CN113636625B

CN113636625B - Electrode capable of self-generating oxidant and preparation method and application thereof

Info

Publication number: CN113636625B
Application number: CN202110907895.7A
Authority: CN
Inventors: 周进进; 仓龙; 郝秀珍; 高娟
Original assignee: Institute of Soil Science of CAS
Current assignee: Institute of Soil Science of CAS
Priority date: 2021-08-09
Filing date: 2021-08-09
Publication date: 2022-04-29
Anticipated expiration: 2041-08-09
Also published as: CN113636625A

Abstract

Electrode capable of self-generating oxidant and preparation method and application thereofFirstly, Ti/Sn-SbO is prepared from Ti sheets by a sol-gel method_xBy electrodeposition on Ti/Sn-SbO_xSurface preparation of alpha-PbO₂Layer, then doping Mn into PbO by DC electrodeposition₂Electroplating to alpha-PbO₂Layer formation of Ti/Sn-SbO_x/Mn‑PbO₂And an electrode. The preparation method of the electrode is simple, the operation is convenient and fast, the process flow is simple, the degradation rate of the pollutant anthracene is high, the corrosion resistance of the electrode is good, and the degradation efficiency is higher than that of the common Ti/Sn-SbO_x/PbO₂The electrode is very high, the degradation rate of anthracene after 120min reaches 91.28%, and the degradation efficiency can still reach more than 70% under the condition of wider pH.

Description

Electrode capable of self-generating oxidant and preparation method and application thereof

Technical Field

The invention belongs to the field of environmental pollution treatment, and particularly relates to an electrode capable of generating an oxidant by itself, and a preparation method and application thereof.

Background

With the rapid development of developing countries, more and more pollutants such as heavy metals and organic compounds enter water. Anthracene is generally used as a luminescent material, a manufacturing dye, an insecticide, a bactericide, a herbicide, an anti-coagulant, and the like, and exists in a water body during use or after being discharged, thereby causing pollution to the water body.

Advanced oxidation techniques (AOPs) are one of the most efficient methods for treating refractory organic wastewater, and the core of the method is to input energy light energy, electric energy, heat energy or oxidizing agent (H) into the wastewater₂O₂，Na₂S₂O₈，O₃) And the like, after a series of reaction processes, hydroxyl radical (OH) with strong oxidizing capability is produced in situ^-) Or sulfate radicals (SO)₄ ^·-) Etc. to oxidize organic pollutant in waste water into CO₂，H₂O, and the like. Electrocatalytic Advanced Oxidation (EAOPs) can generate water oxidation catalytic reaction on the surface of an anode under the condition of low voltage to generate HO with strong oxidation capacity^-Or directly on the anode surface by losing electrons to achieve oxidative degradation of contaminants, EAOPs can show a number of advantages compared to conventional AOPs: HO can be generated in situ without adding exogenous oxidant^-Often times, theCan be operated at normal temperature and pressure, has the advantages of short oxidation time, convenient operation and the like.

In recent years, PbO has been used as a material for the optical fibers₂The anode has the advantages of good electrocatalytic activity, mature manufacturing process, high stability, good corrosion resistance and the like, so that the anode can be used for PbO₂The anode is being studied more and more. Most of the current methods are Ti as a substrate and Sb-doped SnO₂（Sb-SnO_x) Adding PbO as intermediate layer₂The stability and the service life of the active surface layer are improved, and the electrocatalytic activity of the electrode is changed by doping metal elements such as Ce, Bi, Fe, Cu, F and the like or nonmetal elements.

For the modified lead dioxide electrode, OH is generated only by original generation^-Etc. to oxidize the organic contaminants. Compared with rare earth metals, Mn has the advantage of easy obtainment, and researches show that the Mn is doped to increase MnO in a system₄ ^-Concentration of (b), MnO₄ ^-The removal rate of contaminants can be increased. However, the Mn is rarely used to mix into PbO at present₂The modified electrode of (1) reports that the modification of the above electrode is yet to be further developed.

Disclosure of Invention

The technical problem to be solved is as follows: the electrode capable of self-generating the oxidant, the preparation method and the application thereof do not need an exogenous oxidant, and Ti/Sn-SbO is utilized_x/Mn-PbO₂Loss of Mn from the anode to yield MnO₄ ^-And PbO₂By electrolysis of water on the surface of the anode^·OH is used for oxidizing organic pollutants, the electrode preparation method is simple, the operation is convenient, the process flow is simple, the degradation rate of anthracene as the pollutants is high, the corrosion resistance of the electrode is good, and the degradation efficiency is higher than that of common Ti/Sn-SbO_x/PbO₂The electrode is very high, the degradation rate of anthracene after 120min reaches 91.28%, and the degradation efficiency can still reach more than 70% under the condition of wider pH.

The technical scheme is as follows: a process for preparing the electrode able to generate oxidant by itself includes such steps as preparing Ti/Sn-SbO from Ti plate by sol-gel method_xBy electrodeposition on Ti/Sn-SbO_xSurface preparation of alpha-PbO₂Layer, then doping Mn into PbO by DC electrodeposition₂Electroplating ofTo alpha-PbO₂Layer formation of Ti/Sn-SbO_x/Mn-PbO₂And an electrode.

Preferably, the method comprises the following specific steps: step 1, firstly, ultrasonically cleaning a titanium sheet in acetone and absolute ethyl alcohol with the mass fraction of 20% for 20min, and then, placing 15-20wt.% of HCl to corrode for 10-20 min at the corrosion temperature of 85-90 ℃ to obtain a Ti substrate; step 2, coating SnCl on the surface of the Ti substrate prepared in the step 1₄·4H₂O and SbCl₃Alcohol solution of (1), in which the glycol is SnCl₄·4H₂O:SbCl₃The molar charge ratio is 30:9:1, then the electrode is dried at the temperature of 130-_xAn electrode; step 3, the Ti/Sn-SbO prepared in the step 2_xThe electrode is used as an anode, the Ti sheet is used as a cathode, and the electrode is placed in alkaline electrolyte for electrodeposition at the temperature of 40 ℃, wherein the alkaline electrolyte comprises the following components: NaOH =120-150 g/L, PbO =20-30 g/L, K₂CrO₄=5-15 g/L, the current density of electrodeposition is 2-4 mA/cm²The electrodeposition time is 50-60 min, the electrodeposition process is always stirred, deionized water is used for cleaning after the electrodeposition is finished, and the mixture is dried at room temperature; and 4, putting the electrode prepared in the step 3 as an anode and the Ti sheet as a cathode into 100mL of acid electroplating solution, wherein the electroplating solution comprises the following components: pb (NO)₃)₂＝0.45-0.55 mol/L、HNO₃0.1-0.12 mol/L, NaF-0.03-0.05 mol/L and Mn (NO)₃)₂=2-5 mM; adopting direct current electrodeposition with electrodeposition parameters of current density of 15-25 mA/cm²Controlling the temperature to be 55-60 ℃ and the deposition time to be 40-60min to obtain Ti/Sn-SbO_x/Mn-PbO₂And an electrode.

Further preferably, the method comprises the following specific steps: step 1, firstly, ultrasonically cleaning a titanium sheet in acetone and absolute ethyl alcohol with the mass fraction of 20% for 20min, and then putting 18wt.% of HCl to erode for 15 min, wherein the eroding temperature is 85 ℃, so as to obtain a Ti substrate; step 2, coating SnCl on the surface of the Ti substrate prepared in the step 1₄·4H₂O and SbCl₃Alcohol solution of (1), in which the glycol is SnCl₄·4H₂O:SbCl₃The molar charge ratio of the Ti/Sn-SbO is 30:9:1, the electrode is dried at 140 ℃ for 10 min and heated at 500 ℃ for 30 min, the coating, the drying and the heating are repeated for 10 rounds, and finally the annealing at 500 ℃ is carried out for 2 h to prepare the Ti/Sn-SbO_xAn electrode; step 3, the Ti/Sn-SbO prepared in the step 2_xThe electrode is used as an anode, the Ti sheet is used as a cathode, and the electrode is placed in alkaline electrolyte for electrodeposition at the temperature of 40 ℃, wherein the alkaline electrolyte comprises the following components: NaOH =140 g/L, PbO =22.32 g/L, K₂CrO₄=10 g/L, current density of electrodeposition 2 mA/cm²The electrodeposition time is 60min, the electrodeposition process is always stirred, deionized water is used for cleaning after the electrodeposition is finished, and the mixture is dried at room temperature; and 4, putting the electrode prepared in the step 3 as an anode and the Ti sheet as a cathode into 100mL of acid electroplating solution, wherein the electroplating solution comprises the following components: pb (NO)₃)₂＝0.5 mol/L、HNO₃0.1 mol/L, NaF-0.04 mol/L and Mn (NO)₃)₂=3 mM; adopting direct current electrodeposition with electrodeposition parameters of current density of 20 mA/cm²Controlling the temperature at 60 ℃ and the deposition time at 60min to obtain Ti/Sn-SbO_x/Mn-PbO₂And an electrode.

Ti/Sn-SbO prepared by the preparation method_x/Mn-PbO₂And an electrode.

The above Ti/Sn-SbO_x/Mn-PbO₂The application of the electrode in electrocatalytic degradation of anthracene.

The above Ti/Sn-SbO_x/Mn-PbO₂The application of the electrode in preparing a device for degrading anthracene through electrocatalysis.

The electrode of the device for degrading anthracene through electrocatalysis is the Ti/Sn-SbO_x/Mn-PbO₂And an electrode.

Has the advantages that: (1) the electrode of the invention is prepared by a sol-gel method to prepare Ti/Sn-SbO_xThen adding a certain amount of K into the alkaline electroplating solution₂CrO₄In the presence of Ti/Sn-SbO_xSurface electrodeposition of more uniform alpha-PbO₂Particles capable of increasing not only surface active coating and alpha-PbO₂The binding force of the middle layer can further improve the service life of the electrode. (2) The electrode of the present invention is prepared by using an acidic plating solutionAdding Mn (NO)₃)₂Electrodepositing a layer of Mn-doped PbO₂The active plating layer has good reaction activity, high catalytic efficiency and better corrosion resistance. (3) The electrode of the invention can generate 55 mu M MnO in the electrolyte₄ ^-，MnO₄ ^-The temperature is 25 ℃, and the current density is 20 mA/cm²The electrolyte is: 0.1 mol/L Na₂SO₄The pH of the solution is 6.9-7.5. (4) The invention relates to Ti/Sn-SbO capable of self-generating oxidant_x/Mn-PbO₂The method for degrading anthracene through electrode electrocatalysis has the advantages of simple electrode preparation method, convenient operation, simple process flow, high degradation rate of pollutant anthracene, good electrode corrosion resistance and degradation efficiency higher than that of common Ti/Sn-SbO_x/PbO₂The electrode is very high, the degradation rate of anthracene after 120min reaches 91.28%, and the degradation efficiency can still reach more than 70% under the condition of wider pH.

Drawings

FIG. 1 shows the synthesis of Ti/Sn-SbO in example 1_x/Mn-PbO₂Scanning electron micrographs of the electrodes;

FIG. 2 shows Ti/Sn-SbO synthesized in example 1_x/PbO₂Synthesis of Ti/Sn-SbO_x/Mn-PbO₂XRD pattern of the electrode;

FIG. 3 shows Ti/Sn-SbO in example 1_x/Mn-PbO₂XPS plot of Mn2p orbitals of the electrode;

FIG. 4 shows Ti/Sn-SbO in example 1_x/Mn-PbO₂XPS plot of Mn 3s orbitals of the electrode;

FIG. 5 shows Ti/Sn-SbO in example 1_x/PbO₂Electrode and Ti/Sn-SbO_x/Mn-PbO₂Comparing the degradation effect of the electrodes on anthracene;

FIG. 6 shows Ti/Sn-SbO at different pH values_x/Mn-PbO₂A graph of the change in concentration of electrode-degraded anthracene;

FIG. 7 shows Ti/Sn-SbO_x/Mn-PbO₂A graph of the absorbance change of the solution during electrode electrolysis;

FIG. 8 shows Ti/Sn-SbO_x/Mn-PbO₂MnO solution of electrode during electrolysis₄ ^-A graph of concentration change;

FIG. 9 shows Ti/Sn-SbO_x/PbO₂Electrode and Ti/Sn-SbO_x/Mn-PbO₂Comparative graph of the effect of degrading anthracene in ten electrode cycles.

Detailed Description

For a further understanding of the present invention, reference will now be made in detail to the following examples.

EXAMPLE 1 Synthesis of self-generating oxidant Ti/Sn-SbO_x/Mn-PbO₂Electrode and Ti/Sn-SbO_x/PbO₂Electrode and comparison of anthracene degrading efficiency of two electrodes

Two electrodes prepared in this example were Ti/Sn-SbO_x/Mn-PbO₂Electrode and Ti/Sn-SbO_x/PbO₂And an electrode.

For Ti/Sn-SbO_x/Mn-PbO₂The electrode is prepared by the following specific steps: step 1, firstly, ultrasonically cleaning a titanium sheet in acetone and absolute ethyl alcohol with the mass fraction of 20% for 20min, and then putting 18wt.% of HCl to erode for 15 min, wherein the eroding temperature is 85 ℃, so as to obtain a Ti substrate; step 2, coating SnCl on the surface of the Ti substrate prepared in the step 1₄·4H₂O and SbCl₃Alcohol solution of (1), in which the glycol is SnCl₄·4H₂O:SbCl₃The molar charge ratio of the Ti/Sn-SbO is 30:9:1, the electrode is dried at 140 ℃ for 10 min and heated at 500 ℃ for 30 min, the coating, the drying and the heating are repeated for 10 rounds, and finally the annealing at 500 ℃ is carried out for 2 h to prepare the Ti/Sn-SbO_xAn electrode; step 3, the Ti/Sn-SbO prepared in the step 2_xThe electrode is used as an anode, the Ti sheet is used as a cathode, and the electrode is placed in alkaline electrolyte for electrodeposition at the temperature of 40 ℃, wherein the alkaline electrolyte comprises the following components: NaOH =140 g/L, PbO =22.32 g/L, K₂CrO₄=10 g/L, current density of electrodeposition 2 mA/cm²The electrodeposition time is 60min, the electrodeposition process is always stirred, deionized water is used for cleaning after the electrodeposition is finished, and the mixture is dried at room temperature; and 4, putting the electrode prepared in the step 3 as an anode and the Ti sheet as a cathode into 100mL of acid electroplating solution, wherein the electroplating solution comprises the following components: pb (NO)₃)₂＝0.5 mol/L、HNO₃0.1 mol/L, NaF-0.04 mol/L and Mn (NO)₃)₂=3 mM; adopting direct current electrodeposition with electrodeposition parameters of current density of 20 mA/cm²Controlling the temperature at 60 ℃ and the deposition time at 60min to obtain Ti/Sn-SbO_x/Mn-PbO₂And an electrode.

The Ti/Sn-SbO prepared by the preparation method_x/Mn-PbO₂And an electrode.

As a comparison with modified electrodes, ordinary Ti/Sn-SbO_x/PbO₂The electrode is an unmodified electrode, and the preparation method comprises the following specific steps: step 1, firstly, ultrasonically cleaning a titanium sheet in acetone and absolute ethyl alcohol with the mass fraction of 20% for 20min, and then putting 18wt.% of HCl to erode for 15 min, wherein the eroding temperature is 85 ℃, so as to obtain a Ti substrate; step 2, coating SnCl on the surface of the Ti substrate prepared in the step 1₄·4H₂O and SbCl₃Alcohol solution of (1), in which the glycol is SnCl₄·4H₂O:SbCl₃The molar charge ratio of the Ti/Sn-SbO is 30:9:1, the electrode is dried at 140 ℃ for 10 min and heated at 500 ℃ for 30 min, the coating, the drying and the heating are repeated for 10 rounds, and finally the annealing at 500 ℃ is carried out for 2 h to prepare the Ti/Sn-SbO_xAn electrode; step 3, the Ti/Sn-SbO prepared in the step 2_xThe electrode is used as an anode, the Ti sheet is used as a cathode, and the electrode is placed in alkaline electrolyte for electrodeposition at the temperature of 40 ℃, wherein the alkaline electrolyte comprises the following components: NaOH =140 g/L, PbO =22.32 g/L, K₂CrO₄=10 g/L, current density of electrodeposition 2 mA/cm²The electrodeposition time is 60min, the electrodeposition process is always stirred, deionized water is used for cleaning after the electrodeposition is finished, and the mixture is dried at room temperature; and 4, putting the electrode prepared in the step 3 as an anode and the Ti sheet as a cathode into 100mL of acid electroplating solution, wherein the electroplating solution comprises the following components: pb (NO)₃)₂＝0.5 mol/L、HNO₃0.1 mol/L and 0.04 mol/L; adopting direct current electrodeposition with electrodeposition parameters of current density of 20 mA/cm²Controlling the temperature at 60 ℃ and the deposition time at 60min to obtain Ti/Sn-SbO_x/PbO₂And an electrode. The Ti/Sn-SbO prepared by the preparation method_x/PbO₂And an electrode.

Prepared by the preparation methodObtaining Ti/Sn-SbO_x/PbO₂And an electrode.

FIG. 1 is a schematic representation of the synthesis of Ti/Sn-SbO_x/Mn-PbO₂Electrode and Ti/Sn-SbO_x/Mn-PbO₂XRD pattern of the electrode, it can be seen that synthesized Ti/Sn-SbO_x/Mn-PbO₂Electrode and Ti/Sn-SbO_x/Mn-PbO₂The electrodes all have the characteristic peaks (the characteristic peaks are consistent with PDF # 76-0564) of (110), (101), (200), (211) and (301) when the electrodes are subjected to XRD diffraction, and the results show that PbO is formed on the surface of the synthesized electrode₂. FIG. 2, FIG. 3 and FIG. 4 are respectively Ti/Sn-SbO_x/Mn-PbO₂SEM electron micrograph, Mn2p orbital map and Mn 3s orbital map of the electrode. SEM scanning electron shows that the electrode has large reaction specific surface area. The Mn2p orbital diagram shows characteristic peaks at 641.90 eV and 653.89 eV, and the spectrogram shows that the valence of Mn is +4, and MnO is formed₂The Mn 3s orbital spectrogram shows that the binding energy difference between two peaks is 4.8 eV, and the spectrogram further proves that Mn is MnO₂Exist in the form of (1).

Ti/Sn-SbO_x/PbO₂Electrode and Ti/Sn-SbO_x/Mn-PbO₂The degradation effect of the electrode on anthracene is compared respectively: the Ti/Sn-SbO synthesized above is mixed_x/Mn-PbO₂Electrode and Ti/Sn-SbO_x/PbO₂The electrodes are respectively used as anodes, the Ti electrode is used as a cathode, the solution containing anthracene and Tween 80 is introduced into an electrochemical reactor, a constant current mode of a direct current power supply is adopted, the temperature is 25 ℃, and the current density is 20 mA/cm²The electrolyte is: 1 mg/L anthracene +5 g/L Tween 80+ 0.1 mol/L Na₂SO₄The pH of the solution is 6.9-7.5.

FIG. 5 shows the synthesis of Ti/Sn-SbO under the same conditions_x/Mn-PbO₂Electrodes and Ti/Sn-SbO_x/Mn-PbO₂The degradation effect of the electrodes on anthracene is compared, and Ti/Sn-SbO in the same system can be observed_x/ Mn-PbO₂Electrodes and Ti/Sn-SbO_x/ PbO₂The degradation rates of the electrode to anthracene are respectively as follows: 91.28% and 40.06%. This indicates that the composition is comparable to Ti/Sn-SbO_x/PbO₂Electrode, Ti/Sn-SbO_x/Mn-PbO₂The electrocatalytic performance of the electrode is greatly improvedHigh.

Example 2

Ti/Sn-SbO capable of self-generating oxidant under different pH conditions_x/Mn-PbO₂Concentration change of electrode-degraded anthracene

150 mL of anthracene solution to be treated (concentration 1 mg/L) was adjusted to

pH

3, 5, 7, 9, 11 with sulfuric acid or sodium hydroxide and introduced into an electrochemical reactor as Ti/Sn-SbO_x/Mn-PbO₂The electrode is an anode, the Ti sheet is a cathode, and a constant current mode of a direct current power supply is adopted, the temperature is 25 ℃, and the current density is 20 mA/cm²The reaction time is 120min, and the degradation liquid is as follows: 1 mg/L anthracene +5 g/L Tween 80+ 0.1 mol/L Na₂SO₄. FIG. 6 is a graph of Ti/Sn-SbO self-generated oxidants at different pH_x/Mn-PbO₂Compared with the degradation effect of the electrode pair anthracene, the degradation rate of the electrode pair anthracene is maintained to be more than 70% in 120min under the condition that the pH is 3-11.

Example 3

Ti/Sn-SbO capable of self-generating oxidant_x/Mn-PbO₂MnO in electrolyte solution when the electrode is anode₄ ^-Change in concentration

150 mL of electrolyte solution was introduced into the electrochemical reactor to self-generate the oxidant Ti/Sn-SbO_x/Mn-PbO₂The electrode is an anode, the Ti sheet is a cathode, and a constant current mode of a direct current power supply is adopted, the temperature is 25 ℃, and the current density is 20 mA/cm²The reaction time is 120min, and the electrolyte is: 0.1 mol/L Na₂SO₄. FIG. 7 is a graph of Ti/Sn-SbO self-generated oxidants at different times_x/Mn-PbO₂Absorbance of the electrode electrolyte solution. As can be seen from the figure, MnO was present at 525nm in the electrolyte solution₄ ^-And then MnO is carried out on the electrolyte solution at 525nm₄ ^-And (4) quantifying the concentration. FIG. 8 is a graph of Ti/Sn-SbO self-generated oxidants at different times_x/Mn-PbO₂MnO in electrode electrolyte solution₄ ^-Graph of concentration change. As can be seen, Ti/Sn-SbO_x/Mn-PbO₂High concentration MnO can be generated when the electrode is an anode₄ ^-To oxidize the organic contaminants.

Example 4

Degradation effect of different recycling times on pollutants

150 mL of anthracene solution to be treated (concentration 1 mg/L) was introduced into an electrochemical reactor to self-produce Ti/Sn-SbO as an oxidant_x/Mn-PbO₂The electrode is an anode, the Ti sheet is a cathode, and a constant current mode of a direct current power supply is adopted, the temperature is 25 ℃, and the current density is 20 mA/cm²The reaction time is 120min, and the degradation liquid is as follows: 1 mg/L anthracene +5 g/L Tween 80+ 0.1 mol/L Na₂SO₄. FIG. 9 is Ti/Sn-SbO which is self-produced oxidant after 10 cycles of degradation under the above conditions_x/Mn-PbO₂Electrodes and Ti/Sn-SbO_x/PbO₂The degradation effect of the electrode on anthracene is compared with that of the electrode, and Ti/Sn-SbO can be observed after 10 times of cyclic degradation_x/Mn-PbO₂The degradation rate of anthracene of the electrode pair in 120min reaches 53.65 percent, and Ti/Sn-SbO_x/PbO₂The degradation rate of anthracene in 120min is only 24.70%. This gives the comparison with Ti/Sn-SbO during the first 10 cycles of degradation_x/PbO₂Electrode, Ti/Sn-SbO_x/Mn-PbO₂The electrode has longer service life and stability and better practical application value.

Claims

1. A preparation method of an electrode capable of self-generating an oxidant is characterized by comprising the following specific steps: step 1, firstly, ultrasonically cleaning a titanium sheet in acetone and absolute ethyl alcohol with the mass fraction of 20% for 20min, and then, placing 15-20wt.% of HCl to corrode for 10-20 min at the corrosion temperature of 85-90 ℃ to obtain a Ti substrate; step 2, coating SnCl on the surface of the Ti substrate prepared in the step 1₄·4H₂O and SbCl₃Alcohol solution of (1), in which the glycol is SnCl₄·4H₂O:SbCl₃The molar charge ratio is 30:9:1, then the electrode is dried at the temperature of 130-_xAn electrode; step 3, the Ti/Sn-SbO prepared in the step 2_xThe electrode is used as an anode, the Ti sheet is used as a cathode, and the anode and the cathode are put into alkaline electrolyte for electrodeposition at the temperature of 40 ℃, wherein the alkaline electrolyteComprises the following components: NaOH =120-150 g/L, PbO =20-30 g/L, K₂CrO₄=5-15 g/L, the current density of electrodeposition is 2-4 mA/cm²The electrodeposition time is 50-60 min, the electrodeposition process is always stirred, deionized water is used for cleaning after the electrodeposition is finished, and the mixture is dried at room temperature; and 4, putting the electrode prepared in the step 3 as an anode and the Ti sheet as a cathode into 100mL of acid electroplating solution, wherein the electroplating solution comprises the following components: pb (NO)₃)₂＝0.45-0.55 mol/L、HNO₃0.1-0.12 mol/L, NaF-0.03-0.05 mol/L and Mn (NO)₃)₂=2-5 mM; adopting direct current electrodeposition with electrodeposition parameters of current density of 15-25 mA/cm²Controlling the temperature to be 55-60 ℃ and the deposition time to be 40-60min to obtain Ti/Sn-SbO_x/Mn-PbO₂And an electrode.

2. The method for preparing the electrode capable of generating the oxidizing agent by oneself according to claim 1, characterized by comprising the steps of: step 1, firstly, ultrasonically cleaning a titanium sheet in acetone and absolute ethyl alcohol with the mass fraction of 20% for 20min, and then putting 18wt.% of HCl to erode for 15 min, wherein the eroding temperature is 85 ℃, so as to obtain a Ti substrate; step 2, coating SnCl on the surface of the Ti substrate prepared in the step 1₄·4H₂O and SbCl₃Alcohol solution of (1), in which the glycol is SnCl₄·4H₂O:SbCl₃The molar charge ratio of the Ti/Sn-SbO is 30:9:1, the electrode is dried at 140 ℃ for 10 min and heated at 500 ℃ for 30 min, the coating, the drying and the heating are repeated for 10 rounds, and finally the annealing at 500 ℃ is carried out for 2 h to prepare the Ti/Sn-SbO_xAn electrode; step 3, the Ti/Sn-SbO prepared in the step 2_xThe electrode is used as an anode, the Ti sheet is used as a cathode, and the electrode is placed in alkaline electrolyte for electrodeposition at the temperature of 40 ℃, wherein the alkaline electrolyte comprises the following components: NaOH =140 g/L, PbO =22.32 g/L, K₂CrO₄=10 g/L, current density of electrodeposition 2 mA/cm²The electrodeposition time is 60min, the electrodeposition process is always stirred, deionized water is used for cleaning after the electrodeposition is finished, and the mixture is dried at room temperature; and 4, putting the electrode prepared in the step 3 as an anode and the Ti sheet as a cathode into 100mL of acid electroplating solution, wherein the electroplating solution comprises the following components: pb (NO)₃)₂＝0.5 mol/L、HNO₃0.1 mol/L, NaF-0.04 mol/L and Mn (NO)₃)₂=3 mM; adopting direct current electrodeposition with electrodeposition parameters of current density of 20 mA/cm²Controlling the temperature at 60 ℃ and the deposition time at 60min to obtain Ti/Sn-SbO_x/Mn-PbO₂And an electrode.

3. Ti/Sn-SbO produced by the production method according to claim 1 or 2_x/Mn-PbO₂And an electrode.

4. Ti/Sn-SbO as defined in claim 3_x/Mn-PbO₂The application of the electrode in electrocatalytic degradation of anthracene.

5. Ti/Sn-SbO as defined in claim 3_x/Mn-PbO₂The application of the electrode in preparing a device for degrading anthracene through electrocatalysis.

6. An anthracene device for electrocatalytic degradation, wherein the electrode is Ti/Sn-SbO as defined in claim 3_x/Mn-PbO₂And an electrode.