CN114988411A - Pure phase W with high specific surface area 2 C nano material and preparation method and application thereof - Google Patents

Pure phase W with high specific surface area 2 C nano material and preparation method and application thereof Download PDF

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CN114988411A
CN114988411A CN202210624746.4A CN202210624746A CN114988411A CN 114988411 A CN114988411 A CN 114988411A CN 202210624746 A CN202210624746 A CN 202210624746A CN 114988411 A CN114988411 A CN 114988411A
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carbonization
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iron
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CN114988411B (en
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陈赵扬
彭荣贵
褚有群
李灵童
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Zhejiang University of Technology ZJUT
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Abstract

The invention discloses a pure phase W with high specific surface area 2 C nano material and its preparation method and application. The preparation method comprises the following steps: (1) preparing tungsten source and iron salt into mixed solution, and collectingGranulating by a spray drying method; (2) calcining and oxidizing the particles obtained by spray drying in the air atmosphere to obtain a tungsten-iron oxide precursor; (3) reducing and carbonizing the oxide precursor by adopting a temperature programming-gas-solid reaction method under the reducing and carbonizing atmosphere to obtain W 2 A C/Fe composite material; (4) w is to be 2 The C/Fe composite material is put into hydrochloric acid solution for acid cleaning, washing, solid-liquid separation and drying to obtain pure phase W 2 And C, nano-materials. The invention provides the pure phase W 2 The application of the C nano material as an electrocatalyst in hydrogen evolution reaction. The pure phase W with high specific surface area 2 Compared with WC, the C nano material can obviously improve the catalytic conversion efficiency.

Description

Pure phase W with high specific surface area 2 C nano material and preparation method and application thereof
(I) technical field
The invention belongs to the technical field of inorganic nano material preparation, and particularly relates to a pure-phase W with a high specific surface area 2 C nano material, a preparation method thereof and application of the C nano material as an electrocatalyst in hydrogen evolution reaction.
(II) background of the invention
The hydrogen is used as an environment-friendly clean energy carrier with high combustion heat value, and has important significance for solving the current increasingly severe problems of energy shortage and environmental pollution. Compared with the traditional hydrogen production by reforming fossil fuels (such as petroleum, natural gas and coal), the hydrogen production by electrolyzing water has the advantages of high product purity, no pollution in the production process, simple and convenient operation, better safety and the like, and is considered to be a method with wide application prospect. For the electrolytic water hydrogen evolution reaction, the high-performance catalyst is mostly limited to noble metals (Pt, Ir, Ru and the like), but the noble metals have rare earth crust reserves and high price, and are not suitable for large-scale production and application. Therefore, the research and development of the electrocatalytic hydrogen evolution reaction catalytic material which is efficient, stable, low in price and rich in reserves has very important application value and theoretical significance.
Tungsten carbide (WC and W) 2 C) The catalyst has the d-band electronic state density similar to that of Pt, is a powerful substitute of a platinum-based catalyst, and can be widely used for the electrolytic water hydrogen evolution reaction. And in a large number of subsequent studies, the Lee topic group was obtained by theoretical calculations, due to W 2 The density of electronic states at the C Fermi level is higher and the Gibbs free energy for hydrogen adsorption is lower, so W 2 C has a higher catalytic activity than WC and is a more suitable catalyst for HER. The results of this study are published in Nature Communication (nat. communication.2016, 7,13216), which is phase-pure W 2 The application of the C nano material in the commercial electrolysis of water to produce hydrogen opens a door.
However, pure phase W of high specific surface area 2 The preparation of the C nano material is challenging and rareAnd (4) reporting. W-C phase diagram indicates W 2 C formation is thermodynamically unstable below 1250 deg.C, so that pure phase W 2 The synthesis of C requires the use of high temperatures (C)>800 ℃ C.), is easy to cause W 2 The excessive growth of C crystal results in the reduction of the nano-crystallization degree of active center of the material, and influences the catalytic performance of the material. Further, W 2 The synthesis of C must be carried out in a carbon deficient environment to avoid WC formation, and most processes using gaseous carbon precursors cannot produce W 2 C is the primary product because the relative amounts of gaseous carbon precursor to tungsten precursor are generally out of control, and the diffusion of gaseous carbon precursor through the solid-gas interface to the tungsten lattice is generally too fast to allow fine control of the product phase.
To date, no reference has been made to the preparation of pure phase W of high specific surface area at low temperatures (< 800 ℃) using gaseous carbon precursors 2 C nanometer material.
Disclosure of the invention
The first technical problem to be solved by the invention is to provide a pure phase W with high specific surface area 2 A preparation method of C nano material, which aims at overcoming the existing pure phase W 2 C nano material is difficult to synthesize at low temperature by using gaseous carbon precursor, and pure-phase W prepared by the method 2 The C particles can reach the nanometer level and have higher specific surface area.
The second technical problem to be solved by the invention is to provide a pure phase W with high specific surface area 2 And C, nano-materials.
The third technical problem to be solved by the present invention is to provide the pure phase W with high specific surface area 2 The application of the C nano material as an electrocatalyst in hydrogen evolution reaction.
The technical solution of the present invention is explained in detail below.
In a first aspect, the present invention provides a pure phase W 2 A method for preparing a C nanomaterial, the method comprising the steps of:
(1) mixing a tungsten source and an iron salt according to the mass ratio of tungsten to iron atoms of 4: 0.25-1, preparing a mixed solution, and granulating by adopting a spray drying method;
(2) calcining and oxidizing the particles obtained by spray drying in the air atmosphere to obtain a ferrotungsten oxide precursor after the oxidation is finished;
(3) reducing and carbonizing the oxide precursor by adopting a temperature programming-gas-solid reaction method under the reducing and carbonizing atmosphere, and cooling to obtain W after carbonization 2 A C/Fe composite material; the reductive carbonization atmosphere is CO with the gas flow rate of 80-160 ml/min; the reduction carbonization conditions are as follows: heating to 700-800 ℃ at a programmed heating rate of 3-7 ℃/min and keeping for 1-2 hours;
(4) w is to be 2 The C/Fe composite material is put into hydrochloric acid solution for acid washing, solid-liquid separation and drying to obtain pure phase W 2 And C, nano-materials.
The mixed solution in the step (1) of the present invention is preferably prepared as follows: mixing ammonium metatungstate and ferric nitrate according to the tungsten-iron atomic mass ratio of 4: 0.25-1, and adding deionized water to prepare a 1-30 wt% solution. Further preferably, the atomic mass ratio of tungsten to iron is 4:0.5 to 1, and more preferably 4: 0.5. Preferably, the total mass fraction of the ammonium metatungstate and the ferric nitrate in the mixed solution is 8-22 wt%. The invention preferably carries out spray drying after fully dispersing the prepared mixed solution through ultrasonic treatment so as to ensure that the mixed components in the spray-dried particles are uniformly distributed; properly prolonging the ultrasonic treatment time is beneficial to obtaining a mixed solution with more uniform dispersion, and preferably, the ultrasonic treatment time is 1-3 minutes.
In the step (1), the mixed solution is granulated by adopting a double-airflow spray drying method, and the inlet temperature of a spray dryer is preferably set to be 180-220 ℃, and more preferably 190-210 ℃.
In step (2) of the present invention, in order to prevent the particles obtained by spray drying from agglomerating due to moisture in the air atmosphere, the particles are preferably calcined and oxidized at 500 to 800 ℃ for 1 to 3 hours in the air atmosphere, and after the oxidation is completed, a ferrotungsten oxide precursor is obtained.
In step (3) of the invention, the solid obtained in step (2) is carbonized in a tubular furnace under a reducing carbonization atmosphere to prepare W 2 C/Fe composite material. The above-mentionedThe preferable reductive carbonization atmosphere is CO with the gas flow rate of 100-120 ml/min.
In the step (4) of the present invention, W obtainable by reduction-carbonization 2 And putting the C/Fe composite material into 10-20 wt% hydrochloric acid solution for acid washing treatment to remove iron elements, wherein the acid washing time is 4-8 h.
In a second aspect, the present invention provides a pure phase W of high specific surface area prepared according to the above-mentioned preparation method 2 And C, nano-materials.
In a third aspect, the invention provides said high specific surface area pure phase W 2 The application of the C nano material as an electrocatalyst in hydrogen evolution reaction. The results show that the high specific surface area pure phase W 2 Compared with WC, the C nano material can obviously improve the catalytic conversion efficiency.
Compared with the prior art, the invention has the beneficial effects that:
(1) the preparation method has the advantages that: with WO 3 As a precursor preparation, especially when using gaseous carbon precursors, WO due to the principle of thermodynamic stability 3 The tungsten carbide obtained by carbonization is often W 2 A mixture of C and WC; the invention adds Fe element into precursor to make carbonization process in W-Fe-C ternary system, to make W element in precursor be Fe 2 (WO 4 ) 3 Form is converted into carbide, and the phenomenon that WO is changed is avoided 3 Preparation of W by carbonization 2 C instability; in the carbonization process, Fe consumes partial CO on the surface of precursor particles to cause the surface of the precursor particles to form a carbon-deficient environment, namely W to a certain extent 2 The stable generation of C provides a carbon-deficient environment; during the carbonization process, the components are separated along with the difference of melting points, so that Fe is dispersed in W 2 C periphery, to achieve suppression of W 2 C, the purpose of agglomeration; by removing Fe by acid washing, W can be further increased 2 C specific surface area.
(2) The pure phase W is prepared 2 The advantages of the C nano material structure are as follows: the pure phase W prepared by the preparation method 2 The C particles have reached the nanometer scale. Abundant pores exist among the nanoparticles, and the abundant pores enable W 2 C has a high specific surface area.
(3) The pure phase W is prepared 2 The advantages of the application of the C nano material as the electro-catalyst in the hydrogen evolution reaction are as follows: pure phase W 2 Compared with a WC catalyst, the performance of the C nano material serving as a non-noble metal electrocatalyst is greatly improved in hydrogen evolution reaction performance.
(IV) description of the drawings
FIG. 1 shows W prepared in example 1 of the present invention 2 X-ray diffraction pattern (XRD) of C nanomaterial.
FIG. 2 shows W prepared in example 1 of the present invention 2 Scanning Electron Microscopy (SEM) of C nanomaterials.
FIG. 3 is W prepared according to example 2 of the present invention 2 Scanning Electron Microscopy (SEM) of C nanomaterials.
FIG. 4 shows W prepared in example 3 of the present invention 2 Scanning Electron Microscopy (SEM) of C nanomaterials.
FIG. 5 shows W prepared in example 4 of the present invention 2 Scanning Electron Microscopy (SEM) of C nanomaterials.
FIG. 6 shows W prepared in examples 1, 2, 3 and 4 of the present invention 2 C nitrogen isothermal adsorption and desorption curve of the nano material, a) example 1; b) example 2; c) example 3; d) example 4.
FIG. 7 is a nitrogen isothermal sorption and desorption curve of a sample prepared in comparative example 5 of the present invention.
FIG. 8 is an X-ray diffraction pattern (XRD) of samples prepared according to comparative example 1 and comparative example 2 of the present invention.
FIG. 9 is an X-ray diffraction pattern (XRD) of a sample prepared in comparative example 5 of the present invention.
FIG. 10 is a Scanning Electron Microscope (SEM) image of a sample prepared in comparative example 3 of the present invention.
FIG. 11 is a Scanning Electron Microscope (SEM) image of a sample prepared according to comparative example 4 of the present invention.
FIG. 12 shows W prepared in examples 1, 2, 3 and 4 of the present invention 2 Characterization plots of catalytic activity of the nanomaterials and samples prepared in comparative example 5 on hydrogen evolution reactions.
(V) detailed description of the preferred embodiments
The invention will be further described in the following examples, which are given by way of illustration, without limiting the scope of the invention:
example 1:
mixing ammonium metatungstate and ferric nitrate according to the tungsten-iron atomic mass ratio of 4:0.5, and adding deionized water to prepare a 22 wt% solution. And (3) carrying out ultrasonic treatment on the prepared mixed solution of ammonium metatungstate and copper nitrate for 3 minutes, fully dispersing, then carrying out spray drying, carrying out drying treatment by utilizing double-airflow spray drying (inlet temperature is 200 ℃), and calcining and oxidizing the obtained particles in an air atmosphere at 600 ℃ for 2 hours to obtain a tungsten-iron oxide precursor. And (2) carrying out reduction carbonization on the oxide precursor, wherein the reduction carbonization atmosphere is CO with the gas flow rate of 100ml/min, and the temperature is raised to 750 ℃ at the stage temperature programming rate of 5 ℃/min by utilizing a temperature programming-gas-solid reaction method and is kept for 1 hour. W obtained by reduction and carbonization 2 And putting the C/Fe composite material into hydrochloric acid solution with the concentration of more than 20 wt% for acid washing treatment to remove iron elements, wherein the acid washing time is 8 hours. After the acid washing is finished, washing, solid-liquid separation and drying are carried out to obtain pure phase W 2 And C, nano-materials. FIG. 1 is an XRD diagram of the obtained sample, and the intensity and position of the diffraction peak and the PDF card W can be seen 2 C #35-0776 coincided and had no other diffraction peaks, confirming that the sample was prepared as pure phase W 2 C. FIG. 2 is an SEM image of a sample showing 0.6 to 1.5 μm spheres consisting of 20 to 50nm nanoparticles, and it can be seen that the obtained pure phase W is 2 The C nano material has rich pore structure and higher specific surface area, and the BET specific surface area of the sample is 33.11m according to a nitrogen adsorption and desorption test (figure 6.a) 2 /g。
The prepared pure phase W 2 The C nano material is used for electrocatalytic hydrogen evolution and comprises the following specific steps:
(1) pretreatment of the working electrode: firstly, using Al as working electrode (glassy carbon electrode) 2 O 3 Polishing the powder to a mirror surface and then cleaning; the glassy carbon electrode was then placed at 0.2mol/LKCl +1mmol/L K 3 Fe(CN) 6 Activating in the solution, wherein the peak potential difference of the obtained cyclic voltammetry curve is about 70mV at the scanning speed of 50 mV/s;
(2) preparation of a working electrode: weighing 3mg of sample material, placing the sample material in a sample tube, adding 390 mu L of ethanol and 10 mu L of 5% Nafion to prepare emulsion, performing ultrasonic dispersion for 30min to obtain uniform catalyst slurry, sucking 5 mu L of catalyst slurry by a micro-pipette, dripping the catalyst slurry on the surface of a glassy carbon electrode, and drying at 50 ℃ to obtain the working electrode.
(3) The counter electrode used for the test is a platinum electrode, and the reference electrode is a saturated calomel electrode; the test solution was 0.5mol/L H 2 SO 4 The solution, at a sweep rate of 5mV/s, gave a linear polarization curve for the hydrogen evolution reaction, the results of which are shown in FIG. 12.
Example 2:
mixing ammonium metatungstate and ferric nitrate according to the tungsten-iron atomic mass ratio of 4: 0.75, and deionized water is added to prepare an 8 wt% solution. And (3) fully dispersing the prepared mixed solution of ammonium metatungstate and copper nitrate by ultrasonic treatment for 3 minutes, then carrying out spray drying, carrying out drying treatment by double-airflow spray drying (inlet temperature 190 ℃), and calcining and oxidizing the obtained particles in an air atmosphere at 500 ℃ for 3 hours to obtain a tungsten-iron oxide precursor. And (3) carrying out reduction carbonization on the oxide precursor, wherein the reduction carbonization atmosphere is CO with the gas flow rate of 100ml/min, and the temperature is raised to 700 ℃ at the stage temperature programming rate of 3 ℃/min by utilizing a temperature programming-gas-solid reaction method and is kept for 1.5 hours. W obtained by reduction and carbonization 2 And putting the C/Fe composite material into a hydrochloric acid solution with the concentration of more than 20 wt% for acid washing treatment to remove iron elements, wherein the acid washing time is 6 hours. After the acid washing is finished, washing, solid-liquid separation and drying are carried out to obtain pure phase W 2 And C, nano-materials. FIG. 3 is W prepared in example 2 2 C nanometer material Scanning Electron Microscope (SEM), the sample presents as a sphere with the grain diameter of about 1.5 mu m, the sphere is composed of nanometer particles with the grain diameter of 50-200 nm, and the BET specific surface area of the sample is 30.77m according to the nitrogen gas absorption and desorption test (figure 6.b) 2 /g。
The prepared pure phase W 2 The specific steps of the C nano material used for electrocatalytic hydrogen evolution are the same as example 1, and the results are shown in FIG. 12.
Example 3:
mixing ammonium metatungstate and ferric nitrate according to the tungsten-iron atomic mass ratio of 4: 1 mixing, adding deionized waterA 22 wt% solution was prepared. And (3) fully dispersing the prepared mixed solution of ammonium metatungstate and copper nitrate by ultrasonic treatment for 3 minutes, then carrying out spray drying, carrying out drying treatment by double-airflow spray drying (inlet temperature 210 ℃), and calcining and oxidizing the obtained particles in an air atmosphere at 700 ℃ for 1 hour to obtain the tungsten-iron oxide precursor. And (3) carrying out reduction carbonization on the oxide precursor, wherein the reduction carbonization atmosphere is CO with the gas flow rate of 120ml/min, and the temperature is raised to 800 ℃ at the stage temperature programming rate of 7 ℃/min by utilizing a temperature programming-gas-solid reaction method and is kept for 1.5 hours. W obtained by reduction and carbonization 2 And putting the C/Fe composite material into a hydrochloric acid solution with the concentration of more than 10 wt% for acid washing treatment to remove iron elements, wherein the acid washing time is 6 h. After the acid washing is finished, washing, solid-liquid separation and drying are carried out to obtain pure phase W 2 And C, nano-materials. FIG. 4 shows W prepared in example 3 2 C nanometer material Scanning Electron Microscope (SEM), the sample presents as a sphere with the particle size of about 1.5 μm, the sphere is composed of 50-100 nm nanometer particles, and the BET specific surface area of the sample is 28.97m according to a nitrogen absorption and desorption test (figure 6.C) 2 /g。
The prepared pure phase W 2 The specific steps of the C nano material used for electrocatalytic hydrogen evolution are the same as example 1, and the results are shown in FIG. 12.
Example 4:
mixing ammonium metatungstate and ferric nitrate according to the tungsten-iron atomic mass ratio of 4:0.5, and adding deionized water to prepare a 22 wt% solution. And (3) carrying out ultrasonic treatment on the prepared mixed solution of ammonium metatungstate and copper nitrate for 3 minutes, fully dispersing, then carrying out spray drying, carrying out drying treatment by utilizing double-airflow spray drying (inlet temperature is 200 ℃), and calcining and oxidizing the obtained particles in an air atmosphere at 600 ℃ for 1 hour to obtain a tungsten-iron oxide precursor. And (3) carrying out reduction carbonization on the oxide precursor, wherein the reduction carbonization atmosphere is CO with the gas flow rate of 120ml/min, and the temperature is raised to 750 ℃ at the stage temperature programming rate of 5 ℃/min by utilizing a temperature programming-gas-solid reaction method and is kept for 2 hours. W obtained by reduction and carbonization 2 The C/Fe composite material is put into hydrochloric acid solution with the concentration of more than 10 wt% for acid cleaning treatment to remove iron element, and the acid cleaning treatment is carried outThe time is 8 h. After the acid washing is finished, washing, solid-liquid separation and drying are carried out to obtain pure phase W 2 And C, nano-materials. FIG. 5 shows W prepared in example 4 2 C nanometer material Scanning Electron Microscope (SEM), the sample presents as a sphere with the grain diameter of about 1.5 μm, the sphere is composed of 50-100 nm nanometer particles, and the BET specific surface area of the sample is 24.00m by nitrogen absorption and desorption test (figure 6.d) 2 /g。
The prepared pure phase W 2 The specific steps of the C nano material used for electrocatalytic hydrogen evolution are the same as example 1, and the results are shown in FIG. 12.
Comparative example 1:
similar to the procedure of example 1, ferrotungsten oxide particles were obtained by the procedure of example 1, and the obtained particles were subjected to reductive carbonization in the atmosphere of CO at a gas flow rate of 100ml/min, and the temperature was raised to 650 ℃ at a temperature-programmed rate of 5 ℃/min by a temperature-programmed gas-solid reaction method and held for 2 hours. The remaining procedure was the same as in example 1, and a sample was finally obtained. From the XRD pattern shown in FIG. 8, it can be seen that the intensity and position of the sample exist together with the PDF card W 2 C #35-0776, but with the presence of WO 2 And FeWO 4 Indicating that the sample was insufficiently carbonized during the carbonization process.
Comparative example 2:
similar to the procedure of example 1, ferrotungsten oxide particles were obtained by the procedure of example 1, and the obtained particles were subjected to reductive carbonization in the atmosphere of CO with a gas flow rate of 100ml/min, and heated to 850 ℃ at a temperature-programmed rate of 5 ℃/min by a temperature-programmed gas-solid reaction method for 1 hour. The remaining procedure was the same as in example 1, and a sample was finally obtained. From the XRD pattern shown in FIG. 8, it can be seen that the intensity and position of the sample and the PDF card W are present 2 The consistent diffraction peaks for C #35-0776, but the presence of both WC and C, indicate that the sample was over-carbonized during this carbonization process.
Comparative example 3:
similar to the procedure of example 1, ammonium metatungstate and ferric nitrate were mixed in a tungsten-iron atomic mass ratio of 4: 0.25, and adding deionized water to prepare a 22 wt% solution. The remaining procedure was the same as in example 1, and a sample was finally obtained. As can be seen from the SEM image (FIG. 10) of the sample, the sample is represented by spheres of 1.5-2.5 μm, and the nanoparticles composing the spheres have obvious agglomeration phenomenon, so that the obtained sample has no abundant pore structure and higher specific surface area. Indicating that insufficient iron was introduced to result in a decrease in the specific surface area of the sample.
Comparative example 4:
similar to the procedure of example 1, ammonium metatungstate and ferric nitrate were mixed in a tungsten-iron atomic mass ratio of 4: 1.5, and adding deionized water to prepare a 22 wt% solution. The remaining procedure was the same as in example 1, and a sample was finally obtained. As can be seen from the SEM image (FIG. 11) of the sample, the sample has other irregular particles distributed on the spherical structure besides the spherical structure of 1-2 μm. Indicating that the introduction of excess iron affected the microstructure of the sample.
Comparative example 5:
similar to the procedure of example 1, ammonium metatungstate was formulated with deionized water to a 22 wt% solution without the addition of ferric nitrate, sonicated for 3 minutes to allow for adequate dispersion, and then spray dried. The remaining procedure was the same as in example 1, and a sample was finally obtained. As can be seen from the XRD pattern (FIG. 9) of the sample, it can be seen that the intensity and position of the diffraction peak coincide with those of the PDF card WC #51-0539 and there are no other diffraction peaks, confirming that the prepared sample is pure phase WC, and the BET specific surface area of the sample is 5.96m by the nitrogen desorption test (FIG. 7) 2 /g。
The prepared pure-phase WC was used for electrocatalytic hydrogen evolution, and the specific procedure was the same as in example 1, and the result is shown in fig. 12.

Claims (10)

1. Pure phase W 2 A method for preparing a C nanomaterial, the method comprising the steps of:
(1) mixing a tungsten source and an iron salt according to the mass ratio of tungsten to iron atoms of 4: 0.25-1, preparing a mixed solution, and granulating by adopting a spray drying method;
(2) calcining and oxidizing the particles obtained by spray drying in the air atmosphere to obtain a ferrotungsten oxide precursor after the oxidation is finished;
(3) reducing and carbonizing the oxide precursor by adopting a temperature programming-gas-solid reaction method under the reducing and carbonizing atmosphere, and cooling to obtain W after carbonization 2 A C/Fe composite material; the reductive carbonization atmosphere is CO with gas flow of 80-160 ml/min; the reduction carbonization conditions are as follows: heating to 700-800 ℃ at a programmed heating rate of 3-7 ℃/min and keeping for 1-2 hours;
(4) w is to be 2 The C/Fe composite material is put into hydrochloric acid solution for acid washing, solid-liquid separation and drying to obtain pure phase W 2 And C, nano-materials.
2. The method of claim 1, wherein: the mixed solution in the step (1) is prepared according to the following method: mixing ammonium metatungstate and ferric nitrate according to the tungsten-iron atomic mass ratio of 4: 0.25-1 (preferably 4: 0.5-1, more preferably 4:0.5), and adding deionized water to prepare a 1-30 wt% solution.
3. The method of claim 2, wherein: in the step (1), the total mass fraction of ammonium metatungstate and ferric nitrate in the mixed solution is 8-22 wt%.
4. The method of any one of claims 1 to 3, wherein: in the step (1), the prepared mixed solution is subjected to ultrasonic treatment, fully dispersed and then subjected to spray drying.
5. The method of any one of claims 1 to 3, wherein: in the step (1), the mixed solution is granulated by adopting a double-airflow spray drying method, the inlet temperature of a spray dryer is set to be 180-220 ℃, and the preferred inlet temperature is 190-210 ℃.
6. The method of claim 1, wherein: in the step (2), the particles are calcined and oxidized for 1-3 hours at 500-800 ℃ in the air atmosphere, and a tungsten-iron oxide precursor is obtained after the oxidation is completed.
7. The method of claim 1, wherein: in the step (3), the reductive carbonization atmosphere is CO with the gas flow rate of 100-120 ml/min.
8. The method of claim 1, wherein: in the step (4), W obtained by reduction and carbonization 2 And putting the C/Fe composite material into 10-20 wt% hydrochloric acid solution for acid washing treatment to remove iron elements, wherein the acid washing time is 4-8 h.
9. Pure phase W produced by the method of claim 1 2 And C, nano-materials.
10. Phase-pure W according to claim 9 2 The application of the C nano material as an electrocatalyst in hydrogen evolution reaction.
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