A gap fluorine atom-doped ruthenium dioxide catalyst, a preparation method and application thereof
By doping interstitial fluorine atoms into the ruthenium dioxide catalyst, the problem of poor activity and stability in acidic water electrolysis was solved. The prepared catalyst exhibits excellent electrochemical water oxygen desorption performance and high current stability under acidic conditions, making it suitable for water electrolysis hydrogen production systems.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- SHENZHEN UNIV
- Filing Date
- 2022-11-30
- Publication Date
- 2026-04-28
AI Technical Summary
Existing ruthenium dioxide catalysts exhibit poor activity and stability in acidic water electrolysis, especially in redox reactions where they readily form RuO4 intermediates and dissolve, affecting catalyst durability.
By doping interstitial fluorine atoms into a ruthenium dioxide catalyst, an amorphous fluorocarbon substrate was prepared by high-temperature calcination of a fluorine-containing elastomer and then combined with a Ru precursor to form an interstitial fluorine atom-doped ruthenium dioxide catalyst. This process inhibits the formation of RuO4 intermediates and improves the stability of the catalyst.
The catalyst exhibits significantly improved electrochemical water desorption oxygen stability and activity in acidic electrolytes, especially demonstrating outstanding stability at high current densities, making it suitable as the anode in a three-electrode system for water electrolysis.
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Abstract
Description
Technical Field
[0001] This invention relates to the field of catalyst technology, and in particular to a ruthenium dioxide catalyst doped with interstitial fluorine atoms, its preparation method, and its application. Background Technology
[0002] Electrolysis of water is a clean and efficient method for producing hydrogen, in which the hydrogen evolution reaction (HER) occurs at the cathode and the oxygen evolution reaction (OER) occurs at the anode. However, the efficiency and large-scale application of water electrolysis are limited by these two half-reactions, especially the OER reaction. Therefore, there is an urgent need to develop highly active and stable OER electrocatalysts to reduce the large overpotential and improve the durability of the catalyst.
[0003] Meanwhile, the electrolysis performance of the catalyst varies at different pH levels. Compared with alkaline water splitting, H2 production in acidic media exhibits higher solution conductivity, voltage efficiency, current density, and hydrogen purity, showing broader prospects. However, the OER of the catalyst in acidic media involves complex steps such as adsorption of intermediate products and bonding of catalyst atoms, resulting in slow electrocatalytic kinetics and high potential.
[0004] Ruthenium dioxide (RuO2) has attracted much attention as a benchmark electrocatalyst for oxidation-reduction reactions (OERs) due to its relatively good activity and stability in acidic electrolytes. However, OERs under acidic conditions disrupt the lattice oxygen in the internal structure of RuO2 and enhance the adsorption of intermediate products, which is the most difficult bottleneck to overcome in acidic OERs. Meanwhile, in acidic OERs, the conversion of RuO2 to RuO4 and its subsequent dissolution in the electrolyte is a major obstacle to improving its stability.
[0005] The formation of RuO4 intermediates is closely related to the oxygen vacancy formation energy in the RuO2 structure. The more difficult it is for oxygen vacancies to form in RuO2, the less likely RuO4 intermediates are to form. Introducing non-metallic atoms into the interstitial spaces is a feasible strategy to stabilize the lattice oxygen in the RuO2 structure. These interstitial non-metallic atoms are small and easily enter the octahedral interstices of the RuO2 structure. Through interaction with O atoms, they can lower the oxygen vacancy formation energy and influence the electronic structure of Ru. The doping of interstitial non-metallic atoms may stabilize the lattice oxygen and suppress RuO4 formation. 2- The formation of these interstitial atoms enhances the stability of the catalyst. Currently reported interstitial atoms are mainly carbon atoms, but carbon atoms are easily oxidized under high current densities, detaching from the interstitial spaces and inhibiting the reaction.
[0006] Therefore, existing technologies still need to be improved and developed. Summary of the Invention
[0007] In view of the shortcomings of the prior art, the purpose of this invention is to provide an interstitial fluorine atom-doped ruthenium dioxide catalyst, its preparation method and application, aiming to solve the problem of poor activity and stability of existing ruthenium dioxide catalysts.
[0008] The technical solution of the present invention is as follows:
[0009] A method for preparing an interstitial fluorine atom-doped ruthenium dioxide catalyst, comprising the steps of:
[0010] The fluorinated elastomer was calcined for the first time in an inert gas atmosphere and then cooled to room temperature to obtain an amorphous fluorocarbon substrate.
[0011] The fluorocarbon substrate was dispersed in ethanol and subjected to ultrasonic treatment to obtain a fluorocarbon dispersion.
[0012] The Ru precursor solution was poured into the fluorocarbon dispersion and subjected to further ultrasonic treatment to obtain a Ru precursor / fluorocarbon suspension.
[0013] The Ru precursor / fluorocarbon suspension was dried to obtain Ru precursor / fluorocarbon powder.
[0014] The Ru precursor / fluorocarbon powder was subjected to a second calcination treatment and cooled to room temperature to obtain the interstitial fluorine atom-doped ruthenium dioxide catalyst.
[0015] The method for preparing the interstitial fluorine atom-doped ruthenium dioxide catalyst includes the step of first calcining the fluorine-containing elastomer in an inert gas atmosphere, wherein the temperature is first increased to 200-800℃ at a heating rate of 1-15℃ / min for 1-10h; then the temperature is increased to 800-1500℃ at a heating rate of 1-15℃ / min for 1-10h.
[0016] The method for preparing the interstitial fluorine atom-doped ruthenium dioxide catalyst, wherein the fluorine content of the fluorinated elastomer is greater than 20 wt%.
[0017] The method for preparing the interstitial fluorine atom-doped ruthenium dioxide catalyst, wherein the inert gas is one or more of argon, helium, and nitrogen.
[0018] The method for preparing the interstitial fluorine atom-doped ruthenium dioxide catalyst, wherein the preparation of the Ru precursor solution includes:
[0019] The metal Ru salt precursor is dissolved in ethanol or deionized water, stirred and sonicated until completely dissolved to obtain a Ru precursor solution.
[0020] The method for preparing the interstitial fluorine atom-doped ruthenium dioxide catalyst, wherein the metal Ru salt precursor is selected from one or more of Ru chloride, acetylacetone salt, acetate and iodide.
[0021] In the method for preparing the interstitial fluorine atom-doped ruthenium dioxide catalyst, the drying temperature in the step of drying the Ru precursor / fluorocarbon suspension is 50-150℃.
[0022] The method for preparing the interstitial fluorine atom-doped ruthenium dioxide catalyst, wherein in the step of performing a second calcination treatment on the Ru precursor / fluorocarbon powder, the temperature of the second calcination treatment is 200-800℃ and the time is 2-20h.
[0023] A ruthenium dioxide catalyst doped with interstitial fluorine atoms is prepared by the method for preparing the ruthenium dioxide catalyst doped with interstitial fluorine atoms described in this invention.
[0024] Application of an interstitial fluorine atom-doped ruthenium dioxide catalyst, wherein the interstitial fluorine atom-doped ruthenium dioxide catalyst is used as the anode in a three-electrode system for water electrolysis.
[0025] Beneficial Effects: This invention first obtains amorphous fluorocarbon materials by high-temperature calcination of fluorinated elastomers in an inert atmosphere. Then, a Ru precursor / fluorocarbon powder is prepared using a simple and easily scalable impregnation method. Subsequently, interstitial fluorine-doped ruthenium dioxide catalyst is obtained through air calcination. This process is simple and controllable, and conducive to large-scale industrial production. The catalyst structure prepared by this invention is ruthenium dioxide with interstitial fluorine atoms. The F atoms in the interstitial structure interact with the RuO6 octahedral structure, lengthening the Ru-O bond length, increasing the oxygen vacancy formation energy of ruthenium dioxide, and inhibiting the formation of RuO4 intermediates at the oxidation potential, which dissolve in the electrolyte, thereby improving the stability of the catalyst in the OER. The interstitial F-doped ruthenium dioxide may also contain carbon atoms in its interstitial structure. During the oxidation of the Ru precursor, both F and C atoms in the fluorocarbon substrate may diffuse into the interstitial structure of ruthenium dioxide through thermal diffusion, thus forming a fluorine-carbon co-doped ruthenium dioxide catalyst. The ruthenium dioxide catalyst with interstitial fluorine atom doping prepared in this invention, when used as the anode in a three-electrode system for water electrolysis, exhibits excellent electrochemical water desorption oxygen stability and activity in acidic electrolytes, especially showing outstanding stability at high current densities. Attached Figure Description
[0026] Figure 1 This is a flowchart of a method for preparing an interstitial fluorine atom-doped ruthenium dioxide catalyst according to the present invention.
[0027] Figure 2The image shows the XRD pattern of F-RuO2 / FC prepared in Example 1.
[0028] Figure 3 The image shows a SEM image of the F-RuO2 / FC prepared in Example 1.
[0029] Figure 4 The image shown is an HRTEM image of F-RuO2 / FC prepared in Example 1.
[0030] Figure 5 OER polarization curves of F-RuO2 / FC prepared in Example 1 and RuO2 / C prepared in the comparative example in 0.5M H2SO4 electrolyte.
[0031] Figure 6 The chronovoltammetric curves are shown for the stability tests of F-RuO2 / FC prepared in Example 1 and RuO2 / C prepared in the comparative example in 0.5M H2SO4 electrolyte, where the current density is fixed at 500 mA / cm. -2 . Detailed Implementation
[0032] This invention provides an interstitial fluorine atom-doped ruthenium dioxide catalyst, its preparation method, and its applications. To make the objectives, technical solutions, and effects of this invention clearer and more explicit, the invention is further described in detail below. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
[0033] Please see Figure 1 , Figure 1 The flowchart of a method for preparing an interstitial fluorine atom-doped ruthenium dioxide catalyst provided by the present invention is shown in the figure, which includes the following steps:
[0034] S10. The fluorinated elastomer is subjected to a first calcination treatment in an inert gas atmosphere, and after cooling to room temperature, an amorphous fluorocarbon substrate is obtained.
[0035] S20. The fluorocarbon substrate is dispersed in ethanol and subjected to ultrasonic treatment to obtain a fluorocarbon dispersion.
[0036] S30. Pour the Ru precursor solution into the fluorocarbon dispersion and continue to sonicate to obtain a Ru precursor / fluorocarbon suspension.
[0037] S40. The Ru precursor / fluorocarbon suspension is dried to obtain Ru precursor / fluorocarbon powder.
[0038] S50. The Ru precursor / fluorocarbon powder is subjected to a second calcination treatment and cooled to room temperature to obtain the interstitial fluorine atom-doped ruthenium dioxide catalyst.
[0039] In this invention, the fluorinated elastomer, also known as fluororubber, refers to a synthetic polymer elastomer whose carbon atoms in the main chain or side chain contain fluorine atoms. Considering that fluorine will volatilize during the high-temperature calcination process of the fluorinated elastomer, in order to ensure that the calcined fluorocarbon substrate has a high fluorine content, this invention selects a fluorinated elastomer with a fluorine content greater than 20 wt% for calcination, preferably a commercially available perfluorinated elastomer.
[0040] In this invention, the inert gas is one or more of argon, helium and nitrogen, but is not limited thereto.
[0041] In this invention, the fluorinated elastomer undergoes a first calcination treatment under an inert gas atmosphere. The first calcination treatment involves a first stage at a temperature of 200-800℃, a calcination time of 1-10 hours, and a heating rate of 1-15℃ / min; and a second stage at a temperature of 800-1500℃, a calcination time of 1-10 hours, and a heating rate of 1-15℃ / min. The purpose of the first stage of calcination is to allow the fluorinated elastomer to gradually solidify during the calcination process, while simultaneously causing the decomposition of the low-temperature unstable intermediate. Preferably, the first stage calcination temperature is 300-400℃, the heating rate is 5℃ / min, and the calcination time is 2-4 hours. The purpose of the second stage of calcination is to induce a high degree of decomposition of the carbon and fluorocarbon chains during rapid heating, forming an amorphous fluorocarbon substrate. Therefore, it is necessary to increase the heating rate to prevent the fluorocarbon from undergoing high-level graphitization and crystallization. However, excessively increasing the calcination time and temperature will cause severe fluorine decomposition, reducing the fluorine content in the product. Therefore, it is necessary to control the temperature and calcination time within a certain range. The preferred calcination temperature for the second stage is 1200-1400℃, the heating rate is 10℃ / min, and the calcination time is 2-4 hours.
[0042] In this invention, the preparation of the Ru precursor solution includes: dissolving a metal Ru salt precursor in ethanol or deionized water, stirring and sonicating until completely dissolved to obtain the Ru precursor solution. The metal Ru salt precursor is selected from one or more of Ru chloride, acetylacetone, acetate, and iodide, but is not limited thereto.
[0043] In this invention, the mass fraction of Ru relative to fluorocarbon in the Ru precursor / fluorocarbon suspension is 10-50 wt%, but is not limited thereto.
[0044] In this invention, the above-mentioned Ru precursor / fluorocarbon suspension is placed in a forced-air drying oven for drying to obtain Ru precursor / fluorocarbon powder. The drying temperature in the forced-air drying oven is 50-150°C. Preferably, the drying temperature is 80°C.
[0045] In this invention, the Ru precursor / fluorocarbon powder undergoes a second calcination treatment, and after cooling to room temperature, the interstitial fluorine-doped ruthenium dioxide catalyst is obtained. Preferably, the Ru precursor / fluorocarbon powder is placed in a quartz boat and subjected to a second calcination treatment in a muffle furnace at a temperature of 200-800°C for 2-20 hours. In this invention, excessively high calcination temperatures or excessively long calcination times will cause severe fluorine degradation in the fluorocarbon substrate, resulting in a decrease in the fluorine content that diffuses into the ruthenium dioxide interstices through thermal diffusion.
[0046] This invention first obtains amorphous fluorocarbon materials by high-temperature calcination of a fluorinated elastomer in an inert atmosphere. Then, a Ru precursor / fluorocarbon powder is prepared using a simple and easily scalable impregnation method. Subsequently, interstitial fluorine-doped ruthenium dioxide catalyst is obtained through air calcination. This process is simple and controllable, and conducive to large-scale industrial production. The catalyst structure prepared by this invention is ruthenium dioxide with interstitial fluorine atoms. The F atoms in the interstitial structure interact with the RuO6 octahedral structure, lengthening the Ru-O bond length, increasing the oxygen vacancy formation energy of ruthenium dioxide, and inhibiting the formation of RuO4 intermediates at the oxidation potential, which dissolve in the electrolyte, thereby improving the stability of the catalyst in the OER. The interstitial F-doped ruthenium dioxide may also contain carbon atoms in its interstitial structure. During the oxidation of the Ru precursor, both F and C atoms in the fluorocarbon substrate may diffuse into the interstitial structure of ruthenium dioxide through thermal diffusion, thus forming a fluorine-carbon co-doped ruthenium dioxide catalyst.
[0047] In some embodiments, an interstitial fluorine atom-doped ruthenium dioxide catalyst is also provided, wherein it is prepared by the method for preparing the interstitial fluorine atom-doped ruthenium dioxide catalyst described in this invention.
[0048] In some embodiments, an application of the interstitial fluorine-doped ruthenium dioxide catalyst is also provided, wherein the interstitial fluorine-doped ruthenium dioxide catalyst is used as the anode in a three-electrode system for water electrolysis. The interstitial fluorine-doped ruthenium dioxide catalyst prepared by this invention, as the anode in a three-electrode system for water electrolysis, exhibits excellent electrochemical water desorption oxygen stability and activity in acidic electrolytes (0.5M H₂SO₄ or 0.1M HClO₄), especially demonstrating outstanding stability at high current densities.
[0049] The present invention will be further explained and illustrated below through specific embodiments:
[0050] Example 1
[0051] Take 500g of perfluorinated elastomer, place it in a quartz boat, and then place it in a tube furnace for calcination in an argon atmosphere (purity >99%). First, raise the temperature to 300℃ and maintain it for 2 hours, then continue to raise the temperature to 1300℃ and maintain it for 2 hours. After cooling to room temperature, an amorphous fluorocarbon substrate is obtained.
[0052] 200 mg of anhydrous ruthenium trichloride was dissolved in 20 mL of deionized water and magnetically stirred for one hour, followed by sonication for half an hour to ensure complete dissolution, yielding a RuCl3 precursor solution. Simultaneously, 200 mg of a fluorocarbon substrate was dispersed in 5 mL of ethanol and sonicated for one hour to obtain a homogeneous fluorocarbon dispersion. The RuCl3 precursor solution was then added to the fluorocarbon dispersion and sonicated for another half hour to ensure uniform dispersion, resulting in a RuCl3 / fluorocarbon suspension.
[0053] The RuCl3 / fluorocarbon suspension was placed in a forced-air drying oven and dried at 80°C for 12 hours to obtain RuCl3 / fluorocarbon powder.
[0054] The powder was placed in a quartz boat and calcined in a muffle furnace at a heating rate of 5°C / min. The temperature was increased from room temperature to 300°C and calcined for 10 hours. After cooling to room temperature, the RuO2 catalyst doped with interstitial F atoms was obtained, denoted as F-RuO2 / FC.
[0055] Figure 2 The XRD pattern of the catalyst prepared in Example 1. Observation Figure 2 It can be confirmed that the catalyst prepared in Example 1 is in the form of crystalline ruthenium dioxide.
[0056] Figure 3 SEM image of the catalyst prepared in Example 1. From Figure 3 It can be seen that the interstitial F-atom-doped ruthenium dioxide catalyst is supported on the fluorocarbon substrate, and the macroscopic morphology of the fluorocarbon substrate can be seen by SEM.
[0057] Figure 4 HRTEM image of the catalyst prepared in Example 1. From Figure 4 Clear ruthenium dioxide lattice stripes can be seen on the fluorocarbon substrate, with a crystal plane spacing of 0.324 nm, corresponding to the (110) crystal plane of RuO2.
[0058] Example 2
[0059] Take 500g of fluorine elastomer with a fluorine content of 50wt%, place it in a quartz boat, and then place it in a tube furnace for calcination in an argon atmosphere (purity >99%). First, raise the temperature to 300℃ and maintain it for 2 hours, then continue to raise the temperature to 1300℃ and maintain it for 2 hours. After cooling to room temperature, an amorphous fluorocarbon substrate is obtained.
[0060] 200 mg of ruthenium acetylacetonate was dissolved in 20 mL of deionized water and magnetically stirred for one hour, followed by sonication for half an hour to ensure complete dissolution, yielding a Ru precursor solution. Simultaneously, 200 mg of a fluorocarbon substrate was dispersed in 5 mL of ethanol and sonicated for one hour to obtain a homogeneous fluorocarbon dispersion. The Ru precursor solution was then added to the fluorocarbon dispersion and sonicated for another half hour to ensure uniform dispersion, resulting in a ruthenium acetylacetonate / fluorocarbon suspension.
[0061] The above ruthenium acetylacetone / fluorocarbon suspension was placed in a forced-air drying oven and dried at 80°C for 12 hours to obtain ruthenium acetylacetone / fluorocarbon powder.
[0062] The powder was placed in a quartz boat and calcined in a muffle furnace at a heating rate of 5°C / min. The temperature was increased from room temperature to 300°C and calcined for 10 hours. After cooling to room temperature, the RuO2 catalyst doped with interstitial F atoms was obtained, denoted as F-RuO2 / FC-2.
[0063] Example 3
[0064] Take 500g of perfluorinated elastomer, place it in a quartz boat, and then place it in a tube furnace for calcination in an argon atmosphere (purity >99%). First, raise the temperature to 300℃ and maintain it for 2 hours, then continue to raise the temperature to 1300℃ and maintain it for 2 hours. After cooling to room temperature, an amorphous fluorocarbon substrate is obtained.
[0065] 200 mg of ruthenium acetylacetonate was dissolved in 20 mL of deionized water and magnetically stirred for one hour, followed by sonication for half an hour to ensure complete dissolution, yielding a Ru precursor solution. Simultaneously, 200 mg of a fluorocarbon substrate was dispersed in 5 mL of ethanol and sonicated for one hour to obtain a homogeneous fluorocarbon dispersion. The Ru precursor solution was then added to the fluorocarbon dispersion and sonicated for another half hour to ensure uniform dispersion, resulting in a ruthenium acetylacetonate / fluorocarbon suspension.
[0066] The above ruthenium acetylacetone / fluorocarbon suspension was placed in a forced-air drying oven and dried at 80°C for 12 hours to obtain ruthenium acetylacetone / fluorocarbon powder.
[0067] The powder was placed in a quartz boat and calcined in a muffle furnace at a heating rate of 5°C / min. The temperature was increased from room temperature to 400°C and calcined for 8 hours. After cooling to room temperature, the RuO2 catalyst doped with interstitial F atoms was obtained, denoted as F-RuO2 / FC-3.
[0068] Comparative Example 1
[0069] 200 mg of anhydrous ruthenium trichloride was dissolved in 20 mL of deionized water and magnetically stirred for one hour, followed by sonication for half an hour to ensure complete dissolution, yielding a RuCl3 precursor solution. Simultaneously, 200 mg of commercial toner was dispersed in 5 mL of ethanol and sonicated for one hour to obtain a homogeneous toner dispersion. The RuCl3 precursor solution was then added to the toner dispersion and sonicated for another half hour to ensure uniform dispersion, resulting in a RuCl3 / toner suspension.
[0070] The RuCl3 / carbon powder suspension was placed in a forced-air drying oven and dried at 80°C for 12 hours to obtain RuCl3 / carbon powder.
[0071] The powder was placed in a quartz boat and calcined in a muffle furnace at a heating rate of 5°C / min. The temperature was increased from room temperature to 300°C and calcined for 10 hours. After cooling to room temperature, the RuO2 catalyst was obtained, denoted as RuO2 / C.
[0072] Application examples
[0073] The F-RuO2 / FC from Example 1 and the RuO2 / C from Comparative Example 1 were prepared into inks for later use. The ink preparation method was as follows: 2 mg of catalyst powder was dispersed in 1 mL of ethanol solution, followed by the addition of 200 μL of a 5 wt% perfluorosulfonic acid solution. The mixture was sonicated for 1 hour to obtain a homogeneous catalyst ink. After preparing the ink, 10 μL of the ink was transferred using a pipette and dropped onto a 5 mm diameter glassy carbon electrode. After drying, the working electrode was obtained. A traditional three-electrode system was selected to determine the catalytic oxygen evolution performance of the materials. 0.5 M H2SO4 was used as the electrolyte, the glassy carbon electrode after ink dropping and drying was used as the working electrode, a graphite rod was used as the counter electrode, and a mercurous sulfate electrode (Hg / Hg2SO4) was used as the reference electrode. The oxygen evolution performance of the materials was tested using linear sweep voltammetry, and the long-range stability of the materials under high current density was tested using chronopotentiometric method.
[0074] like Figure 5 As shown, compared with the RuO2 / C prepared in the comparative example, the F-RuO2 / FC prepared in Example 1 exhibited superior oxygen evolution performance, reaching 10 mA cm⁻¹. -2 The overpotential required for the current density is only 220mV, while the comparative RuO2 / C requires 330mV, which is 110mV higher than F-RuO2 / FC.
[0075] Figure 6 The F-RuO2 / FC prepared in Example 1 and the comparative RuO2 / C were tested under acidic conditions (0.5 M H2SO4) with a fixed current density of 500 mA cm⁻¹. -2The change in the potential required for oxygen evolution was investigated. The chronopotential curve results showed that the potential required for F-RuO2 / FC remained almost constant at a fixed current density for over 500 hours, indicating excellent long-range stability under high current, meeting the requirements for industrial-scale water electrolysis for hydrogen production. In contrast, the potential required for the comparative-prepared RuO2 / C increased sharply after 50 hours at a fixed current density, indicating catalyst deactivation.
[0076] It should be understood that the application of the present invention is not limited to the examples above. Those skilled in the art can make improvements or modifications based on the above description, and all such improvements and modifications should fall within the protection scope of the appended claims.
Claims
1. A method for preparing an interstitial fluorine atom-doped ruthenium dioxide catalyst, characterized in that, Including the following steps: The fluorinated elastomer was calcined for the first time in an inert gas atmosphere and then cooled to room temperature to obtain an amorphous fluorocarbon substrate. The fluorocarbon substrate was dispersed in ethanol and subjected to ultrasonic treatment to obtain a fluorocarbon dispersion. The Ru precursor solution was poured into the fluorocarbon dispersion and subjected to further ultrasonic treatment to obtain a Ru precursor / fluorocarbon suspension. The Ru precursor / fluorocarbon suspension was dried to obtain Ru precursor / fluorocarbon powder. The Ru precursor / fluorocarbon powder was subjected to a second calcination treatment and cooled to room temperature to obtain the interstitial fluorine atom-doped ruthenium dioxide catalyst.
2. The method for preparing the interstitial fluorine atom-doped ruthenium dioxide catalyst according to claim 1, characterized in that, In the first calcination treatment of the fluorinated elastomer in an inert gas atmosphere, the temperature is first raised to 200-800℃ at a heating rate of 1-15℃ / min, and the calcination time is 1-10h; then the temperature is raised to 800-1500℃ at a heating rate of 1-15℃ / min, and the calcination time is 1-10h.
3. The method for preparing the interstitial fluorine atom-doped ruthenium dioxide catalyst according to claim 1, characterized in that, The fluorine content of the fluorinated elastomer is greater than 20 wt%.
4. The method for preparing the interstitial fluorine atom-doped ruthenium dioxide catalyst according to claim 1, characterized in that, The inert gas is one or more of argon, helium, and nitrogen.
5. The method for preparing the interstitial fluorine atom-doped ruthenium dioxide catalyst according to claim 1, characterized in that, The preparation of the Ru precursor solution includes: The metal Ru salt precursor is dissolved in ethanol or deionized water, stirred and sonicated until completely dissolved to obtain a Ru precursor solution.
6. The method for preparing the interstitial fluorine atom-doped ruthenium dioxide catalyst according to claim 5, characterized in that, The precursor of metal Ru salt is selected from one or more of Ru chloride, acetylacetone salt, acetate and iodide.
7. The method for preparing the interstitial fluorine atom-doped ruthenium dioxide catalyst according to claim 1, characterized in that, In the step of drying the Ru precursor / fluorocarbon suspension, the drying temperature is 50-150℃.
8. The method for preparing the interstitial fluorine atom-doped ruthenium dioxide catalyst according to claim 1, characterized in that, In the step of performing a second calcination treatment on the Ru precursor / fluorocarbon powder, the temperature of the second calcination treatment is 200-800℃ and the time is 2-20h.
9. A ruthenium dioxide catalyst doped with interstitial fluorine atoms, characterized in that, The ruthenium dioxide catalyst with interstitial fluorine atom doping as described in any one of claims 1-8 was prepared.
10. The application of the ruthenium dioxide catalyst doped with interstitial fluorine atoms as described in claim 9, characterized in that, The interstitial fluorine-doped ruthenium dioxide catalyst was used as the anode in the three-electrode system for water electrolysis.