CN109295475B - Preparation method of selenium-doped vanadium selenide composite material - Google Patents

Preparation method of selenium-doped vanadium selenide composite material Download PDF

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CN109295475B
CN109295475B CN201811176633.2A CN201811176633A CN109295475B CN 109295475 B CN109295475 B CN 109295475B CN 201811176633 A CN201811176633 A CN 201811176633A CN 109295475 B CN109295475 B CN 109295475B
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selenium
porcelain boat
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vanadium
reaction kettle
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CN109295475A (en
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曹丽云
何丹阳
冯亮亮
黄剑锋
吴建鹏
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Shaanxi University of Science and Technology
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
    • C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/02—Hydrogen or oxygen
    • C25B1/04—Hydrogen or oxygen by electrolysis of water
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • 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

Abstract

The invention discloses a preparation method of a selenium-doped vanadium selenide composite material, which comprises the steps of weighing a vanadium source and an alkali source, dissolving the vanadium source and the alkali source in deionized water uniformly to obtain a mixed solution, placing the mixed solution in a high-pressure reaction kettle with a polyparaphenylene lining, reacting for 12-18 h at 80-120 ℃, washing, drying in vacuum and grinding to obtain a precursor of a VOOH compound, placing the precursor in a low-temperature tube furnace for sintering reaction, and grinding into powder after the sintering reaction is finished to obtain the selenium-doped vanadium selenide composite material.

Description

Preparation method of selenium-doped vanadium selenide composite material
Technical Field
The invention belongs to the field of preparation of electrocatalytic energy materials, relates to a composite material applied to the field of hydrogen production by water electrolysis and electrocatalysis, and particularly relates to a preparation method of a selenium-doped vanadium selenide composite material applied to the field of hydrogen production by water electrolysis and electrocatalysis.
Background
With the increasing demand of human beings on energy, the excessive consumption of traditional fossil energy and the environmental pollution become more serious, and the search for sustainable clean energy is expected to become a breakthrough for solving the two problems. Hydrogen is one of the ideal energy sources for human beings in the future as green and sustainable clean energy, and an electrocatalytic hydrogen production technology taking water as a raw material is an important green way for providing hydrogen energy. The core of electrocatalytic hydrogen production is to design an efficient electrocatalyst. At present, noble metal platinum materials are still the catalysts with the highest electrocatalysis efficiency in electrocatalysis hydrogen production, but the defects of high price and low reserves greatly limit the wide application of the catalysts, and are recorded in the document [1 ]. Therefore, it is of great importance to find efficient and inexpensive electrocatalysts that can replace platinum-series materials. At present, non-noble metal hydrogen evolution electrocatalysts with potential application prospects are reported successively, wherein transition metal chalcogen compounds (TMDs) are considered to be one of the electrocatalysts most likely to replace platinum-series materials to produce hydrogen through electrocatalysis due to excellent performance, low price and abundant reserves.
The catalytic activity of electrocatalytic hydrogen production is not only related to the catalytic active sites located at the edges of the layered structure, but also the electron conductivity of the catalyst itself is one of the important determinants, see document [2 ]]The following are described. The metal selenide has a similar structure to the metal sulfide, but the metal selenide has a higher electrical conductivity, and thus the metal selenide may exhibit more unique hydrogen evolution properties than the metal sulfide. Vanadium diselenide (VSe)2) As an important member of TMDs, there are layered structures common to these compounds. Single layer VSe2Is a sandwich structure formed by two layers of selenium atoms and a layer of vanadium atoms which are mutually bonded, and two adjacent layers VSe2There is no chemical bond between them, and only van der Waals interaction is shown in document [3 ]]The following are described. Because selenium atoms have larger radius and stronger metallicity than sulfur atoms, the metal selenide has larger interlayer spacing and higher electrical conductivity than the metal sulfide, and the characteristics enable the metal selenide to have more advantages than the metal sulfide in the fields of electrochemical energy storage and electrocatalysis.
[1]HeeLS,Nitul K,Hyun JS,MaitiJ,Yoon YS.Hydrothermal synthesis of Pt-Runanoparticlessupported on graphene sheets for methanol oxidation in directmethanol fuel cell.Materials Letters,2011,65:3281-3284.
[2]Jaramillo TF,
Figure GDA0002224677910000021
KP,Bonde J,et al.Identification of activeedge sites for electrochemical H2evolution from MoS2nanocatalysts.Science,2007,317:100-102.
[3]Whittingham MS.The electrochemical characteristics of VSe2inlithium cells.Materials Research Bulletin,1978,13:959-969。
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a preparation method of a selenium-doped vanadium selenide composite material with high-efficiency electrocatalysis performance, and the electrocatalysis material has the advantages of simple preparation process, low cost, short preparation period and easily controlled process.
In order to achieve the above object, the present invention adopts the following technical solutions.
A preparation method of a selenium-doped vanadium selenide composite material comprises the following steps:
1) weighing a vanadium source and an alkali source according to a molar ratio of 1 (1-3), dissolving the vanadium source and the alkali source in deionized water, and uniformly stirring by magnetic force to obtain a mixed solution;
2) transferring the mixed solution obtained in the step 1) into a high-pressure reaction kettle with a p-polyphenyl lining, controlling the filling ratio of the solution in the reaction kettle to be 40-60%, sealing the reaction kettle, and placing the reaction kettle in an oven to react for 12-18 h at the temperature of 80-120 ℃;
3) after the reaction is finished, respectively centrifugally washing the reaction product for a plurality of times by using deionized water and absolute ethyl alcohol, and then carrying out vacuum drying and grinding to obtain a precursor of the VOOH compound;
4) weighing VOOH precursor and selenium source according to element molar ratio V (mol) Se (mol) of (2.7-4.9) (7.2-15.8), putting the VOOH precursor into a small porcelain boat, putting the selenium source into a large porcelain boat, putting the small porcelain boat into the large porcelain boat, and covering with a cover to obtain a porcelain boat combination body;
5) placing the magnetic boat combination in the step 4) into a low-temperature tube furnace, and pumping the tube of the low-temperature tube furnace into a vacuum environment;
6) then, carrying out sintering reaction in a low-temperature tube furnace, wherein the sintering reaction temperature is 500-800 ℃, the time is 1-4 h, introducing protective gas for protection after the sintering reaction is finished, and taking out the porcelain boat combination from the low-temperature tube furnace when the temperature is reduced to room temperature;
7) pouring the sample in the porcelain boat combination treated in the step 6) into a mortar, and grinding the sample into a powdery sample to obtain the selenium-doped vanadium selenide composite material.
Further, the vanadium source in the step 1) is one or more of ammonium metavanadate, vanadium chloride and vanadium pentoxide.
Further, the alkali source in the step 1) is one or more of urea, hexamethylenetetramine and dimethylformamide.
Further, the selenium source in the step 4) refers to one or more of selenium powder, selenium dioxide and sodium selenate.
Further, dissolving the weighed vanadium source and alkali source in deionized water with the volume of 30mL in the step 1), and magnetically stirring for 20min to obtain a uniform mixed solution; and in the step 2), transferring the mixed solution obtained in the step 1) to a 50mL high-pressure reaction kettle with a p-polyphenyl lining, sealing the reaction kettle, and placing the reaction kettle in an oven for reaction.
Further, after the reaction in the step 3) is finished, the reaction solution is respectively centrifugally washed for 4 times by deionized water and absolute ethyl alcohol, and then is dried for 4-6 hours in vacuum at 60 ℃, and is ground to obtain a precursor of the VOOH compound.
Further, in the step 5), the magnetic boat combination in the step 4) is placed in a low-temperature tube furnace, firstly, vacuum pumping is carried out, then, protective gas is filled, and the steps are repeated for three times to remove air in the tube, and then, the tube is pumped into a vacuum environment.
Further, the protective gas is argon or nitrogen.
The selenium-doped vanadium selenide composite material prepared by the method is used for electrocatalytic hydrogen production. Compared with the prior art, the invention has the following beneficial technical effects:
(1) the preparation method of selenium-doped vanadium selenide provided by the invention has the advantages of simple process, easy control of conditions, short preparation period and low production cost.
(2) The selenium-doped vanadium selenide composite material prepared by the invention has a lamellar structure, the lamellar shape is more beneficial to full contact of an electrocatalyst and an electrolyte, and the activity of a catalytic site with higher density is exposed, so that the selenium-doped vanadium selenide composite material has higher electron transfer rate, and the electrocatalysis performance is improved.
(3) The selenium-doped vanadium selenide composite material prepared by the invention has excellent electro-catalytic performance, good catalytic activity, strong stability and high hydrogen production efficiency.
Drawings
FIG. 1 is an XRD pattern of a selenium-doped vanadium selenide composite material prepared in example 1 of the present invention
FIG. 2 is an SEM image of a selenium-doped vanadium selenide composite material prepared in example 1 of the invention
FIG. 3 is a graph of the linear sweep voltammetry performance of the selenium-doped vanadium selenide composite prepared in example 1 of the present invention
Detailed Description
The present invention will be described in further detail with reference to the following examples, which are not intended to limit the invention thereto.
Example 1:
1) weighing ammonium metavanadate and urea according to a molar ratio of 1:3, wherein the mass is 116.98mg and 180.18mg respectively, dissolving the ammonium metavanadate and urea in deionized water with the volume of 30mL, and magnetically stirring for 20min to obtain a uniform mixed solution;
2) transferring the mixed solution obtained in the step 1) to a 50mL high-pressure reaction kettle with a p-polyphenyl lining, controlling the filling ratio of the solution in the reaction kettle to be 60%, sealing the reaction kettle, and placing the reaction kettle in an oven to react for 16 hours at 80 ℃;
3) after the reaction is finished, respectively centrifugally washing the mixture for 4 times by using deionized water and absolute ethyl alcohol, then drying the mixture for 4 hours in vacuum at the temperature of 60 ℃, and grinding the dried mixture to obtain a precursor of the VOOH compound;
4) weighing VOOH precursor and selenium powder according to the element molar ratio V (mol) Se (mol) of 2.7:7.2, putting the VOOH precursor into a small porcelain boat, putting the selenium powder into a large porcelain boat, putting the small porcelain boat into the large porcelain boat, and covering with a cover to obtain a porcelain boat combination;
5) placing the magnetic boat combination body in the step 4) into a low-temperature tube furnace, vacuumizing firstly, and then filling argon, repeating the steps for three times to remove the air in the tube, and then vacuumizing the tube to form a vacuum environment;
6) heating the low-temperature tube furnace to 500 ℃, preserving heat for 4 hours, carrying out sintering reaction, introducing argon for protection after the reaction is stopped, and taking out the porcelain boat combination from the low-temperature tube furnace when the temperature is reduced to room temperature;
7) pouring the sample in the porcelain boat combination treated in the step 6) into a mortar, and grinding the sample into a powdery sample to obtain the selenium-doped vanadium selenide composite material.
FIG. 1 is a diffraction pattern of a selenium-doped vanadium selenide composite, from which the sum Se (PDF #73-0465) and VSe can be seen2The diffraction peaks of (PDF #89-1641) have good correspondence.
Fig. 2 is a scanning image of a selenium-doped vanadium selenide composite material, wherein small blocky selenium grows on flaky vanadium selenide, and the flaky shape is beneficial to providing a large number of electrochemical active sites and is easy for the permeation of electrolyte, so that the electrochemical performance of the material is improved.
FIG. 3 is a graph of the linear sweep voltammogram performance of a selenium-doped vanadium selenide composite material measured at a sweep rate of 3mV/s at a current density of 10mA/cm2 with an overpotential of 275mV, giving the material good electrocatalytic performance.
Example 2:
1) weighing vanadium chloride and hexamethylformamide according to a molar ratio of 1:2, wherein the mass of the vanadium chloride and the hexamethylformamide is 157.30mg and 280.36mg respectively, dissolving the vanadium chloride and the hexamethylformamide in deionized water with the volume of 30mL, and magnetically stirring for 20min to obtain a uniform mixed solution;
2) transferring the mixed solution obtained in the step 1) to a 50mL high-pressure reaction kettle with a p-polyphenyl lining, controlling the filling ratio of the solution in the reaction kettle to be 40%, sealing the reaction kettle, and placing the reaction kettle in an oven to react for 15 hours at 90 ℃;
3) after the reaction is finished, respectively centrifugally washing the mixture for 4 times by using deionized water and absolute ethyl alcohol, then carrying out vacuum drying for 5 hours at the temperature of 60 ℃, and grinding the dried mixture to obtain a precursor of the VOOH compound;
4) weighing VOOH precursor and selenium dioxide according to the element molar ratio V (mol) Se (mol) of 4.9:15.8, putting the VOOH precursor into a small porcelain boat, putting the selenium dioxide into a large porcelain boat, putting the small porcelain boat into the large porcelain boat, and covering with a cover to obtain a porcelain boat combination;
5) placing the magnetic boat combination body in the step 4) into a low-temperature tube furnace, vacuumizing firstly, and then filling nitrogen, repeating the steps for three times to remove air in the tube, and then vacuumizing the tube to form a vacuum environment;
6) heating the low-temperature tube furnace to 600 ℃, preserving heat for 3 hours for sintering reaction, introducing nitrogen for protection after the reaction is stopped, and taking out the porcelain boat combination from the low-temperature tube furnace when the temperature is reduced to room temperature;
7) pouring the sample in the porcelain boat combination treated in the step 6) into a mortar, and grinding the sample into a powdery sample to obtain the selenium-doped vanadium selenide composite material.
Example 3:
1) weighing vanadium pentoxide and dimethylformamide according to a molar ratio of 1:1, wherein the mass of vanadium pentoxide and dimethylformamide is 182.00mg and 73.10mg respectively, dissolving the vanadium pentoxide and dimethylformamide in deionized water with the volume of 30mL, and magnetically stirring for 20min to obtain a uniform mixed solution;
2) transferring the mixed solution obtained in the step 1) to a 50mL high-pressure reaction kettle with a p-polyphenyl lining, controlling the filling ratio of the solution in the reaction kettle to be 50%, sealing the reaction kettle, and placing the reaction kettle in an oven to react for 14 hours at 100 ℃;
3) after the reaction is finished, respectively centrifugally washing the mixture for 4 times by using deionized water and absolute ethyl alcohol, then carrying out vacuum drying for 6 hours at the temperature of 60 ℃, and grinding the dried mixture to obtain a precursor of the VOOH compound;
4) weighing VOOH precursor and sodium selenate according to the element molar ratio V (mol) to Se (mol) of 3.8:11.5, putting the VOOH precursor into a small porcelain boat, putting the sodium selenate into a large porcelain boat, putting the small porcelain boat into the large porcelain boat, and covering with a cover to obtain a porcelain boat combination;
5) placing the magnetic boat combination in the step 4) into a low-temperature tube furnace, vacuumizing, filling argon, repeating the steps for three times, removing air in the tube, and vacuumizing the tube;
6) heating the low-temperature tube furnace to 700 ℃, preserving heat for 2h for sintering reaction, introducing argon for protection after the reaction is stopped, and taking out the porcelain boat combination from the low-temperature tube furnace when the temperature is reduced to room temperature;
7) pouring the sample in the porcelain boat combination treated in the step 6) into a mortar, and grinding the sample into a powdery sample to obtain the selenium-doped vanadium selenide composite material.
Example 4:
1) weighing vanadium pentoxide and urea according to a molar ratio of 1:3, wherein the mass of the vanadium pentoxide and the mass of the urea are 182.00mg and 180.18mg respectively, dissolving the vanadium pentoxide and the urea in deionized water with the volume of 30mL, and magnetically stirring for 20min to obtain a uniform mixed solution;
2) transferring the mixed solution obtained in the step 1) to a 50mL high-pressure reaction kettle with a p-polyphenyl lining, controlling the filling ratio of the solution in the reaction kettle to be 40%, sealing the reaction kettle, and placing the reaction kettle in an oven to react for 18h at 80 ℃;
3) after the reaction is finished, respectively centrifugally washing the mixture for 4 times by using deionized water and absolute ethyl alcohol, then drying the mixture for 4 hours in vacuum at the temperature of 60 ℃, and grinding the dried mixture to obtain a precursor of the VOOH compound;
4) weighing VOOH precursor and selenium dioxide according to the element molar ratio V (mol) Se (mol) of 3.2:9.4, putting the VOOH precursor into a small porcelain boat, putting the selenium dioxide into a large porcelain boat, putting the small porcelain boat into the large porcelain boat, and covering with a cover to obtain a porcelain boat combination;
5) placing the magnetic boat combination in the step 4) into a low-temperature tube furnace, vacuumizing, charging nitrogen, repeating the steps for three times, removing air in the tube, and vacuumizing the tube;
6) heating the low-temperature tube furnace to 800 ℃, preserving heat for 1h for sintering reaction, introducing nitrogen for protection after the reaction is stopped, and taking out the porcelain boat combination from the low-temperature tube furnace when the temperature is reduced to room temperature;
7) pouring the sample in the porcelain boat combination treated in the step 6) into a mortar, and grinding the sample into a powdery sample to obtain the selenium-doped vanadium selenide composite material.
Example 5:
1) weighing ammonium metavanadate and dimethylformamide according to a molar ratio of 1:2, wherein the mass is 116.98mg and 146.2mg respectively, dissolving the ammonium metavanadate and the dimethylformamide into deionized water with the volume of 30mL, and magnetically stirring for 20min to obtain a uniform mixed solution;
2) transferring the mixed solution obtained in the step 1) to a 50mL high-pressure reaction kettle with a p-polyphenyl lining, controlling the filling ratio of the solution in the reaction kettle to be 50%, sealing the reaction kettle, and placing the reaction kettle in an oven to react for 12 hours at 120 ℃;
3) after the reaction is finished, respectively centrifugally washing the mixture for 4 times by using deionized water and absolute ethyl alcohol, then carrying out vacuum drying for 5 hours at the temperature of 60 ℃, and grinding the dried mixture to obtain a precursor of the VOOH compound;
4) weighing VOOH precursor and sodium selenate according to the element molar ratio V (mol) to Se (mol) of 4.4:13.6, putting the VOOH precursor into a small porcelain boat, putting the sodium selenate into a large porcelain boat, putting the small porcelain boat into the large porcelain boat, and covering with a cover to obtain a porcelain boat combination;
5) placing the magnetic boat combination in the step 4) into a low-temperature tube furnace, vacuumizing, filling argon, repeating the steps for three times, removing air in the tube, and vacuumizing the tube;
6) heating the low-temperature tube furnace to 600 ℃, preserving heat for 3h for sintering reaction, introducing argon for protection after the reaction is stopped, and taking out the porcelain boat combination from the low-temperature tube furnace when the temperature is reduced to room temperature;
7) pouring the sample in the porcelain boat combination treated in the step 6) into a mortar, and grinding the sample into a powdery sample to obtain the selenium-doped vanadium selenide composite material.
Example 6:
1) weighing vanadium chloride, ammonium metavanadate, urea and dimethylformamide according to the molar ratio of 0.5:0.5:1:1, wherein the mass is 78.65mg, 58.49mg, 60.06mg and 73.10mg respectively, dissolving the vanadium chloride, the ammonium metavanadate, the urea and the dimethylformamide into deionized water with the volume of 30mL, and magnetically stirring the solution for 20min to obtain uniform mixed solution;
2) transferring the mixed solution obtained in the step 1) to a 50mL high-pressure reaction kettle with a p-polyphenyl lining, controlling the filling ratio of the solution in the reaction kettle to be 50%, sealing the reaction kettle, and placing the reaction kettle in an oven to react for 15 hours at 90 ℃;
3) after the reaction is finished, respectively centrifugally washing the mixture for 4 times by using deionized water and absolute ethyl alcohol, then carrying out vacuum drying for 5 hours at the temperature of 60 ℃, and grinding the dried mixture to obtain a precursor of the VOOH compound;
4) weighing VOOH precursor and selenium source according to the element molar ratio V (mol) Se (mol) of 4.9:15.8, wherein the selenium source is selenium powder, selenium dioxide and sodium selenate, putting the VOOH precursor into a small porcelain boat, putting the selenium source into a large porcelain boat, putting the small porcelain boat into the large porcelain boat, and covering to obtain a porcelain boat combination body;
5) placing the magnetic boat combination body in the step 4) into a low-temperature tube furnace, vacuumizing firstly, and then filling nitrogen, repeating the steps for three times to remove air in the tube, and then vacuumizing the tube to form a vacuum environment;
6) heating the low-temperature tube furnace to 600 ℃, preserving heat for 3 hours for sintering reaction, introducing nitrogen for protection after the reaction is stopped, and taking out the porcelain boat combination from the low-temperature tube furnace when the temperature is reduced to room temperature;
7) pouring the sample in the porcelain boat combination treated in the step 6) into a mortar, and grinding the sample into a powdery sample to obtain the selenium-doped vanadium selenide composite material.
Example 7:
1) weighing vanadium pentoxide, vanadium chloride, urea and hexamethylenetetramine according to a molar ratio of 0.2:0.8:2:1, wherein the mass is 36.40mg, 125.84mg, 120.12mg and 140.18mg respectively, dissolving the vanadium pentoxide, the vanadium chloride, the urea and the hexamethylenetetramine in deionized water with the volume of 30mL, and magnetically stirring the solution for 20min to obtain uniform mixed solution;
2) transferring the mixed solution obtained in the step 1) to a 50mL high-pressure reaction kettle with a p-polyphenyl lining, controlling the filling ratio of the solution in the reaction kettle to be 60%, sealing the reaction kettle, and placing the reaction kettle in an oven to react for 16 hours at 80 ℃;
3) after the reaction is finished, respectively centrifugally washing the mixture for 4 times by using deionized water and absolute ethyl alcohol, then drying the mixture for 4 hours in vacuum at the temperature of 60 ℃, and grinding the dried mixture to obtain a precursor of the VOOH compound;
4) weighing VOOH precursor and selenium source according to the element molar ratio V (mol) Se (mol) of 2.7:7.2, wherein the selenium source is selenium powder and selenium dioxide, putting the VOOH precursor into a small porcelain boat, putting the selenium source into a large porcelain boat, putting the small porcelain boat into the large porcelain boat, and covering with a cover to obtain a porcelain boat combination body;
5) placing the magnetic boat combination body in the step 4) into a low-temperature tube furnace, vacuumizing firstly, and then filling argon, repeating the steps for three times to remove the air in the tube, and then vacuumizing the tube to form a vacuum environment;
6) heating the low-temperature tube furnace to 500 ℃, preserving heat for 4 hours, carrying out sintering reaction, introducing argon for protection after the reaction is stopped, and taking out the porcelain boat combination from the low-temperature tube furnace when the temperature is reduced to room temperature;
7) pouring the sample in the porcelain boat combination treated in the step 6) into a mortar, and grinding the sample into a powdery sample to obtain the selenium-doped vanadium selenide composite material.
Example 8:
1) weighing vanadium pentoxide, vanadium chloride, ammonium metavanadate, urea, hexamethylenetetramine and dimethylformamide according to the molar ratio of 0.2:0.4:0.4:1:1, wherein the mass is 36.4mg, 31.46mg, 46.79mg, 60.06mg, 140.18mg and 73.10mg respectively, dissolving the weighed materials in deionized water with the volume of 30mL, and magnetically stirring the materials for 20min to obtain uniform mixed liquid;
2) transferring the mixed solution obtained in the step 1) to a 50mL high-pressure reaction kettle with a p-polyphenyl lining, controlling the filling ratio of the solution in the reaction kettle to be 40%, sealing the reaction kettle, and placing the reaction kettle in an oven to react for 18h at 80 ℃;
3) after the reaction is finished, respectively centrifugally washing the mixture for 4 times by using deionized water and absolute ethyl alcohol, then drying the mixture for 4 hours in vacuum at the temperature of 60 ℃, and grinding the dried mixture to obtain a precursor of the VOOH compound;
4) weighing VOOH precursor and selenium source according to element molar ratio V (mol) Se (mol) of 3.2:9.4, wherein the selenium source is selenium dioxide and sodium selenate, putting the VOOH precursor into a small porcelain boat, putting the selenium source into a large porcelain boat, putting the small porcelain boat into the large porcelain boat, and covering with a cover to obtain a porcelain boat combination body;
5) placing the magnetic boat combination in the step 4) into a low-temperature tube furnace, vacuumizing, charging nitrogen, repeating the steps for three times, removing air in the tube, and vacuumizing the tube;
6) heating the low-temperature tube furnace to 800 ℃, preserving heat for 1h for sintering reaction, introducing nitrogen for protection after the reaction is stopped, and taking out the porcelain boat combination from the low-temperature tube furnace when the temperature is reduced to room temperature;
7) pouring the sample in the porcelain boat combination treated in the step 6) into a mortar, and grinding the sample into a powdery sample to obtain the selenium-doped vanadium selenide composite material.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solutions of the present invention and not for limiting the same, and although the present invention is described in detail with reference to the above embodiments, those of ordinary skill in the art should understand that: modifications and equivalents may be made to the embodiments of the invention without departing from the spirit and scope of the invention, which is to be covered by the claims.

Claims (8)

1. A preparation method of a selenium-doped vanadium selenide composite material is characterized by comprising the following steps:
1) weighing a vanadium source and an alkali source according to a molar ratio of 1 (1-3), dissolving the vanadium source and the alkali source in deionized water, and uniformly stirring by magnetic force to obtain a mixed solution;
2) transferring the mixed solution obtained in the step 1) into a high-pressure reaction kettle with a p-polyphenyl lining, controlling the filling ratio of the solution in the reaction kettle to be 40-60%, sealing the reaction kettle, and placing the reaction kettle in an oven to react for 12-18 h at the temperature of 80-120 ℃;
3) after the reaction is finished, respectively centrifugally washing the reaction product for a plurality of times by using deionized water and absolute ethyl alcohol, and then carrying out vacuum drying and grinding to obtain a precursor of the VOOH compound;
4) weighing VOOH precursor and selenium source according to element molar ratio V (mol) Se (mol) of (2.7-4.9) (7.2-15.8), putting the VOOH precursor into a small porcelain boat, putting the selenium source into a large porcelain boat, putting the small porcelain boat into the large porcelain boat, and covering with a cover to obtain a porcelain boat combination body;
5) placing the magnetic boat combination in the step 4) into a low-temperature tube furnace, and pumping the tube of the low-temperature tube furnace into a vacuum environment;
6) then, carrying out sintering reaction in a low-temperature tube furnace, wherein the sintering reaction temperature is 500-800 ℃, the time is 1-4 h, introducing protective gas for protection after the sintering reaction is finished, and taking out the porcelain boat combination from the low-temperature tube furnace when the temperature is reduced to room temperature;
7) pouring the sample in the porcelain boat combination treated in the step 6) into a mortar, and grinding the sample into a powdery sample to obtain the selenium-doped vanadium selenide composite material.
2. The method of claim 1, wherein: the vanadium source in the step 1) is one or more of ammonium metavanadate, vanadium chloride and vanadium pentoxide.
3. The method of claim 1, wherein: the alkali source in the step 1) is one or more of urea, hexamethylenetetramine and dimethylformamide.
4. The method of claim 1, wherein: the selenium source in the step 4) refers to one or more of selenium powder, selenium dioxide and sodium selenate.
5. The method of claim 1, wherein: dissolving the weighed vanadium source and alkali source in deionized water with the volume of 30mL in the step 1), and magnetically stirring for 20min to obtain a uniform mixed solution; and in the step 2), transferring the mixed solution obtained in the step 1) to a 50mL high-pressure reaction kettle with a p-polyphenyl lining, sealing the reaction kettle, and placing the reaction kettle in an oven for reaction.
6. The method of claim 1, wherein: after the reaction in the step 3) is finished, respectively washing with deionized water and absolute ethyl alcohol for 4 times in a centrifugal mode, then drying in vacuum at 60 ℃ for 4-6 hours, and grinding to obtain a precursor of the VOOH compound.
7. The method of claim 1, wherein: and in the step 5), the magnetic boat combination in the step 4) is placed in a low-temperature tube furnace, firstly, the vacuum is pumped, then, protective gas is filled, the steps are repeated for three times, air in the tube is exhausted, and then, the tube is pumped into a vacuum environment.
8. The method of claim 1, wherein: the protective gas is argon or nitrogen.
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