CN113201765B - Phosphating WS 2 Preparation method and application of nanosphere catalyst - Google Patents

Phosphating WS 2 Preparation method and application of nanosphere catalyst Download PDF

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CN113201765B
CN113201765B CN202110347746.XA CN202110347746A CN113201765B CN 113201765 B CN113201765 B CN 113201765B CN 202110347746 A CN202110347746 A CN 202110347746A CN 113201765 B CN113201765 B CN 113201765B
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black precipitate
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nanosphere
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reaction kettle
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CN113201765A (en
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林健健
孙蕾
高孟友
郑德华
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Qingdao University of Science and Technology
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/28—Deposition of only one other non-metal element
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    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

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Abstract

The invention discloses a phosphating WS 2 The preparation method of the nanosphere catalyst comprises the following steps: s101, dissolving tungsten hexacarbonyl and sulfur powder in an organic solvent under the protection of inert gas, and uniformly mixing at room temperature to obtain brown mixed liquor; fully reacting the brown mixed solution in a high-pressure reaction kettle at the temperature of 100-250 ℃, and fully reacting the brown mixed solution for 10-24 hours; s102, cooling the reacted high-pressure reaction kettle to room temperature, centrifuging the mixture to obtain a black precipitate, and purifying; s103, reacting the purified black precipitate with sodium hypophosphite in a tubular furnace filled with inert gas at the temperature of between 200 and 300 ℃ for 2 to 3 hours to obtain the sodium hypophosphite. The invention provides WS prepared by the method 2 An | P nanosphere catalyst and application thereof. WS of the present invention 2 The preparation method of the | P nanosphere catalyst is simple, and the nanosheet cluster type nanoparticles with uniform size and high specific surface area are obtained.

Description

Phosphating WS 2 Preparation method and application of nanosphere catalyst
Technical Field
The invention relates to the technical field of nano materials, in particular to phosphatized WS 2 A preparation method and application of the nanosphere catalyst.
Background
The environmental pollution caused by the massive combustion of traditional fossil fuels is more serious, so that people look for other renewable energy sources. Hydrogen energy sources have a high energy density and the only product produced after combustion is water, which is the most promising candidate energy carrier. Electrochemical water splitting provides a viable route to hydrogen production, involving two half-reactions, hydrogen Evolution (HER) at the cathode and Oxygen Evolution (OER) at the anode. However, the actual efficiency of hydrogen release during electrochemical water splitting is governed by the kinetics of the hydrogen release reaction (HER, 2H) + +2e - →H 2 ) Is limited strictly. Thus, lowering the energy barrier andthere is an urgent need for high performance HER catalysts to improve energy conversion efficiency. Pt-based metal materials have been considered to be the most advanced HER electrocatalysts so far, but due to their enormous cost and low abundance, their large-scale application is limited and the industrial requirements cannot be met. Therefore, it is of paramount importance to design and develop HER electrocatalysts with high abundance, low cost and high durability to enhance catalytic performance.
In recent years, through the continuous research on electrocatalyst materials, based on MoS 2 、WS 2 、TiS 2 And the layered transition metal-based dihalide metals of FeS (LTMDs) have become alternatives to noble metal catalysts such as platinum (Pt) and gold (Au). With MoS 2 LTMD represented by nanosheets has been developed and made significant progress. Although to WS 2 Is not as good as MoS 2 Broad, but WS 2 And MoS 2 All have special sheet structures, which facilitate electron transfer and provide more active sites for HER process. Let WS be 2 Phosphating can increase active surface area, improve electron conductivity, and improve WS 2 A decrease in catalytic activity due to fewer exposed edge locations and poor electron/ion conductivity. By composition control, phosphated WS 2 The material shows excellent water decomposition catalytic performance.
In recent years, with the development of science and technology, the application of phosphorus sulfide catalysts in the fields of ion batteries, photoelectrocatalysis water decomposition and the like is more and more extensive, and WP is disclosed in the prior art 2 The nanospheres can significantly improve the cycle life and charge-discharge rate of the lithium-sulfur ion battery when used as the anode material, and WS is also disclosed 2 Growing on nanotubes as layered electrodes can significantly enhance the catalytic performance of Hydrogen Evolution Reactions (HER). Through the relative applicability test of the two substance composition phase mixture, it is reported that the phase mixture can effectively accelerate the hydrogen evolution reaction under the acidic condition, and the electrochemical hydrogen evolution catalyst with low cost and high efficiency can be produced by extension. The above prior art shows phosphated WS 2 The nanosphere has good prospects in the aspects of energy storage, energy transfer and the like.
Through the above analysis, although there are many WS in the prior art 2 But there is no WS on phosphating 2 Nor for WS 2 And the relative disclosure of the excellence and the weakness of the electrochemical performance of the | P.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a phosphorized WS 2 A preparation method and application of the nanosphere catalyst.
In order to achieve the purpose, the invention provides the following technical scheme:
phosphating WS 2 The preparation method of the nanosphere catalyst comprises the following steps:
s101, dissolving a proper amount of tungsten hexacarbonyl and sulfur powder in an organic solvent in an inert atmosphere, and uniformly mixing at room temperature to obtain brown mixed liquor; fully reacting the brown mixed solution in a high-pressure reaction kettle at the temperature of between 100 and 250 ℃; preferably, the ratio of the tungsten hexacarbonyl, the sulfur powder and the organic solvent is 1:3-18 in g: g: mL.
Preferably, the brown mixed solution is fully reacted for 10 to 24 hours; preferably, the organic solvent is selected from any one of toluene, p-xylene or nitrogen-nitrogen dimethylformamide.
S102, after the high-pressure reaction kettle after the reaction is cooled to the room temperature, centrifuging the mixture in the high-pressure reaction kettle to obtain a black precipitate;
s103, purifying the black precipitate, and then reacting the black precipitate with sodium hypophosphite in a tubular furnace in an inert atmosphere at the temperature of between 200 and 300 ℃ for 2 to 3 hours to obtain WS 2 An | P nanosphere catalyst.
In one embodiment according to the present invention,
in S101 and S103, the inert atmosphere is achieved by introducing an inert gas into the reaction vessel, wherein the inert gas is selected from one of nitrogen, xenon, neon, helium, argon or krypton.
In one embodiment according to the present invention,
in S102, the centrifugal rotating speed is 12000 r/min, and the centrifugal time is 10min.
In one embodiment according to the present invention,
in S103, the purification treatment is achieved by a method comprising the steps of:
carrying out ultrasonic treatment on the black precipitate, then washing the black precipitate for a plurality of times by water and acetone in sequence, and finally drying the black precipitate; preferably, the drying process comprises drying or freeze-drying in a vacuum dryer.
In one embodiment according to the present invention,
in the step S103, the ratio of the black precipitate to the sodium hypophosphite after purification is 1:2-10.
The invention also provides WS prepared by the preparation method 2 An | P nanosphere catalyst.
The invention also provides the WS 2 The application of the | P nanosphere catalyst in hydrogen catalysis in electrochemical decomposition of water.
The invention also provides a method for realizing the WS 2 An electrode prepared by the | P nanosphere catalyst.
The present invention further provides WS as defined above 2 An application of the | P nanosphere catalyst or electrode in the preparation of a battery.
WS provided by the present invention 2 The | P nanosphere catalyst material has the following beneficial effects:
in the invention, WS is added into inert gas through regulation and control 2 The nano-sheet cluster type WS with controllable appearance, uniform size and high specific surface area is obtained by the feeding ratio of sodium hypophosphite 2 The | P nanosphere catalyst is expected to play an important role in wider emerging fields, such as electrocatalysis, lithium-sulfur ion batteries and the like.
The invention relates to a method for synthesizing WS by solvothermal and chemical vapor deposition 2 Dissolving tungsten hexacarbonyl and sulfur powder in an organic solvent, performing solvothermal reaction, centrifugally washing and drying the obtained product to obtain a black precipitate, and reacting the purified black precipitate with sodium hypophosphite for 3 hours at 300 ℃ in a tubular furnace filled with inert gas to obtain WS (tungsten sulfide) nanosphere catalyst 2 An | P nanosphere catalyst. The invention has low cost and simple operation. By simpleThe WS can be obtained by one-pot hydrothermal reaction and chemical vapor deposition 2 An | P nanosphere catalyst. It is expected to play an important role in more extensive new fields, such as electrocatalysis, ion batteries and the like.
Drawings
FIG. 1 illustrates an embodiment of WS 2 A flow chart of a preparation method of the | P nanosphere catalyst.
FIG. 2 shows WS prepared in example 1, provided by an embodiment of the present invention 2 A Transmission Electron Microscope (TEM) atlas of the | P nanosphere catalyst is shown, and a sample is in a three-dimensional (3D) nanosphere shape.
FIG. 3 shows WS in different proportions prepared in example 1 provided by the present invention 2 The shape of the sample is controllable according to a Scanning Electron Microscope (SEM) atlas of the | P nanosphere catalyst.
FIG. 4 is a scanning electron microscope mapping (SEM mapping) map provided in example 1 of the present invention, which shows the uniform distribution of the three elements.
FIG. 5 shows WS in different ratios prepared in example 1 provided by the present invention 2 lP nanosphere catalyst and unphosphorylated WS 2 Electrochemical performance of the catalyst is compared.
FIG. 6 shows WS in different ratios prepared in example 2 provided by the present invention 2 lP nanosphere catalyst and unphosphorylated WS 2 Electrochemical performance of the catalyst is compared.
FIG. 7 shows WS in different proportions prepared in example 3 provided by an embodiment of the present invention 2 iP nanosphere catalysts and unphosphorylated WS 2 Electrochemical performance of the catalyst is compared.
FIG. 8 shows WS in different ratios prepared in example 4 provided by the present invention 2 lP nanosphere catalyst and unphosphorylated WS 2 Electrochemical performance of the catalyst is compared.
FIG. 9 shows WS in different ratios prepared in example 5 provided by an embodiment of the present invention 2 lP nanosphere catalyst and unphosphorylated WS 2 Electrochemical performance of the catalyst is compared.
Detailed Description
The following detailed description of the preferred embodiments of the present invention, taken in conjunction with the accompanying drawings, will make the advantages and features of the invention more readily understood by those skilled in the art, and thus will more clearly and distinctly define the scope of the invention.
The invention provides a phosphating WS 2 The invention relates to a preparation method of a nanosphere catalyst and application thereof, which are described in detail in the following with reference to the accompanying drawings.
As shown in FIG. 1, WS provided by the present invention 2 The preparation method of the | P nanosphere catalyst comprises the following steps:
s101, dissolving tungsten hexacarbonyl and sulfur powder in an organic solvent under the protection of inert gas, and uniformly mixing at room temperature to obtain brown mixed liquor; fully reacting the brown mixed solution in a high-pressure reaction kettle at the temperature of 100-250 ℃, and fully reacting the brown mixed solution for 10-24 hours;
s102, cooling the reacted high-pressure reaction kettle to room temperature, centrifuging the mixture to obtain a black precipitate, and purifying;
s103, reacting the purified black precipitate with sodium hypophosphite in a tubular furnace filled with inert gas at the temperature of between 200 and 300 ℃ for 2 to 3 hours to obtain WS 2 An | P nanosphere catalyst.
WS provided by the embodiment of the invention 2 The preparation method of the | P nanosphere catalyst specifically comprises the following steps:
in the first step, 0.1g to 0.5g of sublimed sulfur powder and 1.50 g to 1.80g of tungsten hexacarbonyl are dissolved in 30 mL to 50mL of organic solvent under the protection of nitrogen and are fully stirred.
Secondly, rapidly magnetically stirring the mixture at room temperature for 10-20 min, then transferring the mixture to a stainless steel high-pressure reaction kettle, and putting the high-pressure reaction kettle into a drying oven at 100-250 ℃ for 6-24h; and cooling the high-pressure reaction kettle to room temperature, centrifugally washing the mixture to obtain a black precipitate, ultrasonically dispersing the black precipitate, washing the black precipitate for several times by using deionized water and acetone alternately, centrifugally collecting the black precipitate, and drying the black precipitate in a vacuum freeze dryer for 1 to 4 hours to obtain a purified black precipitate.
Thirdly, putting the purified black precipitate into a container filled with argonReacting with sodium hypophosphite in a tube furnace at 200-300 ℃ for 2-3h to obtain WS 2 An | P nanosphere catalyst.
In a preferred embodiment of the present invention, the organic solvent is selected from any one of toluene, p-xylene or nitrogen-nitrogen dimethylformamide.
In a preferred embodiment of the present invention, wherein the magnetic stirring speed in the first step is 700-1500 rpm.
In a preferred embodiment of the present invention, wherein in the second step of centrifugation collection, the centrifugation speed is 3000-12000 r/min, and the centrifugation time is 1-10min.
In a preferred embodiment of the present invention, in the chemical vapor deposition of the third step, in the step S103, the ratio of the black precipitate after purification to the sodium hypophosphite is 1:2-10; preferably 1:5.
WS provided by the present invention 2 Preparation method of | P nanosphere catalyst one of ordinary skill in the art can also implement the WS of fig. 1, which is provided by the present invention, by adopting other steps 2 The preparation method of the | P nanosphere catalyst is just one specific example.
The technical solution of the present invention is further described with reference to the following specific examples.
Example 1: preparation of WS according to the invention 2 | P nanosphere catalyst
Firstly, dissolving 0.33g of sublimed sulfur powder and 1.76g of tungsten hexacarbonyl in 35mL of organic solvent under the protection of nitrogen, rapidly and magnetically stirring for 20min at room temperature, then transferring the mixture into a stainless steel high-pressure reaction kettle, putting the high-pressure reaction kettle into an oven at 230 ℃, and keeping for 24h; finally, cooling the high-pressure reaction kettle to room temperature, centrifugally washing the mixture to obtain a black precipitate, ultrasonically dispersing the black precipitate, alternately washing the black precipitate for a plurality of times by using deionized water and acetone, centrifugally collecting the black precipitate, and drying the black precipitate in a vacuum freeze dryer for 2 hours to obtain a purified black precipitate; reacting the purified black precipitate with sodium hypophosphite in a tube furnace filled with argon at 300 ℃ for 2h to obtain WS 2 An | P nanosphere catalyst.
The properties of the final product obtained were observed, as shown in particular in fig. 2, 3 and 4.
FIG. 2 shows WS prepared in example 1, provided by an embodiment of the present invention 2 And (3) a Transmission Electron Microscope (TEM) spectrum of the | P nanosphere catalyst, wherein the sample is in a 3D nanosphere shape.
FIG. 3 shows WS in different proportions prepared in example 1 provided by the present invention 2 Scanning Electron Microscope (SEM) spectrum of the | P nanosphere catalyst, as shown in FIG. 3, can be known by adjusting and controlling the added WS 2 The nano-sheet cluster type WS with controllable appearance, uniform size and high specific surface area is obtained by the feeding ratio of sodium hypophosphite 2 An | P nanosphere catalyst.
FIG. 4 is a scanning electron microscope mapping (SEM mapping) map provided in example 1 of the present invention, which shows the uniform distribution of the three elements.
Example 2: WS provided by the embodiment of the invention 2 The | P nanosphere catalyst comprises the following steps:
firstly, dissolving 0.33g of sublimed sulfur powder and 1.76g of tungsten hexacarbonyl in 35mL of organic solvent under the protection of nitrogen, rapidly and magnetically stirring for 20min at room temperature, then transferring the mixture into a stainless steel high-pressure reaction kettle, putting the high-pressure reaction kettle into an oven at 230 ℃, and keeping for 24h; finally, cooling the high-pressure reaction kettle to room temperature, centrifugally washing the mixture to obtain a black precipitate, ultrasonically dispersing the black precipitate, alternately washing the black precipitate for a plurality of times by using deionized water and acetone, centrifugally collecting the black precipitate, and drying the black precipitate in a vacuum freeze dryer for 2 hours to obtain a purified black precipitate; reacting the purified black precipitate with sodium hypophosphite in a tube furnace filled with argon at 200 ℃ for 2h to obtain WS 2 An | P nanosphere catalyst.
Example 3: WS provided by the embodiment of the invention 2 The | P nanosphere catalyst comprises the following steps:
firstly, 0.33g of sublimed sulfur powder and 1.76g of tungsten hexacarbonyl are dissolved in 35mL of organic solvent under the protection of nitrogen, the mixture is rapidly magnetically stirred for 20min at room temperature, then the mixture is transferred into a stainless steel high-pressure reaction kettle, and the high-pressure reaction is carried outPutting the kettle into an oven at 230 ℃ and keeping for 24 hours; finally, cooling the high-pressure reaction kettle to room temperature, centrifugally washing the mixture to obtain a black precipitate, ultrasonically dispersing the black precipitate, alternately washing the black precipitate for a plurality of times by using deionized water and acetone, centrifugally collecting the black precipitate, and drying the black precipitate in a vacuum freeze dryer for 2 hours to obtain a purified black precipitate; reacting the purified black precipitate with sodium hypophosphite in a tube furnace filled with argon at 300 ℃ for 3h to obtain WS 2 An | P nanosphere catalyst.
Example 4: WS provided by the embodiment of the invention 2 The | P nanosphere catalyst comprises the following steps:
firstly, dissolving 0.33g of sublimed sulfur powder and 1.76g of tungsten hexacarbonyl in 35mL of organic solvent under the protection of nitrogen, rapidly and magnetically stirring for 20min at room temperature, then transferring the mixture into a stainless steel high-pressure reaction kettle, putting the high-pressure reaction kettle into an oven at 210 ℃, and keeping for 24h; finally, cooling the high-pressure reaction kettle to room temperature, centrifugally washing the mixture to obtain a black precipitate, ultrasonically dispersing the black precipitate, alternately washing the black precipitate for a plurality of times by using deionized water and acetone, centrifugally collecting the black precipitate, and drying the black precipitate in a vacuum freeze dryer for 2 hours to obtain a purified black precipitate; reacting the purified black precipitate with sodium hypophosphite in a tube furnace filled with argon at 300 ℃ for 2h to obtain WS 2 An | P nanosphere catalyst.
Example 5: WS provided by the embodiment of the invention 2 The | P nanosphere catalyst comprises the following steps:
firstly, dissolving 0.33g of sublimed sulfur powder and 1.76g of tungsten hexacarbonyl in 35mL of organic solvent under the protection of nitrogen, rapidly and magnetically stirring for 20min at room temperature, then transferring the mixture into a stainless steel high-pressure reaction kettle, putting the high-pressure reaction kettle into an oven at 230 ℃, and keeping for 16h; finally, cooling the high-pressure reaction kettle to room temperature, centrifugally washing the mixture to obtain a black precipitate, ultrasonically dispersing the black precipitate, alternately washing the black precipitate for a plurality of times by using deionized water and acetone, centrifugally collecting the black precipitate, and drying the black precipitate in a vacuum freeze dryer for 2 hours to obtain a purified black precipitate; after purificationReacting the black precipitate with sodium hypophosphite in a tube furnace filled with argon at 300 ℃ for 2h to obtain WS 2 An | P nanosphere catalyst.
Example 6: performance testing
At room temperature, an electrochemical workstation with a standard three-electrode system was used at 0.5M H 2 SO 4 In which electrochemical tests of all samples were performed. Working electrode on Carbon Fiber Paper (CFP) from WS 2 And | P catalyst. To a mixture of 750. Mu.L of deionized water and 250. Mu.L of ethanol and 40. Mu.L of Nafion solution (5 wt%), 5mg of sample catalyst and 5mg of carbon powder were added, followed by ultrasonic treatment for 40 minutes to obtain a uniform suspension. Then, 70. Mu.L of WS 2 The lp catalyst was dropped onto a clean CFP chip (1 cm x 1 cm). Calibration is performed with reference to a reference and converted to a Reversible Hydrogen Electrode (RHE) by a formula.
E RHE ＝E (Ag/AgCl) +0.059pH+0.197
The three-electrode system was bubbled with high purity nitrogen for 30 minutes prior to each HER test. To explore HER activity, linear sweep voltammetry tests were performed at a rate of 5mV/s at a sweep rate of 0V to-0.5V. Electrochemical Impedance Spectroscopy (EIS) measurements were obtained over a frequency range of 0.01 to 105Hz and fitted by Zview software. 1M H 2 SO 4 An Ag/AgCl electrode in aqueous solution was used as reference electrode.
The catalysts prepared in examples 1-5 were individually tested for performance according to the methods described above, as shown in figures 5-9.
FIG. 5 shows WS in different ratios prepared in example 1 provided by the present invention 2 lP nanosphere catalyst and unphosphorylated WS 2 Electrochemical performance of the catalyst is compared. By comparison, WS was found to be the same current density 2 The overpotential of | P-5 is the smallest, and the performance is the best.
FIG. 6 shows WS in different ratios prepared in example 2 provided by the present invention 2 iP nanosphere catalysts and unphosphorylated WS 2 Electrochemical performance of the catalyst is compared. Also by comparison, WS was found to be the same at the same current density 2 The overpotential of P-5 is the smallest, with the best performance.
FIG. 7 shows WS in different proportions prepared in example 3 provided by an embodiment of the present invention 2 lP nanosphere catalyst and unphosphorylated WS 2 Electrochemical performance of the catalyst is compared. Also by comparison, WS was found to be the same at the same current density 2 The overpotential of P-5 is the smallest, with the best performance.
FIG. 8 shows WS in different ratios prepared in example 4 provided by the present invention 2 iP nanosphere catalysts and unphosphorylated WS 2 Electrochemical performance of the catalyst is compared. Also by comparison, WS was found to be the same at the same current density 2 The overpotential of | P-5 is the smallest, and the performance is the best.
FIG. 9 shows WS in different ratios prepared in example 5 provided by an embodiment of the present invention 2 lP nanosphere catalyst and unphosphorylated WS 2 Electrochemical performance of the catalyst is compared. Also by comparison, WS was found to be the same at the same current density 2 The overpotential of | P-5 is the smallest, and the performance is the best.
Thus demonstrating how the experimental conditions are changed, WS 2 The performance of P-5 is excellent.
Compared with the prior art, the WS is synthesized by the hydrothermal and chemical vapor deposition of sulfur powder and tungsten hexacarbonyl in a paraxylene solvent 2 A | P catalyst. The results presented by the present invention may provide new opportunities for finding effective bifunctional and low cost hydrogen evolution reaction electrocatalyst materials.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention.

Claims (7)

1. Phosphating WS 2 The preparation method of the nanosphere catalyst is characterized by comprising the following steps:
s101, dissolving a proper amount of tungsten hexacarbonyl and sulfur powder in an organic solvent in an inert atmosphere, and uniformly mixing at room temperature to obtain brown mixed liquor; fully reacting the brown mixed solution in a high-pressure reaction kettle at 210-230 ℃; the brown mixed solution fully reacts for 10 to 24h;
s102, after the high-pressure reaction kettle after the reaction is cooled to the room temperature, centrifuging the mixture in the high-pressure reaction kettle to obtain a black precipitate;
s103, purifying the black precipitate, and then reacting the black precipitate with sodium hypophosphite in a tubular furnace in an inert atmosphere at 200-300 ℃ for 2-3h to obtain WS 2 A | P nanosphere catalyst;
in the step S103, the ratio of the black precipitate to the sodium hypophosphite after purification is 1:5.
2. the method of claim 1, wherein the inert atmosphere in S101 or S103 is achieved by introducing an inert gas selected from one of nitrogen, xenon, neon, helium, argon, and krypton into the reaction vessel.
3. The method according to claim 1, wherein in S102, the centrifugation is performed at 12000 rpm for 10min.
4. The method according to claim 1, wherein in S103, the purification treatment is carried out by a method comprising: and (3) carrying out ultrasonic treatment on the black precipitate, then washing the black precipitate for a plurality of times by using water and acetone in sequence, and finally drying the black precipitate.
5. The method of claim 4, wherein the drying process comprises drying in a vacuum dryer or lyophilization.
6. WS prepared by the process according to any one of claims 1 to 5 2 An | P nanosphere catalyst.
7. WS of claim 6 2 The application of the | P nanosphere catalyst in hydrogen catalysis in electrochemical decomposition of water.
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