Preparation of phosphorus-doped high-curvature-regulated titanium black porous electrode and application of phosphorus-doped high-curvature-regulated titanium black porous electrode in deep reduction of resistance gene in electrochemical enhanced medical wastewater

Abstract

The invention belongs to the technical field of environmental engineering, and provides preparation of a phosphorus-doped high-curvature regulated titanium black porous electrode and application of the phosphorus-doped high-curvature regulated titanium black porous electrode in deep reduction of an electrochemical enhanced pharmaceutical wastewater resistance gene. The high-curvature tip nanotube structure is prepared through NH4F electrochemical etching, the increased electrochemical active surface area and the tip enhanced electric field effect synergistically promote charge enrichment and electron accumulation, and the average current density of the system is remarkably improved. P doping further optimizes the surface curvature of titanium black, lattice expansion is induced by regulating lattice tensile strain, Ti track overlapping is reduced, a d band is narrowed, and the energy level of the d band is shifted upwards. The ratio of Ti < 3 + > and oxygen vacancies in the doped material are remarkably increased, the generation capacity of. OH is enhanced, the generation rate of < 1 > O2 is increased, and high-efficiency and low-power-consumption catalytic degradation of resistance genes and antibiotics in pharmaceutical wastewater is realized by combining the characteristics of two free radicals. The electrode is simple in preparation process, raw materials are cheap and easy to obtain, and the electrode has large-scale production potential.

Description

Technical Field

[0001] The present invention belongs to the field of environmental engineering technology, and relates to a preparation method of a phosphorus-doped high-curvature regulated titanium dioxide porous electrode and its electrochemically enhanced application in deep reduction of resistance genes in pharmaceutical wastewater. Background Art

[0002] Antibiotics are new pollutants in the water environment. With their widespread use, microorganisms with antibiotic resistance are frequently detected in natural water bodies. The uncontrolled use of this type of new pollutant has posed a major threat to environmental safety and human health. Antibiotic resistance genes (ARGs) are often detected in groundwater around the world, especially in areas near hospitals, animal husbandry, aquaculture and landfills. Traditional ARG treatment methods include chlorination, ultraviolet (UV) radiation and ozone oxidation. However, given their limited efficiency in inactivating highly resistant waterborne bacteria, these traditional technologies usually require the addition of large amounts of disinfectants, which may lead to the accumulation of carcinogenic disinfection by-products. Compared with traditional treatment methods, electrochemical oxidation is simple to operate, has mild conditions, does not require the addition of chemical reagents, and can produce various oxidants (such as ⋅ H2O2, O3 and highly reactive free radicals, such as · OH and O2 ·− ) inactivates bacteria and is considered an efficient and safe water disinfection technology. Hydroxyl radicals ( · OH) has a strong oxidizing property. Under the action of current, the ·OH has a high reactivity to the sugar or polyphosphosugar skeleton of ARG, which can lead to the inactivation of most ARGs. However, flat electrodes have problems such as low electron utilization, low current density limitation, and difficulty in simultaneously removing antibiotics and ARGs in the process of electrochemical oxidation to remove ARGs, resulting in low degradation and inactivation efficiency and high energy consumption. Therefore, strategies need to be adopted to increase the electrode current density, but the current density of flat electrodes during operation is generally low. Titanium dioxide has a high oxygen evolution potential, excellent conductivity and corrosion resistance, and shows high efficiency in the inactivation of pathogens and the oxidation of various stubborn compounds. It has been widely used to remove ARGs and organic pollutants. However, flat titanium dioxide exhibits a relatively low interfacial charge transfer rate, which cannot provide sufficient current density. At the same time, the mass transfer efficiency in the reaction system is low, so 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 enhanced the removal of ARG by using molybdenum carbide (Mo2C) electrode assisted electrochemical disinfection process and MgFe2O4-loaded biochar (MFBC) three-dimensional particle electrode peroxymonosulfate. Although the above studies can increase the specific surface area and mass transfer performance of the electrode to a certain extent, the additional addition of oxidants increases the cost. In addition, the above modified materials have the effect of regulating the production of active species at the active sites ( · OH) and other aspects still have much room for improvement.

[0003] Based on this, the present invention selects porous titanium suboxide fiber felt as the anode base material, uses ammonium fluoride electrolyte for electrochemical etching, and prepares a high-curvature tip nanocone structure. This structure effectively increases the electrochemically active surface area, and its tip electric field enhancement effect triggers the formation of 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 improving the average current density of the system. At the same time, the curvature of the titanium suboxide surface is further enhanced by phosphorus doping, and the lattice tensile strain is precisely controlled: the strain-induced lattice expansion can reduce the overlap of titanium atomic orbitals, resulting in the narrowing of the d-band energy level and its migration to high energy levels. As · The proportion of Ti³⁺, an active site for OH generation, and the concentration of oxygen vacancies are significantly increased after phosphorus doping, which promotes · OH is generated stably and continuously; at the same time, the introduction of P sites can regulate the local electron arrangement, and combined with the stretching effect of lattice strain, it can enhance its adsorption and catalytic effect on oxygen molecules and reduce singlet oxygen ( 1 O2) conversion energy barrier, increasing the production rate. · OH has strong oxidative ability and can react efficiently with organic pollutants such as difficult-to-degrade antibiotics, but its lifespan is short and it is difficult to fully remove larger resistance genes in water; 1 The empty orbital characteristics of O2 give it strong electrophilicity, which enables it to react with the unsaturated bonds in the resistance gene and destroy its stability. In addition, singlet oxygen has a long life span and a wide pH range. · OH, which is more resistant to interference from background ions and shows high selectivity for specific pollutants. · OH and 1 The reaction characteristics of the two O2 free radicals with resistance genes can effectively achieve high-efficiency and low-consumption electrocatalytic degradation of resistance genes and antibiotics in pharmaceutical wastewater. Summary of the Invention

[0004] The present invention provides a method for preparing a phosphorus-doped high-curvature controlled titanium dioxide porous electrode, and is applied to the electrochemical degradation of resistance genes and antibiotics in pharmaceutical wastewater. A high-curvature tip nanotube structure is prepared by NH4F electrochemical etching. Its 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 dioxide, and induces lattice expansion by regulating lattice tensile strain, reducing Ti orbital overlap to narrow the d band and shift its energy level upward. Ti in the doped material 3+ The ratio of oxygen vacancies increased significantly, strengthening the · OH generation capacity and increased 1 The O2 production rate, combined with the characteristics of the two free radicals, ultimately achieves efficient and low-energy catalytic degradation of resistance genes and antibiotics in pharmaceutical wastewater.

[0005] The technical solution of the present invention:

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

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

[0008] Step 2: 0.1 g / mL ammonium fluoride solution and ethylene glycol are uniformly mixed to prepare an electrolyte, and the volume ratio of 0.1 g / mL ammonium fluoride solution to ethylene glycol is 1:20~1:10; the treated titania fiber felt obtained in step 1 is used as a working anode, and two titanium mesh electrodes are used as dual cathodes to construct a dual-cathode single-anode electrochemical etching system; electrochemical etching is carried out under the conditions of 20~30 V voltage and 2~3 A current for 3~6 h. After etching, it is rinsed with deionized water and the surface moisture is blown dry; the treated working anode is transferred to a muffle furnace, and the temperature is programmed to 300~500 °C at a heating rate of 2~5 °C / min and maintained for 2~4 h; after calcination, it is naturally cooled to room temperature, and the electrode is removed to obtain the calcined titania fiber felt;

[0009] Step 3: Place the titanium dioxide fiber felt and sodium hypophosphite monohydrate calcined in step 2 in two porcelain boats respectively, and then place the two porcelain boats in the middle of the tube furnace, with the sodium hypophosphite monohydrate in the upwind direction of the tube furnace, and the distance between the calcined titanium dioxide fiber felt and the sodium hypophosphite monohydrate is 2~6 cm; under a nitrogen atmosphere, the heating rate is 0.5~10 ℃ / min, the reaction temperature is 250~400 ℃, the reaction time is 1~4 h, and after the calcination is completed, it is naturally cooled to room temperature. Take out the treated titanium dioxide fiber felt and place it in an electrochemical reduction reaction device as the cathode, the lead oxide electrode as the anode, the electrolyte is 20~200 mmol / L ammonium sulfate aqueous solution, and the reaction temperature is 2~3 mA / cm 2 The electrode was operated in constant current mode for 2 to 10 minutes to obtain a phosphorus-doped high-curvature controlled titanium dioxide porous electrode.

[0010] Application of a phosphorus-doped high-curvature controlled sub-titanium oxide porous electrode to electrochemically enhance the deep reduction of resistance genes in pharmaceutical wastewater

[0011] The electrochemical oxidation system was constructed by using a phosphorus-doped high-curvature titanium oxide porous electrode as the anode and a Ti plate as the cathode. 2 Under constant current conditions, reaction temperature of 24-26 ℃, plasmid pUC57 carrying sulfonamide, tetracycline and cephalosporin resistance genes (ARGs) was used as the target ARGs, the ARGs concentration was 50 ng / L, and the reaction time was 10 min, the removal rate of the three ARGs could reach more than 90%.

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

[0013] The electrochemical oxidation system was constructed by using a phosphorus-doped high-curvature titanium oxide porous electrode as the anode and a Ti plate as the cathode. 2 Under constant current conditions, the reaction temperature was 24-26 ℃, the effluent from the biological treatment unit of pharmaceutical wastewater containing sulfonamides, tetracyclines and cephalosporins was used as the target water body (actual wastewater COD: 150~250 mg / L), the reaction time was 30 minutes, and the removal rates of the three types of ARGs could reach more than 90%, and the COD removal rates could reach more than 80%.

[0014] Beneficial effects of the present invention: The method of the present invention coordinates the surface curvature and lattice structure of the porous titanium oxide electrode material through ammonium fluoride electrochemical etching and in-situ phosphorus doping, thereby increasing the average current density of the electrooxidation system and strengthening the · OH generation rate, to achieve efficient and low-consumption degradation of resistance genes and antibiotics in pharmaceutical wastewater. Through the electrochemical etching of ammonium fluoride in steps 1 and 2, a high-curvature nanostructure is constructed on the surface of the material, effectively expanding the electrochemically active specific surface area. Its tip electric field enhancement effect induces the formation of a local strong electric field and charge accumulation phenomenon in the high-curvature area, promoting the local charge density at the active reaction site during the electrochemical reaction, thereby improving the conductivity of the system. Through in-situ phosphorus doping in step 3, the redox reaction of PH3 on the titanium dioxide surface is utilized to further increase the surface curvature of the material, and the synergistic effect of P doping into the titanium dioxide lattice induces the tensile strain effect of the local structure, which increases the lattice spacing, reduces the degree of Ti orbital overlap, narrows its d energy band, and moves the d band center upward, thereby reducing the conversion of water molecules into · The reaction energy barrier of OH promotes ·OH generation rate. In addition, the strain stretching effect can also regulate the local electron arrangement of the P site, forming an effective electron migration channel, which can enhance the adsorption capacity of the P site for oxygen molecules and reduce the conversion of oxygen molecules to singlet oxygen ( 1 The energy barrier of O2 conversion is reduced; combined with the high curvature-induced tip electric field enhancement effect, a strong electric field distribution and charge-enriched area are formed at the tip of the nanocone on the electrode surface, which promotes the rapid accumulation of electrons in the electrochemical reaction and strengthens the local P site. 1 The O2 production rate is further improved. Therefore, the material can simultaneously achieve · OH and 1 The efficient production of O₂ enhances the system's ability to effectively and deeply remove ARGs and antibiotics from real water. Furthermore, the preparation method is simple and low-cost, suggesting potential for industrial production. BRIEF DESCRIPTION OF THE DRAWINGS

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

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

[0017] Figure 3 The degradation diagram of FN2-4-P0.5 electrode treated with different concentrations of SMX. DETAILED DESCRIPTION

[0018] The specific implementation of the present invention is described in detail below in conjunction with the technical solutions and drawings.

[0019] Example 1

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

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

[0022] 25 mL of 0.1 g / mL ammonium fluoride solution was thoroughly mixed with 500 mL of ethylene glycol. Using titania fiber felt as the anode and a Ti plate as the dual cathode, electrochemical etching was performed at 30 V and 3 A for 4 h. After completion of the reaction, the electrodes were rinsed twice with deionized water and ethanol alternately, and the surface moisture was blown dry. The electrodes were placed in a muffle furnace and heated at a rate of 2.5 °C / min to 450 °C for 2 h. After calcination, the electrodes were allowed to cool naturally to room temperature and removed.

[0023] 0.5 g of sodium hypophosphite monohydrate was placed in a porcelain boat, placed upstream of a tube furnace, and a titania electrode was placed downstream. The boat was calcined in a tube furnace 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, the electrode was cooled to room temperature and removed. It was washed alternately with deionized water and ethanol twice, and reduced with 1 M (NH4)2SO4 solution for 2 min to obtain a phosphorus-doped porous high-curvature titania electrode (FN2-4-P0.5).

[0024] The same preparation conditions as in Example 1 were followed, except that the P dosage was changed to 0 g, 0.1 g, 1 g, 2 g, and 3 g, respectively. Other conditions remained unchanged to prepare a series of FN-P electrodes, whose electrode samples were numbered FN2-4-P0, FN2-4-P0.1, FN2-4-P1, FN2-4-P2, and FN2-4-P3, respectively, for subsequent comparative tests of antibiotic and resistance gene removal performance.

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

[0026] A series of FN-P electrodes were prepared under the same preparation conditions as in Example 1, except that the electrochemical etching time was changed to 2 h, 3 h, and 6 h, respectively. Other conditions remained unchanged. The electrode samples were numbered FN2-1-P0.5, FN2-3-P0.5, and FN2-6-P0.5, respectively, for subsequent comparative tests of antibiotic and resistance gene removal performance.

[0027] Application Example 1

[0028] Electrochemical oxidation to remove ARGs: Simulated wastewater containing sulfonamide, tetracycline, and cephalosporin ARGs was added to a 100 mL (50 ng / L) electrooxidation reactor using an FN-P series electrode as the anode and a Ti plate as the cathode. The reaction time was 10 minutes. DNA damage and removal of extracellular resistance genes (eARGs) were assessed by DNA gel electrophoresis and real-time polymerase chain reaction (qPCR). Within 10 minutes, the removal rates of all three target ARGs reached over 70%. Among them, 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 were able to remove 90% of the ARGs in the solution after a 10-minute reaction. FN2-4-P0 without P doping can only remove 40% of the three types of target ARGs. FN2-4-P0.5 can remove more than 95% of the target ARGs after 5 minutes of reaction. This shows that excessive electrochemical etching time and excessive P dosage will affect the ARG removal ability 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 the preparation conditions, thereby inhibiting the 1 O2 production rate. Compared with FN2-4-P0, P doping regulates the lattice tensile strain and induces lattice expansion, making the FN-P electrode better in removing ARG than the FN2-4-P0 electrode.

[0029] Application Example 2

[0030] Electrocatalytic degradation of typical antibiotics: 30 mM Na2SO4 electrolyte was weighed and added to 100 mL of sulfamethoxazole, tetracycline, and cefixime (5 mg / L) in an electrocatalytic reactor. An FN-P series electrode was used as the anode, a Ti plate was used as the cathode, and the current density was 5 mA / cm 2 The reaction time was 5 min. The reaction solution was collected once every 1 min, filtered through a 0.22 μm filter membrane, and 1 mL was collected for instrument testing to obtain the degradation rate.

[0031] Ultra-high-performance liquid chromatography (UPLC) assays determined SMX concentrations. Results showed that the FN-P series achieved >80% removal of sulfamethoxazole, tetracycline, and cefixime after a 5-minute reaction. FN2-4-P0.5 achieved a 95% removal rate for these three antibiotics within a 4-minute reaction. After a 30-minute reaction, TOC removal rates reached 80%, 78%, and 68%, respectively. This demonstrates its high degradation and mineralization capabilities for typical antibiotic contaminants in pharmaceutical wastewater.

[0032] Application Example 3

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

[0034] Ultra-high-performance liquid chromatography (UPLC) analysis of SMX concentrations revealed that FN2-4-P0.5 achieved removal efficiencies exceeding 99% for sulfamethoxazole, tetracycline, and cefixime. TOC removal rates for various concentrations of sulfamethoxazole, tetracycline, and cefixime were >85%, 82%, and 75%, respectively. This demonstrates its high degradation and mineralization capabilities for typical antibiotic contaminants in pharmaceutical wastewater at varying concentrations.

[0035] Application Example 4

[0036] Electrocatalytic degradation of actual pharmaceutical wastewater test:

[0037] FN2-4-P0.5 was used as the anode and Ti plate as the cathode, with a current density of 5 mA / cm 2 The removal of antibiotics and ARGs was tested using the effluent from the biological unit of actual pharmaceutical wastewater (containing sulfamethoxazole, tetracycline, and cefixime, respectively) (COD content 150-250 mg / L). The reaction time was 30 minutes, and the effluent was collected every 10 minutes. The collected effluent was directly placed into a 10 mL centrifuge tube and collected together for COD removal testing. In addition, the ARGs content in the wastewater before and after the reaction was examined.

[0038] The effluent COD 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%, respectively, for actual pharmaceutical wastewater. This demonstrates the anode's high removal performance for typical antibiotics in actual pharmaceutical wastewater. Tests of ARGs in the wastewater before and after the reaction showed that the FN2-4-P0.5 anode achieved a 90% removal rate, effectively reducing the potential ecological hazards of wastewater discharge into natural water bodies.

Claims

1. A method for preparing a phosphorus-doped high-curvature controlled titanium dioxide porous electrode, characterized in that: Here are the steps: Step 1: Pre-treating the titanium dioxide fiber felt; Step 2: The treated titania fiber felt obtained in step 1 was used as a working anode and two titanium mesh electrodes were used as dual cathodes to construct a dual-cathode single-anode electrochemical etching system; electrochemical etching was performed at a voltage of 20-30 V and a current of 2-3 A for 3-6 h. After etching, the treated working anode was rinsed with deionized water and the surface moisture was blown dry; the treated working anode was transferred to a muffle furnace, heated to 300-500 °C, and maintained for 2-4 h; after calcination, it was naturally cooled to room temperature, and the electrode was removed to obtain the calcined titania fiber felt; Step 3: Place the titanium dioxide fiber felt and sodium hypophosphite monohydrate calcined in step 2 in two porcelain boats respectively, and then place the two porcelain boats in the middle of the tube furnace; under a nitrogen atmosphere, the reaction temperature is 250~400 ℃, the reaction time is 1~4 h, and after the calcination is completed, it is naturally cooled to room temperature. Take out the treated titanium dioxide fiber felt and place it in an electrochemical reduction reaction device as the cathode, the lead oxide electrode as the anode, the electrolyte is 20~200 mmol / L ammonium sulfate aqueous solution, and the reaction temperature is 2~3 mA / cm 2 The electrode was operated in constant current mode for 2 to 10 minutes to obtain a phosphorus-doped high-curvature controlled titanium dioxide porous electrode.

2. The method for preparing a phosphorus-doped high-curvature controlled titanium dioxide porous electrode according to claim 1, characterized in that: Step 1 The specific steps of pre-treating the titanium dioxide fiber felt are as follows: The titania 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 titania fiber felt was taken out and ultrasonically cleaned with deionized water to remove residual alkali on the surface. The treated titania fiber felt was then transferred to a 10-15 wt.% oxalic acid solution and treated at a constant temperature of 70-85 ℃ for 1-3 h. The titania fiber felt was taken out and the surface acidic residue was thoroughly removed with deionized water to obtain the treated titania fiber felt.

3. The method for preparing a phosphorus-doped high-curvature controlled titania porous electrode according to claim 1, characterized in that: The electrolyte of the dual-cathode single-anode electrochemical etching system in step 2 is prepared by uniformly mixing 0.1 g / mL ammonium fluoride solution and 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 titania porous electrode according to claim 1, characterized in that: In step 3, the sodium hypophosphite monohydrate is in the upwind direction of the tubular furnace, and the distance between the calcined titanium dioxide fiber felt and the sodium hypophosphite monohydrate is 2 to 6 cm.

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

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