CN114573079B - Method for removing organic micropollutants by electrochemically generating sulfate radicals - Google Patents

Method for removing organic micropollutants by electrochemically generating sulfate radicals Download PDF

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CN114573079B
CN114573079B CN202210241395.9A CN202210241395A CN114573079B CN 114573079 B CN114573079 B CN 114573079B CN 202210241395 A CN202210241395 A CN 202210241395A CN 114573079 B CN114573079 B CN 114573079B
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water
sulfate
titanium
flow
anode
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CN114573079A (en
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刘艳彪
尤世界
郑文天
李方
赵志远
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Harbin Institute of Technology
Donghua University
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Donghua University
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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
    • C02F1/4672—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/308—Dyes; Colorants; Fluorescent agents
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/34—Organic compounds containing oxygen
    • C02F2101/345—Phenols
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/38—Organic compounds containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/40—Organic compounds containing sulfur
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00—Technologies for wastewater treatment
    • Y02W10/30—Wastewater or sewage treatment systems using renewable energies
    • Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy

Abstract

The invention belongs to the technical field of water treatment, and provides a method for removing organic micropollutants by electrochemically generating sulfate radicals, wherein a mixed solution containing the organic micropollutants and sulfate is introduced into a flow-type electro-catalytic filtration system, and the degradation of the organic micropollutants in the mixed solution is realized under the action of an electric field; the flow rate of the flow-through electro-catalytic filtration system is 1.0-3.0 mL/min, and the current density of the electric field is 1.5-2.5 mA/cm 2 . The invention adopts a method combining membrane separation and electrochemical technology, and operates in a flow-through operation mode, convection-enhanced mass transfer can obviously enhance the transfer process of target pollutant molecules to active sites on the surface of the membrane, and the invention can efficiently degrade various organic micropollutants in water, thereby not only effectively avoiding the addition of chemical reagents, saving the cost, but also not causing secondary pollution, and effectively solving the pollution problem caused by the micropollutants in the water.

Description

Method for removing organic micropollutants by electrochemically generating sulfate radicals
Technical Field
The invention relates to the technical field of water treatment, in particular to a method for removing organic micropollutants by electrochemically generating sulfate radicals.
Background
In recent years, the widespread presence of organic micropollutants in aqueous environments has attracted global attention. Micropollutants are typically present in aqueous environments at minute concentrations ranging from nanograms per liter to milligrams per liter, and their limited concentration and diversity not only complicates the relevant detection techniques, but also poses significant challenges to wastewater treatment. Current wastewater treatment technologies are not specifically designed to eliminate micropollutants, which are likely to re-enter the water due to their persistence, high toxicity, and difficult degradability. Notably, the concentration of micropollutants is typically several orders of magnitude lower than the concentration of other coexisting materials in natural and artificial aqueous environments. Some coexisting materials may alter the degradation pathway of the target pollutant, thereby affecting its conversion process and removal efficiency.
Among these coexisting materials, sulfate is a common anion, and its typical concentration is several tens to several hundreds of mg/l. Unlike other anions, sulfate can be converted under specific conditions into highly reactive sulfate radicals (SO) 4 ·– ) And is used for degrading various organic pollutants which are difficult to degrade in water. Multiple preparation of SO based on persulfate activation 4 ·– Methods have been reported, but such methods tend to have limitations. For example, transition metal catalysts are the most widely used and most effective activation methods. However, this technique reacts by dissolving metal ions into water, which causes secondary pollution. Ultraviolet light and ultrasound can also be used to activate persulfates, however these techniques are costly, energy intensive and only suitable for low volumes of wastewater.
Therefore, the study of a direct and separate use of sulfate anions commonly present in water for SO production 4 ·– The principle and the technology of the method have important significance for developing a sustainable and environment-friendly water purification method.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a method for removing organic micropollutants by electrochemically generating sulfate radicals.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a method for removing organic micropollutants by electrochemically generating sulfate radicals, which comprises the following steps:
introducing the mixed solution containing the organic micro-pollutants and sulfate into a flow-type electro-catalytic filtration system, and degrading the organic micro-pollutants in the mixed solution under the action of an electric field;
the flow rate of the flow-through electro-catalysis filtering system is 1.0-3.0 mL/min, and the current density of the electric field is 1.5-2.5 mA/cm 2 。
Preferably, the concentration of the organic micropollutants is 0.05-15 mg/L.
Preferably, the organic micropollutants comprise one or more of aniline, sulfamethoxazole, methyl blue, methyl orange, tetracycline and bisphenol A.
Preferably, the concentration of the sulfate is 10-50 mmol/L; the sulfate is an electrolyte of a flow-through electrocatalytic filtration system.
Preferably, the solvent of the mixed solution is water, and the water includes ultrapure water, tap water, lake water, or industrial wastewater containing sulfate.
Preferably, the flow-through electrocatalytic filtration system comprises a shell, wherein an anode, a cathode and a reference electrode are arranged in the shell, wherein the anode is a titanium suboxide-carbon nanotube electrode, the cathode is a titanium sheet, and the reference electrode is an Ag/AgCl electrode.
Preferably, a water inlet and a water outlet are respectively arranged on two sides of the shell, a titanium ring is arranged on one side of the anode close to the water inlet, and an insulating silica gel separator is arranged between the anode and the cathode.
Preferably, the method for preparing the titanium suboxide-carbon nanotube electrode comprises the following steps:
1) Reducing titanium dioxide in a hydrogen atmosphere to obtain titanium suboxide powder;
2) And mixing the titanium monoxide powder, the carbon nanotube powder and ethanol, and sequentially performing ultrasonic dispersion, filtration and cleaning on the obtained mixed solution to obtain the titanium monoxide-carbon nanotube electrode.
Preferably, the reduction temperature in the step 1) is 1000-1100 ℃, and the time is 20-28 h; the mass ratio of the titanium protoxide powder to the carbon nanotube powder in the step 2) is 0.5-1.5; the ultrasonic dispersion time is 25-35 min, and the filtration adopts a polytetrafluoroethylene membrane with the aperture of 0.2-0.25 mu m.
The beneficial effects of the invention include:
1) The invention can generate persulfate with redox activity in situ, and generate sulfate radical free radical with strong oxidation capacity by reducing persulfate through single electron, thereby degrading various organic micropollutants in water with high efficiency; the method not only effectively avoids adding chemical reagents, saves cost, but also can not cause secondary pollution, and effectively solves the problem of pollution caused by micropollutants in water.
2) The invention adopts a method of combining membrane separation and electrochemical technology and operates in a flow-through operation mode, in the system, convection-enhanced mass transfer can obviously enhance the transfer process of target pollutant molecules to active sites on the surface of the membrane, and the invention has the advantages of easy control and amplification and is hopeful to realize engineering application.
Drawings
FIG. 1 is a graph showing the degradation performance of various electrolytes on aniline in example 1 and comparative example 1;
FIG. 2 is electron paramagnetic resonance spectra of active materials generated from different electrolytes in example 1 and comparative example 1;
FIG. 3 is a graph showing the degradation performance of various water bases on aniline in examples 1 to 3;
FIG. 4 is a graph of the degradation performance of different organic micropollutants in examples 4-8;
FIG. 5 is a block diagram of a flow-through electro-catalytic filtration system of the present invention.
Detailed Description
The invention provides a method for removing organic micropollutants by electrochemically generating sulfate radicals, which comprises the following steps:
introducing the mixed solution containing the organic micro-pollutants and sulfate into a flow-type electro-catalytic filtration system, and degrading the organic micro-pollutants in the mixed solution under the action of an electric field;
the flow rate of the flow-through electro-catalytic filtration system is 1.0-3.0 mL/min, and the current density of the electric field is 1.5-2.5 mA/cm 2 。
The flow rate of the flow-through electro-catalytic filtration system is preferably 1.2-2.7 mL/min, more preferably 1.5-2.2 mL/min, and even more preferably 1.8-2 mL/min; the current density of the electric field is preferably 1.7 to 2.2mA/cm 2 More preferably 1.9 to 2.1mA/cm 2 More preferably 2mA/cm 2 。
The concentration of the organic micro-pollutants is preferably 0.05-15 mg/L, more preferably 5-12 mg/L, and even more preferably 8-10 mg/L.
The organic micro-pollutants preferably comprise one or more of aniline, sulfamethoxazole, methyl blue, methyl orange, tetracycline and bisphenol A.
The concentration of the sulfate is preferably 10-50 mmol/L, more preferably 20-40 mmol/L, and even more preferably 30mmol/L; the sulfate is preferably an electrolyte of a flow-through electrocatalytic filtration system; the sulfate is preferably sodium sulfate or potassium sulfate, and the sulfate is added sulfate or sulfate existing in the water body.
The time for degradation in the present invention is preferably 30 to 60min, and more preferably 40 to 50min.
The solvent of the mixed solution of the present invention is water, and the water preferably contains ultrapure water, tap water, lake water, or industrial wastewater containing sulfate.
The flow-through electrocatalytic filtration system of the present invention comprises a housing, wherein an anode, a cathode and a reference electrode are preferably disposed in the housing, wherein the anode is preferably a titanium suboxide-carbon nanotube electrode (TiSO-CNT electrode), the cathode is preferably a titanium sheet, and the reference electrode is preferably an Ag/AgCl electrode.
The two sides of the shell are respectively provided with a water inlet and a water outlet, and the mixed liquid containing the organic micro-pollutants and the sulfate is preferably introduced from the water inlet of the flow-type electro-catalytic filtration system; a titanium ring is preferably arranged on one side of the anode close to the water inlet and is used for connecting the anode; an insulating silica gel separator is preferably provided between the anode and the cathode.
The method for preparing the titanium monoxide-carbon nanotube electrode preferably comprises the following steps:
1) Reducing titanium dioxide in a hydrogen atmosphere to obtain titanium suboxide powder;
2) And mixing the titanium monoxide powder, the carbon nanotube powder and ethanol, and sequentially performing ultrasonic dispersion, filtration and cleaning on the obtained mixed solution to obtain the titanium monoxide-carbon nanotube electrode.
The titanium dioxide in step 1) of the present invention is preferably rutile type titanium dioxide; the temperature of the reduction is preferably 1000 to 1100 ℃, more preferably 1030 to 1070 ℃, and more preferably 1050 ℃, and the time of the reduction is preferably 20 to 28 hours, more preferably 22 to 26 hours, and more preferably 24 hours.
The mass ratio of the titanium monoxide powder and the carbon nanotube powder in the step 2) of the invention is preferably 0.5-1.5; the particle diameter of the titanium suboxide powder is preferably 200 to 300nm, more preferably 220 to 270nm, and still more preferably 240 to 250nm; the diameter of the carbon nanotube powder is preferably 10 to 20nm, more preferably 12 to 18nm, and still more preferably 15 to 16nm; the length of the carbon nanotube powder is preferably 10 to 30 μm, more preferably 15 to 25 μm, and still more preferably 20 μm; the mass-volume ratio of the titanium monoxide powder to the ethanol is preferably 5 to 15mg:25 to 50mL, more preferably 10mg: 30-40 mL; the mass concentration of the ethanol is preferably more than or equal to 96 percent.
In the present invention, the ethanol serves to disperse the uniform titanium monoxide powder and the carbon nanotube powder.
The time for ultrasonic dispersion in the step 2) is preferably 25-35 min, and more preferably 30min; the ultrasonic dispersion is preferably performed by an ultrasonic instrument; the filtration is preferably a polytetrafluoroethylene membrane with the pore diameter of 0.2-0.25 mu m, and is further preferably a polytetrafluoroethylene membrane with the pore diameter of 0.22 mu m; and after the filtration is finished, obtaining a mixed filter membrane containing titanium monoxide and the carbon nano tube, and cleaning the mixed filter membrane by using ultrapure water to obtain the titanium monoxide-carbon nano tube anode.
In the invention, sulfate is oxidized into persulfate at the anode, and persulfate is reduced and decomposed into sulfate radicals at the cathode; the whole experimental process does not need to add extra chemical reagents, and efficient degradation of organic micro-pollutants in water is realized based on strong oxidizing capability of sulfate radicals.
The technical solutions provided by the present invention are described in detail below with reference to examples, but they should not be construed as limiting the scope of the present invention.
Example 1
Mixing rutile type TiO 2 Reducing the titanium dioxide powder for 24 hours at 1050 ℃ in a hydrogen atmosphere to obtain titanium dioxide powder. 10mg of titanium monoxide powder (particle size of 250 nm) and 20mg of carbon nanotube powder (diameter of 15nm, length of 20 μm) were mixed with 30mL of ethanol (mass concentration of 96%), the mixed solution was dispersed for 30min using an ultrasonic instrument, and then the mixed solution was filtered with a 0.22 μm polytetrafluoroethylene membrane, and the resulting mixed membrane was washed with ultrapure water, to obtain a titanium monoxide-carbon nanotube electrode.
Aniline and sodium sulfate were dissolved in 50mL of ultrapure water to obtain a mixture containing 10mg/L of aniline and 50mmol/L of sodium sulfate.
And moving the mixed solution to a flow-type three-electrode electro-catalysis filtration system, wherein a titanium sub-oxide-carbon nano tube electrode is used as an anode, a titanium sheet is used as a cathode, and an Ag/AgCl electrode is used as a reference electrode. The mixed solution is introduced from the water inlet of the flow-through electro-catalytic filtration system, flows through the anode at the flow rate of 2mL/min and then flows through the cathode at the current density of 2.5mA/cm 2 Reacting for 40min under the action of an electric field to obtain the degraded organic micropollutants.
Example 2
Tap water was used in place of the ultrapure water of example 1, and the other conditions were the same as in example 1.
Example 3
The ultrapure water of example 1 was replaced with lake water, and the other conditions were the same as in example 1.
Example 4
Sulfamethoxazole was used in place of the aniline of example 1 and the other conditions were the same as in example 1.
Example 5
Methyl blue was used instead of the aniline of example 1, and other conditions were the same as in example 1.
Example 6
Methyl orange was used instead of the aniline of example 1, and the other conditions were the same as in example 1.
Example 7
Tetracycline was used in place of the aniline of example 1, and the other conditions were the same as in example 1.
Example 8
Bisphenol A was used in place of the aniline of example 1, and the other conditions were the same as in example 1.
Example 9
The aniline of example 1 was replaced with sulfate-containing industrial waste water under the same conditions as in example 1.
Example 10
Methyl blue and potassium sulfate were dissolved in 50mL of tap water to obtain a mixture containing 5mg/L of methyl blue and 20mmol/L of potassium sulfate.
The mixed solution was transferred to a flow-through three-electrode electrocatalytic filtration system, in which a titanium suboxide-carbon nanotube electrode was used as the anode (the preparation method of the titanium suboxide-carbon nanotube electrode was the same as in example 1), a titanium sheet was used as the cathode, and an Ag/AgCl electrode was used as the reference electrode. The mixed solution is introduced from the water inlet of the flow-through electro-catalytic filtration system, flows through the anode at the flow rate of 1.5mL/min and then flows through the cathode at the current density of 1.5mA/cm 2 Reacting for 50min under the action of the electric field to obtain the degraded organic micropollutants.
Example 11
Bisphenol A and sodium sulfate were dissolved in 50mL of lake water to obtain a mixed solution containing 13mg/L of bisphenol A and 30mmol/L of sodium sulfate.
The mixed solution was transferred to a flow-through three-electrode electrocatalytic filtration system, in which a titanium suboxide-carbon nanotube electrode was used as the anode (the preparation method of the titanium suboxide-carbon nanotube electrode was the same as in example 1), a titanium sheet was used as the cathode, and an Ag/AgCl electrode was used as the reference electrode. The mixed solution is introduced from the water inlet of the flow-through electro-catalytic filtration system, flows through the anode at the flow rate of 2.5mL/min and then flows through the cathode at the current density of 2mA/cm 2 Reacting for 35min under the action of the electric field to obtain the degraded organic micropollutants.
Comparative example 1
Sodium perchlorate of equal conductivity was used instead of sodium sulfate in example 1, and the other conditions were the same as in example 1.
The degradation performance of the electrolytes of example 1 and comparative example 1 on aniline is shown in fig. 1. As can be seen from fig. 1, when sodium sulfate was used as the electrolyte, the degradation rate of aniline reached 100%, whereas when sodium perchlorate was used as the electrolyte, the degradation kinetics of aniline was significantly suppressed, and only about 10% degradation rate of aniline was obtained. The main reason is that the active substances generated by the sodium sulfate in the electro-oxidation process have high oxidation capacity, and aniline can be efficiently and quickly removed; sodium perchlorate is an inert electrolyte which can not generate reactive substances in the electrooxidation reaction, and the degradation of aniline is only dependent on the action of an electric field.
The active materials generated in the electrochemical systems of example 1 and comparative example 1 were measured, as shown in fig. 2. The results show that SO is detected in an electrooxidation system using sodium sulfate as electrolyte 4 ·– The characteristic peaks of free radicals are equal, but are not detected in the electrooxidation system taking sodium perchlorate as electrolyte, and the phenomenon proves that the precursor of the free radicals is SO 4 2– The importance of sodium sulfate electrolyte is illustrated.
The degradation performance of the different water bases on aniline in examples 1-3 is shown in FIG. 3. The results show that the sulfate radical oxidation system mediated by the in-situ generated persulfate intermediate can realize the high-efficiency degradation of aniline in various water matrixes, and the method has strong anti-interference capability.
The degradation performance of the different organic micropollutants of examples 4 to 8 is shown in figure 4. The result shows that the method can effectively degrade different types of organic micropollutants, the degradation rate is more than or equal to 95%, wherein the degradation rate of aniline, sulfamethoxazole, methyl blue, methyl orange and tetracycline is more than or equal to 98%, and the method has the potential of wide application.
The degradation rates of the organic micropollutants of examples 9, 10 and 11 were 98%, 99% and 97.5%, respectively.
The embodiment shows that the method not only effectively avoids adding an additional reagent, saves the cost, but also does not cause secondary pollution, and effectively solves the pollution problem of various water qualities. The invention can generate persulfate with redox activity in situ, and generate sulfate radical free radical with strong oxidation capacity by reducing persulfate through single electron, thus being capable of efficiently degrading various organic micropollutants in water.
The invention adopts a method of combining membrane separation and electrochemical technology and operates in a flow-through operation mode, in the system, convection-enhanced mass transfer can obviously enhance the transfer process of target pollutant molecules to active sites on the surface of the membrane, and the invention has the advantages of easy control and amplification and is hopeful to realize engineering application.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (5)

1. A method for removing organic micropollutants by electrochemically generating sulfate radicals, which is characterized by comprising the following steps:
introducing the mixed solution containing the organic micro-pollutants and sulfate into a flow-type electro-catalytic filtration system, and degrading the organic micro-pollutants in the mixed solution under the action of an electric field;
the flow rate of the flow-through electrocatalytic filtration system is 1.0-3.0 mL/min, and the current density of an electric field is 1.5-2.5 mA/cm 2 ；
The flow-through electro-catalytic filtration system comprises a shell, wherein an anode, a cathode and a reference electrode are arranged in the shell, wherein the anode is a titanium suboxide-carbon nanotube electrode, the cathode is a titanium sheet, and the reference electrode is an Ag/AgCl electrode;
a water inlet and a water outlet are respectively arranged on two sides of the shell, and a mixed solution containing organic micro-pollutants and sulfate is introduced from the water inlet of the flow-through electro-catalytic filtration system; a titanium ring is arranged on one side of the anode close to the water inlet and is used for connecting the anode; an insulating silica gel separator is arranged between the anode and the cathode;
the preparation method of the titanium suboxide-carbon nanotube electrode comprises the following steps:
1) Reducing titanium dioxide in a hydrogen atmosphere to obtain titanium suboxide powder;
2) Mixing titanium monoxide powder, carbon nanotube powder and ethanol, and sequentially performing ultrasonic dispersion, filtration and cleaning on the obtained mixed solution to obtain a titanium monoxide-carbon nanotube electrode;
the reduction temperature in the step 1) is 1000 to 1100 ℃, and the time is 20 to 28h; the mass ratio of the titanium oxide powder to the carbon nanotube powder in the step 2) is 0.5 to 1.5; the time of ultrasonic dispersion is 25 to 35min, and a polytetrafluoroethylene membrane with the aperture of 0.2 to 0.25 mu m is adopted for filtration; and after the filtration is finished, obtaining a mixed filter membrane containing titanium monoxide and the carbon nano tube, and cleaning the mixed filter membrane by using ultrapure water to obtain the titanium monoxide-carbon nano tube anode.
2. The method as claimed in claim 1, wherein the concentration of the organic micropollutants is 0.05 to 15mg/L.
3. The method of claim 1 or 2, wherein the organic micropollutants comprise one or more of aniline, sulfamethoxazole, methyl blue, methyl orange, tetracycline and bisphenol a.
4. The method according to claim 3, wherein the concentration of the sulfate is 10 to 50mmol/L; the sulfate is an electrolyte of a flow-through electrocatalytic filtration system.
5. The method according to claim 4, wherein the solvent of the mixed liquid is water, and the water includes ultrapure water, tap water, lake water, or industrial wastewater containing sulfate.
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