A high-oxygen-evolution-potential catalytic anode and a preparation method and application thereof

Abstract

The application provides a high-oxygen-evolution-potential catalytic anode and a preparation method and application thereof. The preparation of the high-oxygen-evolution-potential catalytic anode specifically comprises the following steps: polishing and etching a conductive substrate, sequentially placing the treated conductive substrate and dry conductive particles into a graphite mold, sintering, and taking out and electro-oxidizing to obtain the high-oxygen-evolution-potential catalytic anode. The high-oxygen-evolution-potential catalytic anode is used as an anode material to form a "dual-energy oxidation system" of pulse electro-catalysis coupled with advanced oxidation together with a cathode, a pulse power source and a catalyst of ozone or persulfate. When treating wastewater, the high-oxygen-evolution-potential catalytic anode is pulsed powered, and then the high-oxygen-evolution-potential catalytic anode is pulsed powered off, so that the high-efficiency degradation of refractory organic matter in wastewater can be realized. The application can effectively solve the problems of high production cost of electrodes, high energy consumption of system operation and high technical requirements of traditional electrochemical oxidation method. The overall production and degradation process has the characteristics of low cost, low energy consumption, high degradation efficiency and high pollutant removal rate.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of wastewater resource utilization, and particularly relates to a catalytic anode with high oxygen evolution potential and a preparation method and application thereof. BACKGROUND

[0002] In recent years, the state has vigorously promoted the construction of ecological civilization, and the water ecological environment in China has been improving. The treatment technology of domestic sewage and easily degradable industrial wastewater has been widely used. Coal chemical industry, petroleum, power, papermaking, printing and dyeing industries will produce high-concentration salt-containing wastewater. The wastewater from these industries has large output and complex pollutant composition. In addition to organic pollutants such as polycyclic aromatic hydrocarbons, phenols, polychlorinated biphenyls, alkanes and lipids, it also contains a large amount of soluble inorganic salts such as Cl - , SO4 2- , Ca 2+ , etc. The water quality is complex, the pH changes greatly, the biodegradability is poor, and the toxicity is high. If the high-salt water is not properly treated, it will cause the water quality mineralization degree of rivers and lakes to increase, soil salinization, and harm to the water ecological environment. At present, it is difficult to treat such high-salt wastewater by traditional water treatment technology, and the cost is high, which is difficult for enterprises to bear. Therefore, the treatment and disposal of refractory high-salt wastewater has become the most difficult and realistic problem in the field of water environment governance in China, and has received high attention. Wastewater resourceization and energy utilization are the development direction of current water treatment technology, and wastewater is just a misplaced resource. The heavy metals and inorganic salts contained in wastewater can be recovered or oxidized to become valuable resources, and renewable water can be obtained at the same time. The chemical energy contained in wastewater can be effectively converted into electrical energy through new wastewater treatment processes and technologies, and the wastewater resourceization provides a solution for the disposal of high-salt refractory wastewater. At present, wastewater resourceization in China is still in its infancy, and the development is not sufficient, and the technical level is not high. Under the background of "double carbon", wastewater resourceization urgently needs the support of new materials, new technologies and new processes.

[0003] In the prior art, the treatment of high-salt and hard-degradable wastewater generally adopts (1) biological method, (2) physical method and (3) chemical method. Among them, (1) biological method is the most mature wastewater treatment technology at present, which is economic and efficient, but for the wastewater with poor biodegradability of BOD / COD less than 0.3, the treatment effect of biological method is poor. In addition, because the inorganic salt in high-salt water can inhibit the growth of microorganisms in the biological treatment system, it is difficult to effectively treat high-salt wastewater by using traditional activated sludge method. Compared with aerobic biological treatment, anaerobic biological treatment can simultaneously achieve the removal of organic matter and salt. However, in the anaerobic environment, for example, sulfate will be converted to sulfide by sulfate-reducing bacteria (SRB). Compared with sulfate, sulfide is more toxic and corrosive, which can inhibit the activity of methanogens in the system, and even cause the system to collapse in severe cases. Moreover, the discharge of wastewater containing sulfide can cause sulfur enrichment in water bodies, causing ecological and health hazards. (2) Coagulation and adsorption method is to transfer pollutants from water phase to solid phase, and the real removal of pollutants has not been achieved, and the subsequent solid waste treatment, adsorbent regeneration and secondary pollution problems need to be solved. (3) Advanced oxidation technology is widely used in wastewater treatment for pre-oxidation and advanced treatment because it can achieve efficient degradation of organic matter in water. It can produce free radicals with strong oxidizing ability to degrade pollutants into small molecular substances or directly mineralize into CO2. Common advanced oxidation methods include ① Fenton, ② photocatalytic method, ③ ozone catalytic oxidation method and ④ electrochemical oxidation method. ① Fenton method uses catalyst and hydrogen peroxide to produce hydroxyl radicals to degrade organic matter, but it faces the problems of secondary pollution of iron sludge, catalyst recovery and large use of hydrogen peroxide. ② Photocatalytic method has been widely used in industry, and the most typical photocatalyst is TiO2. With the help of absorbed visible light or ultraviolet light energy, the electrons of the catalyst jump, producing electron-hole pairs, and then a large number of hydroxyl radicals with strong oxidizing properties are produced to degrade organic matter in water. However, in wastewater treatment, photocatalysis needs to solve the problems of light transmittance and catalyst recovery. ③ Ozone can degrade pollutants through direct or indirect reaction, but there is a problem of low ozone utilization rate in catalytic ozonation wastewater treatment, resulting in high water treatment cost.

[0004] ④ Electrochemical oxidation method is to degrade organic pollutants through electrode reaction under the action of external electric field, which can directly degrade pollutants or indirectly degrade organic pollutants by using strong oxidizing free radicals generated by electrode, and is suitable for treatment of high-salt wastewater. The required equipment is simple, occupies small area, and has no secondary pollution, so it is a wastewater treatment advanced oxidation technology with wide application prospect. It is applied in the fields of papermaking wastewater, printing and dyeing wastewater, chemical wastewater, tanning wastewater, petroleum wastewater, coking wastewater, landfill leachate, membrane concentrate and the like. However, electrochemical oxidation method for wastewater treatment also faces many problems. First of all, the electrode material, although the active electrode is mature in technology and low in preparation cost, the oxygen evolution reaction is serious during electrolysis, the removal rate of organic matter is slow, and the operation cost is high. Although the non-active electrode is a coating electrode, such as SnO2 electrode, PbO2 electrode and Ti4O7 electrode, the oxygen evolution overpotential is greatly improved, but the electrode preparation cost is high, and the coating is unstable during electrolysis, which is easy to fall off, causing the electrode to fail, and the operation cost is increased. In addition, in the electrocatalytic oxidation system, the anode interface is a strong oxidizing acidic environment, which has high requirements for the stability of the electrode itself. For example, PbO2 electrode is easy to cause Pb 4+ leakage, resulting in secondary pollution, which limits its application in water treatment field. Further, in addition to the limitation of electrode material, the operation and optimization of electrocatalytic oxidation system are also the key to energy saving and consumption reduction of electrochemical oxidation technology. The traditional electrocatalytic oxidation system adopts direct current power supply mode, and the electrode continuously reacts. The polarization phenomenon is easy to occur in the electrode interface due to the concentration of pollutants or ions, which causes the rate of electrode side reaction to increase. At the same time, a large amount of heat energy is generated and consumed during the operation of the electrocatalytic oxidation system, which does not meet the current energy saving and carbon reduction demand. As can be seen, although electrochemical oxidation method can degrade organic matter in high-salt environment, and even can treat some toxic pollutants that cannot be degraded by biological method, the performance of the current electro-oxidation anode material and the operation and optimization method of the electrocatalytic oxidation system cannot meet the industrial demand. The high cost of electrode, high operation energy consumption and high technical requirements are contrary to the development concept of carbon reduction and emission reduction in wastewater treatment industry, which limits the application of electrochemical oxidation method in wastewater treatment field.

[0005] In summary, optimizing electrode material and electrocatalytic oxidation system, and reducing investment and operation cost are the key to the large-scale application of electrochemical oxidation method in wastewater treatment field. SUMMARY

[0006] The purpose of the present application is to provide a preparation method of a catalytic anode with high oxygen evolution potential, which specifically comprises the following steps:

[0007] S1 takes conductive particles and dries them; takes a conductive substrate, first polishes it, and then immerses it in an alkaline reagent and an acidic reagent in sequence for treatment;

[0008] S2 In a graphite mold, place the treated conductive substrate, and then evenly distribute dry conductive particles on the surface of the conductive substrate, and sinter.

[0009] S3 Place the sintered material in a sulfuric acid solution for electro-oxidation, and obtain a catalytic anode with high oxygen evolution potential.

[0010] In a preferred embodiment, in step S1, the shape of the conductive particles includes but is not limited to one or more of spherical particles, flaky particles, porous particles, and fibrous particles, preferably the shape of the conductive particles is spherical particles.

[0011] In a preferred embodiment, in step S1, the conductive particles include but are not limited to one or more of graphdiyne particles, titanium suboxide particles, tin dioxide particles, and lead dioxide particles.

[0012] In a preferred embodiment, in step S1, the particle size of the conductive particles is 500-1000 mesh.

[0013] In a preferred embodiment, in step S1, the resistivity of the conductive particles is 0.05-0.5 Ω·cm.

[0014] In a preferred embodiment, in step S1, the drying method can use conventional methods mastered by those skilled in the art to achieve the purpose of drying the conductive particles, such as drying in an oven at 60-100°C for 6-24 hours.

[0015] In a preferred embodiment, in step S1, the conductive substrate material includes but is not limited to one or more of titanium, aluminum, tungsten.

[0016] In a preferred embodiment, in step S1, the thickness of the conductive substrate is 0.5-2 mm.

[0017] In a preferred embodiment, in step S1, the method of roughening the conductive substrate includes using sandpaper to polish, preferably the grit of the sandpaper is 400-100 mesh, more preferably the roughness of the polished conductive substrate is 50-100 nm.

[0018] In a preferred embodiment, in step S1, the alkaline reagent includes a sodium hydroxide solution, preferably the mass concentration of the sodium hydroxide solution is 20-50%, and the alkaline reagent soaking treatment conditions are: soaking temperature 60-90°C, soaking time 10-30 min.

[0019] In a preferred embodiment, in step S1, the acidic reagent comprises oxalic acid solution, preferably, the oxalic acid solution has a weight percentage of 5-15wt%, and the acidic reagent soaking treatment condition is: soaking temperature of 90-98℃, soaking time of 30-120min.

[0020] In a preferred embodiment, in step S1, after the acidic reagent soaking treatment, a rinsing step to remove the residual reagent on the surface and a drying step are further included, preferably, the rinsing is performed by using ultrapure water, and the drying method can be a conventional method mastered by those skilled in the art.

[0021] In a preferred embodiment, in step S2, the distribution density of the conductive particles on the surface of the conductive substrate is 0.02-0.06g / cm 2 .

[0022] In a preferred embodiment, in step S2, the sintering temperature is 600-1000℃, the sintering pressure is 40-50MPa, and the sintering time is 2-5min.

[0023] In a preferred embodiment, in step S2, after the sintering, a rinsing step to remove the surface impurities and a drying step are further included, preferably, the rinsing is performed by using deionized water, and the drying method can be a conventional method mastered by those skilled in the art.

[0024] In a preferred embodiment, in step S3, the sulfuric acid solution has a concentration of 0.5-2M, the voltage for the electro-oxidation is 4-6V, and the electrolysis time is 1-3 hours.

[0025] In a preferred embodiment, in step S3, after the electro-oxidation, a rinsing step to remove the surface electrolyte and a drying step are further included, preferably, the rinsing is performed by using deionized water, and the drying method can be a conventional method mastered by those skilled in the art.

[0026] Another object of the present application is to provide a high-oxygen-evolution-potential catalytic anode prepared by any of the above methods.

[0027] Another object of the present application is to provide a dual-energy oxidation system for pulse electro-catalytic coupling advanced oxidation, specifically, the dual-energy oxidation system adopts a circulating flow type single-tank electrolytic cell, which is internally provided with an anode, a cathode and a catalyst filled between the electrodes, and the anode and the cathode are connected by a pulse power supply.

[0028] In the dual-energy oxidation system, the anode material is a high-oxygen-evolution-potential catalytic anode prepared by any of the above methods.

[0029] The cathode material is one or more of titanium, graphite and titanium suboxide.

[0030] The catalyst comprises one or both of ozone or persulfate catalysts; preferably, the catalyst is a manganese oxide catalyst.

[0031] In a preferred embodiment, the electrode spacing is 1-3 cm.

[0032] Another object of the present application is to provide a method for using the above-mentioned dual-energy oxidation system for pulse electro-catalytic coupling advanced oxidation, which specifically comprises the following steps:

[0033] The sulfate concentrate liquid wastewater is pumped into the electrolytic cell and circulated, and after the circulation is stabilized, the pulse power supply is turned on to perform electro-catalytic degradation to generate ozone or persulfate, and then the power supply is turned off, the catalyst in the electrolytic cell catalyzes the ozone and persulfate to further degrade through advanced oxidation reaction, and the power-on and power-off operations are repeated, so that the high-salt wastewater can be efficiently degraded.

[0034] In a preferred embodiment, when the power supply is turned on, the pulse current is 2-6 A, the pulse voltage is 4-6 V, and the power supply time is 10-300 s.

[0035] In a preferred embodiment, the power-off time is 10-300 s.

[0036] In a preferred embodiment, after the dual-energy oxidation system is used to alternately perform power-on and power-off operations for 10 hours, the COD removal rate in the aniline wastewater can reach 97.4%.

[0037] Another object of the present application is to provide the above-mentioned dual-energy oxidation system for pulse electro-catalytic coupling advanced oxidation for use in degrading high-concentration salt-containing wastewater.

[0038] In a preferred embodiment, the high-concentration salt-containing wastewater is derived from coal chemical industry, petroleum industry, power industry, papermaking industry, printing and dyeing industry, etc.

[0039] Compared with the prior art, the technical scheme of the present application has the following advantages:

[0040] 1. The present application aims to solve the problem of high investment cost and operation cost of traditional electro-catalytic oxidation systems, and proposes to use conductive particles uniformly distributed on the surface of a conductive substrate to prepare a high-oxygen evolution site catalytic anode material through electro-oxidation reaction, and to build a dual-energy oxidation system for pulse electro-catalytic coupling advanced oxidation, so as to realize efficient and low-consumption treatment of high-salt and difficult-to-degrade wastewater and realize the resource utilization of wastewater.

[0041] 2, The dual-energy oxidation system provided by the application can carry out electrocatalysis process to degrade organic matters when being powered, and can generate ozone or persulfate by using water or ions such as sulfate in water due to the high oxygen evolution potential of the electrode; the manganese oxide catalyst moving in the tank plays a role to catalyze the ozone and persulfate to further degrade the organic matters during the intermittent period when the power is off. Meanwhile, the heat generated during the electrolysis process can be used to consume the heat during the indirect period, reduce the influence on the stability of the electrode, and promote the mass transfer efficiency during the advanced oxidation process in the intermittent period, thereby accelerating the degradation of pollutants.

[0042] 3, The method for preparing the anode material with high oxygen evolution potential provided by the application has low cost, simple process, low energy consumption, short sintering time, and can greatly improve the production efficiency of the anode material. The dual-energy oxidation system of pulse electrocatalysis coupled with advanced oxidation is constructed by using the obtained anode with high oxygen evolution potential, the heat energy and intermediate products generated during the electrocatalysis process can be fully utilized, the efficient treatment of high-salt refractory wastewater is realized, and the technical problem of high operation energy consumption during the degradation process is effectively solved. BRIEF DESCRIPTION OF DRAWINGS

[0043] These and / or other aspects and advantages of the present application will become more apparent and more readily appreciated from the following detailed description of the exemplary embodiments of the present application, taken in conjunction with the accompanying drawings in which:

[0044] Figure 1 The oxygen evolution potentials of the anodes prepared for the present application example 1 and the conventional commercially available electrodes are compared;

[0045] Figure 2 The oxygen evolution potentials of the anodes prepared for the present application examples 2-6 are compared;

[0046] Figure 3 The structure schematic diagram of the dual-energy oxidation system of pulse electrocatalysis coupled with advanced oxidation prepared for the present application effect example 2 is shown.

[0047] Explanation of main reference signs:

[0048] 1 is a pulse power supply; 2 is an electrocatalytic anode; 3 is a cathode, and 4 is an embedded catalyst particle. DETAILED DESCRIPTION

[0049] In order to make the skilled in the art better understand the present application, the present application will be further described in detail below in combination with the drawings and specific embodiments, but it should be understood that the protection scope of the present application is not limited by the specific embodiments.

[0050] The embodiment of the application provides a catalytic anode with high oxygen evolution potential and a preparation method and application thereof, solves the problems of high electrode production cost, high system operation energy consumption and high technical requirement in the prior art, and obtains the catalytic anode with high oxygen evolution potential by a simple, rapid and low-energy-consumption method. The double-energy oxidation system of pulse electro-catalysis coupled with advanced oxidation is prepared, and the double-energy oxidation system can efficiently and low-energy-consumptionly treat high-salt refractory wastewater.

[0051] The technical scheme of the application is described in detail below through specific embodiments:

[0052] If not specifically indicated, the technical means used in the application are conventional means familiar to those skilled in the art, and various raw materials, reagents, instruments and equipment used in the application can be purchased from the market or prepared by the prior art. The reagents used in the application are analytical pure unless otherwise specified. The conductive particles used in the embodiments of the application are all spherical particles.

[0053] Embodiment 1

[0054] The embodiment provides a preparation method of an electro-catalytic particle anode, and specifically includes the following steps:

[0055] S1. 0.1 g of spherical graphiteyne particles with a particle size of 500 mesh and an electrical resistivity of 0.5 Ω·cm are weighed and placed in a 60℃ oven for drying for 24 hours;

[0056] S2. A titanium plate with a diameter of 2 cm and a thickness of 0.5 mm is polished with 400 mesh and 800 mesh sandpaper to a roughness of 100 nm in turn and washed with deionized water; the titanium plate is immersed in a 40% NaOH solution for 30 min at a water temperature of 80℃, and then washed with deionized water; then the titanium plate is immersed in a 10wt% oxalic acid solution for 2 h at a water temperature of 95℃, and then washed with deionized water and stored in ethanol;

[0057] S3. A graphite mold is placed on the workbench, and a graphite paper with a diameter of 2 cm is placed in the concave cavity of the mold; then the circular titanium plate treated in step S2 is taken out, dried and placed on the graphite paper in the concave cavity of the mold;

[0058] The graphiteyne particles dried in step S1 are evenly distributed on the surface of the titanium plate in the concave cavity of the mold; then a graphite paper with a diameter of 2 cm is placed above the conductive particles, and finally a graphite boss is placed;

[0059] The graphite mold containing the conductive substrate and the conductive particles is placed in a vacuum hot-pressing sintering furnace for sintering, the sintering temperature is 1000℃, the pressure is 50 MPa, and the sintering time is 3 min; after sintering, the sample is taken out and washed with deionized water;

[0060] S4: The electrode obtained in step S3 is placed in a 2M sulfuric acid solution as an anode, titanium as a cathode, and a voltage of 6V is applied for 2 hours of electrolysis; after electrolysis, the electrode is washed with deionized water and dried in a 60℃ oven for 5 hours to obtain a graphyne anode material.

[0061] The oxygen evolution potential of the graphyne anode material prepared in Example 1 is tested, and the specific steps include:

[0062] The oxygen evolution potential of the electrode is determined by using a Chenhua electrochemical workstation, with a graphyne electrode as an anode, a Pt electrode as a cathode, an Ag / AgCl reference electrode, a sodium sulfate solution as an electrolyte, a scanning range of 0-2.8V (vs Ag / AgCl), and a scanning speed of 100mV / s, and the results are shown in Figure 1 .

[0063] As can be seen from Figure 1 , compared with a traditional electrocatalytic anode, the graphyne electrode (Graphd iyne) prepared in Example 1 has the highest oxygen evolution potential of 2.4V (vs Ag / AgCl).

[0064] Example 2

[0065] The difference from Example 1 is only that the sintering temperature in step S3 is 900℃, and the rest of the raw materials and methods are completely consistent with Example 1.

[0066] Example 3

[0067] The difference from Example 1 is only that the sintering temperature in step S3 is 800℃, and the rest of the raw materials and methods are completely consistent with Example 1.

[0068] Example 4

[0069] The difference from Example 1 is only that the conductive particles in step S1 are titanium suboxide particles, and the rest of the raw materials and methods are completely consistent with Example 1.

[0070] Example 5

[0071] The difference from Example 1 is only that the conductive particles in step S1 are lead dioxide particles, and the rest of the raw materials and methods are completely consistent with Example 1.

[0072] Example 6

[0073] The difference from Example 1 is only that the conductive particles in step S1 are a mixture of graphyne particles and titanium suboxide particles in a mass ratio of 1:1, and the rest of the raw materials and methods are completely consistent with Example 1.

[0074] The test method of Example 1 was used to test the oxygen evolution potential of the anode material prepared in Examples 2-6, and the results are shown in Table 1. Figure 2

[0075] Comparative Example 1

[0076] The difference between Example 1 and Comparative Example 1 is that the resistivity of the graphdiyne particles used in Comparative Example 1 is 1.0 Ω·cm, and the rest of the raw materials and methods are exactly the same as Example 1. After electrochemical testing, the conductivity of the electrode material obtained is not as good as Example 1.

[0077] Comparative Example 2

[0078] The difference between Example 4 and Comparative Example 2 is that the titanium suboxide particles used in Comparative Example 2 are 300 mesh and 1500 mesh, and the rest of the raw materials and methods are exactly the same as Example 4. The results show that the 300 mesh conductive particles cannot completely cover the surface of the substrate, and the 1500 mesh conductive particles are prone to fall off from the surface of the electrode.

[0079] Comparative Example 3

[0080] The difference between Example 5 and Comparative Example 3 is that the voltage for step S4 electrooxidation in Comparative Example 3 is 3V or 8V, and the rest of the raw materials and methods are exactly the same as Example 5. The results show that a voltage of 3V is too low to oxidize the electrode, and a voltage of 8V is too high, resulting in a large current that can corrode the surface of the electrode.

[0081] Example 1

[0082] An electrolysis device as shown in Figure 3 was used, with the graphdiyne electrode material prepared in Example 1 as the anode, an equal-area titanium plate as the cathode, an electrode spacing of 2 cm, and 5 g of mixed-valence manganese oxide (MnOx) catalyst particles filled between the electrodes, to obtain a "dual-energy oxidation system" for pulse electrocatalytic coupling advanced oxidation. The preparation method of the mixed-valence manganese oxide (MnOx) catalyst is as follows: 1 g of MnSO4·H2O is dissolved in 50 mL of a mixed solvent of deionized water and ethanol, and 40 mL of an aqueous solution containing 2.5 g of KMnO4 is quickly added. Then, the mixture is stirred thoroughly for a few minutes, then transferred to a 150 mL polytetrafluoroethylene-lined stainless steel autoclave, heated to 140°C, and kept for 2 hours. The product is washed with deionized water and ethanol, then dried in air at 60°C for 12 hours to obtain nanostructured MnOx catalyst particles.

[0083] The degradation effect of the "dual-energy oxidation system" obtained was tested, and the specific steps are as follows:

[0084] ​First, aniline wastewater was pumped into the device by a peristaltic pump, and circulated at a flow rate of 200 mL / min; after the circulation was stable, the pulse power was turned on, the "dual-energy oxidation system" was started, the current was 4 A, the voltage was 5 V, the pulse power-on time was 30 s, and the power-off time was 30 s, to degrade alternately. 10 mL of sample was taken every two hours for analysis of COD change, and the running time was 10 hours.

[0085] After 10 hours of experiment, the COD of aniline wastewater was reduced from 5000 mg / L to 130 mg / L, with a removal rate of 97.4%.

[0086] Effect Example 2

[0087] The difference from Effect Example 1 is only that the pulse power-on time is 60 s and the power-off time is 60 s. The rest of the raw materials and methods are exactly the same as Effect Example 2.

[0088] After 10 hours of experiment, the COD of aniline wastewater was reduced from 5000 mg / L to 300 mg / L, with a removal rate of 94%.

[0089] Effect Example 3

[0090] The difference from Effect Example 1 is only that the pulse power-on time is 10 s and the power-off time is 10 s.

[0091] After 10 hours of experiment, the COD of aniline wastewater was reduced from 5000 mg / L to 2000 mg / L, with a removal rate of 60%.

[0092] Effect Example 4

[0093] The difference from Effect Example 1 is only that the pulse power-on time is 300 s and the power-off time is 300 s.

[0094] After 10 hours of experiment, the COD of aniline wastewater was reduced from 5000 mg / L to 1000 mg / L, with a removal rate of 80%.

[0095] Effect Example 5

[0096] The difference from Effect Example 1 is only that the graphite yne electrode material prepared in Comparative Example 1 is used as the anode.

[0097] After 10 hours of experiment, the COD of aniline wastewater was reduced from 5000 mg / L to 3000 mg / L, with a removal rate of 40%.

[0098] The foregoing description of specific exemplary embodiments of the application has been presented for the purposes of illustration and description. It is not intended to be exhaustive or to limit the application to the precise forms disclosed, and obviously many modifications and variations are possible in light of the above teaching. It is intended that the scope of the application be limited not with this detailed description, but rather by the claims appended hereto.

Claims

1. A method for producing a catalytic anode of high oxygen evolution potential, characterized by, It comprises the following steps: S1: take conductive particles, dry; take conductive substrate, first polish rough, then sequentially soak in alkaline reagent and acidic reagent for treatment; S2: place the treated conductive substrate in a graphite mold, then evenly distribute the dry conductive particles on the surface of the conductive substrate, and sinter; S3: place the sintered material in a sulfuric acid solution for electro-oxidation, and obtain a catalytic anode with high oxygen evolution potential; In step S1, the particle size of the conductive particles is 500-1000 mesh; the resistivity of the conductive particles is 0.05-0.5 Ω·cm; In step S2, the sintering temperature is 600-1000℃, the sintering pressure is 40-50MPa, and the sintering time is 2-5 min; In step S3, the voltage for electro-oxidation is 4-6V, and the electrolysis time is 1-3 hours.

2. The preparation method of the catalytic anode with high oxygen evolution potential according to claim 1, wherein in step S1, the conductive particles comprise one or more of graphdiyne particles, titanium suboxide particles, tin dioxide particles, and lead dioxide particles.

3. The preparation method of the catalytic anode with high oxygen evolution potential according to claim 1, wherein in step S1, the conductive substrate material comprises one or more of titanium, aluminum, and tungsten; and the thickness of the conductive substrate is 0.5-2mm; The alkaline reagent comprises a sodium hydroxide solution, and the soaking treatment conditions of the alkaline reagent are: soaking temperature 60-90℃, and soaking time 10-30min; The acidic reagent comprises an oxalic acid solution, and the soaking treatment conditions of the acidic reagent are: soaking temperature 90-98℃, and soaking time 30-120min.

4. The preparation method of the catalytic anode with high oxygen evolution potential according to claim 1, wherein in step S3, the concentration of the sulfuric acid solution is 0.5-2M.

5. The catalytic anode with high oxygen evolution potential prepared by the method according to any one of claims 1-4. The dual-energy oxidation system adopts a circulating flow type single-tank electrolytic cell, which is internally provided with an anode, a cathode, and a catalyst filled between the anode and the cathode; the anode and the cathode are connected through a pulse power supply; The anode material is the catalytic anode with high oxygen evolution potential prepared by the method according to any one of claims 1-4; The cathode material is one or more of titanium, graphite, and titanium suboxide; 6. A dual energy oxidation system of pulsed electro-catalytic coupled advanced oxidation, characterized in that, The catalyst comprises one or both of an ozone or a persulfate catalyst. It comprises the following steps: Pump high-salinity wastewater into the electrolytic tank, and circulate the wastewater; after the circulation is stable, turn on the pulse power supply to supply power, perform electro-catalytic degradation, generate ozone or persulfate, then turn off the power supply, and the catalyst in the electrolytic tank catalyzes the ozone and the persulfate to further degrade through a high-level oxidation reaction; repeat the power supply and power-off operations, and high-salinity wastewater can be efficiently degraded. When the power supply is on, the pulse current is 2-6A, the pulse voltage is 4-6V, and the power supply time is 10-300s; the power-off time is 10-300s.

7. The method of using the dual energy oxidation system of pulsed electrocatalytic coupled advanced oxidation of claim 6, wherein, 9. Application of the pulse electro-catalytic coupled advanced oxidation dual-energy oxidation system according to claim 6 in degrading high-concentration salinity-containing wastewater. ​ 8. The method of using the dual energy oxidation system of pulsed electrocatalytic coupled advanced oxidation of claim 7, wherein, ​ ​

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