Phosphorus-doped iridium dioxide, preparation method thereof, and application thereof

Abstract

The present invention discloses a phosphorus-doped iridium dioxide and its preparation method and application. The preparation method of the phosphorus-doped iridium dioxide comprises the following steps: S1, using a microwave-assisted ethylene glycol reduction method to load an Ir precursor salt on porous graphene to obtain an Ir-loaded porous graphene precursor substance; S2, heat-treating the Ir-loaded porous graphene precursor substance to obtain IrO2 nanoparticles; S3, dispersing the IrO2 nanoparticles in a NiSO4 aqueous solution, then adding MH2PO2, reacting to obtain phosphorus-doped IrO2 nanoparticles; wherein M is an alkali metal cation. The present invention modulates the Ir-O active sites and the adsorption energy of the reaction intermediates through electronic structure modulation, thereby enhancing the OER reaction kinetics, thereby achieving an improvement in the intrinsic activity of IrO2 and a substantial reduction in the amount of Ir used.

Description

Technical Field

[0001] The invention relates to phosphorus-doped iridium dioxide and a preparation method and application thereof. Background Art

[0002] Hydrogen has high energy density, is low-carbon and green, and its combustion product is water, resulting in zero pollution. Therefore, it is suitable as a large-scale energy storage medium for energy conservation. Proton exchange membrane water electrolysis (PEMWE) hydrogen production, with its high energy efficiency, high gas purity, fast startup, and strong power adaptability, is currently a major research direction in the development of green hydrogen production. However, the performance of the electrolyzer determines the cost of hydrogen production and the future scale of its industrialization.

[0003] Due to the strong acid and strong oxidizing environment of the proton exchange membrane system, the choice of anodic oxygen evolution reaction (OER) catalysts is relatively limited. Currently, the commonly used ones are still mainly noble metal Ir oxides or Ru oxides, and the loading is relatively high (>1.5 mg cm -2 (Ir)), which has greatly restricted the market development of PEMWE.

[0004] Therefore, it is particularly urgent to develop efficient, stable and low-noble metal catalysts.

[0005] At present, IrO2 catalyst is usually used as the anodic oxygen evolution reaction (OER) catalyst, and the dosage is about 1.5 mg cm -2 , which is relatively high, mainly due to the low intrinsic catalytic activity of IrO2.

[0006] Therefore, there is an urgent need to provide IrO2 with low dosage, high intrinsic activity and strong OER reaction kinetics. Summary of the Invention

[0007] To address the existing shortcomings of IrO2, which suffer from low intrinsic catalytic activity and high IrO2 dosage, this invention provides phosphorus-doped iridium dioxide, its preparation method, and its application. By modulating the electronic structure, the invention modulates the Ir-O active sites and the adsorption energy of reaction intermediates, enhancing the OER reaction kinetics. This improves the intrinsic activity of IrO2 and significantly reduces the Ir dosage.

[0008] The present invention solves the above technical problems through the following technical solutions.

[0009] One of the technical solutions of the present invention is: a method for preparing phosphorus-doped iridium dioxide. The preparation method comprises the following steps:

[0010] S1. Using a microwave-assisted ethylene glycol reduction method, an Ir precursor salt is loaded on porous graphene to obtain an Ir-loaded porous graphene precursor material;

[0011] S2, heat-treating the Ir-loaded porous graphene precursor material to obtain IrO2 nanoparticles;

[0012] S3. Dispersing IrO2 nanoparticles in a NiSO4 aqueous solution, and then adding MH2PO2 to react to obtain P-doped IrO2 nanoparticles; wherein M is an alkali metal cation.

[0013] In S1 of the present invention, the operation and conditions of the microwave-assisted ethylene glycol reduction method can be conventional in the art. For example, a metal source is dissolved in an ethylene glycol solution to obtain a metal salt solution (i.e., an Ir precursor salt); the porous graphene is added to the metal salt solution, and then placed in a microwave reactor for reaction.

[0014] Wherein, the metal source is preferably chloroiridic acid.

[0015] The concentration of the metal salt in the metal salt solution is preferably 5-10 mg / L.

[0016] The porous graphene is generally in powder form. The specific surface area of ​​the porous graphene is preferably 2000-1000m 2 ·g -1 The pore size distribution of the porous graphene is preferably 3-20 nm, more preferably 5-10 nm. The ratio of the mass of the metal salt in the metal salt solution to the mass of the porous graphene is 1:(10-20).

[0017] The reaction temperature is preferably 80-180° C., more preferably 80-140° C., such as 120° C. The reaction time is preferably 5-30 min.

[0018] After the reaction is completed, the steps of filtration and washing are generally further included.

[0019] In S2 of the present invention, the operation and conditions of the heat treatment may be conventional in the art.

[0020] Wherein, the heat treatment equipment is preferably a muffle furnace.

[0021] The atmosphere for the heat treatment is preferably an air atmosphere.

[0022] The target temperature of the heat treatment is preferably 450-650° C. During the heating process to the target temperature, the heating rate is preferably 2° C. / min. Preferably, the target temperature is maintained for 1-4 hours.

[0023] In S2 of the present invention, the heat treatment can oxidize Ir into IrO2 and remove the porous graphene.

[0024] In the present invention S2, the spatial barrier effect of graphene is utilized to effectively prevent the agglomeration of IrO2 nanoparticles during the heat treatment process. Preferably, the particle size distribution of the IrO2 nanoparticles is 2-5 nm, and is used to form non-supported IrO2 nanoparticles (IrO2-NPs).

[0025] In S3 of the present invention, the step of dispersing IrO2 nanoparticles in NiSO4 aqueous solution is preferably to disperse IrO2 in aqueous solution, ultrasonically disperse it, and then add NiSO4 solution.

[0026] The ultrasonic dispersion time is preferably 2-4 hours. The amount of NiSO4 solution added is preferably 5-10 mL. The concentration of NiSO4 solution is preferably 1 mol / L.

[0027] In S3 of the present invention, IrO2 nanoparticles are dispersed in a NiSO4 aqueous solution to obtain a dispersion, and then MH2PO2 is added.

[0028] The amount of MH2PO2 added is generally excessive relative to the dispersion, for example, 10-20 times the amount of MH2PO2 added relative to the dispersion in molar ratio.

[0029] In S3 of the present invention, the alkali metal cation can be conventional in the art, such as sodium ion or potassium ion.

[0030] The MH2PO2 is preferably NaH2PO2 or KH2PO2.

[0031] In S3 of the present invention, the reaction is preferably carried out under stirring and the reaction time may be 0.5-2 h.

[0032] In S3 of the present invention, after the reaction, the steps of centrifugal washing and drying are generally further included.

[0033] The centrifugal washing can be performed conventionally in the art, for example, the number of centrifugal washings is 2-3 times.

[0034] The drying can be conventional in the art, such as oven drying. After the oven drying, P-doped IrO2 nanoparticles can be obtained. It will be understood by those skilled in the art that in the phosphorus-doped iridium dioxide, phosphorus atoms are generally doped into the iridium dioxide lattice in the form of replacing oxygen atoms. The P-doped IrO2 nanoparticles are generally in powder form, denoted as P x -(IrO2) y Wherein, x is the mass ratio of P, and y is the mass ratio of IrO2. x can be 5%-0.5%, for example, 2%-3.5%.

[0035] The second technical solution of the present invention is: a phosphorus-doped iridium dioxide, which is prepared by the preparation method of phosphorus-doped iridium dioxide as described above.

[0036] In the present invention, the phosphorus-doped iridium dioxide is preferably in the form of nanoparticles.

[0037] The third technical solution of the present invention is: a phosphorus-doped iridium dioxide, wherein the molecular formula of the phosphorus-doped iridium dioxide is P x (IrO2) y ; Wherein, x is the mass ratio of P, y is the mass ratio of IrO2; x+y=100%; the range of x is 5%-0.5%, and the range of y is 95% to 99.5%;

[0038] The phosphorus-doped iridium dioxide is nanoparticles; the particle size of the nanoparticles ranges from 3 to 10 nm;

[0039] In the phosphorus-doped iridium dioxide, phosphorus atoms are doped into the iridium dioxide lattice in a manner of replacing oxygen atoms.

[0040] In the present invention, preferably, the range of x is 2%-3.5%, and the range of y is 98%-96.5%.

[0041] In the present invention, the iridium dioxide is preferably prepared from an Ir precursor salt and porous graphene, for example, using S1 and S2 as described above.

[0042] The fourth technical solution of the present invention is: the use of phosphorus-doped iridium dioxide as a catalyst in electrolysis of water.

[0043] In the present invention, the electrolyzed water can be conventional in the art and is generally used for hydrogen production. The electrolyzed water is preferably proton exchange membrane electrolyzed water.

[0044] On the basis of conforming to the common sense in this field, the above-mentioned preferred conditions can be arbitrarily combined to obtain the preferred embodiments of the present invention.

[0045] The reagents and raw materials used in the present invention are commercially available.

[0046] The positive progress effect of the present invention is:

[0047] (1) The present invention uses lattice stress to regulate the electronic structure of IrO2 and utilizes a carbon template method combined with in-situ P doping technology to controllably synthesize P-doped IrO2 nanoparticle catalysts. The efficient introduction of P helps to induce IrO2 lattice distortion, thereby changing the charge distribution of the active center (Ir center) and the adsorption energy of oxygen-containing intermediates (OH) through the stress effect, thereby accelerating the OER reaction kinetics, significantly improving the intrinsic catalytic activity of the IrO2 catalyst, and achieving the purpose of reducing the amount of precious metals used, thereby realizing the preparation of low-Ir water electrolysis anode catalysts and membrane electrode applications.

[0048] (2) The preparation method of phosphorus-doped iridium dioxide in the present invention utilizes the porous structure of graphene to uniformly and efficiently load Ir metal particles. Subsequently, through air heat treatment, the graphene carrier acts as a space barrier to prevent the metal particles from agglomerating and growing. Finally, during the heat treatment process, the graphene is oxidized and decomposed, and the Ir is oxidized to form a non-supported small-sized IrO2 nanoparticle catalyst. BRIEF DESCRIPTION OF THE DRAWINGS

[0049] Figure 1 2 are X-ray single crystal diffraction patterns of the P-doped IrO2 catalysts in Examples 1 and 2 and the IrO2 in Comparative Example 1.

[0050] Figure 2 These are the linear scan curves of electrochemical oxygen evolution of the P-doped IrO2 catalysts in Examples 1-2 and the IrO2 in Comparative Example 1. DETAILED DESCRIPTION

[0051] The present invention is further illustrated by way of examples below, but the present invention is not limited to the scope of the examples. Experimental methods in the following examples where specific conditions are not specified were performed according to conventional methods and conditions, or selected according to the product specifications.

[0052] Example 1P2-(IrO2) 98 Preparation

[0053] S1. Preparation of Ir-loaded porous graphene precursor: Weigh 500 mg of chloroiridic acid as a metal source and dissolve it in ethylene glycol solution with a metal salt concentration of 10 mg / L. Then add a certain amount of porous graphene (with a specific surface area of ​​1200 m 2 ·g -1 The resulting mixture is a powder (with a pore size distribution of 5-10 nm) with a mass approximately 10 times that of the metal salt. The mixture is then placed in a microwave reactor at 120°C for 30 minutes. After the reaction is complete, the mixture is filtered and washed to obtain an Ir-loaded porous graphene precursor (i.e., Ir / PG material).

[0054] S2. Preparation of IrO2 nanoparticles: Weigh the Ir / PG material prepared above, place it in a muffle furnace, raise the temperature to 650℃ at a heating rate of 2℃ / min, and keep it in air atmosphere for 1 hour to obtain IrO2 nanoparticles (with a particle size distribution of 2-5nm).

[0055] S3. Preparation of P-doped IrO2 catalyst: IrO2 was dispersed in aqueous solution, ultrasonically dispersed for 2 hours, 5 mL of 1 mol / L NiSO4 solution was added, followed by a 10-fold excess of NaH2PO2. After stirring for 1 hour, the mixture was centrifuged and washed 2-3 times, and dried to obtain a P-doped IrO2 catalyst.

[0056] The P content in the P-doped IrO2 catalyst was determined by XPS, and the mass ratio of P in the catalyst was 2%, that is, the catalyst prepared in Example 1 was P2-(IrO2). 98 .

[0057] Example 2P 3.5 (IrO2) 96.5 Preparation

[0058] S1. Preparation of Ir-loaded porous graphene precursor: 500 mg of chloroiridic acid was weighed as a metal source and dissolved in ethylene glycol solution with a metal salt concentration of 10 mg / L. Then a certain amount of porous graphene powder (with a specific surface area of ​​1200 m 2 ·g -1 The resulting mixture is placed in a microwave reactor, set at 120°C for 30 minutes, and filtered and washed to obtain an Ir-loaded porous graphene precursor (i.e., Ir / PG material).

[0059] S2. Preparation of IrO2 nanoparticles: Weigh the Ir / PG material prepared above, place it in a muffle furnace, raise the temperature to 650℃ at a heating rate of 2℃ / min, and keep it in air atmosphere for 1 hour to obtain IrO2 nanoparticles (with a particle size distribution of 2-5nm).

[0060] S3. Preparation of P-doped IrO2 catalyst: IrO2 was dispersed in aqueous solution, ultrasonically dispersed for 2 hours, 10 mL of 1 mol / L NiSO4 solution was added, followed by a 20-fold excess of NaH2PO2. After stirring for 1 hour, the mixture was centrifuged and washed 2-3 times, and dried to obtain a P-doped IrO2 catalyst.

[0061] The P content in the P-doped IrO2 catalyst was determined by XPS, and the mass ratio of P in the catalyst was 3.5%, that is, the catalyst prepared in Example 1 was P. 3.5 -(IrO2) 96.5 .

[0062] Comparative Example 1 Preparation of IrO2

[0063] S1. Preparation of Ir-loaded porous graphene precursor: 500 mg of chloroiridic acid was weighed as a metal source and dissolved in ethylene glycol solution with a metal salt concentration of 10 mg / L. Then a certain amount of porous graphene powder (with a specific surface area of ​​1200 m 2 ·g -1 The resulting mixture is placed in a microwave reactor, set at 120°C for 30 minutes, and filtered and washed to obtain an Ir-loaded porous graphene precursor (i.e., Ir / PG material).

[0064] S2. Preparation of IrO2 nanoparticles: Weigh the Ir / PG material prepared above, place it in a muffle furnace, raise the temperature to 650℃ at a heating rate of 2℃ / min, and keep it in air atmosphere for 1 hour to obtain IrO2 nanoparticles (with a particle size distribution of 2-5nm).

[0065] Comparative Example 2

[0066] S1. Preparation of Ir nanoparticles: 500 mg of chloroiridic acid (a metal source) was weighed and dissolved in ethylene glycol solution at a metal salt concentration of 10 mg / L. The solution was then placed in a microwave reactor at 120°C for 30 minutes. After the reaction, Ir nanoparticles (Ir-NPs) were obtained by filtration and washing.

[0067] S2. Preparation of IrO2 nanoparticles: Weigh the Ir-NPs material prepared above, place it in a muffle furnace, raise the temperature to a target temperature of 650°C at a heating rate of 2°C / min, and keep it in an air atmosphere for 1 hour to obtain IrO2 nanoparticles with a particle size distribution range of 12-15 nm.

[0068] S3. Preparation of P-doped IrO2 catalyst: IrO2 was dispersed in aqueous solution, ultrasonically dispersed for 2 hours, 10 mL of 1 mol / L NiSO4 solution was added, followed by a 20-fold excess of NaH2PO2. After stirring for 1 hour, the mixture was centrifuged and washed 2-3 times, and dried to obtain a P-doped IrO2 catalyst.

[0069] The P content in the P-doped IrO2 catalyst was determined by XPS, and the mass ratio of P in the catalyst was 1.5%, that is, the catalyst prepared in Example 1 was P. 1.5 -(IrO2) 98.5 .

[0070] It can be seen from the above results that when graphene is not added as a carbon template, the particle size distribution range of the obtained IrO2 nanoparticles is 12-15nm, which is larger than that of Examples 1 to 2, and cannot have a positive effect on subsequent P doping and achieve the improvement of IrO2 intrinsic activity.

[0071] Effect Example 1

[0072] The microstructure of the P-doped IrO2 catalysts in Examples 1 and 2 and the IrO2 in Comparative Example 1 were tested. Figure 1 shown.

[0073] Depend on Figure 1 It can be seen from the X-ray single crystal diffraction surface that the structure of the prepared catalyst is IrO2, and the diffraction peak position of the P atom-doped sample moves to a smaller angle relative to that of pure IrO2, representing lattice stretching, proving that P atoms do replace O sites in the doped IrO2 lattice. Since the radius of P atoms is larger than that of O, it will cause lattice stretching.

[0074] Effect Example 2

[0075] The OER catalytic activity of P-doped IrO2 catalyst in 0.5M H2SO4 was tested as follows: a certain mass of P-IrO2 catalyst was weighed and prepared into 2 mL of solution with isopropanol / water (1:1) solution at a concentration of 1 mg / mL. After ultrasonic dispersion for 2 hours, the solution was dropped onto a previously polished and washed glassy carbon (GC, 5 mm) electrode, and the loading was controlled at 15-25 μg (Pt) / cm 2 Subsequently, electrochemical OER tests were carried out in 0.5 M H2SO4 solution using a three-electrode system.

[0076] The test method for the OER catalytic activity of the P-doped IrO2 catalyst in 0.5M H2SO4 in Example 1 is as follows: 2 mg of P-IrO2 catalyst was weighed, 1 mL of isopropanol, 950 μL of water and 50 μL of 5% Nafion solution were added to prepare 2 mL of a dispersion with a concentration of 1 mg / mL. After ultrasonic dispersion for 2 hours, the dispersion was dropped onto a previously polished and washed glassy carbon (GC, 5 mm) electrode, and the catalyst loading was controlled at 15 μg / cm 2 Subsequently, electrochemical OER tests were carried out in 0.5 M H2SO4 solution using a three-electrode system.

[0077] The OER test results of P-doped IrO2 catalyst in Example 1 are as follows: Figure 2 As shown. Figure 2 The curve corresponding to P-IrO2-1 shows that its performance is significantly improved after P doping. -2The overpotential corresponding to the current density is significantly reduced, from 236 mV to 212 mV, proving that P doping does enhance the intrinsic water oxidation catalytic activity of IrO2.

[0078] The test method for the OER catalytic activity of the P-doped IrO2 catalyst in 0.5M H2SO4 in Example 2 is as follows: 2 mg of P-IrO2 catalyst was weighed, 1 mL of isopropanol, 950 μL of water and 50 μL of 5% Nafion solution were added to prepare 2 mL of a dispersion with a concentration of 1 mg / mL. After ultrasonic dispersion for 2 hours, the dispersion was dropped onto a previously polished and washed glassy carbon (GC, 5 mm) electrode, and the catalyst loading was controlled at 15 μg / cm 2 Subsequently, electrochemical OER tests were carried out in 0.5 M H2SO4 solution using a three-electrode system.

[0079] The OER test results of P-doped IrO2 catalyst in Example 2 are as follows: Figure 2 As shown. Figure 2 The curve corresponding to P-IrO2-2 shows that after P doping, the performance is improved compared with that of IrO2 without P doping. -2 The overpotential corresponding to the current density decreased from 236 mV to 225 mV, but the performance was slightly reduced compared with Example 1. From the above comparison, it can be seen that the more P doping amount, the better.

[0080] The OER catalytic activity of IrO2 catalyst in 0.5M H2SO4 in Comparative Example 1 was tested as follows: 2 mg of IrO2 catalyst was weighed, 1 mL of isopropanol, 950 μL of water, and 50 μL of 5% Nafion solution were added to prepare 2 mL of a dispersion with a concentration of 1 mg / mL. After ultrasonic dispersion for 2 hours, the dispersion was dropped onto a previously polished and washed glassy carbon (GC, 5 mm) electrode, and the catalyst loading was controlled at 15 μg / cm 2 Subsequently, electrochemical OER tests were carried out in 0.5 M H2SO4 solution using a three-electrode system.

[0081] The OER test results of IrO2 catalyst in Comparative Example 1 are as follows: Figure 2 From the curve corresponding to IrO2, it can be seen that its performance is obviously inferior to that of Examples 1 and 2.

[0082] After analyzing the above effect data, the inventors found that: x -(IrO2) yIn the reaction, P atoms replace O sites. Due to the different electronegativity of O and P, the local charge distribution of Ir-O will be destroyed, and electrons will be more inclined to the Ir center, realizing charge enrichment of the Ir center, which will lead to a decrease in the d-band orbital energy level and reduce the adsorption energy of oxygen-containing intermediates in the water oxidation reaction, thereby accelerating the adsorption and desorption behavior of the intermediates and the energy barrier of the reaction rate-determining step, thereby achieving improved OER performance.

Claims

1. A method for preparing phosphorus-doped iridium dioxide, characterized in that: It includes the following steps: S1. Using a microwave-assisted ethylene glycol reduction method, an Ir precursor salt is loaded on porous graphene to obtain an Ir-loaded porous graphene precursor material; S2, heat-treating the Ir-loaded porous graphene precursor material to obtain IrO2 nanoparticles; S3. Dispersing IrO2 nanoparticles in a NiSO4 aqueous solution, and then adding MH2PO2 to react to obtain phosphorus-doped IrO2 nanoparticles; wherein M is an alkali metal cation.

2. The method for preparing phosphorus-doped iridium dioxide as claimed in claim 1, wherein In S1, the microwave-assisted ethylene glycol reduction method includes the following steps: dissolving a metal source in an ethylene glycol solution to obtain a metal salt solution; adding porous graphene to the metal salt solution, and placing the solution in a microwave reactor for reaction.

3. The method for preparing phosphorus-doped iridium dioxide as claimed in claim 2, wherein: The preparation method of phosphorus-doped iridium dioxide satisfies one or more of the following conditions ① to ⑨: ①, the metal source is chloroiridic acid; ②, the concentration of the metal salt in the metal salt solution is 5-10 mg / L; ③. The porous graphene is in powder form; ④. The specific surface area of ​​the porous graphene is 1000-2000m 2 ·g -1 ; ⑤. The pore size distribution of the porous graphene is 3-20 nm; ⑥. The ratio of the mass of the metal salt in the metal salt solution to the mass of the porous graphene is 1:(10-20); ⑦, the reaction temperature is 80-180°C; ⑧, the reaction time is 5-30min; ⑨. After the reaction is completed, the process further comprises the steps of filtration and washing.

4. The method for preparing phosphorus-doped iridium dioxide as claimed in claim 3, wherein: The specific surface area of ​​the porous graphene is 1200 m 2 ·g -1 .

5. The method for preparing phosphorus-doped iridium dioxide according to claim 3, wherein: The pore size distribution of the porous graphene is 5-10 nm.

6. The method for preparing phosphorus-doped iridium dioxide according to claim 3, wherein: The reaction temperature is 80-140°C.

7. The method for preparing phosphorus-doped iridium dioxide according to claim 6, wherein: The reaction temperature was 120°C.

8. The method for preparing phosphorus-doped iridium dioxide as claimed in claim 3, wherein: The method for preparing phosphorus-doped iridium dioxide satisfies conditions ① to ⑨ at the same time.

9. The method for preparing phosphorus-doped iridium dioxide according to claim 1, wherein The preparation method of phosphorus-doped iridium dioxide satisfies one or more of the following conditions a to d: a. In S2, the heat treatment equipment is a muffle furnace; b. In S2, the atmosphere of the heat treatment is an air atmosphere; c. In S2, the target temperature of the heat treatment is 450-650°C; d. In S2, the particle size distribution of the IrO2 nanoparticles is 2-5 nm.

10. The method for preparing phosphorus-doped iridium dioxide according to claim 9, wherein: In condition c, during the process of heating to the target temperature, the heating rate is 2°C / min.

11. The method for preparing phosphorus-doped iridium dioxide according to claim 10, wherein: In condition c, the target temperature was maintained for 1-4 h.

12. The method for preparing phosphorus-doped iridium dioxide according to claim 9, wherein: The method for preparing phosphorus-doped iridium dioxide satisfies conditions a to d simultaneously.

13. The method for preparing phosphorus-doped iridium dioxide according to claim 1, wherein: In S3, the step of dispersing IrO2 nanoparticles in NiSO4 aqueous solution is to disperse IrO2 in aqueous solution, ultrasonically disperse it, and then add NiSO4 solution; Wherein, the ultrasonic dispersion time is 2-4h; The amount of NiSO4 solution added is 5-10 mL.

14. The method for preparing phosphorus-doped iridium dioxide according to claim 13, wherein: The concentration of the NiSO4 solution is 1 mol / L.

15. The method for preparing phosphorus-doped iridium dioxide according to claim 1, wherein: The preparation method of phosphorus-doped iridium dioxide satisfies one or more of the following conditions I to IV: In I and S3, the alkali metal cation is a sodium ion or a potassium ion; the MH2PO2 is NaH2PO2 or KH2PO2; II. In S3, the reaction is carried out under stirring; III. In S3, the reaction time is 0.5-2h; In IV and S3, after the reaction, the process further comprises the steps of centrifugal washing and drying.

16. The method for preparing phosphorus-doped iridium dioxide according to claim 15, wherein: The number of centrifugal washings is 2-3 times.

17. The method for preparing phosphorus-doped iridium dioxide according to claim 15, wherein: The drying is oven drying.

18. The method for preparing phosphorus-doped iridium dioxide according to claim 15, wherein: The method for preparing phosphorus-doped iridium dioxide satisfies conditions I to IV at the same time.

19. A phosphorus-doped iridium dioxide, characterized in that: The invention discloses a method for preparing phosphorus-doped iridium dioxide according to any one of claims 1 to 18.

20. The phosphorus-doped iridium dioxide according to claim 19, wherein The phosphorus-doped iridium dioxide is in the form of nanoparticles; And / or, in the phosphorus-doped iridium dioxide, phosphorus atoms are doped into the iridium dioxide lattice in a manner of replacing oxygen atoms.

21. A phosphorus-doped iridium dioxide, characterized in that The molecular formula of the phosphorus-doped iridium dioxide is P x (IrO2) y ; Wherein, x is the mass ratio of P, y is the mass ratio of IrO2; x+y=100%; the range of x is 5%-0.5%, and the range of y is 95% to 99.5%; The phosphorus-doped iridium dioxide is nanoparticles; the particle size of the nanoparticles ranges from 3 to 10 nm; In the phosphorus-doped iridium dioxide, phosphorus atoms are doped into the iridium dioxide lattice in a manner of replacing oxygen atoms.

22. Use of the phosphorus-doped iridium dioxide according to any one of claims 19 to 21 as a catalyst in water electrolysis.

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