Phosphorus and molybdenum co-doped trinickel disulfide three-dimensional material and preparation method and application thereof

Abstract

The invention discloses a phosphorus and molybdenum co-doped trinickel disulfide three-dimensional material as well as a preparation method and application thereof, and relates to a doped trinickel disulfide three-dimensional material as well as a preparation method and application thereof. The technical problem that an existing trinickel disulfide catalyst is low in catalytic activity is solved. According to the material, foamed nickel serves as a conductive substrate, phosphorus and molybdenum co-doped trinickel disulfide of a nanorod structure vertically grows on the surface of the foamed nickel, and wrinkled nanosheets are stacked on the surfaces of nanorods. The preparation method comprises the following steps: firstly immersing the foamed nickel in a mixed solution of powdered sulfur, diethylenetriamine and ethanol for hydrothermal reaction, then immersing the foamed nickel in a water and ethanol mixed solution of thioacetamide and phosphomolybdic acid for secondary hydrothermal reaction to obtain the nickel foam, the nickel foam can drive 10 mA cm <-2 > / 100 mA cm <-2 > in a 1.0 M KOH + 0.33 M urea solution only by 1.315 V / 1.345 V, and the nickel foam can be used in the field of conventional alkaline or urea oxidation assisted energy-saving hydrogen production.

Description

Technical Field

[0001] The invention relates to a nickel disulfide-doped three-dimensional material and a preparation method and application thereof. Background Art

[0002] Developing sustainable energy technologies is crucial to meeting growing energy demands and addressing environmental pollution. Hydrogen, a clean energy carrier due to its high energy density and non-polluting properties, can be produced at the anode via electrochemical water splitting. Conventional water electrolysis suffers from high cell voltages due to the sluggish kinetics of the oxygen evolution reaction (OER) at the anode. To this end, urea-assisted water electrolysis, by coupling the urea oxidation reaction (UOR) with the hydrogen evolution reaction (HER), has been proposed. Compared to conventional water electrolysis, urea-assisted water electrolysis can achieve hydrogen production with approximately 70% energy savings. This not only provides a viable strategy for replacing the unfavorable OER with UOR to improve the efficiency of electrochemical conversion devices but also holds promise for widespread treatment of urea-rich wastewater. However, urea-assisted water electrolysis suffers from unsatisfactory reaction kinetics due to multi-step electron transfer and complex pathways, such as the adsorption of urea molecules and the subsequent six-electron process. Therefore, the construction of efficient and stable alkaline UOR / HER electrocatalysts is urgently needed.

[0003] Transition metal sulfides have become a research hotspot in the field of energy conversion and storage due to their abundant earth resources, excellent electrochemical activity, high durability, and relatively simple synthesis process. Nickel disulfide, due to its high conductivity, natural abundance, and eco-friendliness, has made significant progress in electrocatalysis in recent years. However, limitations such as insufficient intrinsic catalytic activity and limited exposure of surface active sites have hampered the performance improvement of these catalysts. Summary of the Invention

[0004] The present invention aims to solve the technical problem of low catalytic activity of existing nickel disulfide catalysts and provides a phosphorus and molybdenum co-doped nickel disulfide three-dimensional material and its preparation method and application.

[0005] The phosphorus-molybdenum co-doped nickel disulfide three-dimensional material of the present invention uses nickel foam as a conductive substrate. Nanorods of phosphorus-molybdenum co-doped nickel disulfide are vertically grown on the surface of the nickel foam. The nanorods are 200 to 400 nm in size, and wrinkled nanosheets are accumulated on the surface of the nanorods. The phosphorus-molybdenum co-doped nickel disulfide three-dimensional material of the present invention uses a two-step hydrothermal method to in-situ construct the phosphorus-molybdenum co-doped nickel disulfide nanorod structure on the three-dimensional porous nickel foam. By introducing phosphorus and molybdenum elements, the vertically grown nanorod structure not only exposes abundant edge active sites, but also has a unique channel structure that more effectively promotes reaction kinetics, ultimately achieving a synergistic improvement in catalyst activity and stability.

[0006] The preparation method of the phosphorus and molybdenum co-doped nickel disulfide three-dimensional material is carried out according to the following steps:

[0007] 1. Pre-treat the nickel foam to remove the oxide layer and impurities on the surface of the nickel foam;

[0008] 2. Dissolve sulfur powder in diethylenetriamine and stir until completely dissolved, then add ethanol and stir until a transparent solution is formed;

[0009] 3. Transfer the transparent solution obtained in step 2 to a stainless steel autoclave lined with polytetrafluoroethylene, add the nickel foam treated in step 1 to the stainless steel autoclave, and then maintain the autoclave at a temperature of 150-170° C. for 20-28 hours for a first hydrothermal reaction. After cooling to room temperature, the reaction product is cleaned with ethanol and deionized water, and then naturally dried to obtain nickel foam loaded with nickel disulfide;

[0010] 4. Dissolve thioacetamide in a mixed solution of deionized water and ethanol and stir until completely dissolved, then add phosphomolybdic acid and continue stirring until a uniform solution is formed to obtain a mixed solution;

[0011] 5. Transfer the mixed solution to a stainless steel autoclave lined with polytetrafluoroethylene, add the nickel foam loaded with nickel disulfide prepared in step 3 to the stainless steel autoclave, and then maintain the autoclave at a temperature of 170-190°C for 10-14 hours for a second hydrothermal reaction, cool, wash, and dry to obtain a phosphorus and molybdenum co-doped nickel disulfide three-dimensional material.

[0012] Furthermore, in the transparent solution described in step 2, the concentration of sulfur powder is 0.033-0.067 mol / L.

[0013] Furthermore, in the transparent solution described in step 2, the volume ratio of diethylenetriamine to ethanol is 1:6.5.

[0014] Furthermore, in the mixed solution described in step 4, the concentration of thioacetamide is 0.033 to 0.067 mol / L.

[0015] Furthermore, in the mixed solution described in step 4, the concentration of phosphomolybdic acid is 0.33-1 mmol / L.

[0016] Furthermore, in the mixed solution described in step 4, the volume ratio of water to ethanol is 1:1.

[0017] The application of the above-mentioned phosphorus and molybdenum co-doped nickel disulfide three-dimensional material is to use the phosphorus and molybdenum co-doped nickel disulfide three-dimensional material in alkaline hydrogen evolution reaction, alkaline oxygen evolution reaction, urea-assisted oxygen evolution reaction, alkaline electrocatalytic water decomposition reaction or urea-assisted electrocatalytic water decomposition reaction.

[0018] The advantages of the present invention are as follows:

[0019] 1. The present invention adopts three-dimensional porous nickel foam as a conductive substrate. On the basis of synthesizing nickel disulfide, phosphorus and molybdenum co-doped nickel disulfide three-dimensional material is further obtained by hydrothermal reaction. By introducing phosphorus and molybdenum elements, vertically grown nanorods and a structure in which the surface of the nanorods is stacked by highly wrinkled nanosheets are obtained. This not only increases the number of accessible active sites and improves catalytic performance, but also the synergistic effect of phosphorus and molybdenum elements can optimize the electronic structure of the material, accelerate charge transfer, effectively promote reaction kinetics, and ultimately achieve a synergistic improvement in catalyst activity and stability. In 1 mol / L potassium hydroxide (1M KOH) solution, the phosphorus and molybdenum co-doped nickel disulfide three-dimensional material of the present invention only requires 158mV / 299mV to reach 100mA cm for HER / OER. -2 In 1.0M KOH+0.33M urea solution, only 1.315V / 1.345V is required to drive 10mA cm -2 / 100mAcm -2 .

[0020] 2. The phosphorus and molybdenum co-doped nickel disulfide three-dimensional material prepared by the present invention does not require the addition of an additional nickel source. The nickel source mainly comes from the nickel ions released in situ from the nickel foam, which can effectively reduce the cost price.

[0021] 3. Through step-by-step hydrothermal synthesis, reaction conditions can be flexibly optimized, and the morphology and crystal structure of the material can be finely controlled, reducing the impact caused by simultaneous changes in multiple variables. At the same time, the synthesis process is simple, the reaction conditions are mild, the production cost is low, and it can be produced on a large scale, and can be used in the field of water electrolysis. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] Figure 1 is the X-ray diffraction pattern of the materials prepared in Example 1, Comparative Example 1, and Comparative Example 2;

[0023] Figure 2 3D nickel disulfide material (P,Mo-Ni3S2-R) co-doped with phosphorus and molybdenum prepared in Example 1 is a scanning electron microscope image at different resolutions;

[0024] Figure 3 1. Transmission electron microscope image and element distribution diagram of phosphorus and molybdenum co-doped nickel disulfide three-dimensional material prepared in Example 1;

[0025] Figure 4 This is an X-ray photoelectron spectrum of the phosphorus and molybdenum co-doped nickel disulfide three-dimensional material prepared in Example 1;

[0026] Figure 5 The scanning electron microscope images of phosphorus and molybdenum co-doped nickel disulfide three-dimensional material (P,Mo-Ni3S2-H) prepared in comparative example 1 at different resolutions;

[0027] Figure 6 3D nickel disulfide material (Ni3S2) prepared in Comparative Example 2 is a scanning electron microscope image at different resolutions;

[0028] Figure 7 It is a polarization curve diagram of the electrocatalytic hydrogen evolution reaction of the materials prepared in Example 1 and Comparative Examples 1 and 2 in 1.0M KOH solution.

[0029] Figure 8 It is a polarization curve diagram of the electrocatalytic oxygen evolution reaction of the materials prepared in Example 1 and Comparative Examples 1 and 2 in 1.0M KOH solution.

[0030] Figure 9 It is a polarization curve diagram of the urea-assisted oxygen evolution reaction of the materials prepared in Example 1 and Comparative Examples 1 and 2 in 1.0M KOH+0.33M Urea solution.

[0031] Figure 10 This is the electrocatalytic water splitting curve of the material prepared in Example 1 tested as a dual electrode in 1.0 M KOH and 1.0 M KOH + 0.33 M urea solutions. DETAILED DESCRIPTION

[0032] The beneficial effects of the present invention are demonstrated with the following examples.

[0033] Example 1: The preparation method of the phosphorus and molybdenum co-doped nickel disulfide three-dimensional material of this embodiment is carried out according to the following steps:

[0034] 1. Pretreatment of nickel foam: First, cut the nickel foam into 3cm×3cm blocks, then ultrasonicate in acetone solution and 1M hydrochloric acid solution for 15 minutes each, then wash with deionized water three times, and finally ultrasonicate in deionized water for 5 minutes to remove the oxide layer and impurities on the surface of the nickel foam, and dry it to complete the pretreatment;

[0035] 2. Dissolve 1.5 mmol of sulfur powder in 4 mL of diethylenetriamine and stir until completely dissolved. Then add 26 mL of ethanol and stir until a transparent solution is formed.

[0036] 3. The transparent solution obtained in step 2 was transferred to a 50 mL polytetrafluoroethylene-lined stainless steel autoclave, and the nickel foam treated in step 1 was also added to the stainless steel autoclave. The autoclave was then kept at 160° C. for 24 h for the first hydrothermal reaction. After cooling to room temperature, the reaction product was washed with ethanol and deionized water three times each, and then naturally dried to obtain nickel foam loaded with trinickel disulfide;

[0037] 4. Dissolve 1.5 mmol of thioacetamide in a mixed solution of 15 mL of deionized water and 15 mL of ethanol and stir until completely dissolved, then add 0.02 mmol of phosphomolybdic acid and continue stirring until a homogeneous solution is formed to obtain a mixed solution;

[0038] 5. The mixed solution obtained in step 4 was transferred to a 50 mL polytetrafluoroethylene-lined stainless steel autoclave, and the nickel foam loaded with nickel disulfide prepared in step 3 was also added to the stainless steel autoclave. The autoclave was then kept at 180°C for 12 hours for a second hydrothermal reaction. The mixture was cooled to room temperature, washed with ethanol and deionized water three times each, and dried naturally in air to obtain a phosphorus and molybdenum co-doped nickel disulfide three-dimensional material, recorded as P,Mo-Ni3S2-R.

[0039] Comparative Example 1: This comparative example is a one-step hydrothermal reaction to prepare phosphorus and molybdenum co-doped nickel disulfide three-dimensional material (P,Mo-Ni3S2-H). The specific method is carried out according to the following steps:

[0040] 1. Pretreatment of nickel foam: First, cut the nickel foam into 3cm×3cm blocks, then ultrasonicate in acetone solution and 1M hydrochloric acid solution for 15 minutes each, then wash with deionized water three times, and finally ultrasonicate in deionized water for 5 minutes to remove the oxide layer and impurities on the surface of the nickel foam, and dry it to complete the pretreatment;

[0041] 2. Dissolve 3 mmol of thioacetamide in 4 mL of diethylenetriamine and stir until a transparent solution is formed. Then, add 10 mL of deionized water and 16 mL of ethanol respectively and continue stirring. Finally, add 0.02 mmol of phosphomolybdic acid to the mixed solution and stir to form a mixed solution;

[0042] 3. Transfer the mixed solution to a 50 mL polytetrafluoroethylene-lined stainless steel autoclave, add the nickel foam treated in step 1, and react at 180°C for 12 hours for hydrothermal reaction. After the reaction, cool to room temperature. Rinse the obtained sample with ethanol and deionized water several times, and dry it naturally to obtain phosphorus and molybdenum co-doped nickel disulfide three-dimensional material, recorded as P,Mo-Ni3S2-H.

[0043] Comparative Example 2: This comparative example is to prepare nickel disulfide (Ni3S2), and the specific preparation method is carried out according to the following steps:

[0044] 1. Pretreatment of nickel foam: First, cut the nickel foam into 3cm×3cm blocks, then ultrasonicate in acetone solution and 1M hydrochloric acid solution for 15 minutes each, then wash with deionized water three times, and finally ultrasonicate in deionized water for 5 minutes to remove the oxide layer and impurities on the surface of the nickel foam, and dry it to complete the pretreatment;

[0045] 2. Dissolve 1.5 mmol of sulfur powder in 4 mL of diethylenetriamine and stir until completely dissolved. Then add 26 mL of ethanol and stir until a transparent solution is formed.

[0046] 3. Transfer the transparent solution obtained in step 1 to a 50 mL polytetrafluoroethylene-lined stainless steel autoclave, add the nickel foam treated in step 1, and react at 160°C for 24 hours. After cooling to room temperature, wash the reacted sample with ethanol and deionized water three times and dry it naturally to obtain nickel disulfide, recorded as Ni3S2.

[0047] Figure 1 The X-ray diffraction patterns of the three-dimensional materials prepared in Example 1, Comparative Example 1 and Comparative Example 2 show eight diffraction peaks at 21.7°, 31.1°, 38.2°, 50.1°, 55.3°, 69.3°, 73.0° and 77.9°, which are respectively attributed to the (101), (110), (021), (211), (300), (131), (214) and (401) crystal planes of nickel disulfide. Figure 1 It can be seen that the diffraction peaks of Example 1, Comparative Example 1 and Comparative Example 2 correspond to nickel disulfide, and no diffraction peaks of P and Mo phases appear, indicating that the materials prepared in Example 1 and Comparative Example 1 are nickel disulfide co-doped with phosphorus and molybdenum.

[0048] Figure 2 The scanning electron microscope images of phosphorus and molybdenum co-doped nickel disulfide three-dimensional material prepared in Example 1 at different resolutions are shown. Figure 2 As can be seen in the figure, phosphorus- and molybdenum-co-doped nickel disulfide exhibits a vertically distributed nanorod structure, with the surface of the nanorods composed of highly wrinkled nanosheets. This not only increases the specific surface area of the catalyst, providing abundant active sites and enhancing catalytic activity, but also promotes electron transfer, accelerates reaction kinetics, and improves catalytic performance.

[0049] Figure 3 The transmission electron microscope image and element distribution diagram of the phosphorus and molybdenum co-doped nickel disulfide three-dimensional material prepared in Example 1. The nanosheet structure on the surface of the nanorods can be clearly observed from the transmission electron microscope image. From the X-ray spectrum element distribution diagram, it can be seen that the phosphorus and molybdenum co-doped nickel disulfide three-dimensional material prepared in Example 1 contains four elements: phosphorus, molybdenum, nickel and sulfur, and the elements are evenly distributed.

[0050] Figure 4 This is the X-ray photoelectron spectrum of the phosphorus and molybdenum co-doped nickel disulfide three-dimensional material prepared in Example 1. From the figure, diffraction peaks of phosphorus, molybdenum, nickel and sulfur elements in the phosphorus and molybdenum co-doped nickel disulfide three-dimensional material can be observed, indicating that the four elements exist at the same time.

[0051] Figure 5 Scanning electron microscope images of the phosphorus and molybdenum co-doped nickel disulfide three-dimensional material prepared in Comparative Example 1 at different resolutions show that the microstructure of the phosphorus and molybdenum co-doped nickel disulfide three-dimensional material prepared in Comparative Example 1 is shaped like a "hill". Compared with Example 1, the structure of the material in Comparative Example 1 cannot provide the same number of active sites, thereby affecting the catalytic performance.

[0052] Figure 6 These are scanning electron microscope images of nickel disulfide prepared in comparative example 2 at different resolutions, showing that the surface of the three-dimensional porous nickel foam is covered with nickel disulfide nanoparticles.

[0053] In order to evaluate the electrochemical performance of Example 1 in 1.0M KOH solution and 1.0M KOH + 0.33M urea solution, the specific test steps are as follows: in the alkaline system, the electrolyte solution is 1.0M KOH, the phosphorus and molybdenum co-doped nickel disulfide three-dimensional material prepared in Example 1 is directly used as the working electrode, and the carbon rod and mercuric oxide electrode are used as the counter electrode and reference electrode respectively to form a three-electrode system; in the urea system, the electrolyte solution is 1.0M KOH + 0.33M urea solution, the phosphorus and molybdenum co-doped nickel disulfide three-dimensional material prepared in Example 1 is used as the working electrode, and the carbon rod and Ag / AgCl electrode are used as the counter electrode and reference electrode respectively to form a three-electrode system. -1 After 50 cycles of CV activation at a scan rate of 100 nm, LSV polarization curve testing was performed. To better evaluate the catalytic activity of the catalyst, a three-electrode system was constructed using Comparative Examples 1 and 2 as working electrodes, and the electrochemical performance was compared and analyzed using the test method of Example 1.

[0054] Figure 7 The polarization curves of the materials prepared in Example 1, Comparative Example 1 and Comparative Example 2 for the electrocatalytic hydrogen evolution reaction in 1.0M KOH solution are shown in Table 1. Figure 7 As shown in Table 1, in 1.0 M KOH solution, the hydrogen evolution overpotential of the phosphorus and molybdenum co-doped nickel disulfide three-dimensional material of Example 1 only needs 81 mV / 158 mV to reach 10 mA cm -2 / 100mA cm -2 , the overpotential is lower than that of common nickel disulfide materials.

[0055] Table 1 HER and OER performances of materials prepared in Example 1, Comparative Examples 1 and 2 in 1.0 M KOH solution

[0056]

[0057] Figure 8The polarization curves of the materials prepared in Example 1, Comparative Examples 1 and 2 for electrocatalytic oxygen evolution reaction in 1.0M KOH solution are shown in Table 1. Figure 8 As shown in Table 1, in 1.0 M KOH solution, the oxygen evolution overpotential of Example 1 only needs 222 mV / 299 mV to reach 10 mA cm -2 / 100mA cm -2 The overpotential is lower than that of common nickel disulfide materials and has good industrialization potential.

[0058] Figure 9 The polarization curves of the materials prepared in Example 1, Comparative Examples 1 and 2 in 1.0M KOH + 0.33M urea solution for urea-assisted oxygen evolution reaction are shown in Figure 1. In 1.0M KOH and 1.0M KOH + 0.33M Urea solution, only 1.315V and 1.345V are required to drive 10mA cm -2 and 100mA cm -2 .

[0059] Table 2 UOR performance test table of Example 1, Comparative Example 1 and Comparative Example 2 materials in 1.0M KOH solution

[0060]

[0061] Figure 10 The electrocatalytic water splitting curves of the material prepared in Example 1 were tested as dual electrodes in 1.0M KOH and 1.0M KOH + 0.33M urea solutions. Figure 10 It can be seen that in 1.0M KOH+0.33M urea solution, the material prepared in Example 1 is used as a double electrode, and only a low voltage of 1.501V is required to drive 100mA cm -2 In 1.0M KOH solution, the material prepared in Example 1 was used as a double electrode at 100mA cm -2 The voltage required at the current density is 1.757V.

[0062] Example 2: This example differs from Example 1 in that the concentration of sulfur powder in step 2 is 0.033 mol / L, and the other steps and parameters are the same as those in Example 1, to obtain a phosphorus and molybdenum co-doped nickel disulfide three-dimensional material.

[0063] Example 3: This example differs from Example 1 in that the concentration of sulfur powder in step 2 is 0.067 mol / L, and the other steps and parameters are the same as those in Example 1, to obtain a phosphorus and molybdenum co-doped nickel disulfide three-dimensional material.

[0064] Example 4: This example differs from Example 1 in that the concentration of thioacetamide in step 4 is 0.033 mol / L, and the other steps and parameters are the same as those in Example 1, to obtain a phosphorus and molybdenum co-doped nickel disulfide three-dimensional material.

[0065] Example 5: This example differs from Example 1 in that the concentration of thioacetamide in step 4 is 0.067 mol / L, and the other steps and parameters are the same as those in Example 1, to obtain a phosphorus and molybdenum co-doped nickel disulfide three-dimensional material.

[0066] Example 6: This example differs from Example 1 in that the concentration of phosphomolybdic acid in step 4 is 0.33 mmol / L, and the other steps and parameters are the same as those in Example 1, to obtain a phosphorus and molybdenum co-doped nickel disulfide three-dimensional material.

[0067] Example 7: This example differs from Example 1 in that the concentration of phosphomolybdic acid in step 4 is 1 mmol / L, and the other steps and parameters are the same as those in Example 1, to obtain a phosphorus and molybdenum co-doped nickel disulfide three-dimensional material.

[0068] Using the same test method as Example 1, the HER and OER performances of the above example in 1.0 M KOH solution are as follows:

[0069] Table 3 HER and OER performance test table of phosphorus and molybdenum co-doped nickel disulfide three-dimensional materials of Examples 2 to 7 in 1.0 M KOH solution

[0070]

Claims

1. A phosphorus and molybdenum co-doped nickel disulfide three-dimensional material, characterized in that: The material uses nickel foam as a conductive substrate, with phosphorus and molybdenum co-doped nickel disulfide in a nanorod structure growing vertically on the surface of the nickel foam. The nanorod size is between 200 and 400 nm, and wrinkled nanosheets are accumulated on the surface of the nanorods.

2. The method for preparing the phosphorus and molybdenum co-doped nickel disulfide three-dimensional material according to claim 1, characterized in that: The following steps should be followed:

1. Pre-treat the nickel foam to remove the oxide layer and impurities on the surface of the nickel foam; 2. Dissolve sulfur powder in diethylenetriamine and stir until completely dissolved, then add ethanol and stir until a transparent solution is formed; 3. Transfer the transparent solution obtained in step 2 to a stainless steel autoclave lined with polytetrafluoroethylene, add the nickel foam treated in step 1 to the stainless steel autoclave, and then maintain the autoclave at a temperature of 150-170° C. for 20-28 hours for a first hydrothermal reaction. After cooling to room temperature, the reaction product is cleaned with ethanol and deionized water, and then naturally dried to obtain nickel foam loaded with nickel disulfide; 4. Dissolve thioacetamide in a mixed solution of deionized water and ethanol and stir until completely dissolved, then add phosphomolybdic acid and continue stirring until a uniform solution is formed to obtain a mixed solution; 5. Transfer the mixed solution to a stainless steel autoclave lined with polytetrafluoroethylene, add the nickel foam loaded with nickel disulfide prepared in step 3 to the stainless steel autoclave, and then maintain the autoclave at a temperature of 170-190°C for 10-14 hours for a second hydrothermal reaction, cool, wash, and dry to obtain a phosphorus and molybdenum co-doped nickel disulfide three-dimensional material.

3. The method for preparing a phosphorus and molybdenum co-doped nickel disulfide three-dimensional material according to claim 2, characterized in that: In the transparent solution described in step 2, the concentration of sulfur powder is 0.033-0.067 mol / L.

4. The method for preparing a phosphorus and molybdenum co-doped nickel disulfide three-dimensional material according to claim 2 or 3, characterized in that: In the transparent solution described in step 2, the volume ratio of diethylenetriamine to ethanol is 1:6.

5.

5. The method for preparing a phosphorus and molybdenum co-doped nickel disulfide three-dimensional material according to claim 2 or 3, characterized in that: In the mixed solution described in step 4, the concentration of thioacetamide is 0.033-0.067 mol / L.

6. The method for preparing a phosphorus and molybdenum co-doped nickel disulfide three-dimensional material according to claim 2 or 3, characterized in that: In the mixed solution described in step 4, the concentration of phosphomolybdic acid is 0.33-1 mmol / L.

7. The method for preparing a phosphorus and molybdenum co-doped nickel disulfide three-dimensional material according to claim 2 or 3, characterized in that: In the mixed solution described in step 4, the volume ratio of water to ethanol is 1:

1.

8. The use of a phosphorus and molybdenum co-doped nickel disulfide three-dimensional material according to claim 1, characterized in that: The application is to use the phosphorus and molybdenum co-doped nickel disulfide three-dimensional material in alkaline hydrogen evolution reaction, alkaline oxygen evolution reaction, urea-assisted oxygen evolution reaction, alkaline electrocatalytic water decomposition reaction or urea-assisted electrocatalytic water decomposition reaction.

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