ORR polarization curve double-platform current material and preparation method and application thereof

Abstract

The invention discloses an ORR polarization curve double-platform current material and a preparation method and application thereof, and belongs to the technical field of multifunctional catalytic material preparation. According to the invention, organic iron is taken as a precursor, single-layer graphite is taken as a substrate, and 1-40 ALD cycles and a gradient annealing process are combined, so that the ORR catalyst with double current platform characteristics is successfully prepared. The material prepared by the invention efficiently generates reactive oxygen free radicals (. OH) in a voltage interval (2 electron paths) of 0.7-0.5 V, so that rapid degradation of antibiotics is realized; meanwhile, in the interval of 0.4-0.1 V (4 electron paths), H2O is reduced through high-selectivity oxygen, and the catalytic requirement of a solid-state battery is met. The limit diffusion current of the sample prepared through 20 times of ALD circulation reaches a theoretical limit value, the process automation degree is high, the technical barriers of single function and large-scale production of a traditional method are broken through, and a new normal form is provided for multi-scene catalytic material design.

Description

Technical Field

[0001] The present invention relates to a material with a dual - platform current for ORR polarization curves, its preparation method and application, belonging to the technical field of preparation of multifunctional catalytic materials. Background Art

[0002] In recent years, the development of multifunctional catalytic materials has attracted much attention in the fields of energy conversion and environmental governance. As a core material, the oxygen reduction reaction (ORR) catalyst is widely used in fuel cells, metal - air batteries, and antibiotic degradation. Currently, iron - based catalysts have become a research hotspot due to their low cost and excellent activity. However, there are still significant bottlenecks in the preparation technology of iron - based catalysts: (1) Functional singularity: Existing catalysts are usually designed for a single reaction path (such as generating H2O2 through a 2 - electron process or generating H2O through a 4 - electron process), and it is difficult to simultaneously meet the composite requirements of generating reactive oxygen species through a 2 - electron process for antibiotic degradation and efficient mass transfer through a 4 - electron process for solid - state battery catalysis. (2) Difficulty in large - scale production of multifunctional iron - based catalysts: Most processes rely on complex post - treatments, such as high - temperature carbonization, acid etching, etc. The batch repeatability is poor, and it is difficult to be compatible with industrial production.

[0003] To address the above problems, atomic layer deposition (ALD) technology has been attempted for the precise construction of catalysts due to its advantages of atomic - level precision and uniformity. However, existing ALD schemes still have limitations: (1) The choice of precursors is restricted. For example, the thermal stability of metal - organic compounds is insufficient, resulting in a low loading of active components. (2) Existing ALD technologies are difficult to optimize the valence state of Fe species (such as the Fe 2+ / Fe 3+ ratio) and the lattice matching. (3) It is impossible to balance the electron - transfer requirements of different application scenarios. Summary of the Invention

[0004] In order to overcome the problems in the background art, the purpose of the present invention is to provide a material with a dual - platform current for ORR polarization curves, its preparation method and application.

[0005] To achieve the above purpose, the present invention is realized through the following technical solutions:

[0006] A preparation method of a material with a dual - platform current for ORR polarization curves, comprising the following steps:

[0007] (1) Place monolayer graphene into the chamber of the atomic layer deposition equipment, close the equipment door and start the vacuum pump to evacuate the chamber. Set the heating temperature to 180°C - 200°C and turn on the heating device; at the same time, heat the organic iron precursor, and set the temperature to 100°C - 120°C; then, purge the equipment with high - purity nitrogen for 2 - 2.5 hours. After the chamber temperature stably reaches 195 - 200°C, close the purge gas valve;

[0008] (2) Initiate atomic layer deposition, where the process parameters of atomic layer deposition are as follows: the Fe dosage time is 0.5 - 1 second, the holding time is 60 - 80 seconds, the nitrogen purge time is 20 - 30 seconds, the vacuum release time is 180 - 210 seconds, the chamber rotation speed is 20 - 30 RPM, the forward rotation speed is 5 - 10 CW / S, and the reverse rotation speed is 5 - 10 CCW / S;

[0009] (3) Repeat the atomic layer deposition process in step (2) 0 - 39 times. After the experiment is completed, turn off the chamber heating device and the precursor heating device. After the equipment cools down to room temperature, take out the sample;

[0010] (4) Anneal the sample in high - purity hydrogen gas to finally obtain the ORR polarization curve double - plateau current material.

[0011] More preferably, the organic iron precursor is bis(N,N'-di - tert - butylethylamidinato)iron(II), tris(2,2,6,6 - tetramethyl - 3,5 - heptanedionato)iron, 1,1'-diethylferrocene, cyclohexadienetricarbonyliron, dicyclopentadienyliron dicarbonyl dimer, ethylferrocene, ferrocene, tert - butylferrocene, or iron carbonyl.

[0012] More preferably, the temperature of the annealing treatment is 750 - 800 °C, the holding time is 2 - 3 hours, the heating rate is 2.5 - 5 °C / min, and the pressure is normal pressure.

[0013] More preferably, in step (2), open the precursor valve and let it stand for 2 - 5 minutes before initiating atomic layer deposition.

[0014] The present invention also claims the ORR polarization curve double - plateau current material prepared by the preparation method of the ORR polarization curve double - plateau current material.

[0015] The present invention also claims the application of the ORR polarization curve double - plateau current material in the electro - Fenton degradation of antibiotics.

[0016] The present invention also claims the application of the ORR polarization curve double - plateau current material in solid - state batteries.

[0017] The ORR polarization curve double - plateau current material of the present invention has an ORR polarization curve double - plateau current. In the voltage range of 0.7 - 0.5 V, it is a 2 - electron path; meanwhile, in the range of 0.4 - 0.1 V, it is a 4 - electron path. In acidic media, the 4 - electron path directly reduces oxygen to water (H2O), with high reaction efficiency, which is an ideal path for high - performance devices such as fuel cells. The 2 - electron path first reduces oxygen to hydrogen peroxide (H2O2), with lower efficiency and possible generation of by - products. In alkaline media, the 4 - electron path reduces oxygen to hydroxide (OH -), also exhibits the advantages of high efficiency and fewer by-products, and is suitable for systems such as metal-air batteries. In contrast, the 2-electron pathway first generates superoxide (HO2 - ) in an alkaline environment, and then is further reduced to hydroxide (OH - ). Therefore, the ORR polarization curve dual-platform current material described in the present invention is a multifunctional material and has good applications in both electro-Fenton degradation of antibiotics and solid-state batteries.

[0018] The specific reactions are as follows:

[0019] Reaction equations in acidic medium:

[0020] 4e - Pathway: O2 + 4H + + 4e - → 2H2O

[0021] 2e - Pathway: O2 + 2H + + 2e - → H2O2

[0022] H2O2 + 2H + + 2e - → 2H2O

[0023] 2H2O2 → 2H2O + O2

[0024] Reaction equations in alkaline medium:

[0025] 4e - Pathway: O2 + 2H2O + 4e - → 4OH -

[0026] 2e - Pathway: O2 + H2O + 2e - → HO2 - + OH -

[0027] HO2 - + H2O + 2e - → 3OH -

[0028] 2HO2 - → 2OH - + O2

[0029] Advantages of the present invention: The present invention uses organic iron as a precursor and single-layer graphite as a substrate, combines the number of ALD cycles with a gradient annealing process, and for the first time synthesizes an ORR catalyst with dual-current plateau characteristics. The dual plateau has two reaction paths, namely 2-electron and 4-electron paths. The prepared materials can be used for a variety of purposes. Among them, in the voltage range of 0.7 - 0.5V, the 2-electron path can efficiently generate reactive oxygen radicals (·OH) to achieve rapid degradation of antibiotics; at the same time, the 4-electron path in the range of 0.4 - 0.1V reduces oxygen to H2O with high selectivity to meet the catalytic requirements of solid-state batteries. The limiting diffusion current of the sample prepared by 20 ALD cycles reaches the theoretical limit value, and the process has a high degree of automation, breaking through the technical barriers of single function and large-scale production of traditional methods, providing a new paradigm for the design of catalytic materials for multiple scenarios. Description of the Drawings

[0030] Figure 1 The ORR polarization curves of the materials prepared in Examples 1 - 5 and Comparative Examples 1 and 3. (a) The ORR polarization curves of the materials prepared in Examples 1 - 5. (b) The ORR polarization curves of the materials prepared in Example 4 and Comparative Example 1. (c) The ORR polarization curves of the materials prepared in Example 4 and Comparative Example 3.

[0031] Figure 2 The ORR polarization curve of the material prepared in Comparative Example 2.

[0032] Figure 3 The device diagram and effect diagram of the degradation of tetracycline by the material prepared in Example 4. (a) The device diagram of the degradation of tetracycline by the electro-Fenton method; (b) The ultraviolet fluorescence spectrometer curve of the degradation of tetracycline by the material prepared in Example 4; (c) The standard curve equation of tetracycline; (d) The degradation rate diagram of the degradation of tetracycline by the material prepared in Example 4.

[0033] Figure 4 The performance diagram of the rechargeable button-type solid-state zinc-air battery assembled with Example 4. (a) The discharge polarization curve and power density curve; (b) The stepped discharge curve; (c) The charge-discharge cycle curve at a current density of 1 mA / cm 2 20, and (d) The corresponding diagram of the open-circuit voltage and time. Detailed Embodiments

[0034] The following further describes the present invention in detail with specific embodiments, but the protection scope of the present invention is not limited thereto.

[0035] Example 1

[0036] A preparation method of a dual-platform current material for an ORR polarization curve, comprising the following steps:

[0037] (1) Preparation of single-atom catalysts by ALD technology: First, weigh 120 mg of monolayer graphene and place it in the chamber of the atomic layer deposition equipment. Close the equipment door and start the vacuum pump to evacuate the chamber. Set the heating temperature to 200 °C, turn on the heating device, and at the same time start the heating jacket to heat the ferrocene precursor, with the temperature of the heating jacket set to 100 °C. Subsequently, purge the equipment with high-purity nitrogen, and the gas flow rate is controlled by a gas flow meter. After 2 hours, when the chamber temperature stabilizes at 200 °C, close the purge gas valve.

[0038] (2) Input process parameters on the computer terminal of the equipment control system: Fe dose time: 1 second, Hold time: 60 seconds, N2 time: 20 seconds, Vacuum out time: 180 seconds, chamber rotation speed: 20 RPM, forward rotation speed: 5 CW / S, reverse rotation speed: 5 CCW / S. After saving the input process program, open the precursor valve and let it stand for 2 minutes. Start the process program for automatic operation. After the experiment is completed, turn off the chamber heating device and the precursor heating device. After the equipment cools down to room temperature, take out the sample.

[0039] (3) Subsequently, anneal the sample obtained in step (2) by introducing high-purity hydrogen in CVD. The heating temperature is 800 °C, the holding time is 2 hours, the heating rate is 5 °C / min, and the pressure is atmospheric pressure. The finally obtained sample is labeled as Fe@C1.

[0040] Example 2

[0041] The only difference between this example and Example 1 is that: step (2) is cycled 4 times, and the atomic layer deposition process is carried out 5 times in total. The finally obtained sample is labeled as Fe@C5.

[0042] Example 3

[0043] The only difference between this example and Example 1 is that: step (2) is cycled 9 times, and the atomic layer deposition process is carried out 10 times in total. The finally obtained sample is labeled as Fe@C10.

[0044] Example 4

[0045] The only difference between this example and Example 1 is that: step (2) is cycled 19 times, and the atomic layer deposition process is carried out 20 times in total. The finally obtained sample is labeled as Fe@C20.

[0046] Example 5

[0047] The only difference between this example and Example 1 is that: step (2) is cycled 39 times, and the atomic layer deposition process is carried out 40 times in total. The finally obtained sample is labeled as Fe@C40.

[0048] Example 6

[0049] A method for preparing an ORR polarization curve dual - platform current material, comprising the following steps:

[0050] (1) Preparation of single - atom catalyst by ALD technology: First, weigh 120 mg of monolayer graphene and place it in the cavity of the atomic layer deposition equipment. Close the equipment door and start the vacuum pump to evacuate the cavity. Set the heating temperature to 180 °C, turn on the heating device, and at the same time start the heating jacket to heat the bis(N,N'-di - tert - butylethylamidinato)iron(II) precursor, and set the temperature of the heating jacket to 120 °C. Subsequently, purge the equipment, and the purge gas is high - purity nitrogen, and the gas flow rate is controlled by a gas flow meter. After 2.5 hours, when the cavity temperature stabilizes at 195 °C, close the purge gas valve.

[0051] (2) Input process parameters on the computer terminal of the equipment control system: Fe dose time: 0.5 s, Hold time: 80 s, N2 time: 30 s, Vacuum outtime: 210 s, cavity rotation speed: 30 RPM, forward rotation speed: 10 CW / S, reverse rotation speed: 10 CCW / S. After saving the input process program, open the precursor valve and let it stand for 5 minutes. Start the process program for automatic operation.

[0052] (3) Repeat step (2) 19 times, and perform the atomic layer deposition process 20 times in total. After the experiment is completed, turn off the cavity heating device and the precursor heating device. After the equipment cools to room temperature, take out the sample.

[0053] (4) Subsequently, introduce high - purity hydrogen into the CVD to anneal the sample obtained in step (2). The heating temperature is 750 °C, keep the temperature for 3 hours, the heating rate is 2.5 °C / min, the pressure is atmospheric pressure, and the finally obtained sample is marked as Fe@C. The ORR polarization curve test of the material prepared in Example 6 has two limiting diffusion current platforms, which are 2 - electron path and 4 - electron path.

[0054] According to Figure 1 (a), the catalyst sample prepared by atomic layer deposition technology and annealed with hydrogen shows two limiting diffusion current platforms. For the materials prepared in Examples 1 - 5, the current density of the second - stage current platform changes significantly with the increase of the number of cycles. Especially at 20 cycles, the limiting current density reaches the highest value of 8.5 mA / cm 2 , while at 40 cycles, the limiting current density drops to 6.1 mA / cm instead 2 .

[0055] Comparative Example 1

[0056] The only difference between this comparative example and Example 4 is that: the final hydrogen annealing treatment is not carried out, and the prepared sample is marked as Fe@C20U.

[0057] According to Figure 1 (b), for the ORR polarization curve test, the Fe@C20U material has only one current plateau, and it is a 4-electron path. The sample prepared by atomic layer deposition technology without annealing treatment does not show a second current plateau in the cyclic voltammogram, and the limiting current density (the limiting current density is 4 mA / cm 2 ) and the half-wave potential (0.7 V) are not much different from those of the samples prepared by traditional wet chemical methods. It shows that the annealing treatment is crucial for improving the electrochemical activity of the catalyst. Annealing can improve the structure of the catalyst, enhance the catalytic activity, and may cause changes in the surface state of the catalyst, resulting in a more significant double-plateau behavior.

[0058] Comparative Example 2

[0059] The only difference between this comparative example and Example 4 is that: Fe dose time: 2 seconds, Holdtime: 65 seconds, N2 time: 20 seconds, Vacuum out time: 200 seconds, chamber rotation speed: 20 RPM, forward rotation speed: 10 CW / S, reverse rotation speed: 5 CCW / S.

[0060] According to Figure 2 it can be seen that for the ORR polarization curve test, the material prepared in Comparative Example 2 has only one current plateau, and it is a 4-electron path.

[0061] Comparative Example 3

[0062] Preparation of Iron Supported on Monolayer Graphene by Wet Chemical Method: First, weigh 0.05 g of ferrocene using an electronic balance, place it in a clean beaker, and add 100 mL of absolute ethanol to it. Place the beaker containing 0.05 g of ferrocene and 100 mL of absolute ethanol on a magnetic stirrer, start the stirring function, and adjust to a moderate stirring speed to ensure that ferrocene is fully dissolved or evenly dispersed in ethanol. Set the stirring time to 24 hours to ensure that ferrocene and ethanol are fully mixed and reach the desired state. After stirring, transfer the solution to an oven for drying to remove the solvent and obtain a dry ferrocene sample. The drying temperature needs to be controlled at 60 °C to avoid the decomposition of ferrocene caused by high temperature. After drying, transfer the treated ferrocene sample to a tubular furnace, set the heating rate to 2 °C / min, ensure that the temperature rises slowly and evenly, and avoid rapid temperature rise causing violent changes or uneven heating of the material. When the temperature rises to 800 °C, keep it at a constant temperature for 2 hours. After the annealing process is completed, turn off the heating device. After the temperature in the tubular furnace naturally cools to room temperature, carefully take out the sample and store it properly. The sample is labeled as Fe@CI.

[0063] Figure 1 (c) Cyclic Voltammetry Analysis of Catalyst Samples Prepared by Traditional Wet Chemical Method: The catalyst samples prepared by the wet chemical method only show a single limiting current plateau, which is a 4-electron path, and the half-wave potential is 0.7 V, and the limiting current density is 3 mA / cm 2 . This indicates that the electrochemical performance of the wet chemical method catalyst is relatively simple, lacking multiple current plateaus like the samples prepared by atomic layer deposition technology, and is lower in terms of electrochemical activity. In contrast, the 20-cycle catalyst samples prepared by atomic layer deposition technology show two limiting current plateaus, and both in terms of half-wave potential and limiting current density, they are significantly higher than the wet chemical method samples, showing higher catalytic activity.

[0064] Effect Example 1

[0065] Antibiotic Degradation Application: Since the materials prepared by atomic layer deposition technology and annealing treatment show excellent 2-electron reaction paths on the first plateau (voltage range 0.7 V to 0.5 V), therefore, apply it to antibiotic degradation. The specific steps include:

[0066] The reaction was carried out in a 50 mL two-compartment cell under a three-electrode system. One compartment was filled with an electrolyte H2SO4 solution, and the other compartment was filled with wastewater containing tetracycline at a concentration of 5 mg / L. An appropriate amount of ferrous sulfate heptahydrate was added as the source of the electro-Fenton reagent. The working electrode (the materials prepared in Examples 1-6 and Comparative Examples 1-3 were respectively coated on carbon cloth as the working electrode) was placed in the electrolytic cell containing H2SO4, and the counter electrode (Pt wire) and the reference electrode (saturated calomel electrode, SCE) were placed in the electrolytic cell containing the wastewater. The two compartments were separated by a Nafion N117 membrane. Since there are adsorption and other effects in the electro-Fenton reaction, the Nafion membrane was used to separate the two compartments to remove the adsorption effect of the carbon cloth in the electro-Fenton reaction. The Nafion membrane was treated as follows before use: First, the membrane was treated with hydrogen peroxide solution to remove the organic impurities in the membrane; second, it was treated with sulfuric acid solution to convert the membrane into the H+ form. The optimal conditions for the degradation of antibiotics in the present invention are that the voltage is set to -0.4 V (vs. SCE), pH = 3 (when no experiment is carried out, the pH of the two electrolytic cells is 3), and Fe 2+ in ferrous sulfate heptahydrate is 2 mmol / L. Pure carbon cloth was used as a blank control experiment. In order to detect the change in the absorbance of the solution, samples were taken every 15 min and analyzed by an ultraviolet-visible spectrophotometer. The degradation rate of tetracycline is shown in Table 1.

[0067] Table 1

[0068] Degradation rate (%) Example 1 35 Example 2 40 Example 3 50 Example 4 60 Example 5 65 Example 6 65 Comparative Example 1 0 Comparative Example 2 0 Comparative Example 3 0

[0069] According to Figure 3 and Table 1, when the material prepared in Example 4 was coated on carbon cloth as the working electrode to degrade tetracycline, after 1 h of degradation, the absorbance of the solution basically did not change, and the degradation rate reached more than 65%, and the solution gradually became clear. The materials prepared in Examples 1-6 have two limiting current platforms. One of them is a 2-electron path, which can generate hydrogen peroxide and degrade the antibiotic tetracycline. However, since the polarization curve current of the materials prepared in Comparative Examples 1-3 has only one current platform, which is a 4-electron path and cannot generate hydrogen peroxide, the antibiotic cannot be degraded.

[0070] Effect Example 2

[0071] Application of solid-state battery: Since the materials prepared by atomic layer deposition technology and annealing treatment have a 4-electron reaction path on the second platform (voltage range 0.4 V to 0.1 V) and exhibit excellent ORR activity, the materials prepared in Examples 1-6 and Comparative Examples 1-3 were respectively coated on carbon paper and assembled into a rechargeable button-type solid-state zinc-air battery as the air cathode. The solid-state zinc-air battery was installed in a blue electrical system and subjected to a stepped discharge test, and the currents were 1 mA / cm 2 , 2 mA / cm 2 , 5 mA / cm2 , 8 mA / cm 2 , 10 mA / cm 2 , 2 mA / cm 2 , 1 mA / cm 2 . Meanwhile, at 1 mA / cm 2 , 2 mA / cm 2 , 5 mA / cm 2 , constant current discharge tests were carried out, and the energy density of the battery was calculated. In addition, charge-discharge cycle tests at 1 mA / cm 2 were carried out, and open-circuit voltage tests and polarization curve tests were carried out on the electrochemical workstation.

[0072] Figure 4 (a) The experiment set the output voltage to drop from 1.6 V to 0.2 V. As the current density increased, the voltage decreased. When the current density reached 140 mA / cm 2 , the voltage dropped to 0.2 V; the battery power density was 80 mW / cm 2 . Figure 4 (b) At 1 mA / cm 2 , 2 mA / cm 2 , 5 mA / cm 2 under constant current, the energy densities of the battery were 682.5 Wh / kg, 703 Wh / kg, and 813 Wh / kg, respectively. Figure 4 (c) Charge-discharge cycle test of the battery and its round-trip efficiency at 10 hours and 90 hours. The charge-discharge cycle duration was 100 hours. At about the first 10 hours, the input voltage of the battery was 1.94 V, the output voltage was 1.07 V, and the round-trip efficiency was 55.2%. When the charge-discharge cycle reached about 100 hours, the input voltage of the battery was 1.91 V, the output voltage was 1.29 V, and the round-trip efficiency was 67.5%. Figure 4 (d) Open-circuit voltage test was carried out on the zinc-air battery assembled with the material prepared in Example 4. The voltage was set to 1.6 V - 0.2 V, the open-circuit voltage was 1.38 V, the voltage was stable without large fluctuations, and it was still about 1.38 V after 60 minutes. At 1 mA / cm 2 current density, the voltage was about 1.325 V; at 2 mA / cm 2 current density, the voltage was 1.30 V; at 5 mA / cm 2 , the voltage was 1.27 V; at 8 mA / cm 2 , it was 1.25 V; at 10 mA / cm 2 , the voltage dropped from 1.25 V to 1.22 V and stabilized at 1.22 V. When the current density dropped to 2 mA / cm 2 , the voltage recovered to 1.28 V, and at 1 mA / cm 2When the voltage reaches 1.30V, no obvious loss occurs. The battery with this catalyst has excellent stability, durability and potential application prospects.

[0073] The materials prepared in Examples 1-6 and Comparative Examples 1-3 all have a 4-electron path and can be used as catalysts for solid-state zinc-air batteries. The higher the limiting diffusion current, the better the catalytic effect. The currents of Examples 1-6 are all higher than those of Comparative Examples 1-3. Among them, the current of Example 5 is the highest, the catalytic effect is the best, and the service life of the primary battery is the longest.

[0074] Finally, it should be noted that the above preferred embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit them. Although the present invention has been described in detail through the above preferred embodiments, those skilled in the art should understand that various changes can be made in form and details without departing from the scope defined by the claims of the present invention.

Claims

1. A method for preparing an ORR polarization curve dual-platform current material, characterized in that: The steps include: (1) placing a single layer of graphene into the chamber of an atomic layer deposition device, closing the device door and starting a vacuum pump to evacuate the chamber, setting the heating temperature to 180°C-200°C, and turning on a heating device; and simultaneously heating an organic iron precursor, setting the temperature to 100°C-120°C; then, purging the device with high-purity nitrogen for 2-2.5 hours, and closing the purge valve after the chamber temperature reaches a stable temperature of 195-200°C; (2) starting atomic layer deposition, wherein the process parameters of the atomic layer deposition are as follows: Fe dosage time is 0.5-1 second, holding time is 60-80 seconds, nitrogen purge time is 20-30 seconds, vacuum release time is 180-210 seconds, chamber speed is 20-30 RPM, forward speed is 5-10 CW / S, and reverse speed is 5-10 CCW / S; (3) Repeat the atomic layer deposition process of step (2) 0-39 times. After the experiment is completed, turn off the chamber heating device and the precursor heating device, wait for the equipment to cool to room temperature, and then take out the sample; (4) The sample is annealed in high-purity hydrogen to finally obtain a double-platform current material with an ORR polarization curve.

2. The method for preparing the ORR polarization curve dual-platform current material according to claim 1, characterized in that: The organic iron precursor is bis(N,N'-di-tert-butylacetamidine)iron(II), tris(2,2,6,6-tetramethyl-3,5-heptanedione)iron, 1,1'-diethylferrocene, cyclohexadiene tricarbonyl iron, dicarbonylcyclopentadienyl iron dimer, ethylferrocene, ferrocene, tert-butylferrocene or carbonyl iron.

3. The method for preparing the ORR polarization curve dual-platform current material according to claim 1, characterized in that: The annealing treatment is carried out at a temperature of 750-800° C., a holding time of 2-3 hours, a heating rate of 2.5-5° C. / min, and a pressure of normal pressure.

4. The method for preparing the ORR polarization curve dual-platform current material according to claim 1, characterized in that: In the step (2), the precursor valve is opened and left to stand for 2-5 minutes before starting the atomic layer deposition.

5. The ORR polarization curve double-platform current material prepared according to the preparation method of the ORR polarization curve double-platform current material according to any one of claims 1 to 4.

6. Application of the ORR polarization curve dual-platform current material according to claim 5 in electro-Fenton degradation of antibiotics.

7. Application of the ORR polarization curve dual-platform current material according to claim 5 in solid-state batteries.

8. Application of the ORR polarization curve dual-platform current material according to claim 5 in electro-Fenton degradation of antibiotics and solid-state batteries.

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