CN114717572A - Cobalt-iron bimetal phosphorization nano particle with nitrogen-doped carbon as substrate and preparation method and application thereof - Google Patents

Cobalt-iron bimetal phosphorization nano particle with nitrogen-doped carbon as substrate and preparation method and application thereof Download PDF

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CN114717572A
CN114717572A CN202210326203.4A CN202210326203A CN114717572A CN 114717572 A CN114717572 A CN 114717572A CN 202210326203 A CN202210326203 A CN 202210326203A CN 114717572 A CN114717572 A CN 114717572A
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cobalt
doped carbon
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CN114717572B (en
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徐书生
文艺
史雪荣
邵晓璇
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Shanghai University of Engineering Science
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Abstract

The invention discloses cobalt-iron bimetallic phosphating nanoparticles taking nitrogen-doped carbon as a substrate, and a preparation method and application thereof, and belongs to the field of electrocatalytic materials. Firstly, preparing a spongy nitrogen-doped carbon matrix by high-temperature carbonization, then directly growing and preparing cobalt-iron bimetallic nano-particles on the carbon matrix by a solvothermal method, and then carrying out low-temperature phosphorization to obtain the cobalt-iron bimetallic nano-particles. The cobalt-iron bimetallic phosphating nano-particles with nitrogen-doped carbon as the substrate are used as electrocatalytic materials for electrocatalytic hydrogen evolution reaction of acid electrolyte and alkaline electrolyte, the hydrogen evolution performance in the acid electrolyte of 0.5M sulfuric acid reaches 150mV, the hydrogen evolution performance in the alkaline electrolyte of 1.0M potassium hydroxide reaches 193mV, and the cobalt-iron bimetallic phosphating nano-particles have good full-hydrolytic and circulating stability, are simple in preparation process and are convenient for industrial application.

Description

Cobalt-iron bimetal phosphorization nano particle with nitrogen-doped carbon as substrate and preparation method and application thereof
Technical Field
The invention belongs to the field of electrocatalytic materials, and particularly relates to cobalt-iron bimetallic phosphatized nanoparticles taking nitrogen-doped carbon as a substrate, and a preparation method and application thereof.
Background
Electrocatalysis is a catalysis that accelerates the charge transfer at the electrode-electrolyte interface. The range of electrode catalysts is limited to only electrically active materials such as metals and semiconductors. The electrocatalysis researches are more carried out on skeletal nickel, nickel boride, tungsten carbide, sodium tungsten bronze, spinel-type and tungsten-state ore-type semiconductor oxides, various metal compounds, phthalocyanines and other catalysts, and the electrocatalysis is mainly used for electrocatalysis treatment of organic sewage, electrocatalysis degradation of chromium-containing wastewater, electrolytic desulfurization of flue gas and raw material coal, electrolytic reduction of carbon dioxide and nitrogen and the like.
Electrocatalytic materials are important factors affecting electrocatalytic performance. In recent years, metal nanomaterials have received increasing attention due to their higher porosity, larger specific surface area, and diversity of structure and function. However, the lower conductivity limits the application, nitrogen-doped carbon and phosphorization of materials can effectively improve the conductivity of materials, such as nickel-based phosphide, nickel-cobalt-based phosphide, iron-doped nickel/cobalt-based phosphide and the like, and compared with unitary and binary metal phosphide, multi-metal phosphide with doped components can provide more abundant redox active sites and better conductivity. However, the preparation of the polyphosphates is also more complicated because of the more elements involved and the more complicated parameters to control.
Disclosure of Invention
In order to overcome the defects in the prior art, the main object of the present invention is to provide a method for preparing cobalt-iron bimetallic phosphide nanoparticles using nitrogen-doped carbon as a substrate, wherein a spongy nitrogen-doped carbon matrix is prepared by high-temperature carbonization, cobalt-iron bimetallic nanoparticles are prepared by directly growing on the carbon matrix by a solvothermal method, and then the cobalt-iron bimetallic phosphide nanoparticles are obtained by low-temperature phosphorylation.
The invention also aims to provide the cobalt-iron bimetallic phosphatized nano-particles taking nitrogen-doped carbon as the substrate, which have good electrocatalytic performance and cycling stability.
The invention further aims to provide application of the cobalt-iron bimetallic phosphatized nano particles taking nitrogen-doped carbon as a substrate in electrocatalytic hydrogen evolution reaction of acidic electrolyte and alkaline electrolyte.
The above object of the present invention is achieved by the following technical solutions:
a preparation method of cobalt-iron bimetal phosphorization nano particles with nitrogen-doped carbon as a substrate comprises the following steps:
(1) dissolving zinc nitrate hexahydrate, glucose and carbon nanotubes in ethanol, ultrasonically stirring the solution, heating and preserving heat in a tube furnace under the protection of argon, soaking the obtained black solid in hydrochloric acid, performing suction filtration and washing, and drying overnight to obtain a nitrogen-doped carbon matrix;
(2) mixing the nitrogen-doped carbon matrix with cobalt acetate, iron acetate, ammonia water and ethanol to form a mixed solution, stirring overnight, then putting the mixed solution into a high-pressure reaction kettle for hydrothermal reaction, performing suction filtration and washing after the solvent thermal reaction, and drying overnight to obtain cobalt-iron bimetallic nanoparticles;
(3) and heating and preserving the cobalt-iron bimetallic nano-particles and the sodium hypophosphite in a tubular furnace under the protection of argon gas for low-temperature phosphorization to obtain the cobalt-iron bimetallic phosphorized nano-particles.
Further, in the step (1), the mass of the zinc nitrate hexahydrate is 1.5 g; the mass of glucose is 0.5 g; the concentration of the carbon nanotube is 1mg L-1(ii) a The solvent is selected from ethanol with the mass fraction of 99 percent, and the adding amount of the solvent is 20-40 ml; the ultrasonic time is 5 minutes, and the stirring time is 30 minutes; the high-temperature carbonization temperature is 200 ℃, and the heating rate is 5 ℃ for min-1The heat preservation time is 2 hours; the suction filtration washing is washing by deionized water and ethanol.
Further, in the step (2), the mass of the nitrogen-doped carbon substrate is 40mg, and the concentrations of the cobalt acetate and the iron acetate are both 0.6mol L-11ml of ammonia water; the solvent thermal reaction temperature is 130-160 ℃, and the hydrothermal time is 2-4 h; the drying temperature is 60-70 ℃.
Further, in the step (3), the mass of the cobalt-iron bimetallic nanoparticles is 40mg, and the mass of the sodium hypophosphite is 400 mg; the reaction temperature of low-temperature phosphorization is 350 ℃, and the heating rate is 4 ℃ for min-1The holding time was 2 hours.
The invention also provides cobalt-iron bimetallic phosphatized nano-particles with nitrogen-doped carbon as a substrate, which are prepared by the preparation method of the cobalt-iron bimetallic phosphatized nano-particles with nitrogen-doped carbon as the substrate.
The invention also provides an electrocatalytic material which comprises the cobalt-iron bimetallic phosphatized nano-particles taking nitrogen-doped carbon as a substrate.
The invention also provides application of the cobalt-iron bimetallic phosphating nano-particles or the electro-catalytic material taking nitrogen-doped carbon as the substrate in electro-catalytic hydrogen evolution reaction of acidic electrolyte and alkaline electrolyte.
Compared with the prior art, the invention has the beneficial effects that: the method has the advantages of wide sources of used raw materials and low cost, and the obtained cobalt-iron bimetal phosphorized nano particles taking nitrogen-doped carbon as the substrate are simple and easy to prepare, have good circulating stability and electrocatalysis performance, and can be applied to the electrocatalysis of acidic electrolyte and alkaline electrolyte.
Drawings
FIG. 1 is a flow chart of the process for preparing nitrogen-doped carbon-based cobalt-iron bimetallic phosphide nanoparticles in the example;
FIG. 2 is (a) a low-power SEM photograph and (b) a high-power SEM photograph of nitrogen-doped carbon-based cobalt iron bimetallic phosphide nanoparticles in the example;
FIG. 3 shows (a) a low-power TEM image and (b) a high-power TEM image of cobalt-iron bimetallic phosphide nanoparticles based on nitrogen-doped carbon in the example;
FIG. 4 is a graph showing the full water splitting performance of cobalt iron bimetallic phosphide nanoparticles based on nitrogen-doped carbon in the example;
FIG. 5 is a graph showing the cycling stability of the cobalt iron bimetallic phosphide nanoparticle material based on nitrogen-doped carbon in the example.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the drawings of the embodiments of the present invention. It is to be understood that the embodiments described are only a few embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the described embodiments of the invention without any inventive step, are within the scope of protection of the invention.
Example 1
In this embodiment, cobalt-iron bimetallic phosphatized nanoparticles based on nitrogen-doped carbon are prepared according to the method shown in fig. 1, and the steps are as follows:
step 1, preparing a nitrogen-doped carbon substrate: dissolving 1.5g zinc nitrate hexahydrate, 0.5g glucose and 1mg/ml carbon nanotube in 50ml ethanol, ultrasonically treating the solution for 5 minutes, stirring for half an hour, heating to 200 ℃ in a tube furnace under the protection of argon, and raising the temperature at the rate of 5 ℃ for min-1And keeping the temperature for 2 hours, soaking the obtained black solid in hydrochloric acid, performing suction filtration and washing by using ethanol and purified water, and drying overnight to obtain the nitrogen-doped carbon matrix.
Step 2, preparing cobalt-iron bimetallic nanoparticles: using 40mg of nitrogen doped carbon matrix and 0.4ml of 0.6mol L-10.4ml of cobalt acetate, 0.6mol L-1Stirring the solution formed by the iron acetate, 1ml of ammonia water, 48ml of ethanol and the like overnight, then placing the solution into a high-pressure reaction kettle for hydrothermal reaction at the temperature of 130 ℃ and 160 ℃ for 2-4 h, and then carrying out suction filtration, washing and drying with purified water and ethanol overnight to obtain the cobalt-iron bimetallic nano-particles taking nitrogen-doped carbon as the substrate.
Step 3, preparing cobalt-iron bimetallic phosphide nanoparticles: 40mg of cobalt-iron bimetallic nano-particles and 400mg of sodium hypophosphite are heated and insulated in a tube furnace under the protection of argon, the reaction temperature is 350 ℃, and the heating rate is 4 ℃ for min-1And the heat preservation time is 2 hours, and finally the cobalt-iron bimetal phosphorization nano-particles taking nitrogen-doped carbon as the substrate are obtained.
Example 2
The preparation method of the cobalt-iron bimetallic phosphating nanoparticles comprises the following steps:
step 1, preparing cobalt-iron bimetallic nanoparticles: using 0.4ml of a 0.6mol L concentration-10.4ml of cobalt acetate, 0.6mol L-1Stirring the solution of ferric acetate, 1ml ammonia water, 48ml ethanol and the like overnight, and then putting the solution into a high-pressure reaction kettleAnd (3) performing hydrothermal reaction at the solvothermal reaction temperature of 130-160 ℃ for 2-4 h, and then performing suction filtration, washing and drying overnight by using purified water and ethanol to obtain the cobalt-iron bimetallic nanoparticles.
Step 2, preparing cobalt-iron bimetallic phosphide nanoparticles: 40mg of cobalt-iron bimetallic nano-particles and 400mg of sodium hypophosphite are heated and insulated in a tube furnace under the protection of argon, the reaction temperature is 350 ℃, and the heating rate is 4 ℃ for min-1And keeping the temperature for 2 hours to finally obtain the cobalt-iron bimetal phosphorization nano-particles.
Example 3
In this embodiment, cobalt-iron bimetallic phosphatized nanoparticles based on nitrogen-doped carbon are prepared according to the method shown in fig. 1, and the steps are as follows:
step 1, preparing a nitrogen-doped carbon substrate: dissolving 1.5g zinc nitrate hexahydrate, 0.5g glucose and 1mg/ml carbon nano tube in 50ml ethanol, ultrasonically treating the solution for 5 minutes, stirring for half an hour, heating to 200 ℃ in a tube furnace under the protection of argon, and raising the temperature at the rate of 5 ℃ for min-1And keeping the temperature for 2 hours, soaking the obtained black solid in hydrochloric acid, performing suction filtration and washing by using ethanol and purified water, and drying overnight to obtain the nitrogen-doped carbon matrix.
Step 2, preparing cobalt-iron bimetallic nanoparticles: using 40mg of nitrogen doped carbon matrix and 0.2ml of 0.6mol L-10.6ml of cobalt acetate, 0.6mol L-1Stirring the solution formed by iron acetate, 1ml of ammonia water, 48ml of ethanol and the like overnight, then placing the solution into a high-pressure reaction kettle for hydrothermal reaction at the temperature of 130 ℃ and 160 ℃ for 2-4 h, and then carrying out suction filtration, washing and drying with purified water and ethanol overnight to obtain the cobalt-iron bimetallic nano-particles taking nitrogen-doped carbon as the substrate.
Step 3, preparing cobalt-iron bimetallic phosphide nano-particles: 40mg of cobalt-iron bimetallic nano-particles and 400mg of sodium hypophosphite are heated and insulated in a tube furnace under the protection of argon, the reaction temperature is 350 ℃, and the heating rate is 4 ℃ for min-1And the heat preservation time is 2 hours, and finally the cobalt-iron bimetal phosphorization nano-particles taking nitrogen-doped carbon as the substrate are obtained.
Example 4
In this embodiment, cobalt-iron bimetallic phosphatized nanoparticles based on nitrogen-doped carbon are prepared according to the method shown in fig. 1, and the steps are as follows:
step 1, preparing a nitrogen-doped carbon substrate: dissolving 1.5g zinc nitrate hexahydrate, 0.5g glucose and 1mg/ml carbon nanotube in 50ml ethanol, ultrasonically treating the solution for 5 minutes, stirring for half an hour, heating to 200 ℃ in a tube furnace under the protection of argon, and raising the temperature at the rate of 5 ℃ for min-1And preserving the heat for 2 hours, soaking the obtained black solid in hydrochloric acid, performing suction filtration and washing by using ethanol and purified water, and drying overnight to obtain the nitrogen-doped carbon matrix.
Step 2, preparing cobalt-iron bimetallic nanoparticles: using 40mg of nitrogen doped carbon matrix and 0.6ml of 0.6mol L-10.2ml of cobalt acetate, 0.6mol L-1Stirring the solution formed by iron acetate, 1ml of ammonia water, 48ml of ethanol and the like overnight, then placing the solution into a high-pressure reaction kettle for hydrothermal reaction at the temperature of 130 ℃ and 160 ℃ for 2-4 h, and then carrying out suction filtration, washing and drying with purified water and ethanol overnight to obtain the cobalt-iron bimetallic nano-particles taking nitrogen-doped carbon as the substrate.
Step 3, preparing cobalt-iron bimetallic phosphide nanoparticles: heating 40mg of cobalt-iron bimetal nanoparticles and 400mg of sodium hypophosphite in a tubular furnace under the protection of argon, and keeping the temperature, wherein the reaction temperature is 350 ℃, and the heating rate is 4 ℃ for min-1And the heat preservation time is 2 hours, and finally the cobalt-iron bimetal phosphorization nano-particles taking nitrogen-doped carbon as the substrate are obtained.
Example 5
In this embodiment, cobalt-iron bimetallic phosphatized nanoparticles based on nitrogen-doped carbon are prepared according to the method shown in fig. 1, and the steps are as follows:
step 1, preparing a nitrogen-doped carbon substrate: dissolving 1.5g zinc nitrate hexahydrate, 0.5g glucose and 1mg/ml carbon nanotube in 50ml ethanol, ultrasonically treating the solution for 5 minutes, stirring for half an hour, heating to 200 ℃ in a tube furnace under the protection of argon, and raising the temperature at the rate of 5 ℃ for min-1And keeping the temperature for 2 hours, soaking the obtained black solid in hydrochloric acid, performing suction filtration and washing by using ethanol and purified water, and drying overnight to obtain the nitrogen-doped carbon matrix.
Step 2, preparing cobalt-iron bimetallic nanoparticles: using 40mg of nitrogen doped carbon matrix and 0.8ml of 0.6mol L-1The cobalt acetate, 1ml of ammonia water, 48ml of ethanol and the like form a solution, the solution is stirred overnight, then the solution is placed into a high-pressure reaction kettle for hydrothermal reaction, the solvothermal reaction temperature is 130-160 ℃, the hydrothermal time is 2-4 h, and then purified water and ethanol are used for suction filtration, washing and drying overnight, so that the cobalt-iron bimetallic nano-particles taking nitrogen-doped carbon as the substrate are obtained.
Step 3, preparing cobalt-iron bimetallic phosphide nanoparticles: 40mg of cobalt-iron bimetallic nano-particles and 400mg of sodium hypophosphite are heated and insulated in a tube furnace under the protection of argon, the reaction temperature is 350 ℃, and the heating rate is 4 ℃ for min-1And keeping the temperature for 2 hours to finally obtain the cobalt-iron bimetal phosphorization nano-particles taking the nitrogen-doped carbon as the substrate.
Example 6
In this embodiment, cobalt-iron bimetallic phosphatized nanoparticles based on nitrogen-doped carbon are prepared according to the method shown in fig. 1, and the steps are as follows:
step 1, preparing a nitrogen-doped carbon substrate: dissolving 1.5g zinc nitrate hexahydrate, 0.5g glucose and 1mg/ml carbon nano tube in 50ml ethanol, ultrasonically treating the solution for 5 minutes, stirring for half an hour, heating to 200 ℃ in a tube furnace under the protection of argon, and raising the temperature at the rate of 5 ℃ for min-1And keeping the temperature for 2 hours, soaking the obtained black solid in hydrochloric acid, performing suction filtration and washing by using ethanol and purified water, and drying overnight to obtain the nitrogen-doped carbon matrix.
Step 2, preparing cobalt-iron bimetallic nanoparticles: 0.8ml of 0.6mol L of concentration using 40mg of nitrogen-doped carbon substrate-1Stirring the solution formed by iron acetate, 1ml of ammonia water, 48ml of ethanol and the like overnight, then placing the solution into a high-pressure reaction kettle for hydrothermal reaction at the temperature of 130 ℃ and 160 ℃ for 2-4 h, and then carrying out suction filtration, washing and drying with purified water and ethanol overnight to obtain the cobalt-iron bimetallic nano-particles taking nitrogen-doped carbon as the substrate.
Step 3, preparing cobalt-iron bimetallic phosphide nanoparticles: 40mg of cobalt-iron bimetallic nanoparticles and 400mg of sodium hypophosphite were heated in a tube furnace under argon protectionKeeping the temperature, wherein the reaction temperature is 350 ℃, and the heating rate is 4 ℃ for min-1And the heat preservation time is 2 hours, and finally the cobalt-iron bimetal phosphorization nano-particles taking nitrogen-doped carbon as the substrate are obtained.
Example 7
In this embodiment, cobalt-iron bimetallic phosphatized nanoparticles based on nitrogen-doped carbon are prepared according to the method shown in fig. 1, and the steps are as follows:
step 1, preparing a nitrogen-doped carbon substrate: dissolving 1.5g zinc nitrate hexahydrate, 0.5g glucose and 1mg/ml carbon nanotube in 50ml ethanol, ultrasonically treating the solution for 5 minutes, stirring for half an hour, heating to 200 ℃ in a tube furnace under the protection of argon, and raising the temperature at the rate of 5 ℃ for min-1And keeping the temperature for 2 hours, soaking the obtained black solid in hydrochloric acid, performing suction filtration and washing by using ethanol and purified water, and drying overnight to obtain the nitrogen-doped carbon matrix.
Step 2, preparing cobalt-iron bimetallic nanoparticles: using 40mg of nitrogen doped carbon matrix and 0.5ml of 0.6mol L-10.5ml of cobalt acetate, 0.6mol L-1Stirring the solution formed by iron acetate, 1ml of ammonia water, 48ml of ethanol and the like overnight, then placing the solution into a high-pressure reaction kettle for hydrothermal reaction at the temperature of 130 ℃ and 160 ℃ for 2-4 h, and then carrying out suction filtration, washing and drying with purified water and ethanol overnight to obtain the cobalt-iron bimetallic nano-particles taking nitrogen-doped carbon as the substrate.
Step 3, preparing cobalt-iron bimetallic phosphide nanoparticles: 40mg of cobalt-iron bimetallic nano-particles and 400mg of sodium hypophosphite are heated and insulated in a tube furnace under the protection of argon, the reaction temperature is 350 ℃, and the heating rate is 4 ℃ for min-1And the heat preservation time is 2 hours, and finally the cobalt-iron bimetal phosphorization nano-particles taking nitrogen-doped carbon as the substrate are obtained.
Example 8
In this embodiment, cobalt-iron bimetallic phosphatized nanoparticles based on nitrogen-doped carbon are prepared according to the method shown in fig. 1, and the steps are as follows:
step 1, preparing a nitrogen-doped carbon substrate: dissolving 1.5g zinc nitrate hexahydrate, 0.5g glucose and 1mg/ml carbon nanotube in 50ml ethanol, subjecting the solution to ultrasonic treatment for 5 min, stirring for half an hour, and subjecting to ultrasonic treatmentHeating to 200 deg.C in a tube furnace under the protection of argon, and heating at a rate of 5 deg.C for 5 min-1And keeping the temperature for 2 hours, soaking the obtained black solid in hydrochloric acid, performing suction filtration and washing by using ethanol and purified water, and drying overnight to obtain the nitrogen-doped carbon matrix.
Step 2, preparing the cobalt-iron bimetallic nanoparticles: using 40mg of nitrogen doped carbon matrix and 0.3ml of 0.6mol L-10.3ml of cobalt acetate, 0.6mol L-1Stirring the solution formed by iron acetate, 1ml of ammonia water, 48ml of ethanol and the like overnight, then placing the solution into a high-pressure reaction kettle for hydrothermal reaction at the temperature of 130-160 ℃ for 2-4 h, and then carrying out suction filtration, washing and drying by using purified water and ethanol overnight to obtain the cobalt-iron bimetallic nano-particles taking nitrogen-doped carbon as a substrate.
Step 3, preparing cobalt-iron bimetallic phosphide nanoparticles: 40mg of cobalt-iron bimetallic nano-particles and 400mg of sodium hypophosphite are heated and insulated in a tube furnace under the protection of argon, the reaction temperature is 350 ℃, and the heating rate is 4 ℃ for min-1And the heat preservation time is 2 hours, and finally the cobalt-iron bimetal phosphorization nano-particles taking nitrogen-doped carbon as the substrate are obtained, and the microstructure of the nano-particles is shown in figures 2 and 3.
The electrode material prepared in this example was used as a working electrode, mercury/mercury oxide as a reference electrode, a platinum electrode of the same area as the reference electrode, and 1.0mol L of the auxiliary electrode-1The potassium hydroxide solution is alkaline electrolyte to form a three-electrode system, silver/silver chloride is used as a reference electrode, a platinum electrode with the same area is used as an auxiliary electrode, and 0.5mol L of the platinum electrode is used-1The sulfuric acid solution is an acid electrolyte to form a three-electrode system. Constant current charge and discharge test was carried out in CHI660E electrochemical workstation at a potential range of 0-0.6V. The obtained cobalt-iron bimetallic phosphatized nano-particles taking nitrogen-doped carbon as a substrate have a layered porous structure and relatively high BET specific surface area so as to promote electron transfer and increase the activity of electrocatalytic reaction and the active sites of electrolyte, and the current density is 10mA cm-2When the reaction solution showed an overpotential of 150(193) mV in a 0.5M sulfuric acid solution (1.0M potassium hydroxide solution), and 59(80) mV dec-1Low Tafel slope, indicating that the material has the property of being an electrocatalytic materialHigh stability and good electrocatalytic performance.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.

Claims (10)

1. The preparation method of the cobalt-iron bimetal phosphorization nano-particles with nitrogen-doped carbon as a substrate is characterized by comprising the following steps of:
(1) dissolving zinc nitrate hexahydrate, glucose and carbon nanotubes in ethanol, ultrasonically stirring the solution, heating and preserving heat in a tube furnace under the protection of argon gas for high-temperature carbonization, soaking the obtained black solid in hydrochloric acid, performing suction filtration and washing, and drying overnight to obtain a nitrogen-doped carbon matrix;
(2) mixing the nitrogen-doped carbon matrix with cobalt acetate, iron acetate, ammonia water and ethanol to form a mixed solution, stirring overnight, then putting the mixed solution into a high-pressure reaction kettle for hydrothermal reaction, performing suction filtration and washing after the solvent thermal reaction, and drying overnight to obtain cobalt-iron bimetallic nanoparticles;
(3) and heating and preserving the cobalt-iron bimetallic nano-particles and the sodium hypophosphite in a tubular furnace under the protection of argon gas for low-temperature phosphorization to obtain the cobalt-iron bimetallic phosphorized nano-particles.
2. The method for preparing N-doped carbon-based CoFebimetallic phosphide nanoparticles as claimed in claim 1, wherein in the step (1), the mass of zinc nitrate hexahydrate is 1.5g, the mass of glucose is 0.5g, and the concentration of carbon nanotubes is 1mg L-1The solvent is selected from 99% ethanol by mass, and the addition amount of the solvent is 20-40 ml.
3. The method for preparing nitrogen-doped carbon-based cobalt-iron bimetallic phosphatized nanoparticles as claimed in claim 1, wherein in the step (1), the ultrasonic time is 5 minutes, and the stirring time is 30 minutes; the high-temperature carbonization temperature is 200 ℃, and the heating rate is 5 ℃ for min-1The heat preservation time is 2 hoursIn this case, the suction filtration washing is washing with deionized water and ethanol.
4. The method for preparing N-doped carbon-based CoFe bimetallic phosphide nanoparticles as claimed in claim 1, wherein in the step (2), the mass of the N-doped carbon matrix is 40mg, and the concentrations of the cobalt acetate and the iron acetate are both 0.6mol L-11ml of ammonia water.
5. The method as claimed in claim 1, wherein in the step (2), the solvothermal reaction temperature is 130-160 ℃ and the hydrothermal time is 2-4 h; the drying temperature is 60-70 ℃.
6. The method for preparing nitrogen-doped carbon-based cobalt-iron bimetallic phosphatized nanoparticles as claimed in claim 1, wherein in step (3), the mass of the cobalt-iron bimetallic nanoparticles is 40mg, and the mass of the sodium hypophosphite is 400 mg.
7. The method for preparing N-doped carbon-based Co-Fe bimetallic phosphide nanoparticles as claimed in claim 1, wherein in the step (3), the reaction temperature of low-temperature phosphorization is 350 ℃, and the heating rate is 4 ℃ for min-1The holding time was 2 hours.
8. A nitrogen-doped carbon-based cobalt-iron bimetallic phosphatized nanoparticle prepared by the method for preparing the nitrogen-doped carbon-based cobalt-iron bimetallic phosphatized nanoparticle as claimed in any one of claims 1 to 7.
9. An electrocatalytic material comprising the nitrogen-doped carbon-based cobalt-iron bimetallic phosphatized nanoparticles of claim 8.
10. Use of the nitrogen-doped carbon-based cobalt-iron bimetallic phosphide nanoparticles of claim 8 or the electrocatalytic material of claim 9 in electrocatalytic hydrogen evolution reactions of acidic and alkaline electrolytes.
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