Oxygen reduction functional electrode material, preparation method and application thereof

Abstract

The invention discloses an oxygen reduction functional electrode material, a preparation method and application thereof. The preparation method comprises the following steps: mixing SCC with deionized water, stirring, carrying out solid-liquid separation, carrying out evaporative crystallization on a liquid phase to collect a villiaumite-containing component, mixing a separated solid phase with an acid solution, heating, and filtering and separating the solid phase to obtain relatively pure graphite solid powder; carrying out liquid-phase interlayer oxidation intercalation on the obtained graphite solid powder to obtain SCC-GO dispersion liquid; the preparation method comprises the following steps: collecting SCC-GO dispersion liquid, ultrasonically dispersing the SCC-GO dispersion liquid into a cerium nitrate solution with a certain concentration, dispersing collected sodium fluoride into a solution, adding the solution, adjusting the pH value by using dilute sulphuric acid and a sodium hydroxide solution, carrying out a hydrothermal reaction, washing and drying a reaction product, and calcining to obtain the CeF3 (at) SCC-rGO electrode material. According to the method, resource conversion and utilization of the aluminum electrolysis waste cathode carbon are achieved, and meanwhile sustainability and wide application prospects are shown.

Description

Technical Field

[0001] The present invention belongs to the technical field of electrocatalytic materials, and particularly relates to a method for preparing an oxygen reduction functional electrode material for degrading tetracycline hydrochloride by using waste cathode carbon from aluminum electrolysis and a preparation method thereof. Background Art

[0002] SCC is a solid waste generated after long-term operation of an aluminum electrolysis cell due to the failure of the cathode material. It is the main component of the overhaul slag of electrolytic aluminum, with an annual global output of over 1 million tons, and China accounts for about 60%. In addition, resource utilization of SCC is a key measure to solve the contradictions among environmental pollution, resource shortage and industrial development. Through technological innovation and policy guidance, not only can the reduction and harmless treatment of hazardous waste be achieved, but it can also be transformed into high-value-added products to promote the development of circular economy. Resource utilization of SCC is of great significance for building a green and low-carbon society. From the perspective of energy security, SCC, as a solid waste containing graphite carbon and fluoride, has considerable recycling value. If a complete downstream industrial chain for SCC treatment can be developed through technology research and development and policy guidance, it will greatly alleviate the energy crisis in the primary aluminum industry in China. It is worth mentioning that the soluble fluoride in SCC is toxic and also an important resource. Therefore, if it cannot be effectively enriched or reasonably utilized, it will cause a large amount of resource waste and environmental pollution. The graphite carbon in SCC has excellent electrical conductivity. Therefore, SCC is a good choice for preparing high-value-added fluorine-containing functional carbon materials. However, how to comprehensively utilize graphite carbon and fluoride and achieve high-value-added utilization is still a challenge.

[0003] Electrocatalytic technology is a class of technologies that use electrocatalysts to accelerate electrochemical reactions on the electrode surface and is widely used in fields such as energy conversion, environmental protection and chemical synthesis. Its core is to optimize the design and performance of the catalyst to reduce the reaction activation energy and improve the reaction rate and selectivity. Currently, the materials used in electrocatalysts are mostly commercial materials, which increases the additional procurement cost. Utilizing SCC for resource utilization and applying it to electrocatalytic technology not only provides a new way for the high-value utilization of hazardous waste, but also helps to promote the development of clean energy technology and the promotion of circular economy. Therefore, comprehensively utilizing fluoride and graphite carbon in SCC to prepare electrocatalytic materials is of great significance for realizing the high-value utilization of SCC.

[0004] As an important inorganic anion, fluoride ion (F-) has a wide range of applications in industries, medicine, agriculture, and high-tech fields. Due to its unique chemical properties such as high electronegativity and strong coordination ability, it has become an indispensable part of many key technologies and products. At the same time, fluorine, as an important strategic resource, is widely used in industries, medicine, and technology. An appropriate amount of fluorine is beneficial to human health (such as preventing dental caries, etc.). However, the fluoride recovery technology has limitations in large-scale applications due to its high cost and low efficiency. It is worth noting that with the acceleration of the industrialization process and the increase in human activities, the environmental pollution problem in the aluminum electrolysis industry is becoming increasingly serious, especially the fluorine pollution poses a serious threat to the ecosystem and human health. After fluoride ions enter surface water and groundwater, they are difficult to degrade naturally, resulting in excessive fluorine content in water bodies. In order to fix most of the fluoride ions and utilize them in the field of electrocatalysis, we plan to develop a fluoride electrode. However, due to the poor conductivity of fluorides, there are very few reports on the direct use of independent fluorides as electrodes in the field of electrocatalysis. The high carrier mobility on the surface of graphite carbon materials can improve their conductivity and activity, which provides the possibility for the application of fluorides in electrocatalysis. This scheme has the advantages of low energy consumption, low cost, and easy operation.

[0005] So far, no researchers have fully utilized the fluorine-containing components and graphite resources in spent cathode carbon of aluminum electrolysis to prepare composite materials. However, some work has been carried out only on the preparation of fluorine-doped carbon materials and metal fluorides as electrode materials. Patent CN119433760A discloses a method for preparing fluorine-doped composite micro / mesoporous carbon materials based on collaborative pore formation. After ultrasonic dispersing the mesoporous pore-forming agent in N,N-dimethylformamide, the microporous pore-forming agent is added and stirred to obtain the first dispersion liquid. Polyacrylonitrile is added to the first dispersion liquid and stirred evenly to obtain the second dispersion liquid. The second dispersion liquid is electrospun to obtain a spun sample, and the spun sample is pyrolyzed to obtain fluorine-doped composite micro / mesoporous carbon materials. This invention forms a uniform solid electrolyte interface and inhibits the excessive decomposition of the electrolyte on the electrode surface. Patent CN117512657A discloses a transition metal fluoride / MXene composite material, its preparation method and application. The composite material consists of transition metal fluoride nanoparticles uniformly distributed on the surface of accordion-shaped MXene sheets. MXene is a two-dimensional crystal material of transition metal carbides or transition metal nitrides. The preparation method of the above composite material requires simple equipment, convenient operation and low cost, and can effectively solve the problems of high price, poor stability and low reserves of traditional commercial noble metal catalysts. The transition metal fluoride / MXene composite material has excellent electrocatalytic activity as a catalyst in the electrocatalytic oxygen evolution reaction under alkaline conditions and has a high specific surface area and high conductivity. Patent CN115849357A discloses a method for preparing and applying graphene fluoride. By controlling the amount of polyvinylidene fluoride, the generation amount of hydrogen fluoride gas can be effectively regulated, thereby reducing the emission of harmful gases and improving the production safety. This material can effectively reduce the interfacial thermal resistance inside the thermal conductive film, thereby improving the thermal conductivity and has strong application value. Patent CN115028163A discloses a method for preparing highly fluorinated graphene. Using graphene oxide as the raw material and potassium permanganate and hydrofluoric acid as fluorinating agents, highly fluorinated graphene is prepared by combining ultrasonic dispersion and ultrasonic-hydrothermal coupling technology. This preparation method not only effectively saves energy consumption, but also increases the fluorine content in graphene fluoride, further improving the quality of graphene fluoride products, and the process is simple, low-cost, non-toxic and environmentally friendly. Patent CN116288471A discloses a method for preparing and applying a nickel-iron-based transition metal fluoride catalyst. This invention first uses nickel foam as the substrate, pretreats the nickel foam by dielectric barrier discharge plasma, then obtains a catalyst with in-situ grown transition metals through one-step hydrothermal treatment, and finally obtains a nickel-iron-based transition metal fluoride through fluorination and activation. The catalyst is directly in-situ grown on the nickel foam and its performance is improved through fluorination, significantly improving the performance of the catalyst for electrocatalytic water splitting and also greatly improving the stability of the catalyst.

[0006] It can be seen that although there are many cases of preparing electrode materials from fluorine-doped carbon and metal fluorides, there are currently no relevant patent cases in the field of treating hazardous / solid waste, especially in the field of using carbon-based materials of hazardous / solid waste to prepare electrocatalytic oxygen reduction functional electrodes for degrading tetracycline hydrochloride. Summary of the Invention

[0007] Aiming at the above-mentioned disadvantages and deficiencies of the prior art, the purpose of the present invention is to provide a method for preparing an oxygen reduction functional electrode for degrading tetracycline hydrochloride by using waste cathode carbon from aluminum electrolysis.

[0008] Another object of the present invention is to provide a CeF3@SCC-rGO composite material prepared by the above method.

[0009] Another object of the present invention is to provide the application of the above CeF3@SCC-rGO composite material in electrocatalytic oxygen reduction for degrading pollutants.

[0010] The present invention uses the potential value components of SCC to prepare a composite material for electrocatalytic oxygen reduction reaction to synthesize hydroxyl radicals, which is used for electrocatalytic oxygen reduction to degrade tetracycline hydrochloride, realizing the resource utilization and application of hazardous / solid waste.

[0011] The object of the present invention is achieved by the following technical solutions:

[0012] A preparation method of an oxygen reduction functional electrode material, comprising the following steps:

[0013] (1) Mix aluminum electrolysis waste cathode carbon powder (SCC) with deionized water, stir, and then separate the solid and liquid.

[0014] (2) Evaporate and crystallize the liquid phase separated in step (1) to collect the fluorine-containing salt components.

[0015] (3) Mix the solid phase separated in step (1) with acid solution, heat, filter and separate the solid phase to obtain relatively pure graphite solid powder.

[0016] (4) Perform liquid-phase interlayer oxidation intercalation on the graphite solid powder obtained in step (3) to obtain a dispersion of waste cathode carbon-derived graphene oxide (SCC-GO).

[0017] (5) Drop the SCC-GO dispersion obtained in step (4) into a cerium nitrate solution, adjust the pH of the reaction solution with dilute sulfuric acid and sodium hydroxide solution under ultrasonic assistance, then perform a hydrothermal reaction, and wash and dry the reaction product to obtain a CeF3@SCC-GO precursor.

[0018] (6) Pyrolyze the obtained CeF3@SCC-GO precursor at high temperature to obtain a composite electrode material of cerium trifluoride and reduced graphene oxide (CeF3@SCC-rGO).

[0019] Further, in step (1), the particle size of the SCC is 20 - 1000 mesh; the solid-liquid ratio of the mixture of SCC and deionized water is 1:20 - 1:50.

[0020] Further, in step (2), the temperature of the evaporation crystallization is 50 - 100 °C; the device for the evaporation crystallization is one of a blast drying oven, an electromagnetic heating furnace, and an electric heating platform plate.

[0021] Further, in step (3), the acid solution is a phosphoric acid solution or a sulfuric acid solution with an acid concentration of 0.5 - 1.5 M; the temperature of the heat treatment is 50 - 80 °C, and the time of the heat treatment is 2 - 10 h.

[0022] Further, in step (4), the method of liquid-phase intercalation oxidation is one of the Hummers method, the improved Hummers method, the Brodie method, the Staudenmaier method, the electrochemical oxidation method, the photocatalytic oxidation method, and the ball milling oxidation method.

[0023] Further, in step (5), the cerium nitrate solution is prepared by mixing 0.1 - 0.5 g of cerium nitrate hexahydrate (Ce(NO3)3) powder and 15 - 20 mL of deionized water; the concentration of the dilute sulfuric acid is 0.1 - 0.5 M; the sodium hydroxide is 0.5 - 1 M; the adjusted pH value is 5 - 7.

[0024] Further, in step (5), the temperature of the hydrothermal reaction is 180 - 200 °C, and the time of the hydrothermal reaction is 8 - 16 h; in step (6), the pyrolysis temperature is 7 -1 00 - 1000 °C, and the pyrolysis time is 3 - 6 h.

[0025] The present invention also provides an oxygen reduction functional electrode material, and the morphology of CeF3@SCC-rGO is that spherical cerium trifluoride nanoparticles are uniformly loaded on graphene sheets.

[0026] The present invention also provides an application of the oxygen reduction functional electrode material. The CeF3@SCC-rGO electrode material is prepared into a slurry and sprayed on carbon paper, and tetracycline hydrochloride is degraded in an electrochemical device at a certain current.

[0027] Further, the slurry ratio is active substance: absolute ethanol: naphthol solution = 20 - 50 mg: 4 - 10 mL: 100 - 300 μL; the electrochemical device is a single-cell container; the electrochemical anode carbon paper is hydrophilic, and the cathode is a hydrophobic carbon paper; the constant current magnitude is 10 - 100 mA; the concentration of tetracycline hydrochloride is 20 mg·L -1 - 100 mg·L. -1 ~100mg·L -1 .

[0028] Compared with the prior art, the beneficial effects of the present invention are:

[0029] (1) The CeF3@SCC-rGO composite material obtained in the present invention has strong metal and fluorine bonding energy, which is conducive to the fixation of fluoride ions, thereby helping to avoid fluoride ion pollution and achieve fluoride ion recovery.

[0030] (2) The CeF3@SCC-rGO composite material obtained in the present invention has a considerable selectivity for electrocatalytic oxygen reduction to synthesize hydrogen peroxide, with a hydrogen peroxide selectivity of 46% at 0.24 V (relative to the reversible hydrogen electrode) and an electron transfer number close to 3.

[0031] (3) As a hazardous waste stipulated by the state, the cathode carbon from aluminum electrolysis contains a large amount of carbon and fluorine elements. Using it as a raw material to produce new energy electrocatalytic materials can realize the transformation and utilization of industrial waste resources and provide a reference for the sustainable development of the aluminum electrolysis industry. BRIEF DESCRIPTION OF THE DRAWINGS

[0032] Figure 1 X-ray diffraction pattern (XRD) of CeF3@SCC-rGO composite material prepared in Example 1;

[0033] Figure 2 This is a scanning electron microscopy (SEM) image of the CeF3@SCC-rGO composite material prepared in Example 1;

[0034] Figure 3 Transmission electron microscopy (TEM) image of the CeF3@SCC-rGO composite material prepared in Example 1;

[0035] Figure 4 Element mapping of the CeF3@SCC-rGO composite material prepared in Example 1;

[0036] Figure 5 LSV curve of the CeF3@SCC-rGO composite material prepared in Example 1 tested in 1M Na2SO4 electrolyte;

[0037] Figure 6 The selectivity and transferred electron number of CeF3@SCC-rGO composite material prepared in Example 1 for H2O2 in 1M Na2SO4 electrolyte;

[0038] Figure 7 The spin-trapping EPR spectra of ·OH detected at different times during the degradation experiment of the CeF3@SCC-rGO composite material prepared in Example 1 in 1M Na2SO4 electrolyte;

[0039] Figure 8The concentration diagram of ·OH detected at different times in the degradation experiment of the CeF3@SCC-rGO composite material prepared in Example 1 in 1M Na2SO4 electrolyte;

[0040] Figure 9 The degradation concentration diagram of the CeF3@SCC-rGO composite material prepared in Example 1 for the degradation of 100 mg·L -1 tetracycline hydrochloride at different currents;

[0041] Figure 10 The degradation concentration diagram of the CeF3@SCC-rGO composite material prepared in Example 2 for the degradation of 50 mg·L -1 tetracycline hydrochloride at different currents;

[0042] Figure 11 The degradation concentration diagram of the CeF3@SCC-rGO composite material prepared in Example 3 for the degradation of 20 mg·L -1 tetracycline hydrochloride at different currents. Detailed implementation manners

[0043] The present invention will be further described in detail below in conjunction with the embodiments and the drawings, but the implementation manners of the present invention are not limited thereto.

[0044] Example 1

[0045] (1) Mix 10.0 g of SCC (ground to a particle size of 200 mesh) with 500 mL of deionized water, magnetically stir for 48 h and then filter to collect the filtrate and the filter residue.

[0046] (2) Place the filtrate in a blast drying oven and evaporate to crystallization at 80-100 °C, collect, grind and weigh to obtain the fluorinated salt component.

[0047] (3) Mix the filter residue with 100 mL of 0.5M dilute sulfuric acid, heat-treat in a water bath at 60 °C for 3 h and then filter, take the solid phase and dry it to obtain a relatively pure graphite phase.

[0048] (4) Use the improved Hummers method to prepare a graphene oxide (GO) dispersion from the obtained graphite phase.

[0049] (5) Drop the SCC-GO dispersion obtained in step (4) into a cerium nitrate solution, adjust the pH of the reaction solution to about 5 with dilute sulfuric acid and sodium hydroxide solution under ultrasonic assistance, and finally carry out a hydrothermal reaction. The reaction product is washed and dried to obtain CeF3@SCC-GO.

[0050] (6) Pyrolyze the obtained CeF3@SCC-GO precursor at high temperature to obtain CeF3@SCC-rGO.

[0051] (7) The obtained CeF3@SCC-rGO powder was prepared into a slurry and sprayed on carbon paper, and degradation experiments of 100 mg·L -1 tetracycline hydrochloride were carried out in an electrochemical device at a current of 10 mA / 20 mA / 50 mA.

[0052] The X-ray diffraction pattern (XRD) of the CeF3@SCC-rGO composite material obtained in this example is as Figures 1-4 shown. It shows the characteristics of CeF3 and rGO, indicating that the CeF3@SCC-rGO composite material was successfully prepared.

[0053] The linear sweep voltammogram of the CeF3@SCC-rGO composite material obtained in this example in 1 M Na2SO4 electrolyte is as Figure 5 shown. It can be seen from the figure that the initial potential of the obtained CeF3@SCC-rGO composite material for electrocatalytic oxygen reduction reaction in 1 M Na2SO4 electrolyte is about 0.6 V (relative to the reversible hydrogen electrode).

[0054] The selectivity for hydrogen peroxide and the number of electron transfers of the CeF3@SCC-rGO composite material obtained in this example at -0.2 to 0.3 V (relative to the reversible hydrogen electrode) are as Figure 6 shown. It can be seen from the figure that the selectivity for hydrogen peroxide of the obtained CeF3@SCC-rGO composite material is about 46% and the number of electron transfers is about 2.8 at about 0.24 V (relative to the reversible hydrogen electrode).

[0055] In the constant current test of the CeF3@SCC-rGO composite material obtained in this example in 1 M Na2SO4 electrolyte ( Figures 7-8 ), ·OH radicals were successfully detected and there was a small amount of accumulation at different times, and the concentration was the highest at 0.036 mmol·L -1 at 30 min.

[0056] In the experiment of constant current degradation of 100 mg·L -1 tetracycline hydrochloride with different current magnitudes of the CeF3@SCC-rGO composite material obtained in this example in 1 M Na2SO4 electrolyte ( Figure 9 ), when the current magnitude was 50 mA, the degradation effect of the oxygen reduction electrode on tetracycline hydrochloride was the most obvious, and the degradation rate reached about 37.5%.

[0057] Example 2

[0058] (1) 10.0 g of SCC (ground to a particle size of 500 mesh) was mixed with 300 ml of deionized water, magnetically stirred for 12 h and then filtered, and the filtrate and filter residue were collected.

[0059] (2) Put the filtrate into a blast drying oven and evaporate to crystallize at 80 - 90 °C, collect and weigh to obtain the fluorine-containing salt component.

[0060] (3) Mix the filter residue with 25 ml of 2M hydrochloric acid, heat-treat in a water bath at 50 °C for 5 h, then filter, take the solid phase and dry it to obtain a relatively pure graphite phase.

[0061] (4) Use the improved Hummers method to prepare the obtained graphite phase into a graphene oxide (GO) dispersion.

[0062] (5) Drop the SCC-GO dispersion obtained in step (4) into the cerium nitrate solution, adjust the pH of the reaction solution to about 6 with dilute sulfuric acid and sodium hydroxide solution under ultrasonic assistance, and finally carry out a hydrothermal reaction. After washing and drying the reaction product, CeF3@SCC-GO is obtained.

[0063] (6) Pyrolyze the obtained CeF3@SCC-GO precursor at high temperature to obtain CeF3@SCC-rGO.

[0064] (7) Prepare the obtained CeF3@SCC-rGO powder into a slurry and spray it on carbon paper, and carry out the experiment of degrading 50 mg·L -1 tetracycline hydrochloride at a current of 10 mA / 20 mA / 50 mA in an electrochemical device.

[0065] In the experiment of degrading 50 mg·L -1 tetracycline hydrochloride with the CeF3@SCC-rGO composite material obtained in this example under constant current degradation with different current magnitudes in 1M Na2SO4 electrolyte ( Figure 10 ), when the current magnitude is 50 mA, the oxygen reduction electrode has the most obvious degradation effect on tetracycline hydrochloride, and the degradation rate reaches about 33.6%.

[0066] Example 3

[0067] (1) Mix 5.0 g of SCC (ground to a particle size of 100 mesh) with 300 ml of deionized water, stir magnetically for 48 h, then filter, and collect the filtrate and filter residue.

[0068] (2) Put the filtrate into a blast drying oven and evaporate to crystallize at 100 - 110 °C, collect and weigh to obtain the fluorine-containing salt component.

[0069] (3) Mix the filter residue with 25 ml of 0.5M sulfuric acid, heat-treat in a water bath at 80 °C for 2 h, then filter, take the solid phase and dry it to obtain a relatively pure graphite phase.

[0070] (4) Use the improved Hummers method to prepare the obtained graphite phase into a graphene oxide (GO) dispersion.

[0071] (5) The SCC-GO dispersion obtained in step (4) was dripped into a cerium nitrate solution. The pH of the reaction solution was adjusted to approximately 7 with dilute sulfuric acid and sodium hydroxide solution under ultrasound assistance, and a hydrothermal reaction was performed. The reaction product was washed and dried to obtain CeF3@SCC-GO.

[0072] (6) The obtained CeF3@SCC-GO precursor was pyrolyzed at high temperature to obtain CeF3@SCC-rGO.

[0073] (7) The obtained CeF3@SCC-rGO powder was prepared into a slurry and sprayed on carbon paper. The degradation of 20 mg·L was carried out in an electrochemical device with a current of 10 mA / 20 mA / 50 mA. -1 Tetracycline hydrochloride experiment.

[0074] The CeF3@SCC-rGO composite material obtained in this example was subjected to constant current degradation of 20 mg·L in 1 M Na2SO4 electrolyte at different current sizes. -1 In the tetracycline hydrochloride experiment ( Figure 11 ), when the current is 50mA or 20mA, the oxygen reduction electrode has a significant degradation effect on tetracycline hydrochloride, and the degradation rate reaches about 55.1%.

[0075] It can be seen from the results of Example 1 that:

[0076] (1) The CeF3@SCC-rGO composite material obtained in the present invention has strong metal and fluorine bonding energy, which is conducive to the fixation of fluoride ions, thereby helping to avoid fluoride ion pollution and achieve fluoride ion recovery.

[0077] (2) The CeF3@SCC-rGO composite material obtained in the present invention has a considerable selectivity for electrocatalytic oxygen reduction to synthesize hydrogen peroxide, with a hydrogen peroxide selectivity of 46% at 0.24 V (relative to the reversible hydrogen electrode) and an electron transfer number close to 3.

[0078] (3) As a hazardous waste stipulated by the state, the cathode carbon from aluminum electrolysis contains a large amount of carbon and fluorine elements. Using it as a raw material to produce new energy electrocatalytic materials can realize the transformation and utilization of industrial waste resources and provide a reference for the sustainable development of the aluminum electrolysis industry.

[0079] The above embodiments are preferred implementations of the present invention, but the implementations of the present invention are not limited to the above embodiments. Any other changes, modifications, substitutions, combinations, and simplifications that do not deviate from the spirit and principles of the present invention should be considered as equivalent replacement methods and are included in the scope of protection of the present invention.

Claims

1. A preparation method of an oxygen reduction functional electrode material, characterized in that, It includes the following steps: (1) Mix SCC with deionized water and then stir, followed by solid-liquid separation; (2) Evaporate and crystallize the liquid phase separated in step (1) to collect the fluorine salt component; (3) Mix the solid phase separated in step (1) with acid solution and then heat, and filter to separate the solid phase to obtain relatively pure graphite solid powder; (4) Perform liquid-phase interlayer oxidation intercalation on the graphite solid powder obtained in step (3) to obtain an SCC-GO dispersion; (5) Drop the SCC-GO dispersion obtained in step (4) into a cerium nitrate solution, adjust the pH of the reaction solution with dilute sulfuric acid and sodium hydroxide solution under ultrasonic assistance, and then carry out a hydrothermal reaction. After washing and drying the reaction product, a CeF3@SCC-GO precursor is obtained; (6) Pyrolyze the obtained CeF3@SCC-GO precursor at high temperature to obtain a CeF3@SCC-rGO electrode material.

2. The preparation method of an oxygen reduction functional electrode material according to claim 1, wherein In step (1), the particle size of the SCC is 20 - 1000 mesh; the solid-liquid ratio of the SCC mixed with deionized water is 1:20 - 1:

50.

3. The preparation method of an oxygen reduction functional electrode material according to claim 1, characterized in that, In step (2), the temperature of the evaporation and crystallization is 50 - 100 °C; the device for the evaporation and crystallization is one of a blast drying oven, an electromagnetic heating furnace, and an electric heating platform plate.

4. The preparation method of an oxygen reduction functional electrode material according to claim 1, characterized in that In step (3), the acid solution is a phosphoric acid solution or a sulfuric acid solution with an acid concentration of 0.5 - 1.5 M; the temperature of the heating treatment is 50 - 80 °C, and the heating treatment time is 2 - 10 h.

5. The preparation method of an oxygen reduction functional electrode material according to claim 1, characterized in that, In step (4), the method of the liquid-phase interlayer oxidation intercalation is one of the Hummers method, the improved Hummers method, the Brodie method, the Staudenmaier method, the electrochemical oxidation method, the photocatalytic oxidation method, and the ball milling oxidation method.

6. The preparation method of an oxygen reduction functional electrode material according to claim 1, characterized in that, In step (5), the cerium nitrate solution is prepared by mixing 0.1 - 0.5 g of cerium nitrate hexahydrate (Ce(NO3)3) powder and 15 - 20 mL of deionized water; the concentration of the dilute sulfuric acid is 0.1 - 0.5 M; the sodium hydroxide is 0.5 - 1 M; the adjusted pH value is 5 - 7.

7. The preparation method of an oxygen reduction functional electrode material according to claim 1, wherein In step (5), the temperature of the hydrothermal reaction is 180 - 200 °C, and the hydrothermal reaction time is 8 - 16 h; in step (6), the pyrolysis temperature is 700 - 1000 °C, and the pyrolysis time is 3 - 6 h.

8. An oxygen reduction functional electrode material prepared by the method according to any one of claims 1 to 7, characterized in that The morphology of CeF3@SCC-rGO is that graphene sheets uniformly carry spherical cerium trifluoride nanoparticles.

9. Use of the oxygen reduction functional electrode material according to claim 8, characterized in that, Prepare the CeF3@SCC-rGO electrode material into a slurry and spray it on carbon paper, and perform the degradation of tetracycline hydrochloride in an electrochemical device at a certain current.

10. Use of the oxygen reduction functional electrode material according to claim 9, characterized in that, The slurry ratio is active substance: absolute ethanol: naphthol solution = 20 - 50 mg: 4 - 10 mL: 100 - 300 μL; the electrochemical device is a single-cell container; the electrochemical anodic carbon paper is hydrophilic and the cathode is hydrophobic carbon paper; the constant current magnitude is 10 - 100 mA; the concentration of tetracycline hydrochloride is 20 mg·L -1 ~100 mg·L -1 .

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