed by washing with acetone to obtain RF-CW.

[0201] The above-mentioned RF-CW was immersed in a polytetrafluoroethylene solution, removed and dried, and then placed in a muffle furnace at 300°C for 2 hours of heat treatment to obtain a cathode;

[0202] By merging the cathode and anode into a transverse reaction system, the above-mentioned floating cathode electro-Fenton system is obtained.

[0203] A method for degrading tetracycline in solution using the above-mentioned floating cathode electro-Fenton system includes the following steps:

[0204] A solution containing tetracycline and a catalyst were added to the above-mentioned floating cathode Fenton system to obtain a mixed solution with a pH of 3. The solution was then electrolyzed to degrade the tetracycline in the solution.

[0205] The above catalyst contains Fe 2+ The compound in which Fe 2+ The concentration in the mixed solution is 0.4 mol / L.

[0206] During the electrolysis process described above, a current of 200 mA and a current density of 10 mA / cm² were applied. -2 .

[0207] Example 9

[0208] The difference between Example 9 and Example 1 lies in the current density during electrolysis. Specifically, the current density in Example 9 is 15 mA cm⁻¹. -2 .

[0209] A floating cathode electro-Fenton system includes a floating cathode and an anode that forms a transverse reaction system with the floating cathode.

[0210] The cathode comprises carbonized pine wood having ordered vertical channels, and phenolic resin and polytetrafluoroethylene loaded in the carbonized pine wood.

[0211] The thickness of the carbonized pine wood is 2mm.

[0212] The phenolic resin loading in the carbonized pine wood was 223 mg.

[0213] The polytetrafluoroethylene loading in the carbonized pine wood was 524 mg.

[0214] In the above-mentioned floating cathode electro-Fenton system, an MMO (metal oxide) electrode is used as the counter electrode, and silver / silver chloride is used as the reference electrode.

[0215] The method for preparing the above-mentioned floating cathode electro-Fenton system includes the following steps:

[0216] Natural pine wood measuring 4cm × 8cm was selected and cut into 2mm thick pine chips perpendicular to its growth direction. The pine chips were placed in a tube furnace and heat-treated under an argon atmosphere. After 6 hours of high-temperature treatment at 800℃, carbonization was achieved. The carbonized pine wood was then immersed in a mixed solution containing resorcinol, formaldehyde, ammonia, and pure water. The reaction was carried out in a high-temperature reactor at 250℃ for 24 hours, allowing phenolic resin to form in situ in the wood pores. Free phenolic resin and excess precursors were removed by washing with acetone to obtain RF-CW.

[0217] The above-mentioned RF-CW was immersed in a polytetrafluoroethylene solution, removed and dried, and then placed in a muffle furnace at 300°C for 2 hours of heat treatment to obtain a cathode;

[0218] By merging the cathode and anode into a transverse reaction system, the above-mentioned floating cathode electro-Fenton system is obtained.

[0219] A method for degrading tetracycline in solution using the above-mentioned floating cathode electro-Fenton system includes the following steps:

[0220] A solution containing tetracycline and a catalyst were added to the above-mentioned floating cathode Fenton system to obtain a mixed solution with a pH of 3. The solution was then electrolyzed to degrade the tetracycline in the solution.

[0221] The above catalyst contains Fe 2+ The compound in which Fe 2+ The concentration in the mixed solution is 0.4 mol / L.

[0222] During the electrolysis process described above, the applied current was 200 mA and the current density was 15 mA cm⁻¹. -2 .

[0223] Example 10

[0224] The difference between Example 10 and Example 1 is that the current is different during the electrolysis process. In Example 10, the current is 100mA.

[0225] A floating cathode electro-Fenton system includes a floating cathode and an anode that forms a transverse reaction system with the floating cathode.

[0226] The cathode comprises carbonized pine wood having ordered vertical channels, and phenolic resin and polytetrafluoroethylene loaded in the carbonized pine wood.

[0227] The thickness of the carbonized pine wood is 2mm.

[0228] The phenolic resin loading in the carbonized pine wood was 223 mg.

[0229] The polytetrafluoroethylene loading in the carbonized pine wood was 524 mg.

[0230] In the above-mentioned floating cathode electro-Fenton system, an MMO (metal oxide) electrode is used as the counter electrode, and silver / silver chloride is used as the reference electrode.

[0231] The method for preparing the above-mentioned floating cathode electro-Fenton system includes the following steps:

[0232] Natural pine wood measuring 4cm × 8cm was selected and cut into 2mm thick pine chips perpendicular to its growth direction. The pine chips were placed in a tube furnace and heat-treated under an argon atmosphere. After 6 hours of high-temperature treatment at 800℃, carbonization was achieved. The carbonized pine wood was then immersed in a mixed solution containing resorcinol, formaldehyde, ammonia, and pure water. The reaction was carried out in a high-temperature reactor at 250℃ for 24 hours, allowing phenolic resin to form in situ in the wood pores. Free phenolic resin and excess precursors were removed by washing with acetone to obtain RF-CW.

[0233] The above-mentioned RF-CW was immersed in a polytetrafluoroethylene solution, removed and dried, and then placed in a muffle furnace at 300°C for 2 hours of heat treatment to obtain a cathode;

[0234] By merging the cathode and anode into a transverse reaction system, the above-mentioned floating cathode electro-Fenton system is obtained.

[0235] A method for degrading tetracycline in solution using the above-mentioned floating cathode electro-Fenton system includes the following steps:

[0236] A solution containing tetracycline and a catalyst were added to the above-mentioned floating cathode Fenton system to obtain a mixed solution with a pH of 3. The solution was then electrolyzed to degrade the tetracycline in the solution.

[0237] The above catalyst contains Fe 2+ The compound in which Fe 2+ The concentration in the mixed solution is 0.4 mol / L.

[0238] During the electrolysis process described above, the applied current was 100 mA and the current density was 20 mA cm⁻¹. -2 .

[0239] Example 11

[0240] The difference between Example 11 and Example 1 is that the current is different during the electrolysis process. In Example 11, the current is 150mA.

[0241] A floating cathode electro-Fenton system includes a floating cathode and an anode that forms a transverse reaction system with the floating cathode.

[0242] The cathode comprises carbonized pine wood having ordered vertical channels, and phenolic resin and polytetrafluoroethylene loaded in the carbonized pine wood.

[0243] The thickness of the carbonized pine wood is 2mm.

[0244] The phenolic resin loading in the carbonized pine wood was 223 mg.

[0245] The polytetrafluoroethylene loading in the carbonized pine wood was 524 mg.

[0246] In the above-mentioned floating cathode electro-Fenton system, an MMO (metal oxide) electrode is used as the counter electrode, and silver / silver chloride is used as the reference electrode.

[0247] The method for preparing the above-mentioned floating cathode electro-Fenton system includes the following steps:

[0248] Natural pine wood measuring 4cm × 8cm was selected and cut into 2mm thick pine chips perpendicular to its growth direction. The pine chips were placed in a tube furnace and heat-treated under an argon atmosphere. After 6 hours of high-temperature treatment at 800℃, carbonization was achieved. The carbonized pine wood was then immersed in a mixed solution containing resorcinol, formaldehyde, ammonia, and pure water. The reaction was carried out in a high-temperature reactor at 250℃ for 24 hours, allowing phenolic resin to form in situ in the wood pores. Free phenolic resin and excess precursors were removed by washing with acetone to obtain RF-CW.

[0249] The above-mentioned RF-CW was immersed in a polytetrafluoroethylene solution, removed and dried, and then placed in a muffle furnace at 300°C for 2 hours of heat treatment to obtain a cathode;

[0250] By merging the cathode and anode into a transverse reaction system, the above-mentioned floating cathode electro-Fenton system is obtained.

[0251] A method for degrading tetracycline in solution using the above-mentioned floating cathode electro-Fenton system includes the following steps:

[0252] A solution containing tetracycline and a catalyst were added to the above-mentioned floating cathode Fenton system to obtain a mixed solution with a pH of 3. The solution was then electrolyzed to degrade the tetracycline in the solution.

[0253] The above catalyst contains Fe 2+ The compound in which Fe 2+ The concentration in the mixed solution is 0.4 mol / L.

[0254] During the electrolysis process described above, the applied current was 150 mA and the current density was 20 mA cm⁻¹. -2 .

[0255] Example 12

[0256] The difference between Example 12 and Example 1 is that: Fe 2+ The concentrations of Fe differ in the mixed solution. Specifically, in Example 12, Fe... 2+ The concentration in the mixed solution is 0 mol / L.

[0257] A floating cathode electro-Fenton system includes a floating cathode and an anode that forms a transverse reaction system with the floating cathode.

[0258] The cathode comprises carbonized pine wood having ordered vertical channels, and phenolic resin and polytetrafluoroethylene loaded in the carbonized pine wood.

[0259] The thickness of the carbonized pine wood is 2mm.

[0260] The phenolic resin loading in the carbonized pine wood was 223 mg.

[0261] The polytetrafluoroethylene loading in the carbonized pine wood was 524 mg.

[0262] In the above-mentioned floating cathode electro-Fenton system, an MMO (metal oxide) electrode is used as the counter electrode, and silver / silver chloride is used as the reference electrode.

[0263] The method for preparing the above-mentioned floating cathode electro-Fenton system includes the following steps:

[0264] Natural pine wood measuring 4cm × 8cm was selected and cut into 2mm thick pine chips perpendicular to its growth direction. The pine chips were placed in a tube furnace and heat-treated under an argon atmosphere. After 6 hours of high-temperature treatment at 800℃, carbonization was achieved. The carbonized pine wood was then immersed in a mixed solution containing resorcinol, formaldehyde, ammonia, and pure water. The reaction was carried out in a high-temperature reactor at 250℃ for 24 hours, allowing phenolic resin to form in situ in the wood pores. Free phenolic resin and excess precursors were removed by washing with acetone to obtain RF-CW.

[0265] The above-mentioned RF-CW was immersed in a polytetrafluoroethylene solution, removed and dried, and then placed in a muffle furnace at 300°C for 2 hours of heat treatment to obtain a cathode;

[0266] By merging the cathode and anode into a transverse reaction system, the above-mentioned floating cathode electro-Fenton system is obtained.

[0267] A method for degrading tetracycline in solution using the above-mentioned floating cathode electro-Fenton system includes the following steps:

[0268] A solution containing tetracycline was added to the above-mentioned floating cathode Fenton system to obtain a mixed solution with a pH of 3. The solution was then electrolyzed to degrade the tetracycline in the solution.

[0269] During the electrolysis process described above, the applied current was 200 mA and the current density was 20 mA cm⁻¹. -2 .

[0270] Example 13

[0271] The difference between Example 13 and Example 1 is that: Fe 2+ The concentrations of Fe differ in the mixed solution. Specifically, in Example 13, Fe... 2+ The concentration in the mixed solution is 0.2 mol / L.

[0272] A floating cathode electro-Fenton system includes a floating cathode and an anode that forms a transverse reaction system with the floating cathode.

[0273] The cathode comprises carbonized pine wood having ordered vertical channels, and phenolic resin and polytetrafluoroethylene loaded in the carbonized pine wood.

[0274] The thickness of the carbonized pine wood is 2mm.

[0275] The phenolic resin loading in the carbonized pine wood was 223 mg.

[0276] The polytetrafluoroethylene loading in the carbonized pine wood was 524 mg.

[0277] In the above-mentioned floating cathode electro-Fenton system, an MMO (metal oxide) electrode is used as the counter electrode, and silver / silver chloride is used as the reference electrode.

[0278] The method for preparing the above-mentioned floating cathode electro-Fenton system includes the following steps:

[0279] Natural pine wood measuring 4cm × 8cm was selected and cut into 2mm thick pine chips perpendicular to its growth direction. The pine chips were placed in a tube furnace and heat-treated under an argon atmosphere. After 6 hours of high-temperature treatment at 800℃, carbonization was achieved. The carbonized pine wood was then immersed in a mixed solution containing resorcinol, formaldehyde, ammonia, and pure water. The reaction was carried out in a high-temperature reactor at 250℃ for 24 hours, allowing phenolic resin to form in situ in the wood pores. Free phenolic resin and excess precursors were removed by washing with acetone to obtain RF-CW.

[0280] The above-mentioned RF-CW was immersed in a polytetrafluoroethylene solution, removed and dried, and then placed in a muffle furnace at 300°C for 2 hours of heat treatment to obtain a cathode;

[0281] By merging the cathode and anode into a transverse reaction system, the above-mentioned floating cathode electro-Fenton system is obtained.

[0282] A method for degrading tetracycline in solution using the above-mentioned floating cathode electro-Fenton system includes the following steps:

[0283] A solution containing tetracycline and a catalyst were added to the above-mentioned floating cathode Fenton system to obtain a mixed solution with a pH of 3. The solution was then electrolyzed to degrade the tetracycline in the solution.

[0284] The above catalyst contains Fe 2+ The compound in which Fe 2+ The concentration in the mixed solution is 0.2 mol / L.

[0285] During the electrolysis process described above, the applied current was 200 mA and the current density was 20 mA cm⁻¹. -2 .

[0286] Example 14

[0287] The difference between Example 14 and Example 1 is that the pH of the mixed solution is different. In Example 14, the pH of the mixed solution is 1.

[0288] A floating cathode electro-Fenton system includes a floating cathode and an anode that forms a transverse reaction system with the floating cathode.

[0289] The cathode comprises carbonized pine wood having ordered vertical channels, and phenolic resin and polytetrafluoroethylene loaded in the carbonized pine wood.

[0290] The thickness of the carbonized pine wood is 2mm.

[0291] The phenolic resin loading in the carbonized pine wood was 223 mg.

[0292] The polytetrafluoroethylene loading in the carbonized pine wood was 524 mg.

[0293] In the above-mentioned floating cathode electro-Fenton system, an MMO (metal oxide) electrode is used as the counter electrode, and silver / silver chloride is used as the reference electrode.

[0294] The method for preparing the above-mentioned floating cathode electro-Fenton system includes the following steps:

[0295] Natural pine wood measuring 4cm × 8cm was selected and cut into 2mm thick pine chips perpendicular to its growth direction. The pine chips were placed in a tube furnace and heat-treated under an argon atmosphere. After 6 hours of high-temperature treatment at 800℃, carbonization was achieved. The carbonized pine wood was then immersed in a mixed solution containing resorcinol, formaldehyde, ammonia, and pure water. The reaction was carried out in a high-temperature reactor at 250℃ for 24 hours, allowing phenolic resin to form in situ in the wood pores. Free phenolic resin and excess precursors were removed by washing with acetone to obtain RF-CW.

[0296] The above-mentioned RF-CW was immersed in a polytetrafluoroethylene solution, removed and dried, and then placed in a muffle furnace at 300°C for 2 hours of heat treatment to obtain a cathode;

[0297] By merging the cathode and anode into a transverse reaction system, the above-mentioned floating cathode electro-Fenton system is obtained.

[0298] A method for degrading tetracycline in solution using the above-mentioned floating cathode electro-Fenton system includes the following steps:

[0299] A solution containing tetracycline and a catalyst were added to the above-mentioned floating cathode Fenton system to obtain a mixed solution with a pH of 1. The solution was then electrolyzed to degrade the tetracycline in the solution.

[0300] The above catalyst contains Fe 2+ The compound in which Fe 2+ The concentration in the mixed solution is 0.4 mol / L.

[0301] During the electrolysis process described above, the applied current was 200 mA and the current density was 20 mA cm⁻¹. -2 .

[0302] Example 15

[0303] The difference between Example 15 and Example 1 is that the pH of the mixed solution is different. In Example 15, the pH of the mixed solution is 5.

[0304] A floating cathode electro-Fenton system includes a floating cathode and an anode that forms a transverse reaction system with the floating cathode.

[0305] The cathode comprises carbonized pine wood having ordered vertical channels, and phenolic resin and polytetrafluoroethylene loaded in the carbonized pine wood.

[0306] The thickness of the carbonized pine wood is 2mm.

[0307] The phenolic resin loading in the carbonized pine wood was 223 mg.

[0308] The polytetrafluoroethylene loading in the carbonized pine wood was 524 mg.

[0309] In the above-mentioned floating cathode electro-Fenton system, an MMO (metal oxide) electrode is used as the counter electrode, and silver / silver chloride is used as the reference electrode.

[0310] The method for preparing the above-mentioned floating cathode electro-Fenton system includes the following steps:

[0311] Natural pine wood measuring 4cm × 8cm was selected and cut into 2mm thick pine chips perpendicular to its growth direction. The pine chips were placed in a tube furnace and heat-treated under an argon atmosphere. After 6 hours of high-temperature treatment at 800℃, carbonization was achieved. The carbonized pine wood was then immersed in a mixed solution containing resorcinol, formaldehyde, ammonia, and pure water. The reaction was carried out in a high-temperature reactor at 250℃ for 24 hours, allowing phenolic resin to form in situ in the wood pores. Free phenolic resin and excess precursors were removed by washing with acetone to obtain RF-CW.

[0312] The above-mentioned RF-CW was immersed in a polytetrafluoroethylene solution, removed and dried, and then placed in a muffle furnace at 300°C for 2 hours of heat treatment to obtain a cathode;

[0313] By merging the cathode and anode into a transverse reaction system, the above-mentioned floating cathode electro-Fenton system is obtained.

[0314] A method for degrading tetracycline in solution using the above-mentioned floating cathode electro-Fenton system includes the following steps:

[0315] A solution containing tetracycline and a catalyst were added to the above-mentioned floating cathode Fenton system to obtain a mixed solution with a pH of 5. The solution was then electrolyzed to degrade the tetracycline in the solution.

[0316] The above catalyst contains Fe 2+ The compound in which Fe 2+ The concentration in the mixed solution is 0.4 mol / L.

[0317] During the electrolysis process described above, the applied current was 200 mA and the current density was 20 mA cm⁻¹. -2 .

[0318] Example 16

[0319] The difference between Example 16 and Example 1 is that in the floating cathode electro-Fenton system, a Ti electrode is used as the counter electrode.

[0320] A floating cathode electro-Fenton system includes a floating cathode and an anode that forms a transverse reaction system with the floating cathode.

[0321] The cathode comprises carbonized pine wood having ordered vertical channels, and phenolic resin and polytetrafluoroethylene loaded in the carbonized pine wood.

[0322] The thickness of the carbonized pine wood is 2mm.

[0323] The phenolic resin loading in the carbonized pine wood was 223 mg.

[0324] The polytetrafluoroethylene loading in the carbonized pine wood was 524 mg.

[0325] In the above-mentioned floating cathode electro-Fenton system, a Ti plate is used as the counter electrode and silver / silver chloride is used as the reference electrode.

[0326] The method for preparing the above-mentioned floating cathode electro-Fenton system includes the following steps:

[0327] Natural pine wood measuring 4cm × 8cm was selected and cut into 2mm thick pine chips perpendicular to its growth direction. The pine chips were placed in a tube furnace and heat-treated under an argon atmosphere. After 6 hours of high-temperature treatment at 800℃, carbonization was achieved. The carbonized pine wood was then immersed in a mixed solution containing resorcinol, formaldehyde, ammonia, and pure water. The reaction was carried out in a high-temperature reactor at 250℃ for 24 hours, allowing phenolic resin to form in situ in the wood pores. Free phenolic resin and excess precursors were removed by washing with acetone to obtain RF-CW.

[0328] The above-mentioned RF-CW was immersed in a polytetrafluoroethylene solution, removed and dried, and then placed in a muffle furnace at 300°C for 2 hours of heat treatment to obtain a cathode;

[0329] By merging the cathode and anode into a transverse reaction system, the above-mentioned floating cathode electro-Fenton system is obtained.

[0330] A method for degrading tetracycline in solution using the above-mentioned floating cathode electro-Fenton system includes the following steps:

[0331] A solution containing tetracycline and a catalyst were added to the above-mentioned floating cathode Fenton system to obtain a mixed solution with a pH of 3. The solution was then electrolyzed to degrade the tetracycline in the solution.

[0332] The above catalyst contains Fe 2+ The compound in which Fe 2+ The concentration in the mixed solution is 0.4 mol / L.

[0333] During the electrolysis process described above, the applied current was 200 mA and the current density was 20 mA cm⁻¹. -2 .

[0334] Example 17

[0335] The difference between Example 17 and Example 1 is that in Example 17, carbonized pine wood was directly immersed in phenolic resin to obtain RF-CW with the same loading as in Example 1.

[0336] A floating cathode electro-Fenton system includes a floating cathode and an anode that forms a transverse reaction system with the floating cathode.

[0337] The cathode comprises carbonized pine wood having ordered vertical channels, and phenolic resin and polytetrafluoroethylene loaded in the carbonized pine wood.

[0338] The thickness of the carbonized pine wood is 2mm.

[0339] The phenolic resin loading in the carbonized pine wood was 223 mg.

[0340] The polytetrafluoroethylene loading in the carbonized pine wood was 524 mg.

[0341] In the above-mentioned floating cathode electro-Fenton system, an MMO (metal oxide) electrode is used as the counter electrode, and silver / silver chloride is used as the reference electrode.

[0342] The method for preparing the above-mentioned floating cathode electro-Fenton system includes the following steps:

[0343] Select natural pine wood with a size of 4cm×8cm, cut it into 2mm thick pine wood chips perpendicular to its growth direction, place the pine wood chips in a tube furnace, and heat treat it under an argon atmosphere. After 6 hours of high-temperature treatment at 800℃, it will carbonize. The carbonized pine wood is then soaked in a solution containing phenolic resin, and the free phenolic resin is removed by washing with acetone to obtain RF-CW.

[0344] The above-mentioned RF-CW was immersed in a polytetrafluoroethylene solution, removed and dried, and then placed in a muffle furnace at 300°C for 2 hours of heat treatment to obtain the cathode.

[0345] By merging the cathode and anode into a transverse reaction system, the above-mentioned floating cathode electro-Fenton system is obtained.

[0346] A method for degrading tetracycline in solution using the above-mentioned floating cathode electro-Fenton system includes the following steps:

[0347] A solution containing tetracycline and a catalyst were added to the above-mentioned floating cathode Fenton system to obtain a mixed solution with a pH of 3. The solution was then electrolyzed to degrade the tetracycline in the solution.

[0348] The above catalyst contains Fe 2+ The compound in which Fe 2+ The concentration in the mixed solution is 0.4 mol / L.

[0349] During the electrolysis process described above, the applied current was 200 mA and the current density was 20 mA cm⁻¹. -2 .

[0350] Comparative Example 1

[0351] The difference between Comparative Example 1 and Example 1 is that the floating cathode of Comparative Example 1 is carbonized pine wood with ordered vertical channels, but without phenolic resin and polytetrafluoroethylene loaded on it.

[0352] Comparative Example 2

[0353] The difference between Comparative Example 2 and Example 1 is that the floating cathode of Comparative Example 2 is carbonized pine wood with ordered vertical channels loaded with phenolic resin, but polytetrafluoroethylene is not loaded on the carbonized pine wood.

[0354] Comparative Example 3

[0355] The difference between Comparative Example 3 and Example 1 is that the floating cathode of Comparative Example 3 is carbonized pine wood with ordered vertical channels loaded with polytetrafluoroethylene, but no phenolic resin is loaded on the carbonized pine wood.

[0356] Comparative Example 4

[0357] The difference between Comparative Example 4 and Example 1 is that Comparative Example 3 does not use a floating cathode, and the cathode of Comparative Example 3 is immersed in the electrolyte.

[0358] Performance testing:

[0359] The yield of H2O2 in the electro-Fenton systems of Examples 1-17 and Comparative Examples 1-4 was tested using the following methods: The concentration of H2O2 was determined by cerium sulfate spectrophotometry. During the experiment, 0.2 mL of sample was added to 4 mL of 0.5 mM cerium sulfate solution every 10 minutes. After complete reaction, the absorbance was measured at 318 nm using a UV-Vis spectrophotometer. The concentration of tetracycline was determined by high-performance liquid chromatography (HPLC). A C18 column equipped with a 280 nm UV fluorescence detector was used. The injection volume was 50 μL, the mobile phase was methanol:water (1 wt% formic acid) = 70:30, the flow rate was 1 mL / min, the column temperature was 30 °C, and the detection wavelength was 270 nm.

[0360] The difference between Examples 1-3 is the thickness of the carbonized pine wood. The H2O2 yield tests for Examples 1-3 are as follows: Figure 3 As shown, a 2mm thickness of carbonized pine wood is more conducive to the production of H2O2.

[0361] The difference between Examples 1 and 4-5 lies in the loading of phenolic resin in the carbonized pine wood. The H2O2 yield tests for Examples 1 and 4-5 are as follows: Figure 4 As shown.

[0362] The difference between Example 1 and Examples 6-7 lies in the different loading amounts of polytetrafluoroethylene in the carbonized pine wood. The H2O2 yield tests for Examples 1 and 6-7 are as follows: Figure 5 As shown, concentration is the concentration.

[0363] Figure 5 The results showed that H2O2 production peaked at a PTFE loading of 524 mg. When the PTFE loading was reduced to 391 mg, the concentration of generated H2O2 decreased to 383.1 mg·L⁻¹. -1 This phenomenon can be attributed to the reduced hydrophobicity of the electrode material, allowing liquid to penetrate into the internal pores and thus hindering O2 transport within the electrode. However, when the PTFE loading was further increased to 780 mg, a significant decrease in H2O2 production was observed, plummeting to only 175.6 mg·L⁻¹. -1 .

[0364] The contact angle test diagrams for Examples 1 and 6-7 are shown below. Figure 6 As shown, where, Figure 6 (a) corresponds to the polytetrafluoroethylene loading in Example 6. Figure 6 (b) corresponds to the load amount in Example 1. Figure 6 (c) corresponds to the loading amount in Example 7. Although the hydrophobic design can enhance O2 diffusion and achieve a rich three-phase interface, thereby synergistically improving performance, excessive use of the PTFE coating may hinder e- The transport of PTFE can negate its potential advantages. Therefore, finding the optimal PTFE loading is crucial for optimizing electrocatalytic efficiency.

[0365] The difference between Example 1 and Examples 10-11 lies in the different currents used during electrolysis. The H2O2 yield tests for Examples 1 and 10-11 are as follows: Figure 7 As shown.

[0366] The difference between Example 1 and Examples 12-13 is that Fe 2+ The concentrations are different in the mixed solution.

[0367] The H2O2 yield tests of Examples 1 and 12-13 are as follows: Figure 8 As shown.

[0368] The difference between Example 1 and Examples 14-15 lies in the pH of the mixed solution. The H2O2 yield tests for Examples 1 and 14-15 are as follows: Figure 9 As shown.

[0369] The differences between Examples 1, 16, and Comparative Example 4 lie in the selection of the cathode position or the counter electrode. Specifically, Example 1 uses a floating cathode that floats on the surface of the electrolyte, while the cathode in Comparative Example 4 is directly immersed in the electrolyte. Although Example 16 also uses a floating cathode, the counter electrode uses a Ti plate with low OER catalytic activity to limit the amount of O2 generated by the anode OER.

[0370] The H2O2 yield tests of Examples 1, 16 and 4 are as follows: Figure 10 As shown. From Figure 10 It can be seen that, in Comparative Example 4, because the cathode is immersed in the electrolyte, the H2O2 production efficiency is significantly lower than that in Example 1. In Example 16, by limiting the amount of O2 produced by the anode OER, the reduced oxygen production at the anode led to a decrease in H2O2 production. Comparing Example 1 and Example 16, it can be demonstrated that the high H2O2 production at the cathode in Example 1 is supported by the synergistic effect of oxygen production from the OER and oxygen in the air. Its pore structure enables effective oxygen transport in both the upper and lower channels, meaning that the structure of the electro-Fenton system of this invention can better utilize oxygen from both the upper and lower channels simultaneously.

[0371] Among them, the H2O2 yield tests of Example 1 and Comparative Examples 1-3 are as follows: Figure 11 As shown.

[0372] The difference between Example 1 and Example 17 is that Example 1 uses an in-situ hydrothermal method to load phenolic resin into carbonized pine wood, while Example 17 uses a direct impregnation method to load phenolic resin into carbonized pine wood. Figure 12The image shows a SEM image of the P / RF-CW prepared in Example 1. As can be seen from the image, the phenolic resin is uniformly distributed inside the pores of the carbonized pine wood. Figure 13 The image shows a SEM image of the P / RF-CW prepared in Example 17. As can be seen from the image, the phenolic resin was not evenly distributed inside the pores. This is because phenolic resin is poorly soluble in water. The impregnation method in Example 17 requires stirring, which damages the pore structure inside the wood to some extent, making it difficult for the phenolic resin to be evenly distributed inside the pores. Figure 14 The graphs show the H2O2 yield test results of P / RF-CW prepared in Examples 1 and 17, where Example 1 uses a hydrothermal method and Example 17 uses an impregnation method.

[0373] The stability of the electrode was tested using the floating cathode Fenton system from Example 1, undergoing seven cycles of stability testing, with the electrolyte replaced every 60 minutes during this process. Figure 15 As shown, the yield of H2O2 remained at approximately 467.6 mg·L⁻¹. -1 ·h -1 This demonstrates the operational stability of the process.

[0374] The above are merely embodiments of the present invention and do not limit the patent scope of the present invention. Any equivalent modifications made based on the content of the present invention specification, or direct or indirect applications in related technical fields, are similarly included within the patent protection scope of the present invention.

Claims

1. A floating cathode electro-Fenton system, characterized in that: It includes a floating cathode and an anode that forms a transverse reaction system with the floating cathode; The floating cathode comprises carbonized wood with ordered vertical channels, and phenolic resin and hydrophobic organic polymer loaded in the carbonized wood. The preparation method of the floating cathode electro-Fenton system includes the following steps: After carbonizing the wood, it is immersed in a phenolic resin precursor solution. Through hydrothermal reaction, the phenolic resin is formed in situ in the wood pores to obtain RF-CW. The RF-CW was immersed in a hydrophobic organic polymer solution, removed, dried, and then heat-treated to obtain a floating cathode. The floating cathode and coupled anode are combined to form a transverse reaction system, thus obtaining the floating cathode electro-Fenton system; The carbonization of wood also includes the following steps: cutting the wood into chips perpendicular to its growth direction, placing them in a protective atmosphere, and heating them at 800-850°C to obtain carbonized wood with ordered vertical channels.

2. The floating cathode electro-Fenton system according to claim 1, characterized in that: The floating cathode floats above the solution to be treated, and the anode is placed below the solution to be treated, thus forming a horizontal reactor.

3. The floating cathode electro-Fenton system according to claim 1, characterized in that: The mass ratio of the phenolic resin and the hydrophobic organic polymer loaded in the carbonized wood is 16-110:391-780.

4. The floating cathode electro-Fenton system according to claim 1, characterized in that: The carbonized wood includes carbonized pine.

5. A floating cathode electro-Fenton system according to claim 1, characterized in that: The raw materials for the phenolic resin precursor solution include the following components: resorcinol, formaldehyde, and ammonia.

6. A method for degrading tetracycline in solution using a floating cathode electro-Fenton system as described in any one of claims 1 to 5, characterized in that: Includes the following steps: A solution containing tetracycline and a catalyst are added to the floating cathode Fenton system to obtain a mixed solution, which is then electrolyzed to degrade the tetracycline in the solution.

7. The method according to claim 6, characterized in that: The catalyst includes Fe... 2+ The compound in which Fe 2+ The concentration in the mixed solution is 0.2-0.4 mol / L.

8. The method according to claim 6, characterized in that: The pH of the mixed solution is 1-5.

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