Preparation of phosphorus-doped high-curvature regulated titanium sub-oxide porous electrode and its application in electrochemical strengthening of pharmaceutical wastewater resistance gene

Abstract

This invention belongs to the field of environmental engineering technology, and provides a method for preparing a phosphorus-doped, high-curvature-controlled porous titanium suboxide electrode and its application in electrochemically enhancing the deep reduction of resistance genes in pharmaceutical wastewater. A high-curvature-tipped nanotube structure is prepared by electrochemical etching with NH4F. The increased electrochemically active surface area and the tip-enhanced electric field effect synergistically promote charge enrichment and electron accumulation, significantly improving the average current density of the system. P doping further optimizes the surface curvature of titanium suboxide, and lattice expansion is induced by controlling lattice tensile strain, reducing Ti orbital overlap to narrow the d-band and shift its energy level upward. The Ti content in the doped material... 3+ The ratio and oxygen vacancies increased significantly, enhancing the · The ability to generate OH, and increased 1 By leveraging the O2 generation rate and the characteristics of both free radicals, this invention achieves highly efficient and low-consumption electrocatalytic degradation of resistance genes and antibiotics in pharmaceutical wastewater. The electrode preparation process of this invention is simple, and the raw materials are inexpensive and readily available, making it suitable for large-scale production.

Description

Technical Field

[0001] This invention belongs to the field of environmental engineering technology and relates to the preparation of a phosphorus-doped high-curvature regulated sub-titanium oxide porous electrode and its application in electrochemically enhancing the deep reduction of resistance genes in pharmaceutical wastewater. Background Technology

[0002] Antibiotics, as a novel pollutant in the aquatic environment, have led to the frequent detection of antibiotic-resistant microorganisms in natural water bodies due to their widespread use. The uncontrolled use of these new pollutants has posed a significant threat to environmental safety and human health. Antibiotic resistance genes (ARGs) are frequently detected in groundwater worldwide, particularly in areas near hospitals, livestock farms, aquaculture, and landfills. Traditional ARG treatment methods include chlorination, ultraviolet (UV) radiation, and ozone oxidation. However, given their limited efficiency in inactivating highly resistant aquatic bacteria, these traditional technologies often require the addition of large amounts of disinfectants, which can lead to the accumulation of carcinogenic disinfection byproducts. Compared to traditional treatment methods, electrochemical oxidation, due to its simple operation, mild conditions, and lack of requirement for chemical reagents, can generate various oxidants (such as... . H2O2, O3, and highly reactive free radicals, such as · OH and O2 .- Hydroxyl radicals (H2O) are considered a highly effective and safe water disinfection technology for inactivating bacteria. · OH) has extremely strong oxidizing properties; under the influence of electric current, it adsorbs onto the electrode surface. ·OH radicals are highly reactive to the sugar or polyphosphate backbone of ARG, leading to the inactivation of most ARGs. However, planar electrodes suffer from low electron utilization, low current density limitations, and difficulty in simultaneously removing antibiotics and ARGs during electrochemical oxidation, resulting in low degradation and inactivation efficiency and high energy consumption. Therefore, strategies to increase electrode current density are needed, but the current density of planar electrodes is generally low during operation. Titanium suboxide possesses a high oxygen evolution potential, excellent conductivity, and corrosion resistance, exhibiting high efficiency in the inactivation of pathogens and the oxidation of various stubborn compounds, and has been widely used for the removal of ARGs and organic pollutants. However, planar titanium suboxide exhibits a relatively low interfacial charge transfer rate, resulting in insufficient current density, and the mass transfer efficiency in the reaction system is also low. Therefore, electrocatalysis alone cannot effectively remove ARGs. Based on the above problems, the articles "Simultaneous removal of antibiotic-resistant bacteria and antibiotic resistance genes by molybdenum carbide assisted electrochemical disinfection" and "Enhanced removal of antibiotic-resistant bacteria and resistance genes by three-dimensional electrochemical process using MgFe2O4-loaded biochar as both particle electrode and catalyst for peroxymonosulfate activation" respectively employed a molybdenum carbide (Mo2C) electrode-assisted electrochemical disinfection process and a MgFe2O4-loaded biochar (MFBC) three-dimensional particle electrode for peroxymonosulfate enhancement to remove ARG. While these studies increased the specific surface area and mass transfer performance of the electrodes to some extent, the additional addition of oxidants increased costs. Furthermore, the modified materials described above, in regulating the generation of active species at active sites (… · There is still considerable room for improvement in areas such as OH).

[0003] Based on this, this invention selects porous titanium suboxide fiber felt as the anode substrate material and uses ammonium fluoride electrolyte for electrochemical etching to prepare a high-curvature pointed nanocone structure. This structure effectively increases the electrochemically active surface area, and its tip electric field enhancement effect induces a strong electric field distribution and charge enrichment in the high-curvature region, promoting a large accumulation of electrons in the electrochemical reaction and significantly increasing the average current density of the system. Simultaneously, phosphorus doping further enhances the surface curvature of titanium suboxide and precisely controls the lattice tensile strain: strain-induced lattice expansion reduces titanium atom orbital overlap, leading to a narrowing of the d-band energy level and migration to higher energy levels. · Ti, an active site for OH generation 3+ After phosphorus doping, its proportion and oxygen vacancy concentration are significantly increased, promoting · OH is stably and continuously generated; at the same time, the introduction of P sites can regulate the local electronic configuration, and combined with the stretching effect of lattice strain, it can enhance its adsorption and catalytic effect on oxygen molecules, and reduce singlet oxygen (OH). 1 O2) conversion energy barrier, increasing the production rate. · OH has a strong oxidizing ability and can react efficiently with organic pollutants such as antibiotics that are difficult to degrade, but its lifespan is short and it is difficult to fully remove larger resistance genes in water. 1 The empty orbital nature of O2 endows it with strong electrophilicity, enabling it to react with unsaturated bonds in resistance genes and disrupt their stability. Furthermore, singlet oxygen has a long lifetime and a wide pH tolerance range compared to... · OH, which is more resistant to interference from background ions and exhibits high selectivity for specific pollutants. Therefore, combining · OH and 1 The reaction characteristics of O2 and two free radicals with resistance genes can effectively achieve efficient and low-energy-consumption catalytic degradation of resistance genes and antibiotics in pharmaceutical wastewater. Summary of the Invention

[0004] This invention provides a method for preparing porous titanium suboxide electrodes with high curvature controlled by phosphorus doping, and applies it to the electrochemical degradation of resistance genes and antibiotics in pharmaceutical wastewater. High-curvature pointed nanotube structures are prepared by electrochemical etching with NH4F. The increased electrochemically active surface area and the tip-enhanced electric field effect synergistically promote charge enrichment and electron accumulation, significantly improving the average current density of the system. P doping further optimizes the surface curvature of titanium suboxide and induces lattice expansion by controlling lattice tensile strain, reducing Ti orbital overlap to narrow the d-band and shift its energy level upward. The Ti content in the doped material... 3+ The ratio and oxygen vacancies increased significantly, enhancing the · The ability to generate OH, and increased 1 By leveraging the O2 generation rate and combining the characteristics of the two free radicals, the efficient and low-electro-consumption catalytic degradation of resistance genes and antibiotics in pharmaceutical wastewater can be achieved.

[0005] The technical solution of this invention:

[0006] A method for preparing a phosphorus-doped, high-curvature-controlled porous titanium suboxide electrode includes the following steps:

[0007] Step 1: Immerse the titanium dioxide fiber felt in a 5-10 wt.% sodium hydroxide solution and treat it at a constant temperature of 70-85 ℃ for 0.5-1 h; remove the titanium dioxide fiber felt and ultrasonically clean it with deionized water to remove residual alkali solution from the surface; then transfer the treated titanium dioxide fiber felt to a 10-15 wt.% oxalic acid solution and continue to treat it at a constant temperature of 70-85 ℃ for 1-3 h; remove the titanium dioxide fiber felt and thoroughly remove the acidic residue from the surface with deionized water to obtain the treated titanium dioxide fiber felt;

[0008] Step 2: Prepare an electrolyte by uniformly mixing 0.1 g / mL ammonium fluoride solution with ethylene glycol at a volume ratio of 1:20 to 1:10. Use the treated sub-titanium oxide fiber felt obtained in Step 1 as the working anode and two titanium mesh electrodes as dual cathodes to construct a dual-cathode single-anode electrochemical etching system. Electrochemically etch for 3-6 h at a voltage of 20-30 V and a current of 2-3 A. After etching, rinse thoroughly with deionized water and dry the surface. Transfer the treated working anode to a muffle furnace and heat it to 300-500 °C at a rate of 2-5 °C / min, maintaining the temperature for 2-4 h. After calcination, allow it to cool naturally to room temperature, remove the electrode, and obtain the calcined sub-titanium oxide fiber felt.

[0009] Step 3: Place the calcined titanium suboxide fiber felt and sodium hypophosphite monohydrate from Step 2 into two ceramic boats, respectively. Then, place the two ceramic boats in the middle of a tube furnace, with the sodium hypophosphite monohydrate facing upwind. The distance between the calcined titanium suboxide fiber felt and the sodium hypophosphite monohydrate should be 2–6 cm. Under a nitrogen atmosphere, the heating rate is 0.5–10 °C / min, the reaction temperature is 250–400 °C, and the reaction time is 1–4 h. After calcination, allow it to cool naturally to room temperature. Remove the treated titanium suboxide fiber felt and place it in an electrochemical reduction reactor as the cathode, with a lead oxide electrode as the anode. The electrolyte is a 20–200 mmol / L ammonium sulfate aqueous solution, and the reaction is carried out at a rate of 2–3 mA / cm². 2 Running in constant current mode for 2~10 min, a phosphorus-doped high-curvature regulated sub-titanium oxide porous electrode was obtained.

[0010] An application of phosphorus-doped high-curvature regulated titanium suboxide porous electrode for electrochemical enhancement of deep reduction of resistance genes in pharmaceutical wastewater

[0011] An electrochemical oxidation system was constructed using a phosphorus-doped, high-curvature-controlled porous titanium suboxide electrode as the anode and a Ti plate as the cathode; the oxidation rate was 1–20 mA / cm². 2 Under constant current conditions and reaction temperatures of 24-26 °C, plasmid pUC57 carrying sulfonamide, tetracycline, and cephalosporin resistance genes (ARGs) was used as the target ARGs. The concentration of ARGs added was 50 ng / L, and the reaction time was 10 min. The removal rate of the three ARGs could reach more than 90%.

[0012] An electrochemical oxidation system was constructed using a phosphorus-doped, high-curvature-controlled porous titanium suboxide electrode as the anode and a Ti plate as the cathode; the oxidation rate was 1–10 mA / cm². 2 Under constant current conditions and a reaction temperature of 24-26 ℃, with sulfamethoxazole, tetracycline, and cefixime antibiotics at concentrations of 1 μg / L-1000 μg / L as target pollutants, and a reaction time of 5 min, the pollutant removal rate can reach over 95%.

[0013] An electrochemical oxidation system was constructed using a phosphorus-doped, high-curvature-controlled porous titanium suboxide electrode as the anode and a Ti plate as the cathode; at 10 mA / cm 2 Under constant current conditions and a reaction temperature of 24-26 ℃, using the effluent from a biological treatment unit containing pharmaceutical wastewater containing sulfonamides, tetracyclines, and cephalosporins as the target water body (actual wastewater COD: 150~250 mg / L), and a reaction time of 30 min, the removal rate of all three types of ARGs can reach over 90%, and the COD removal rate can reach over 80%.

[0014] The beneficial effects of this invention: The method of this invention, through the synergistic regulation of the surface curvature and lattice structure of porous sub-titanium oxide electrode materials by ammonium fluoride electrochemical etching and in-situ phosphorus doping, improves the average current density of the electro-oxidation system and simultaneously strengthens... · The OH generation rate is improved, enabling efficient and low-consumption degradation of resistance genes and antibiotics in pharmaceutical wastewater. High-curvature nanostructures are constructed on the material surface through ammonium fluoride electrochemical etching in steps 1 and 2, effectively expanding the electrochemically active specific surface area. The enhanced electric field effect at the tip induces a localized strong electric field and charge accumulation in the high-curvature region, promoting the local charge density at the active reaction sites during the electrochemical reaction, thereby improving the system's conductivity. In-situ phosphorus doping in step 3 utilizes the redox reaction of PH3 on the titanium suboxide surface to further increase the material's surface curvature. Combined with the synergistic effect of P doping into the titanium suboxide lattice, this induces a tensile strain effect in the local structure, increasing the lattice spacing, reducing the overlap of Ti orbitals, narrowing the d-band, and shifting the d-band center upwards, thereby reducing the conversion of water molecules into active components. · The reaction energy barrier of OH promotes ·The rate of OH generation. Furthermore, strain stretching can modulate the local electron configuration of P sites, forming effective electron migration channels, which can enhance the adsorption capacity of P sites for oxygen molecules and reduce the conversion of oxygen molecules to singlet oxygen (OH). 1 The energy barrier for O2 conversion; combined with the high curvature-induced tip electric field enhancement effect, a strong electric field distribution and charge-rich region are formed at the tip of the nanocone on the electrode surface, promoting rapid electron accumulation in the electrochemical reaction and strengthening the local P sites. 1 The O2 generation rate is further increased. Therefore, this material can achieve simultaneous [O2 generation rate]. · OH and 1 The system efficiently generates O2, thereby enhancing the deep and efficient removal of ARG and antibiotics from actual water bodies. Furthermore, the preparation method is simple and low-cost, possessing the potential for industrial-scale production. Attached Figure Description

[0015] Figure 1 The images are SEM images of the electrode materials, where (a) is a SEM image of pure titanium fiber felt and (b) is a SEM image of FN2-4-P0.5 electrode material.

[0016] Figure 2 The images are EDS surface scans of the FN2-4-P0.5 electrode material, where (a) is a surface scan of P element and (b) is a superimposed surface scan of Ti, O and P elements.

[0017] Figure 3 Degradation of SMX at different concentrations after treatment with FN2-4-P0.5 electrode. Detailed Implementation

[0018] The specific embodiments of the present invention will be described in detail below with reference to the technical solutions and accompanying drawings.

[0019] Example 1

[0020] A method for preparing a phosphorus-doped porous high-curvature titanium suboxide electrode:

[0021] The titanium suboxide fiber felt was placed in a 10 wt.% sodium hydroxide solution and heated at 85 °C for 1 h. After the reaction was completed, the titanium suboxide fiber felt was removed and washed twice alternately with deionized water and ethanol. Then, the titanium suboxide fiber felt was placed in a 15 wt.% oxalic acid solution and heated at 85 °C for 2 h. After the reaction was completed, the titanium suboxide fiber felt was removed and washed twice alternately with deionized water and ethanol.

[0022] 25 mL of 0.1 g / mL ammonium fluoride solution was thoroughly mixed with 500 mL of ethylene glycol. Using a titanium suboxide fiber felt as the anode and a Ti plate as the dual cathode, electrochemical etching was performed for 4 h at 30 V and 2 A. After the reaction, the electrode was rinsed twice alternately with deionized water and ethanol, and the surface moisture was dried. The electrode was then placed in a muffle furnace with a heating rate of 2.5 °C / min, a reaction temperature of 450 °C, and a reaction time of 2 h. After calcination, the electrode was allowed to cool naturally to room temperature before being removed.

[0023] 0.5 g of sodium hypophosphite monohydrate was placed in a ceramic boat and positioned upstream of a tube furnace, with the titanium suboxide electrode positioned downstream. The furnace was calcined under N2 protection, with a heating rate of 3 ℃ / min, a reaction temperature of 350 ℃, and a reaction time of 2 h. After the reaction was completed and cooled to room temperature, the electrode was removed and washed twice with deionized water and ethanol alternately. It was then reduced with 1 M (NH4)2SO4 solution for 2 min to obtain a phosphorus-doped porous high-curvature titanium suboxide electrode (FN2-4-P0.5).

[0024] Following the same preparation conditions as in Example 1, only the amount of P added was changed to 0 g, 0.1 g, 1 g, 2 g, and 3 g, while other conditions remained unchanged. A series of FN-P electrodes were prepared, and the electrode sample numbers were FN2-4-P0, FN2-4-P0.1, FN2-4-P1, FN2-4-P2, and FN2-4-P3, respectively, for subsequent comparative tests on antibiotic and resistance gene removal performance.

[0025] Following the same preparation conditions as in Example 1, only the electrochemical etching current was changed to 1 A and 3 A, while other conditions remained unchanged, to prepare a series of FN-P electrodes. The electrode sample numbers were FN1-4-P0.5 and FN3-4-P0.5, respectively, for subsequent comparative tests on antibiotic and resistance gene removal performance.

[0026] Following the same preparation conditions as in Example 1, only the electrochemical etching time was changed to 2 h, 3 h, and 6 h, while other conditions remained unchanged, to prepare a series of FN-P electrodes. The electrode sample numbers were FN2-2-P0.5, FN2-3-P0.5, and FN2-6-P0.5, respectively, for subsequent comparative tests on antibiotic and resistance gene removal performance.

[0027] Application Example 1

[0028] Electrochemical oxidation removal of ARGs: Wastewater containing simulated resistance genes (eARGs) of sulfonamides, tetracyclines, and cephalosporins was added to a 100 mL (50 ng / L) electro-oxidation reactor. FN-P series electrodes were used as the anode and a Ti plate as the cathode, with a reaction time of 10 min. DNA damage and removal of extracellular resistance genes (eARGs) were detected by DNA gel electrophoresis and real-time polymerase chain reaction (qPCR). The removal rate of all three target ARGs reached over 70% within 10 min of reaction. Specifically, FN2-4-P0.5, FN2-4-P1, FN2-4-P2, FN2-4-P3, FN2-3-P0.5, FN2-6-P0.5, FN1-4-P0.5, and FN3-4-P0.5 removed 90% of the ARGs in the solution after 10 min of reaction. Undoped FN2-4-P0 could only remove 40% of the three types of target ARGs. FN2-4-P0.5, however, could remove over 95% of the target ARGs after only 5 minutes of reaction. This indicates that excessively long electrochemical etching times and excessively high P dosages affect the ARG removal capability of the FN-P electrode. This is because the structural stability of the active sites on the surface of the FN-P material is reduced under these preparation conditions, thus inhibiting... 1 O2 generation rate. Compared with FN2-4-P0, P doping regulates lattice tensile strain-induced lattice expansion, making the FN-P electrode superior to the FN2-4-P0 electrode in removing ARG.

[0029] Application Example 2

[0030] Electrocatalytic degradation of typical antibiotics: 30 mM Na₂SO₄ electrolyte was added to 100 mL of each of the following electrocatalytic reactors: sulfamethoxazole, tetracycline, and cefixime (5 mg / L). FN-P series electrodes were used as the anode, and a Ti plate as the cathode. The current density was 5 mA / cm². 2 The reaction time was 5 min. The reaction solution was sampled every 1 min, filtered through a 0.22 μm filter membrane, and 1 mL was taken for instrument testing to obtain the degradation rate.

[0031] The concentration of SMX was determined by ultra-high performance liquid chromatography (UHPLC). Test results showed that after 5 min of reaction, the series of FN-Ps achieved a removal rate of >80% for sulfamethoxazole, tetracycline, and cefixime. Specifically, FN2-4-P0.5 achieved a removal rate of 95% for these three antibiotics after 4 min of reaction; after 30 min of reaction, the TOC removal rates were 80%, 78%, and 68%, respectively. This indicates that it has high degradation and mineralization performance for typical antibiotic pollutants in pharmaceutical wastewater.

[0032] Application Example 3

[0033] Electrocatalytic degradation tests of different concentrations of sulfamethoxazole, tetracycline, and cefixime: Different concentrations of sulfamethoxazole, tetracycline, and cefixime (1 μg / L, 100 μg / L, and 1000 μg / L) and 30 mM sodium sulfate electrolyte were added to an electrocatalytic reactor containing 100 mL of antibiotic wastewater of different concentrations. FN2-4-P0.5 was used as the anode, a Ti plate as the cathode, and a current density of 5 mA / cm² was applied. 2 The reaction time was 5 min. The reaction solution was sampled every 1 min, filtered through a 0.22 μm filter membrane, and 1 mL was taken for instrument testing to obtain the degradation rate.

[0034] The concentration of SMX was determined by ultra-high performance liquid chromatography (UHPLC). Test results showed that FN2-4-P0.5 achieved a removal rate of over 99% for sulfamethoxazole, tetracycline, and cefixime. The TOC removal rates for different concentrations of sulfamethoxazole, tetracycline, and cefixime were >85%, 82%, and 75%, respectively. This indicates that it has high degradation and mineralization performance for typical antibiotic pollutants at different concentrations in pharmaceutical wastewater.

[0035] Application Example 4

[0036] Electrocatalytic degradation of actual pharmaceutical wastewater test:

[0037] Using FN2-4-P0.5 as the anode and a Ti plate as the cathode, the current density is 5 mA / cm². 2 Using actual pharmaceutical wastewater (containing sulfamethoxazole, tetracycline, and cefixime, respectively) as the target water body, the removal of antibiotics and ARGs was tested. The reaction time was 30 min, and the effluent was sampled every 10 min. The sampled effluent was directly placed into 10 mL centrifuge tubes and collected uniformly for testing COD removal performance. In addition, the ARG content in the wastewater before and after the reaction was investigated.

[0038] The COD of the effluent was tested using the national standard method. The results showed that the FN2-4-P0.5 electrode achieved COD removal rates of 83%, 80%, and 81% for actual pharmaceutical wastewater, respectively. This indicates that the anode has high removal performance for typical antibiotics in actual pharmaceutical wastewater. Tests of ARGs content in the wastewater before and after the reaction showed that the FN2-4-P0.5 anode achieved a 90% removal rate of ARGs in the wastewater, effectively reducing the potential harm to the ecological environment caused by wastewater discharge into natural water bodies.

Claims

1. A method for preparing a phosphorus-doped, high-curvature-controlled porous titanium suboxide electrode, characterized in that, The steps are as follows: Step 1: Pre-treat the titanium dioxide fiber felt; Step 2: Using the treated sub-titanium oxide fiber felt obtained in Step 1 as the working anode and two titanium mesh electrodes as dual cathodes, a dual-cathode single-anode electrochemical etching system is constructed. Electrochemical etching is performed for 3-6 hours under a voltage of 20-30 V and a current of 2-3 A. After etching, the anode is rinsed with deionized water and dried. The treated working anode is transferred to a muffle furnace, heated to 300-500 °C, and maintained for 2-4 hours. After calcination, the anode is allowed to cool naturally to room temperature, and the electrode is removed to obtain the calcined sub-titanium oxide fiber felt. Step 3: Place the calcined titanium suboxide fiber felt and sodium hypophosphite monohydrate from Step 2 into two ceramic boats, respectively. Then, place the two ceramic boats in the middle of a tube furnace. Under a nitrogen atmosphere, the reaction temperature is 250-400 °C, and the reaction time is 1-4 h. After calcination, allow it to cool naturally to room temperature. Remove the treated titanium suboxide fiber felt and place it in an electrochemical reduction reactor as the cathode, with a lead oxide electrode as the anode. The electrolyte is a 20-200 mmol / L ammonium sulfate aqueous solution, and the reaction proceeds at a rate of 2-3 mA / cm². 2 Running in constant current mode for 2~10 min, a phosphorus-doped high-curvature regulated sub-titanium oxide porous electrode was obtained.

2. The method for preparing a phosphorus-doped high-curvature controlled sub-titanium oxide porous electrode according to claim 1, characterized in that, The specific steps for pretreating the titanium dioxide fiber felt in step 1 are as follows: The titanium suboxide fiber felt was immersed in a sodium hydroxide solution with a concentration of 5-10 wt.% and treated at a constant temperature of 70-85 ℃ for 0.5-1 h. The titanium suboxide fiber felt was then removed and ultrasonically cleaned with deionized water to remove residual alkali solution from the surface. Subsequently, the treated titanium suboxide fiber felt was transferred to a 10-15 wt.% oxalic acid solution and treated at a constant temperature of 70-85 ℃ for 1-3 h. The titanium suboxide fiber felt was then removed and the acidic residue on the surface was thoroughly removed with deionized water to obtain the treated titanium suboxide fiber felt.

3. The method for preparing a phosphorus-doped high-curvature controlled sub-titanium oxide porous electrode according to claim 1, characterized in that, In step 2, the electrolyte of the dual-cathode single-anode electrochemical etching system is prepared by uniformly mixing 0.1 g / mL ammonium fluoride solution with ethylene glycol, wherein the volume ratio of 0.1 g / mL ammonium fluoride solution to ethylene glycol is 1:20~1:

10.

4. The method for preparing a phosphorus-doped high-curvature controlled sub-titanium oxide porous electrode according to claim 1, characterized in that, In step 3, the sodium hypophosphite monohydrate is placed in the airflow direction of the tubular furnace, and the distance between the calcined titanium suboxide fiber felt and the sodium hypophosphite monohydrate is 2~6 cm.

5. An application of the phosphorus-doped high-curvature-controlled sub-titanium oxide porous electrode as described in any one of claims 1-4 to electrochemically enhance the deep reduction of resistance genes in pharmaceutical wastewater, characterized in that... An electrochemical oxidation system was constructed using a phosphorus-doped, high-curvature-controlled porous titanium suboxide electrode as the anode and a Ti plate as the cathode; the oxidation rate was 1–20 mA / cm². 2 Under constant current conditions and reaction temperatures of 24-26 °C, plasmid pUC57 carrying resistance genes for sulfonamides, tetracyclines, and cephalosporins was used as the target ARGs. The concentration of ARGs added was 50 ng / L, and the reaction time was 10 min. The removal rate of the three ARGs could reach more than 90%. An electrochemical oxidation system was constructed using a phosphorus-doped, high-curvature-controlled porous titanium suboxide electrode as the anode and a Ti plate as the cathode; the oxidation rate was 1–10 mA / cm². 2 Under constant current conditions and a reaction temperature of 24-26 ℃, with sulfamethoxazole, tetracycline and cefixime antibiotics at concentrations of 1 μg / L-1000 μg / L as target pollutants, and a reaction time of 5 min, the pollutant removal rate can reach over 95%. An electrochemical oxidation system was constructed using a phosphorus-doped, high-curvature-controlled porous titanium suboxide electrode as the anode and a Ti plate as the cathode; at 10 mA / cm 2 Under constant current conditions and a reaction temperature of 24-26 ℃, the effluent from the biological treatment unit containing pharmaceutical wastewater containing sulfonamides, tetracyclines, and cephalosporins was used as the target water body with a COD of 150-250 mg / L and a reaction time of 30 min. The removal rate of the three types of ARGs was over 90%, and the COD removal rate was over 80%.

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