CN113644284B - Carbon material supported fluorine doped niobium carbide nanocomposite and preparation method and application thereof - Google Patents

Carbon material supported fluorine doped niobium carbide nanocomposite and preparation method and application thereof Download PDF

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CN113644284B
CN113644284B CN202110781718.9A CN202110781718A CN113644284B CN 113644284 B CN113644284 B CN 113644284B CN 202110781718 A CN202110781718 A CN 202110781718A CN 113644284 B CN113644284 B CN 113644284B
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niobium carbide
fluorine
niobium
carbon
carbon material
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CN113644284A (en
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岳鑫
邱新卓
冯敏
黄少铭
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Guangdong University of Technology
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H01M4/8878—Treatment steps after deposition of the catalytic active composition or after shaping of the electrode being free-standing body
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H01M4/8878—Treatment steps after deposition of the catalytic active composition or after shaping of the electrode being free-standing body
    • H01M4/8882—Heat treatment, e.g. drying, baking
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
    • H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
    • 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
    • Y02E60/50—Fuel cells

Abstract

The invention provides a carbon material supported fluorine doped niobium carbide nanocomposite and a preparation method and application thereof. The carbon material loaded fluorine-doped niobium carbide nanocomposite is prepared by loading fluorine-doped niobium carbide on a carbon material; the loading 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 obviously improve the electrochemical performance (such as peak current) of the fuel cell.

Description

Carbon material supported fluorine doped niobium carbide nanocomposite and preparation method and application thereof
Technical Field
The invention belongs to the technical field of energy materials, and particularly relates to a carbon material supported fluorine doped niobium carbide nanocomposite, and a preparation method and application thereof.
Background
The world is faced with serious energy crisis and environmental problems due to the over exploitation and use of fossil energy, and the development of new clean energy is urgent. The fuel cell is not subjected to carnot cycle, so that the energy conversion efficiency is high, and the fuel cell is receiving attention. Compared with hydrogen, the liquid alcohols are more convenient in production, storage, transportation and use, so the development of direct alcohol fuel cells is attracting attention, especially in the field of new energy automobiles.
The catalyst is used as a key core component of the fuel cell and has a critical influence on the performance and the price of the fuel cell. Fuel cell catalysts have long been composed mainly of Pt group noble metals and alloys thereof. However, platinum group noble metal resources are scarce and expensive, severely limiting the large-scale application of fuel cells. In addition, the intermediate product in the alcohol oxidation reaction process has strong poisoning effect on Pt, so that the stability of the Pt-based catalyst is poor, and the development of a long-acting stable direct alcohol fuel cell is seriously restricted. Therefore, the development of a non-noble metal catalyst which is excellent in performance, low in cost and wide in raw material source is an important effort in the field of fuel cell research.
So far, for example, fe-N-C, co-N-C, zn 0.4 Ni 0.6 Co 2 O 4 Non-noble metal catalysts such as NCNTs have been reported to exhibit excellent catalytic activity in fuel cell cathodic oxygen reduction reactions,has important application potential. However, research progress on anode non-noble metal catalysts for direct alcohol fuel cells has been recently reported, especially in acidic media. Therefore, developing anodic alcohol oxidation reaction non-noble metal catalysts with application potential in acidic media is a significant challenge and opportunity facing the development of 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 Mo 2 C can be used as hydrogen evolution catalyst, W 2 C@N, P-C can be used as a catalyst for the electro-hydrogen oxidation at full pH, etc. The heteroatom doping can effectively change the electronic structures such as charge density distribution, band gap width and the like of the material, 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 the material [ adv. Mater.2017,29,1604103)]. Previously, we have reported that fluorine doped nano tantalum carbide/graphitized carbon composite materials (chinese patent CN103977827 a) exhibit excellent alcohol catalyzing performance in acidic media, being potential candidates in direct alcohol fuel cell anode catalysts.
In view of the current situation that existing non-noble metal fuel cell catalysts are scarce, it is necessary to develop new non-noble metal fuel cell catalysts.
Disclosure of Invention
The invention aims to overcome the problem of rare non-noble metal fuel cell catalysts in the prior art and provides a novel direct alcohol fuel cell anode non-noble metal catalyst-carbon material supported fluorine doped niobium carbide nanocomposite. The material is applied to a direct alcohol fuel cell and has the capability of catalyzing alcohol oxidation reaction.
The invention also aims to provide a preparation method of the carbon material supported fluorine doped niobium carbide nanocomposite.
The invention further aims to provide an application of the carbon material supported fluorine doped niobium carbide nanocomposite in preparing an anode of a direct alcohol fuel cell.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a carbon material loaded fluorine doped niobium carbide nanocomposite, fluorine doped niobium carbide loaded on the carbon material; the loading of the niobium carbide is 10-70 wt%, and the fluorine doping amount is 0.1-5 mol% of the niobium carbide.
According to the invention, a great number of researches show that if the niobium carbide crystal with a sodium chloride crystal form (hexagonal crystal form) structure is loaded on a carbon material to form a specific carbon material loaded niobium carbide nanocomposite, 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 alcohol oxidation reaction catalyzing capacity, and improves the electrochemical performance (such as peak current) of the fuel cell.
Preferably, the niobium carbide loading is 10-40 wt%, and the fluorine doping amount is 0.5-1 mol% of the niobium carbide.
Preferably, the carbon material graphitizes carbon.
The preparation method of the carbon material supported fluorine doped niobium carbide nanocomposite 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 step S1 into the precursor solution of the step 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 60-120 ℃ to obtain an intermediate product;
s5, drying the obtained intermediate product, and performing heat treatment for 30-120 min at 1000-1500 ℃ in a protective atmosphere to obtain the carbon material supported fluorine doped niobium carbide nanocomposite.
Preferably, in the step s1, the carbon source is one or a combination of several of carbon powder, carbon cloth, multi-walled carbon nanotubes, carbon foam, graphene oxide, anion exchange resin, cation exchange resin, or amphoteric ion exchange resin.
The carbon sources in different forms have differences in the specific surface area, the synthesis of niobium carbide, the doping of fluorine element, the overall stability of the catalyst and other performances, so that the electrocatalytic performance of the prepared composite material is affected.
In order to further improve the electrocatalytic property of the composite material, it is further preferable that the carbon source in step s1 is one or a combination of several of graphene oxide, multi-walled carbon nanotubes or styrene anion resin.
Still further preferably, in step s1, the carbon source is graphene oxide.
It should be noted that, after the above preparation process, various carbon sources are converted into graphitized carbon in the final product.
Preferably, when the carbon source in s1 is one or a combination of several of carbon powder, carbon cloth, multi-walled carbon nanotubes, carbon foam or graphene oxide, the pretreatment is a hydrothermal treatment, where the conditions of the hydrothermal treatment are: adding 30-70 wt% HNO into the carbon material 3 In the aqueous solution, the treatment is carried out for 6 to 12 hours at the temperature of 60 to 120 ℃.
Preferably, the product after the hydrothermal treatment is washed with deionized water and dried in vacuum for 4-24 hours.
Preferably, when the carbon source in s1 is one or a combination of several of anion exchange resin, cation exchange resin or amphoteric ion exchange resin, the pretreatment is one or a combination of two of acid-base treatment or hypochlorite treatment.
Preferably, the anion exchange resin is one or a combination of a plurality of macroporous basic acrylic anion exchange resins or basic styrene anion exchange resins; the cation exchange resin is one or a combination of a plurality of strong acid type cation exchange resins or weak acid type cation exchange resins; the amphoteric ion exchange resin is acrylic acid-styrene series amphoteric ion exchange resin.
Preferably, the acid-base treatment method is carried out according to the GB/T5476-1996 standard.
Preferably, the niobium source is one or a combination of several of niobium oxalate, niobium chloride, potassium heptafluoro-niobate, niobium ethoxide or potassium niobate.
Preferably, the fluorine source is one or a combination of several of potassium heptafluoroniobate, potassium fluoride, sodium fluoride, ammonium fluoride or tetrabutylammonium fluoride.
Preferably, the molar mass ratio of niobium element to carbon source in the niobium source is 0.0005 to 0.01mol/g.
Preferably, the molar ratio of fluorine element in the fluorine source to niobium element in the niobium source is 1:5-10:1.
Preferably, the mixing mode in the step S2 or the step S3 is stirring or ultrasonic treatment.
Preferably, the reaction mode in s4 is any one of microwave hydrothermal reaction, microwave solvothermal reaction, common hydrothermal reaction, common solvothermal reaction, mechanical stirring water bath reaction, magnetic stirring hydrothermal reaction and magnetic stirring solvothermal reaction.
Preferably, the solvent is one or a combination of two of water or nitric acid.
Preferably, when the reaction mode in 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, the drying in s5 is one or a combination of several of vacuum drying, air drying or freeze drying.
Preferably, the drying time in S5 is 10-80 h.
Preferably, the protective atmosphere in the S5 is an atmosphere composed of one or more gases of methane, hydrogen, carbon monoxide, argon or nitrogen.
Preferably, S5, the flow rate of the gas is 20-100 cc/min; further preferably 20 to 80cc/min.
Preferably, the heat treatment described in s5 is performed in a tube furnace or a box furnace.
Preferably, the heating rate of the heat treatment in S5 is 1-10 ℃/min.
Further preferably, the heating rate of the heat treatment in S5 is 2-8 ℃/min.
Preferably, the time of the heat treatment in S5 is 40-100 min.
Preferably, the temperature of the heat treatment in S5 is 1000-1300 ℃.
Preferably, s5. Further comprises a post-treatment, which is grinding, washing and drying.
The preparation method disclosed by the invention has the advantages of low cost, wide raw material sources, simple and convenient process, rapid preparation, safety, environmental friendliness and easiness in realizing industrial production, and the fluorine-doped niobium carbide nanocomposite is loaded on the synthesized carbon material at a relatively low temperature.
The application of the carbon material supported fluorine doped niobium carbide nanocomposite in preparing 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 a plurality of sulfuric acid, perchloric acid or phosphoric acid; the alkaline medium is potassium hydroxide.
Preferably, the concentration of the acidic medium or the basic medium is 0.1 to 5mol/L, and more preferably 0.5 to 3mol/L.
Preferably, the fuel of the fuel cell is methanol or ethanol.
Preferably, the concentration of the fuel is 0.1 to 5mol/L, and more preferably 1 to 5mol/L.
Compared with the prior art, the invention has the beneficial effects that:
the invention loads niobium element and fluorine element into carbon material, and the formed carbon material loads fluorine doped niobium carbide nano composite material, which is applied to direct alcohol fuel cells, has the capability of catalyzing alcohol oxidation reaction, and can obviously improve the electrochemical performance (such as peak current) of the fuel cells.
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 voltammogram of a methanol fuel cell catalyzed by a carbon material supported fluorine doped niobium carbide nanocomposite prepared in example 1.
Detailed Description
The present invention is further illustrated below with reference to specific examples and figures, but the examples are not intended to limit the invention in any way. Unless specifically stated otherwise, the reagents, methods and apparatus employed in the present invention are those conventional in the art. The reagents and materials used in the present invention are commercially available unless otherwise specified.
Example 1
The embodiment provides a carbon material supported fluorine doped niobium carbide nanocomposite, which is prepared by a method comprising the following steps:
s1, placing 200mg of graphene oxide in 40mL of 70% HNO 3 Carrying out ultrasonic treatment in the solution for 30min, then transferring the mixture into a polytetrafluoroethylene reaction kettle, and carrying out hydrothermal reaction for 8h at 90 ℃; then cleaning the reaction product by deionized water, and vacuum drying for 12 hours after suction filtration to obtain a carbon precursor;
s2, placing 72.6mg of potassium heptafluoroniobate into 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 step S1 into the precursor solution of the step S2, and performing ultrasonic treatment for 30min to obtain a carbon precursor-niobium-fluorine intermediate adsorption product;
s4, S3, placing the obtained polytetrafluoroethylene lining filled with the carbon precursor-niobium-fluorine intermediate adsorption product into a reaction kettle, and stirring at 90 ℃ for reaction for 10 hours at the stirring speed of 600rpm to obtain an intermediate product;
s5, transferring the water solution after the reaction into a centrifuge tube, freezing and then freeze-drying for 48 hours; and (3) placing the dried sample in a tube furnace, heating to 1000 ℃ at a heating rate of 5 ℃/min under a methane/hydrogen atmosphere with a flow rate of 20cc/min, maintaining for 30min, grinding the heat-treated sample to disperse, washing with deionized water, and drying at room temperature to obtain the reduced graphene oxide supported fluorine doped niobium carbide nanocomposite.
In the prepared reduced graphene oxide supported fluorine doped niobium carbide nanocomposite, the load amount of niobium carbide is 10wt%, and the fluorine doping amount is 0.5-1 mol% of niobium carbide (it should be noted that, in the embodiment, the fluorine element is obtained by adopting inductively coupled plasma mass spectrometry (ICP-MS) for testing, and the fluorine element moves or evaporates in the material along with the change of temperature in the testing process, so that the obtained fluorine element content is in a range).
Example 2
The present example provides a carbon material supported fluorine doped niobium carbide nanocomposite, which is different from example 1 in that the amount of potassium heptafluoroniobate used in s2 is 163.6mg.
In the prepared composite material, the loading amount of the niobium carbide is 20wt%, and the fluorine doping amount is 0.5-3 mol% of the niobium carbide.
Example 3
The present example provides a carbon material supported fluorine doped niobium carbide nanocomposite, and the preparation method differs from example 1 in that the amount of potassium heptafluoroniobate used in s2 is 280.5mg.
In the prepared composite material, the loading amount of the niobium carbide is 30wt%, and the fluorine doping amount is 0.5-4 mol% of the niobium carbide.
Example 4
The present example provides a carbon material supported fluorine doped niobium carbide nanocomposite, and the preparation method differs from example 1 in that the amount of potassium heptafluoroniobate in s2 is 304.9mg.
In the prepared composite material, the loading amount of the niobium carbide is 40wt%, and the fluorine doping amount is 1.5-5 mol% of the niobium carbide.
Example 5
The present example provides a carbon material supported fluorine doped niobium carbide nanocomposite, the preparation method of which differs from that of example 1 in that 72.6mg of potassium heptafluoroniobate in S2 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 10wt%, and the fluorine doping amount is 0.5-4 mol% of the niobium carbide.
Example 6
The present example provides a carbon material supported fluorine doped niobium carbide nanocomposite, and the preparation method thereof is different from that of example 1 in that the reaction temperature in s4 is 80 ℃.
In the prepared composite material, the loading amount of niobium carbide is 10wt%, and the fluorine doping amount is 0.5-3 mol% of the niobium carbide.
Example 7
The present example provides a carbon material supported fluorine doped niobium carbide nanocomposite, and the preparation method thereof is different from that of example 1 in that the reaction temperature in s4 is 100 ℃.
In the prepared composite material, the loading amount of niobium carbide is 10wt%, and the fluorine doping amount is 0.5-4 mol% of the niobium carbide.
Example 8
The present example provides a carbon material supported fluorine doped niobium carbide nanocomposite, and the preparation method thereof is different from that of example 1 in that the reaction time in s4 is 11h.
In the prepared composite material, the loading amount of the niobium carbide is 10wt%, and the fluorine doping amount is 0.5-5 mol% of the niobium carbide.
Example 9
The present 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 s5, the time of the heat treatment is 120min.
In the prepared composite material, the loading amount of the niobium carbide is 10wt%, and the fluorine doping amount is 0.5-5 mol% of the niobium carbide.
Example 10
The present 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 s5, the temperature of the heat treatment is 1200 ℃.
In the prepared composite material, the loading amount of the niobium carbide is 10wt%, and the fluorine doping amount is 0.5-2 mol% of the niobium carbide.
Example 11
The present 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 tube furnace is an argon/hydrogen mixed gas atmosphere.
In the prepared composite material, the loading amount of the niobium carbide is 10wt%, and the fluorine doping amount is 0.5-2 mol% of the niobium carbide.
Example 12
The present 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 tube furnace is methane.
In the prepared composite material, the loading amount of the niobium carbide is 10wt%, and the fluorine doping amount is 0.5-2 mol% of the niobium carbide.
Example 13
The present example provides a carbon material supported fluorine doped niobium carbide nanocomposite, the preparation method of which differs from that of example 1 in that in s5, the methane/hydrogen flow rate is 40cc/min.
In the prepared composite material, the loading amount of niobium carbide is 10wt%, and the fluorine doping amount is 0.5-3 mol% of the niobium carbide.
Example 14
The present example provides a carbon material supported fluorine doped niobium carbide nanocomposite, the preparation method of which differs from that of example 1 in that in s5, the methane/hydrogen flow is 100cc/min.
In the prepared composite material, the loading amount of the niobium carbide is 10wt%, and the fluorine doping amount is 0.5-2 mol% of the niobium carbide.
Example 15
The embodiment provides a carbon material supported fluorine doped niobium carbide nanocomposite, and the preparation method is different from embodiment 1 in that S1, the carbon source is carbon powder; s5, obtaining the reduced carbon powder loaded fluorine doped niobium carbide nanocomposite.
In the prepared composite material, the loading amount of niobium carbide is 10wt%, and the fluorine doping amount is 0.5-3 mol% of the niobium carbide.
Example 16
The embodiment provides a carbon material supported fluorine doped niobium carbide nanocomposite, and the preparation method is different from embodiment 1 in that S1, the medium carbon source is a multi-walled carbon nanotube; s5, obtaining the reduced carbon cloth supported fluorine doped niobium carbide nanocomposite.
In the prepared composite material, the loading amount of niobium carbide is 10wt%, and the fluorine doping amount is 0.5-3 mol% of the niobium carbide.
Example 17
The embodiment provides a carbon material supported fluorine doped niobium carbide nanocomposite, and the preparation method is different from embodiment 1 in that S1, the carbon source is carbon cloth; s5, obtaining the reduced carbon cloth supported fluorine doped niobium carbide nanocomposite.
In the prepared composite material, the loading amount of niobium carbide is 10wt%, and the fluorine doping amount is 0.5-3 mol% of the niobium carbide.
Example 18
The embodiment provides a carbon material supported fluorine doped niobium carbide nanocomposite, and the preparation method is different from embodiment 1 in that S1, the medium carbon source is foam carbon; s5, obtaining the reduced foam carbon supported fluorine doped niobium carbide nanocomposite.
In the prepared composite material, the loading amount of niobium carbide is 10wt%, and the fluorine doping amount is 0.5-3 mol% of the niobium carbide.
Example 19
The embodiment provides a carbon material supported fluorine doped niobium carbide nanocomposite, which is different from the embodiment 1 in that S1, the carbon source is styrene anion resin, and the styrene anion resin is pretreated according to the standard GB/T5476-1996; s5, obtaining the graphitized carbon-loaded fluorine-doped niobium carbide nanocomposite.
In the prepared composite material, the loading amount of niobium carbide is 10wt%, and the fluorine doping amount is 0.5-3 mol% of the niobium carbide.
The performance test is carried out on the carbon material supported fluorine doped niobium carbide nanocomposite prepared in the embodiment:
1. the carbon material supported fluorine doped niobium carbide nanocomposite prepared in the above embodiment is subjected to structural characterization by using an X-ray diffractometer, and the result is shown in fig. 1;
2. the carbon material-supported fluorine-doped niobium carbide nanocomposite prepared in the above example was subjected to electrochemical test in an acidic (1 mol/L methanol+0.5 mol/L sulfuric acid mixed solution) environment, wherein scanning was performed at a speed of 50mV/s at 30℃and the cyclic voltammograms obtained are shown in FIG. 2 and Table 1.
Table 1 results of electrochemical performance test of nanocomposite materials prepared in examples and comparative examples
As can be seen from FIG. 1, the composite material prepared in example 1 contains peaks of graphite carbon and niobium carbide, and comparison with a standard sample of niobium carbide shows that each peak (peak positions: 34.7, 40.4, 58.5, 69.8, 73.5, 87.2) of niobium carbide in the composite material is slightly shifted from the standard peak (standard peaks: 34.7, 40.3, 58.3, 69.7, 73.3, 87.1) of niobium carbide, indicating that the carbon material-supported fluorine-doped niobium carbide nanocomposite material was successfully synthesized. The XRD patterns of the composites prepared in the other examples were similar to those of example 1.
Fig. 2 is a cyclic voltammogram of the carbon material supported fluorine doped niobium carbide nanocomposite prepared in example 1 in the presence of acid to catalyze a methanol fuel cell, and as can be seen from the graph, 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 the fuel cell, in particular has a larger 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 each example of the present invention has good catalytic activity. In addition, as can be seen from comparison of examples 1 and 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 graphene oxide, multi-wall carbon nanotubes and styrene anion resin are used as carbon sources, and the peak current of the prepared fuel cell is larger, and the peak current of the fuel cell prepared by taking graphene oxide as the carbon source is the largest.
The foregoing description of the embodiments has been provided for the purpose of illustrating the general principles of the invention, and is not meant to limit the scope of the invention, but to limit the invention to the particular embodiments, and any modifications, equivalents, improvements, etc. that fall within the spirit and principles of the invention are intended to be included within the scope of the invention.

Claims (6)

1. The fluorine-doped niobium carbide nanocomposite loaded on the carbon material is characterized in that fluorine-doped niobium carbide is loaded on the carbon material; the loading amount of the niobium carbide is 10-70wt%, and the fluorine doping amount is 0.1-5mol% of the niobium carbide; the preparation method of the carbon material supported fluorine doped niobium carbide nanocomposite 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 step S1 into the precursor solution of the step 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 a solvent, and reacting at 60-120 ℃ under a closed condition to obtain an intermediate product;
s5, drying the obtained intermediate product, and performing heat treatment at 1000-1500 ℃ for 30-120 min in a protective atmosphere to obtain the carbon material supported fluorine doped niobium carbide nanocomposite;
s1, the carbon source is graphene oxide; s5, the protective atmosphere is methane/hydrogen atmosphere and the flow is 20cc/min;
when S1 is the carbonWhen the source is graphene oxide, the pretreatment is hydrothermal treatment, and the conditions of the hydrothermal treatment are as follows: adding 30-70wt% of HNO into the carbon material 3 And (3) treating the mixture in an aqueous solution at 60-120 ℃ for 6-12 hours.
2. The carbon material supported fluorine doped niobium carbide nanocomposite of claim 1, wherein the loading of niobium carbide is 10-40 wt% and the fluorine doping is 0.5-1 mol% of niobium carbide.
3. The carbon material supported fluorine doped niobium carbide nanocomposite of claim 1, wherein the niobium source is one or a combination of several of niobium oxalate, niobium chloride, potassium heptafluoroniobate, niobium ethoxide or potassium niobate; the fluorine source is one or a combination of a plurality of potassium heptafluoroniobate, potassium fluoride, sodium fluoride, ammonium fluoride or tetrabutylammonium fluoride.
4. The carbon material supported fluorine doped niobium carbide nanocomposite material according to claim 1, wherein the molar mass ratio of niobium element to carbon source in the niobium source is 0.0005 to 0.01mol/g.
5. The carbon material supported fluorine doped niobium carbide nanocomposite material of claim 1, wherein the molar ratio of fluorine element in the fluorine source to niobium element in the niobium source is 1:5-10:1.
6. The use of the carbon material supported fluorine doped niobium carbide nanocomposite of any one of claims 1-5 in the preparation of fuel cells.
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