Preparation of a photoelectric integrated catalytic electrode and its application in the degradation of antiviral drug wastewater

Abstract

The present invention discloses the preparation of a photoelectric integrated catalytic electrode and its application in the degradation of antiviral drug wastewater, and relates to the technical field of sewage purification and wastewater resource utilization. The composite catalytic electrode includes a CMO electrocatalytic electrode and a WCN photocatalytic electrode, a nickel foam is placed between the CMO electrocatalytic electrode and the WCN photocatalytic electrode to form a composite catalytic electrode with a sandwich structure; the CMO electrocatalytic electrode uses CuMn2O4 particles as a catalyst material and is prepared by electrodeposition and heat treatment; the WCN photocatalytic electrode is prepared by bonding sodium tungstate, melamine and formaldehyde to a substrate through PVP, and then drying and calcining. The composite catalytic electrode of the present invention is coupled with a photoelectric bio-Fenton reaction to achieve the effective removal of acyclovir in antiviral drug wastewater, and the removal rate of acyclovir in the difficult-to-degrade acyclovir wastewater reaches 100%.

Description

Technical Field

[0001] The present invention relates to the technical field of sewage purification and wastewater resource utilization, and in particular to the preparation of a photoelectric integrated catalytic electrode and the application of antiviral drug wastewater degradation. Background Art

[0002] Antiviral drugs are widely used to treat influenza, herpes or hepatitis in humans and animals. As an effective antiviral drug, acyclovir has a low bioavailability (only 10%-20%), resulting in a residual amount of at least 1.0 ng / L in natural water bodies and a higher residual amount of 1.0 mg / L in pharmaceutical wastewater. Although the concentration of antiviral drugs such as acyclovir in the environment is trace, their continued release in natural water bodies may pose a risk to surrounding organisms. The presence of antiviral drugs in the environment can lead to potential changes in ecosystems and viral resistance. Currently, commonly used methods for removing antiviral drugs from the environment include adsorption, biodegradation, etc., but their energy consumption is high.

[0003] Photocatalytic degradation technology can utilize natural light and reduce energy consumption, and is gradually favored by researchers in water pollution control. Existing technology has achieved good results in degrading Rhodamine B using g-C3N4 / Fe2O3 composite catalysts, but it still has disadvantages such as long degradation time and the composite catalyst is not conducive to recycling and reuse. Summary of the invention

[0004] The purpose of the present invention is to provide a preparation of a photoelectric integrated catalytic electrode and its application in the degradation of antiviral drug wastewater, and to use a photoelectric bio-Fenton reaction device to solve the problems of long degradation time and difficulty in recovering composite catalysts in the above-mentioned prior art, so as to efficiently treat acyclovir antiviral wastewater.

[0005] To achieve the above object, the present invention provides the following solutions:

[0006] One of the technical solutions of the present invention is a composite catalytic electrode (CMNW) CN ), including a CMO electrocatalytic electrode and a WCN photocatalytic electrode, wherein a nickel foam is placed between the CMO electrocatalytic electrode and the WCN photocatalytic electrode to form a sandwich structure composite catalytic electrode ((CMNW) CN );

[0007] The sandwich structure can be used as a composite catalytic electrode (CMNW) CN ) effectively provides electron transfer inside, generates free radical ions, and accelerates the degradation rate.

[0008] The CMO electrocatalytic electrode is prepared by electrodeposition and heat treatment using CuMn2O4 particles as catalyst material;

[0009] The WCN photocatalytic electrode is prepared by bonding sodium tungstate, melamine and formaldehyde on a substrate through PVP, and then drying and calcining.

[0010] The electrodeposition conditions are as follows: using a calomel electrode as the standard, the electrodeposition potential is -0.7 V, and the electrodeposition time is 300 s;

[0011] The heat treatment conditions are as follows: heating to 500° C. at a heating rate of 5° C. / min and keeping the temperature for 2 hours.

[0012] Preferably, the substrate is a stainless steel mesh;

[0013] Furthermore, in terms of mass percentage, the sodium tungstate: melamine: formaldehyde: PVP = 30%: 10%: 50%: 10%;

[0014] The drying is specifically drying at 60-80° C. for 2 hours;

[0015] The calcination is specifically carried out at 650° C. for 2 hours.

[0016] The second technical solution of the present invention is a photoelectric bio-Fenton reaction device, using the above-mentioned composite catalytic electrode ((CMNW) CN ) is used as a cathode, and an activated carbon bioelectrode with metallic iron and microorganisms attached is used as an anode. The cathode and the anode are connected by a wire and a resistor is connected in series, and a visible light source is arranged above the cathode chamber.

[0017] Furthermore, an aeration device is also provided in the cathode chamber to provide oxygen required for the reaction.

[0018] The method for determining the resistance value is specifically as follows: before the positive and negative electrodes form a closed loop, an adjustable resistance box is added to the circuit, a voltmeter is connected in parallel, the resistance is adjusted, a test voltage value is obtained, a power density curve is drawn, and it is determined that the resistance value of the resistance box is 80Ω when the power density is maximum; the resistance box is removed, and an 80Ω resistor is connected in series to the closed loop.

[0019] The parameters of the metal iron are specifically: diameter 0.2 cm, length 10 cm;

[0020] The preparation method of the microorganism-attached activated carbon bioelectrode is specifically as follows: anaerobic sludge is mixed with an activated carbon anode and cultured for one to three weeks to allow the microorganisms to attach to the surface of the activated carbon, and a nutrient medium is added during the culture period; the microorganisms are cultured so that the voltage of the photoelectric bio-Fenton reaction device reaches 0.8V to promote the subsequent electrocatalytic reaction.

[0021] The third technical solution of the present invention is a method for degrading acyclovir wastewater, comprising the following steps:

[0022] Step 1, adjusting the pH of acyclovir wastewater to acidic, adding Na2SO4 solution and PMS to obtain a pre-treated solution;

[0023] Step 2: adding the pretreatment liquid into the above-mentioned photoelectric bio-Fenton reaction device, irradiating the cathode of the photoelectric bio-Fenton reaction device with visible light to carry out redox reaction to degrade the acyclovir in the acyclovir wastewater.

[0024] Furthermore, the acyclovir content in the acyclovir wastewater in step 1 is 1 to 20 mg / L;

[0025] When the acyclovir content is 20 mg / L or less, the photoelectric bio-Fenton reaction device of the present invention can completely degrade it within 30 minutes. When the acyclovir content is higher than 20 mg / L, the degradation time will be extended accordingly.

[0026] The step of adjusting the pH to acidic in step 1 is specifically to adjust the pH to 3-4 using 0.5 mol / L H2SO4.

[0027] The reason for adjusting the pH to 3-4 is that acidic conditions are more conducive to the occurrence of advanced oxidation reactions, but when the pH is lower than 3, H + With ·OH or SO4· - There is a scavenging process between them, which leads to the removal of free radical ions that can degrade pollutants, affecting the degradation efficiency; high pH will cause SO4· - Under alkaline conditions, it is converted into ·OH, which reduces the oxidizing ability of the solution. In addition, with the increase of pH, Cu ions form precipitates such as Cu(OH)2, which affects the subsequent catalytic reaction and leads to a decrease in degradation performance.

[0028] The dosage of the Na2SO4 solution and PMS in step 1 is based on the concentration of 0.5M Na2SO4 solution and 0.6mM PMS per 100mL acyclovir wastewater.

[0029] The redox reaction in step 2 is carried out at room temperature and normal pressure.

[0030] The visible light irradiation in step 2 is specifically irradiation with a xenon lamp for 30 minutes.

[0031] Na2SO4 solution is added as the electrolyte of photobioelectric Fenton to improve the conductivity of acyclovir wastewater; monopersulfate (PMS) is added to provide sulfate radicals required for subsequent reactions. Too much addition will result in excessive production of S2O8 2- , affecting the subsequent activation of PMS. Too little will lead to insufficient production of sulfate free radicals, affecting the subsequent degradation reaction of acyclovir.

[0032] The reaction mechanism of the present invention is as follows: The present invention conducts an electrodeposition experiment on the bimetallic catalyst CuMn2O4 and attaches it to the surface of the stainless steel mesh to form a CMO electrocatalyst electrode, and generates WO3 / g-C3N4 by drying and calcining sodium tungstate, melamine, formaldehyde and PVP, and attaches it to the surface of the stainless steel mesh through adhesion to form a WCN photocatalytic electrode, and adds nickel foam between the electrocatalytic electrode and the photocatalytic electrode to form a sandwich electrode structure. The electrons generated by oxidation and reduction in the CMO electrocatalytic electrode and transmitted by the microorganisms through the wire (the reaction formula of the CMO electrocatalytic electrode is as follows: Cu + / Mn 2+ +H2O2→Cu 2 + / Mn 3+ + OH+OH - , PMS and H2O2 are used to generate free radical ions through redox reaction to degrade acyclovir), and the WCN photocatalytic electrode activates the photoelectrons formed in the valence band through photocatalysis (the reaction formula of the WCN photocatalytic electrode is as follows: WCN+hυ→h VB + +e CB - The WCN photocatalytic electrode generates photogenerated electrons and photogenerated holes under light irradiation. These electrons are effectively transferred inside the sandwich electrode to generate a large number of free radical ions required for degradation, ultimately achieving effective removal of antiviral drugs. The electrode sheet of the present invention can also be effectively recycled.

[0033] The anode reaction formula of the photoelectric bio-Fenton reaction device of the present invention is as follows: C6H 12 O6+6H2O→6CO2+24e - +24H + , the microorganisms in the anode chamber consume organic matter to produce electrons, providing biological power for the reactor. Under the irradiation of the xenon lamp, the anode electrogenic microorganisms are used as the power source for the Fenton reaction, and the H2O2 produced by the cathode reacts with the PMS reagent added to the solution to generate SO4 with strong oxidizing ability. - and ·OH, opening the ring or breaking the acyclovir molecule, thereby achieving the degradation of acyclovir.

[0034] A fourth technical solution of the present invention is an application of the above-mentioned photoelectric bio-Fenton reaction device in degrading acyclovir wastewater.

[0035] The technical concept of the present invention:

[0036] Fenton technology has many advantages, including easy control, good environmental compatibility and easy automation. The present invention uses the improved photoelectric bio-Fenton reaction technology to treat acyclovir wastewater, introduces electrogenic microorganisms as anodes, and uses the microorganisms to generate electricity to provide the required electricity for the Fenton reaction, without the need for additional power sources. Through electrochemical action and visible light irradiation, SO4· - and ·OH, both of which have strong oxidizing properties and are non-selective, and can treat a variety of difficult-to-degrade organic pollutants. The present invention introduces visible light as energy, and catalyzes the degradation of pollutants through the principle of photocatalysis, which can not only improve the redox performance and the degradation efficiency of pollutants, but also save electricity and energy and reduce costs.

[0037] The present invention discloses the following technical effects:

[0038] 1. The composite catalytic electrode (CMNW) of the present invention CN ) coupled with the photoelectric bio-Fenton reaction, the effective removal of acyclovir in antiviral drug wastewater is achieved. The photoelectric bio-Fenton reaction device of the present invention can degrade 100 mL of acyclovir wastewater within 30 minutes, and the removal rate of acyclovir in the difficult-to-degrade acyclovir wastewater reaches 100%.

[0039] 2. The composite catalytic electrode (CMNW) of the present invention CN ) is composed of a CMO electrocatalytic electrode and a WCN photocatalytic electrode. The CMO electrode and the WCN electrode have different catalytic functions and can effectively transfer electrons. They have a large specific surface area, many active sites, low cost, and are easy to prepare.

[0040] 3. The composite catalytic electrode (CMNW) of the present invention CN ) In the acyclovir wastewater degradation experiment, the degradation efficiency was still above 95% after five cycles, which shows that the device has sustainable utilization and can be repeated many times to achieve efficient degradation of pollutants.

[0041] 4. The present invention places a xenon lamp above the cathode chamber to simulate visible light, which significantly increases the SO4 produced by the Fenton reaction. - and ·OH, increasing the efficiency of the Fenton reaction to 30% of that without light. BRIEF DESCRIPTION OF THE DRAWINGS

[0042] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

[0043] Figure 1 The cyclic voltammograms of the reaction devices obtained in Example 1 and Comparative Examples 1-3;

[0044] Figure 2 The cathode polarization curves of the reaction devices obtained in Example 1 and Comparative Examples 1-3;

[0045] Figure 3 The efficiency diagram of acyclovir degradation by the reaction devices obtained in Example 1 and Comparative Examples 1-3;

[0046] Figure 4 is the morphology of the cathode CMO electrode;

[0047] Figure 5 This is the morphology of the anode WCN electrode. DETAILED DESCRIPTION

[0048] Various exemplary embodiments of the present invention will now be described in detail. This detailed description should not be considered as limiting the present invention, but should be understood as a more detailed description of certain aspects, features, and embodiments of the present invention.

[0049] It should be understood that the terms described in the present invention are only for describing special embodiments and are not intended to limit the present invention. In addition, for the numerical range in the present invention, it should be understood that each intermediate value between the upper and lower limits of the scope is also specifically disclosed. Each smaller range between the intermediate value in any stated value or stated range and any other stated value or intermediate value in the described range is also included in the present invention. The upper and lower limits of these smaller ranges can be independently included or excluded in the scope.

[0050] Unless otherwise indicated, all technical and scientific terms used herein have the same meanings as those generally understood by those skilled in the art. Although the present invention describes only preferred methods and materials, any methods and materials similar or equivalent to those described herein may also be used in the implementation or testing of the present invention. All documents mentioned in this specification are incorporated by reference to disclose and describe the methods and / or materials associated with the documents. In the event of a conflict with any incorporated document, the content of this specification shall prevail.

[0051] It will be apparent to those skilled in the art that various modifications and variations may be made to the specific embodiments of the present invention description without departing from the scope or spirit of the present invention. Other embodiments derived from the present invention description will be apparent to those skilled in the art. The present invention description and examples are exemplary only.

[0052] The words “include,” “including,” “have,” “contain,” etc. used in this document are open-ended terms, meaning including but not limited to.

[0053] The "room temperature" described in the present invention is within the range of 20 to 30°C unless otherwise specified.

[0054] In the present invention, a xenon lamp is used to simulate visible light.

[0055] The nutritional components of the nutrient medium of the present invention are as follows: 1 g / L sodium acetate, 50 mmol / L phosphate buffer solution (PBS), 12.5 mL / L mineral solution, and 5 mL / L vitamin solution.

[0056] Example 1

[0057] Step 1, preparation of CuMn2O4 particles: add 4.83gCu(NO3)2·3H2O and 6.76gMnSO4·H2O into 240mL deionized water, and stir at 500r / min for 30min to obtain a mixed solution; heat the mixed solution to 80°C in a water bath, add 1MNa2CO3 solution dropwise until the pH value reaches 10, continue heating in a water bath and stirring for 30min; filter and separate, wash three times with deionized water and ethanol each until the pH value of the filtrate does not change; dry the precipitate in an oven at 60°C for 12 hours, grind into powder, and obtain CuMn2O4 particles.

[0058] Step 2, preparation of CMO electrocatalytic electrode: platinum sheet, saturated calomel electrode and stainless steel mesh (2 cm × 2 cm) were used as counter electrode, reference electrode and working electrode respectively; 100 mL ultrapure aqueous solution containing 0.1 mol CuMn2O4 particles and 1 mol Na2SO4 was used as the electrodeposition solution; at room temperature, the electrodeposition potential was -0.7 V (based on the calomel electrode), and the electrodeposition time was controlled at 300 s to optimize the performance of the electrode; and then heated to 500°C at a heating rate of 5°C / min. After keeping warm for 2 hours, it was cooled to room temperature to obtain a CMO electrocatalytic electrode.

[0059] Step 3, preparation of WCN photocatalytic electrode: take 1g polyvinyl pyrrolidone (PVP), 5g formaldehyde (CH2O), 1g melamine (C3H6N6) and 3g sodium tungstate dihydrate (Na2WO4·2H2O) respectively, stir vigorously at room temperature for 12 hours, and evenly apply the mixed solution on a stainless steel mesh (2 cm × 2 cm) washed three times with hydrochloric acid and ethanol respectively, and dry at 60°C; then raise the temperature to 650°C at a rate of 5°C / min, keep warm for 2 hours, and naturally cool to room temperature to obtain a WCN photocatalytic electrode.

[0060] Step 4, preparation of the activated carbon bioelectrode with metallic iron and microorganisms attached: 50g of anaerobic sludge and 50g of activated carbon bioanode are mixed and cultured at room temperature and normal pressure for one week to allow the microorganisms to completely attach to the surface of the activated carbon. During the culture period, a flowing nutrient medium is added to maintain the activity of the microorganisms; the cultured activated carbon bioelectrode is placed in the anode chamber of the photoelectric bio-Fenton reaction device, and metallic iron is inserted, and nutrient medium is continued to be added to obtain the activated carbon bioelectrode with metallic iron and microorganisms attached.

[0061] Step 5. Preparation of cathode: Place a nickel foam (2 cm × 2 cm) between the CMO electrocatalytic electrode and the WCN photocatalytic electrode to form a sandwich structure (CMNW) CN The composite catalytic electrode is used as the cathode of the photoelectric bio-Fenton reaction device.

[0062] Step 6, preparation of anode: combining metallic iron and activated carbon bioelectrode attached with microorganisms with carbon brush as anode of photoelectric bio-Fenton reaction device.

[0063] Step 7, assembly of the photoelectric bio-Fenton reaction device: fix the prepared anode in the anode chamber, fix the cathode in the cathode chamber, connect the anode and cathode with a wire and connect a resistor in series, the resistor value is set to 80Ω, irradiate the cathode chamber with a xenon lamp, add an aeration pump device at the bottom of the cathode chamber, and obtain the photoelectric bio-Fenton reaction device ((CMNW) CN +Light).

[0064] Example 2

[0065] The only difference from Example 1 is that in step 4, 50 g of anaerobic sludge and 50 g of activated carbon bioanode are mixed and cultured at room temperature and pressure for three weeks.

[0066] Comparative Example 1

[0067] The only difference from Example 1 is that no xenon lamp irradiation is added in step 7 to obtain a reaction device ((CMNW) CN ).

[0068] Comparative Example 2

[0069] The only difference from Example 1 is that the CMO electrocatalytic electrode is not prepared, and the WCN photocatalytic electrode is directly used as the cathode to obtain a reaction device (WCN+Light).

[0070] Comparative Example 3

[0071] The only difference from Example 1 is that the WCN photocatalytic electrode is not prepared, and the CMO electrocatalytic electrode is directly used as the cathode to obtain a reaction device (CMO+Light).

[0072] Effect verification example 1

[0073] The redox properties of the reaction devices obtained in Example 1 and Comparative Examples 1-3 were examined.

[0074] The redox properties of the reaction devices obtained in Example 1 and Comparative Examples 1-3 were tested by cyclic voltammetry in a 1 mol / L Na2SO4 solution at a scan rate of 0.01 V / s. The results are shown in FIG. Figure 1 As shown, the horizontal axis represents voltage, unit V, and the vertical axis represents current, unit mA. Figure 1 This is the scanning cyclic voltammogram in 1 mol / L Na2SO4. Figure 1 It can be seen that by (CMNW) CN The reaction device assembled with composite catalytic electrode under the irradiation of xenon lamp is compared with the reaction device assembled with CMO electrode, the reaction device assembled with WCN electrode and (CMNW) CN The cyclic voltammetry curve of the reaction device assembled with the composite catalytic electrode under light-free conditions has obvious redox peaks, indicating that (CMNW) CN The composite catalytic electrode has a significant promoting effect on the redox reaction under the irradiation of a xenon lamp.

[0075] Effect verification example 2

[0076] The relationship between the polarization potential or overpotential and the current density passing through the reaction device obtained in Example 1 and Comparative Examples 1-3 was examined.

[0077] Use wires to connect the cathode and anode in the reaction device, and connect an adjustable resistance box in series, a voltmeter in parallel, adjust the external resistance, obtain the test voltage value, and draw a power density curve. Figure 2 As shown, the horizontal axis represents the current density, in units of A / m 2 The left side of the vertical axis represents voltage, and the right side of the vertical axis represents power density, in W / m 2 (CMNW) CN Compared with the reaction device assembled with CMO electrode, the reaction device assembled with WCN electrode and (CMNW) under the irradiation of xenon lamp CN The reaction device assembled with composite catalytic electrodes under light-free conditions has a greater power density and can effectively utilize the electrical energy generated by microorganisms for redox reactions.

[0078] Effect verification example 3

[0079] The efficiency of the reaction devices obtained in Example 1 and Comparative Examples 1-3 in treating acyclovir wastewater was tested.

[0080] Step 1, taking 100 mL of acyclovir wastewater containing 10 mg / L acyclovir, adjusting the pH to 3 with 0.5 mol / L H2SO4, adding Na2SO4 solution to a Na2SO4 concentration of 0.5 M, and adding PMS to a PMS concentration of 0.6 mM to obtain a pre-treated solution;

[0081] Step 2: adding the pretreatment solution into the reaction devices obtained in Example 1 and Comparative Examples 1-3 respectively, irradiating the cathode of the reaction device with a xenon lamp to perform an oxidation-reduction reaction to degrade the acyclovir in the acyclovir wastewater.

[0082] The results are as follows Figure 3 As shown. It can be seen that the photobioelectric reaction device of the present invention can effectively remove acyclovir and achieve effective purification of acyclovir wastewater. However, in Comparative Examples 1-3, the electron transfer efficiency is reduced and the free radicals are reduced due to the lack of electrodes or light conditions, which leads to a decrease in the efficiency of the degradation reaction.

[0083] The embodiments described above are only descriptions of the preferred modes of the present invention, and are not intended to limit the scope of the present invention. Without departing from the design spirit of the present invention, various modifications and improvements made to the technical solutions of the present invention by ordinary technicians in this field should all fall within the protection scope determined by the claims of the present invention.

Claims

1. A photoelectric bio-Fenton reaction device, characterized in that: The composite catalytic electrode is used as a cathode, and the activated carbon bioelectrode with metal iron and microorganisms attached is used as an anode. The cathode and the anode are connected by a wire and a resistor is connected in series. A visible light source is arranged above the cathode chamber. The composite catalytic electrode comprises a CMO electrocatalytic electrode and a WCN photocatalytic electrode, wherein a nickel foam is placed between the CMO electrocatalytic electrode and the WCN photocatalytic electrode to form a composite catalytic electrode with a sandwich structure; The CMO electrocatalytic electrode is prepared by electrodeposition and heat treatment using CuMn2O4 particles as catalyst material; The WCN photocatalytic electrode is prepared by bonding sodium tungstate, melamine and formaldehyde on a substrate through PVP, and then drying and calcining.

2. The photoelectric bio-Fenton reaction device according to claim 1, characterized in that: The electrodeposition conditions are as follows: using a calomel electrode as the standard, the electrodeposition potential is -0.7 V, and the electrodeposition time is 300 s; The heat treatment conditions are as follows: heating to 500° C. at a heating rate of 5° C. / min and keeping the temperature for 2 hours.

3. The photoelectric bio-Fenton reaction device according to claim 1, characterized in that: Calculated by mass percentage, the sodium tungstate: melamine: formaldehyde: PVP = 30%: 10%: 50%: 10%; The drying is specifically drying at 60-80° C. for 2 hours; The calcination is specifically carried out at 650° C. for 2 hours.

4. The photoelectric bio-Fenton reaction device according to claim 1, characterized in that: An aeration device is also provided in the cathode chamber.

5. The photoelectric bio-Fenton reaction device according to claim 1, characterized in that: The preparation method of the microorganism-attached activated carbon bioelectrode is specifically as follows: anaerobic sludge is mixed with an activated carbon anode and cultured for one to three weeks to allow the microorganisms to attach to the surface of the activated carbon, and a nutrient medium is added during the culture period; the microorganisms are cultured so that the voltage of the photoelectric bio-Fenton reaction device reaches 0.8V to promote the subsequent electrocatalytic reaction.

6. A method for degrading acyclovir wastewater, characterized in that: The following steps are involved: Step 1, adjusting the pH of acyclovir wastewater to acidic, adding Na2SO4 solution and PMS to obtain a pre-treated solution; Step 2: adding the pretreatment liquid into the photoelectric bio-Fenton reaction device according to claim 1, irradiating the cathode of the photoelectric bio-Fenton reaction device with visible light to carry out redox reaction to degrade the acyclovir in the acyclovir wastewater.

7. The method for degrading acyclovir wastewater according to claim 6, characterized in that: The acyclovir content in the acyclovir wastewater in step 1 is 1 to 20 mg / L; The step of adjusting the pH to acidic in step 1 is specifically to adjust the pH to 3-4 using 0.5 mol / L H2SO4.

8. The method for degrading acyclovir wastewater according to claim 6, characterized in that: The visible light irradiation in step 2 is specifically irradiation with a xenon lamp for 30 minutes.

9. Use of the photoelectric bio-Fenton reaction device according to claim 1 in degrading acyclovir wastewater.

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