CN113644284A - Carbon material loaded fluorine-doped niobium carbide nano composite material and preparation method and application thereof - Google Patents
Carbon material loaded fluorine-doped niobium carbide nano composite material and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a carbon material loaded fluorine-doped niobium carbide nano composite material and a preparation method and application thereof. The carbon material-loaded fluorine-doped niobium carbide nano composite material is prepared by loading fluorine-doped niobium carbide on a carbon material; the load amount of the niobium carbide is 10-70 wt%, and the fluorine doping amount is 0.5-5 mol% of the niobium carbide. The composite material is applied to a direct alcohol fuel cell, has the capability of catalyzing alcohol oxidation reaction, and can remarkably improve the electrochemical performance (such as peak current) of the fuel cell.
Description
Technical Field
The invention belongs to the technical field of energy materials, and particularly relates to a carbon material loaded fluorine-doped niobium carbide nano composite material and a preparation method and application thereof.
Background
Due to the excessive exploitation and use of fossil energy, the world faces severe energy crisis and environmental problems, and the development of new clean energy is urgently needed. Fuel cells are not subjected to carnot cycle, and therefore have received much attention because of their high energy conversion efficiency. Compared with hydrogen, liquid alcohols are more convenient in production, storage, transportation and use, so the development of direct alcohol fuel cells attracts attention, and particularly the application in the field of new energy automobiles attracts great attention.
The catalyst, as a key core component of the fuel cell, has a crucial influence on the performance and price of the fuel cell. Fuel cell catalysts have long been composed primarily of Pt group noble metals and their alloys. However, the platinum group noble metal has scarce resources and high price, and the large-scale application of the fuel cell is severely restricted. In addition, the intermediate product in the alcohol oxidation reaction process has a strong poisoning effect on Pt, so that the Pt-based catalyst has poor stability, and the development of a long-acting and stable direct alcohol fuel cell is severely restricted. Therefore, the development of non-noble metal catalysts with excellent performance, low cost and wide raw material sources is an important effort in the research field of fuel cells.
So far, for example Fe-N-C, Co-N-C, Zn0.4Ni0.6Co2O4Non-noble metal catalysts such as NCNTs have been reported to show excellent catalytic activity in the cathode oxygen reduction reaction of the fuel cell, and have important application potential. However, the research progress of the non-noble metal catalyst of the anode of the direct alcohol fuel cell is rarely reported, especially in an acid medium. Therefore, the development of non-noble metal catalysts for anodic alcohol oxidation with potential applications in acidic media is a significant challenge and opportunity to develop all non-noble metal fuel cells.
Carbides have a platinum-like electronic structure and catalytic behavior. Thus, carbides are widely used in many fields, such as Mo2C can be used as hydrogen evolution catalyst, W2C @ N, P-C can be used as a hydrogen electro-oxidation catalyst at full pH, and the like. And heteroatom doping can effectively change the electronic structures of the material, such as charge density distribution, band gap width and the like, so as to change the electrocatalytic performance of the material. Fluorine has the largest electronegativity and the smallest atomic radius, and researches show that fluorine doping can effectively improve the electronic structure and the catalytic activity of materials [ adv.Mater.2017,29,1604103 ]]. Heretofore, we have reported that fluorine-doped nano tantalum carbide/graphitized carbon composite material (Chinese patent CN103977827A) shows excellent performance of catalyzing alcohol in acid medium, and is a potential candidate in direct alcohol fuel cell anode catalystAnd (6) selecting the selected person.
In order to overcome the shortcomings of the conventional non-noble metal fuel cell catalyst, a new non-noble metal fuel cell catalyst needs to be developed.
Disclosure of Invention
The invention aims to overcome the problem of scarcity of non-noble metal fuel cell catalysts in the prior art and provide a novel direct alcohol fuel cell anode non-noble metal catalyst-carbon material-loaded fluorine-doped niobium carbide nano composite material. The material is applied to a direct alcohol fuel cell and has the capacity of catalyzing alcohol oxidation reaction.
Another object of the present invention is to provide a method for preparing the carbon material-supported fluorine-doped niobium carbide nanocomposite.
The invention also aims to provide application of the carbon material loaded fluorine-doped niobium carbide nanocomposite in preparation of a direct alcohol fuel cell anode.
In order to achieve the purpose, the invention adopts the following technical scheme:
a carbon material loaded fluorine-doped niobium carbide nano composite material is characterized in that fluorine-doped niobium carbide is loaded on a carbon material; the load amount of the niobium carbide is 10-70 wt%, and the fluorine doping amount is 0.1-5 mol% of the niobium carbide.
Through a great deal of research, the invention discovers that if the niobium carbide crystal with a sodium chloride crystal form (hexagonal crystal form) structure is loaded on the carbon material to form the specific carbon material loaded niobium carbide nano composite material, and a certain amount of fluorine element is doped in the niobium carbide crystal, the composite material can be used as an anode catalyst of a fuel cell, has good capacity of catalyzing alcohol oxidation reaction, and improves the electrochemical performance (such as peak current) of the fuel cell.
Preferably, the loading amount of the niobium carbide is 10 to 40 wt%, and the fluorine doping amount is 0.5 to 1 mol% of the niobium carbide.
Preferably, the carbon material is graphitized carbon.
The preparation method of the carbon material loaded fluorine-doped niobium carbide nano composite material comprises the following steps:
s1, pretreating a carbon source to obtain a carbon precursor with an active site;
s2, uniformly mixing a niobium source and a fluorine source in a solvent to obtain a precursor solution;
s3, adding the carbon precursor obtained in the S1 into the precursor solution in the S2, and uniformly mixing to obtain a carbon precursor-niobium-fluorine intermediate adsorption product;
s4, S3, reacting the obtained carbon precursor-niobium-fluorine intermediate adsorption product at the temperature of 60-120 ℃ to obtain an intermediate product;
s5, S4, drying the obtained intermediate product, and carrying out heat treatment for 30-120 min at the temperature of 1000-1500 ℃ in a protective atmosphere to obtain the carbon material loaded fluorine-doped niobium carbide nano composite material.
Preferably, in the step s1, the carbon source is one or a combination of carbon powder, carbon cloth, multi-walled carbon nanotube, carbon foam, graphene oxide, anion exchange resin, cation exchange resin or amphoteric ion exchange resin.
Different forms of carbon sources have differences in specific surface area, niobium carbide synthesis, fluorine doping, overall catalyst stability and other properties, and further influence the electrocatalytic performance of the prepared composite material.
In order to further improve the electrocatalysis of the composite material, it is further preferable that the carbon source in the step s1 is one or a combination of several of graphene oxide, multi-walled carbon nanotubes or styrene anion resin.
Still more preferably, in step s1, the carbon source is graphene oxide.
It should be noted that different forms of carbon sources are converted into graphitized carbon in the final product after the above preparation process.
Preferably, when the carbon source in s1 is one or a combination of carbon powder, carbon cloth, multi-walled carbon nanotube, carbon foam, or graphene oxide, the pretreatment is a hydrothermal treatment, and the conditions of the hydrothermal treatment are as follows: adding 30-70 wt% of HNO into the carbon material3Treating in water solution at 60-120 deg.c for 6-12 hr.
Preferably, the product after the hydrothermal treatment is washed by deionized water and dried for 4-24 hours in vacuum.
Preferably, when the carbon source in s1 is one or a combination of anion exchange resin, cation exchange resin or amphoteric ion exchange resin, the pretreatment is one or a combination of acid-base treatment or hypochlorite treatment.
Preferably, the anion exchange resin is one or a combination of more of macroporous basic acrylic anion exchange resin or basic styrene anion exchange resin; the cation exchange resin is one or a combination of more of strong acid type cation exchange resin or weak acid type cation exchange resin; the amphoteric ion exchange resin is acrylic acid-styrene amphoteric ion exchange resin.
Preferably, the acid-base treatment is carried out according to GB/T5476-1996.
Preferably, the niobium source is one or a combination of several of niobium oxalate, niobium chloride, potassium heptafluoroniobate, niobium ethoxide and potassium niobate.
Preferably, the fluorine source is one or a combination of potassium heptafluoroniobate, potassium fluoride, sodium fluoride, ammonium fluoride or tetrabutylammonium fluoride.
Preferably, the molar mass ratio of the niobium element in the niobium source to the carbon source is 0.0005-0.01 mol/g.
Preferably, the molar ratio of the fluorine element in the fluorine source to the niobium element in the niobium source is 1:5 to 10: 1.
Preferably, the mixing in S2. or S3. is by stirring or sonication.
Preferably, the reaction mode in s4 is any one of a microwave hydrothermal reaction, a microwave solvothermal reaction, a common hydrothermal reaction, a common solvothermal reaction, a mechanically-stirred water bath reaction, a magnetically-stirred hydrothermal reaction, and a magnetically-stirred solvothermal reaction.
Preferably, the solvent is one or a combination of two of water or nitric acid.
Preferably, when the reaction mode in the step S4 is a mechanical stirring hydrothermal reaction or a magnetic stirring hydrothermal reaction, the stirring speed is 200-800 rpm.
Preferably, the reaction time in S4 is 6-12 h.
Preferably, in S5, the drying is one or a combination of vacuum drying, air-blast drying or freeze drying.
Preferably, the drying time in S5 is 10-80 h.
Preferably, in S5, the protective atmosphere is an atmosphere consisting of one or more of methane, hydrogen, carbon monoxide, argon or nitrogen.
Preferably, the flow rate of the gas in the S5 is 20-100 cc/min; more preferably 20 to 80 cc/min.
Preferably, the heat treatment in s5 is performed in a tube furnace or a box furnace.
Preferably, in S5, the heating rate of the heat treatment is 1-10 ℃/min.
Further preferably, in S5, the heating rate of the heat treatment is 2-8 ℃/min.
Preferably, the heat treatment time in S5 is 40-100 min.
Preferably, the temperature of the heat treatment in the S5 is 1000-1300 ℃.
Preferably, the method in S5. further comprises the following steps of grinding, washing and drying.
The preparation method disclosed by the invention is low in cost and wide in raw material source, synthesizes the carbon material loaded fluorine-doped niobium carbide nano composite material at relatively low temperature, is simple and convenient in process, rapid in preparation, safe, environment-friendly and easy to realize industrial production.
The application of the carbon material loaded fluorine-doped niobium carbide nano composite material in the preparation of fuel cells is also within the protection scope of the invention.
The medium of the fuel cell is an acidic medium or an alkaline medium.
Preferably, the acidic medium is one or a combination of sulfuric acid, perchloric acid or phosphoric acid; the alkaline medium is potassium hydroxide.
Preferably, the concentration of the acidic medium or the alkaline medium is 0.1-5 mol/L, and more preferably 0.5-3 mol/L.
Preferably, the fuel of the fuel cell is methanol or ethanol.
Preferably, the concentration of the fuel is 0.1-5 mol/L, and more preferably 1-5 mol/L.
Compared with the prior art, the invention has the beneficial effects that:
the carbon material load fluorine-doped niobium carbide nano composite material formed by loading the niobium element and the fluorine element into the carbon material is applied to a direct alcohol fuel cell, has the capability of catalyzing alcohol oxidation reaction, and can remarkably improve the electrochemical performance (such as peak current) of the fuel cell.
Drawings
FIG. 1 is an XRD spectrum of a carbon material-supported fluorine-doped niobium carbide nanocomposite prepared in example 1;
fig. 2 is a cyclic voltammetry curve diagram of the carbon material-supported fluorine-doped niobium carbide nanocomposite material catalytic methanol fuel cell prepared in example 1.
Detailed Description
The present invention will be further described with reference to the following specific examples and drawings, which are not intended to limit the invention in any manner. Reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated. Unless otherwise indicated, reagents and materials used in the present invention are commercially available.
Example 1
The embodiment provides a carbon material loaded fluorine-doped niobium carbide nano composite material, which is prepared by the following steps:
s1, placing 200mg of graphene oxide in 40mL of 70% HNO3Carrying out ultrasonic treatment on the solution for 30min, immediately transferring the mixture into a polytetrafluoroethylene reaction kettle, and carrying out hydrothermal reaction for 8h at 90 ℃; then, washing the reaction product with deionized water, carrying out suction filtration, and carrying out vacuum drying for 12h to obtain a carbon precursor;
s2, placing 72.6mg of potassium heptafluoroniobate in 100mL of polytetrafluoroethylene lining, adding 60mL of deionized water, and carrying out ultrasonic treatment for 30min to obtain a precursor solution;
s3, adding the carbon precursor obtained in the S1 into the precursor solution in the S2, and carrying out ultrasonic treatment for 30min to obtain a carbon precursor-niobium-fluorine intermediate adsorption product;
s4.S3. the obtained polytetrafluoroethylene lining filled with the carbon precursor-niobium-fluorine intermediate adsorption product is put into a reaction kettle, and is stirred and reacted for 10 hours at the temperature of 90 ℃, and the stirring speed is 600rpm, so that an intermediate product is obtained;
s5, S4, transferring the water solution after reaction into a centrifugal tube, freezing and then carrying out freeze drying for 48 hours; and (3) placing the dried sample in a tubular furnace, heating to 1000 ℃ at a heating rate of 5 ℃/min under a methane/hydrogen atmosphere with a flow rate of 20cc/min, keeping for 30min, grinding the sample subjected to heat treatment until the sample is dispersed, washing with deionized water, and drying at room temperature to obtain the reduced graphene oxide loaded fluorine-doped niobium carbide nanocomposite.
In the prepared reduced graphene oxide loaded fluorine-doped niobium carbide nanocomposite, the loading amount of niobium carbide is 10 wt%, and the fluorine doping amount is 0.5-1 mol% of niobium carbide (it should be noted that, in this embodiment, fluorine is obtained by testing through inductively coupled plasma mass spectrometry (ICP-MS), and in the testing process, fluorine can move or evaporate in the material along with the change of temperature, so that the content of the obtained fluorine is in a range).
Example 2
The embodiment provides a carbon material-supported fluorine-doped niobium carbide nanocomposite, and the preparation method thereof is different from that of embodiment 1 in that the dosage of potassium heptafluoroniobate in S2 is 163.6 mg.
In the prepared composite material, the loading amount of niobium carbide is 20 wt%, and the fluorine doping amount is 0.5-3 mol% of the niobium carbide.
Example 3
The embodiment provides a carbon material-loaded fluorine-doped niobium carbide nanocomposite, and the preparation method thereof is different from that of embodiment 1 in that the dosage of potassium heptafluoroniobate in S2 is 280.5 mg.
In the prepared composite material, the loading amount of niobium carbide is 30 wt%, and the fluorine doping amount is 0.5-4 mol% of the niobium carbide.
Example 4
The embodiment provides a carbon material-supported fluorine-doped niobium carbide nanocomposite, and the preparation method thereof is different from that of embodiment 1 in that the amount of potassium heptafluoroniobate in S2 is 304.9 mg.
In the prepared composite material, the loading amount of niobium carbide is 40 wt%, and the fluorine doping amount is 1.5-5 mol% of the niobium carbide.
Example 5
This example provides a carbon material-supported fluorine-doped niobium carbide nanocomposite, which is prepared by a method different from that of example 1 in that in s2, 72.6mg of potassium heptafluoroniobate is replaced with 249.26mg of niobium chloride and 514.89mg of sodium fluoride.
In the prepared composite material, the loading amount of niobium carbide is 10 wt%, and the fluorine doping amount is 0.5-4 mol% of the niobium carbide.
Example 6
The embodiment provides a carbon material-loaded fluorine-doped niobium carbide nanocomposite, and the preparation method thereof is different from that of embodiment 1 in that the reaction temperature in the s4 is 80 ℃.
In the prepared composite material, the load amount of niobium carbide is 10 wt%, and the fluorine doping amount is 0.5-3 mol% of the niobium carbide.
Example 7
The embodiment provides a carbon material-supported fluorine-doped niobium carbide nanocomposite, and the preparation method thereof is different from that of embodiment 1 in that the reaction temperature in s4 is 100 ℃.
In the prepared composite material, the loading amount of niobium carbide is 10 wt%, and the fluorine doping amount is 0.5-4 mol% of the niobium carbide.
Example 8
The embodiment provides a carbon material-supported fluorine-doped niobium carbide nanocomposite, and the preparation method thereof is different from that of embodiment 1 in that the reaction time in the s4. is 11 hours.
In the prepared composite material, the load amount of niobium carbide is 10 wt%, and the fluorine doping amount is 0.5-5 mol% of the niobium carbide.
Example 9
The embodiment provides a carbon material-supported fluorine-doped niobium carbide nanocomposite, and the preparation method thereof is different from that of embodiment 1 in that the heat treatment time in S5 is 120 min.
In the prepared composite material, the load amount of niobium carbide is 10 wt%, and the fluorine doping amount is 0.5-5 mol% of the niobium carbide.
Example 10
The embodiment provides a carbon material-loaded fluorine-doped niobium carbide nanocomposite, and the preparation method thereof is different from that of embodiment 1 in that the temperature of heat treatment in S5 is 1200 ℃.
In the prepared composite material, the loading amount of niobium carbide is 10 wt%, and the fluorine doping amount is 0.5-2 mol% of the niobium carbide.
Example 11
The embodiment provides a carbon material-supported fluorine-doped niobium carbide nanocomposite, and the preparation method thereof is different from that of embodiment 1 in that in s5, the protective atmosphere in the tubular furnace is an argon/hydrogen mixed gas atmosphere.
In the prepared composite material, the loading amount of niobium carbide is 10 wt%, and the fluorine doping amount is 0.5-2 mol% of the niobium carbide.
Example 12
The embodiment provides a carbon material-supported fluorine-doped niobium carbide nanocomposite, and the preparation method thereof is different from that of embodiment 1 in that in s5, the protective atmosphere in a tubular furnace is methane.
In the prepared composite material, the loading amount of niobium carbide is 10 wt%, and the fluorine doping amount is 0.5-2 mol% of the niobium carbide.
Example 13
The embodiment provides a carbon material-supported fluorine-doped niobium carbide nanocomposite, and the preparation method thereof is different from that of embodiment 1 in that in s5, the flow rate of methane/hydrogen is 40 cc/min.
In the prepared composite material, the load amount of niobium carbide is 10 wt%, and the fluorine doping amount is 0.5-3 mol% of the niobium carbide.
Example 14
The embodiment provides a carbon material-supported fluorine-doped niobium carbide nanocomposite, and the preparation method thereof is different from that of embodiment 1 in that in s5, the flow rate of methane/hydrogen is 100 cc/min.
In the prepared composite material, the loading amount of niobium carbide is 10 wt%, and the fluorine doping amount is 0.5-2 mol% of the niobium carbide.
Example 15
The embodiment provides a carbon material loaded fluorine-doped niobium carbide nano composite material, and the preparation method is different from that of embodiment 1 in that a carbon source in S1 is carbon powder; and S5, obtaining the reduced carbon powder loaded fluorine-doped niobium carbide nano composite material.
In the prepared composite material, the load amount of niobium carbide is 10 wt%, and the fluorine doping amount is 0.5-3 mol% of the niobium carbide.
Example 16
The embodiment provides a carbon material-loaded fluorine-doped niobium carbide nanocomposite, and the preparation method thereof is different from that of embodiment 1 in that, in S1, a carbon source is a multiwall carbon nanotube; and S5, obtaining the reduced carbon cloth loaded fluorine-doped niobium carbide nano composite material.
In the prepared composite material, the load amount of niobium carbide is 10 wt%, and the fluorine doping amount is 0.5-3 mol% of the niobium carbide.
Example 17
The embodiment provides a carbon material loaded fluorine-doped niobium carbide nanocomposite, and the preparation method is different from that of embodiment 1 in that S1. a carbon source is carbon cloth; and S5, obtaining the reduced carbon cloth loaded fluorine-doped niobium carbide nano composite material.
In the prepared composite material, the load amount of niobium carbide is 10 wt%, and the fluorine doping amount is 0.5-3 mol% of the niobium carbide.
Example 18
The embodiment provides a carbon material loaded fluorine-doped niobium carbide nanocomposite, and the preparation method is different from that of embodiment 1 in that a carbon source in S1 is carbon foam; and S5, obtaining the reduced foam carbon loaded fluorine-doped niobium carbide nano composite material.
In the prepared composite material, the load amount of niobium carbide is 10 wt%, and the fluorine doping amount is 0.5-3 mol% of the niobium carbide.
Example 19
The embodiment provides a carbon material loaded fluorine-doped niobium carbide nano composite material, and the preparation method is different from that of embodiment 1 in that a carbon source in S1 is styrene anion resin, and the styrene anion resin is pretreated according to the standard of GB/T5476-1996; and S5, obtaining the graphitized carbon-loaded fluorine-doped niobium carbide nano composite material.
In the prepared composite material, the load amount of niobium carbide is 10 wt%, and the fluorine doping amount is 0.5-3 mol% of the niobium carbide.
The carbon material-supported fluorine-doped niobium carbide nanocomposite prepared in the above example was subjected to a performance test:
1. an X-ray diffractometer is selected for carrying out structural characterization on the carbon material-supported fluorine-doped niobium carbide nanocomposite prepared in the above embodiment, and the result is shown in FIG. 1;
2. the carbon material-supported fluorine-doped niobium carbide nanocomposite prepared in the above example was placed in an acidic (mixed solution of 1mol/L methanol +0.5mol/L sulfuric acid) environment for electrochemical testing, wherein the carbon material-supported fluorine-doped niobium carbide nanocomposite was scanned at 30 ℃ and at a speed of 50mV/s, and the obtained cyclic voltammograms are shown in fig. 2 and table 1.
TABLE 1 examples and comparative examples for electrochemical Performance test results of nanocomposites
As can be seen from FIG. 1, the composite material prepared in example 1 contains peaks of graphitic carbon and niobium carbide, and when compared with a niobium carbide standard sample, the peaks (peak positions: 34.7, 40.4, 58.5, 69.8, 73.5 and 87.2) of niobium carbide in the composite material are slightly shifted from those of standard niobium carbide (standard peaks: 34.7, 40.3, 58.3, 69.7, 73.3 and 87.1), indicating that the carbon material-supported fluorine-doped niobium carbide nanocomposite material is successfully synthesized. Other examples the XRD patterns of the composites prepared were similar to those of example 1.
Fig. 2 is a cyclic voltammetry graph of the carbon material-supported fluorine-doped niobium carbide nanocomposite prepared in example 1 for catalyzing a methanol fuel cell under an acidic condition, and it can be seen from the graph that the peak current is 2.7mA and the peak potential is 1.1V, which indicates that the composite material has good catalytic activity when used as an anode catalyst in a fuel cell, and particularly has a large peak current. The electrochemical properties of other examples are shown in table 1, and it can be seen that the carbon material-supported fluorine-doped niobium carbide nanocomposite prepared in the embodiments of the present invention has very good catalytic activity. In addition, as can be seen from the comparison between example 1 and examples 15 to 19, different carbon sources are selected, and the electrocatalytic performance (especially peak current) of the prepared fuel cell has a certain difference, wherein the peak current of the prepared fuel cell is larger by using the graphene oxide, the multiwalled carbon nanotube and the styrene anion resin as the carbon sources, and the peak current of the fuel cell prepared by using the graphene oxide as the carbon source is the largest.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are merely exemplary embodiments of the present invention, and are not intended to limit the scope of the present invention, and any modifications, equivalent substitutions, improvements and the like made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (10)
1. The carbon material-loaded fluorine-doped niobium carbide nano composite material is characterized in that fluorine-doped niobium carbide is loaded on a carbon material; the load amount of the niobium carbide is 10-70 wt%, and the fluorine doping amount is 0.1-5 mol% of the niobium carbide.
2. The carbon material-supported fluorine-doped niobium carbide nanocomposite as claimed in claim 1, wherein the amount of the niobium carbide supported is 10 to 40 wt% and the amount of fluorine doped is 0.5 to 1 mol% based on the niobium carbide.
3. The carbon material-supported fluorine-doped niobium carbide nanocomposite as claimed in claim 1, wherein the carbon material is graphitized carbon.
4. The method for preparing the carbon material-supported fluorine-doped niobium carbide nanocomposite material according to any one of claims 1 to 3, comprising the steps of:
s1, pretreating a carbon source to obtain a carbon precursor with an active site;
s2, uniformly mixing a niobium source and a fluorine source in a solvent to obtain a precursor solution;
s3, adding the carbon precursor obtained in the S1 into the precursor solution in the S2, and uniformly mixing to obtain a carbon precursor-niobium-fluorine intermediate adsorption product;
s4.S3, mixing the obtained carbon precursor-niobium-fluorine intermediate adsorption product with water or a solvent, and reacting at the temperature of 60-120 ℃ under a closed condition to obtain an intermediate product;
s5, S4, drying the obtained intermediate product, and carrying out heat treatment for 30-120 min at the temperature of 1000-1500 ℃ in a protective atmosphere to obtain the carbon material loaded fluorine-doped niobium carbide nano composite material.
5. The method for preparing the carbon material-supported fluorine-doped niobium carbide nanocomposite material according to claim 4, wherein the carbon source in S1 is one or a combination of carbon powder, carbon cloth, multi-walled carbon nanotubes, carbon foam, graphene oxide, anion exchange resin, cation exchange resin or amphoteric ion exchange resin.
6. The method for preparing the carbon material-supported fluorine-doped niobium carbide nanocomposite material as claimed in claim 5, wherein in S1, the carbon source is carbon powder, carbon cloth, multi-wall carbonWhen one or more of carbon nano tube, carbon foam or graphene oxide are combined, the pretreatment is hydrothermal treatment, and the conditions of the hydrothermal treatment are as follows: adding 30-70 wt% of HNO into the carbon material3Treating in water solution at 60-120 ℃ for 6-12 h;
when the carbon source in S1 is one or a combination of anion exchange resin, cation exchange resin or amphoteric ion exchange resin, the pretreatment is one or a combination of acid-base treatment or hypochlorite treatment.
7. The method for preparing the carbon material-supported fluorine-doped niobium carbide nanocomposite material as claimed in claim 4, wherein the niobium source is one or a combination of niobium oxalate, niobium chloride, potassium heptafluoroniobate, niobium ethoxide or potassium niobate; the fluorine source is one or a combination of more of potassium heptafluoroniobate, potassium fluoride, sodium fluoride, ammonium fluoride or tetrabutylammonium fluoride.
8. The method for preparing the carbon material-supported fluorine-doped niobium carbide nanocomposite as claimed in claim 4, wherein the molar mass ratio of the niobium element in the niobium source to the carbon source is 0.0005 to 0.01 mol/g.
9. The method for preparing the carbon material-supported fluorine-doped niobium carbide nanocomposite material as claimed in claim 4, wherein the molar ratio of fluorine in the fluorine source to niobium in the niobium source is 1:5 to 10: 1.
10. Use of the carbon material-supported fluorine-doped niobium carbide nanocomposite material according to any one of claims 1 to 3 for producing a fuel cell.
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