CN110694658A - Vanadium carbide/carbon sphere composite material and preparation method thereof - Google Patents
Vanadium carbide/carbon sphere composite material and preparation method thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 249
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 249
- INZDTEICWPZYJM-UHFFFAOYSA-N 1-(chloromethyl)-4-[4-(chloromethyl)phenyl]benzene Chemical compound C1=CC(CCl)=CC=C1C1=CC=C(CCl)C=C1 INZDTEICWPZYJM-UHFFFAOYSA-N 0.000 title claims abstract description 174
- 239000002131 composite material Substances 0.000 title claims abstract description 163
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 239000002243 precursor Substances 0.000 claims abstract description 63
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 61
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 61
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 60
- 239000011259 mixed solution Substances 0.000 claims abstract description 42
- 239000002904 solvent Substances 0.000 claims abstract description 32
- 238000001354 calcination Methods 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 21
- 230000001681 protective effect Effects 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000012298 atmosphere Substances 0.000 claims abstract description 16
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 239000007789 gas Substances 0.000 claims description 36
- 239000002245 particle Substances 0.000 claims description 32
- 239000011159 matrix material Substances 0.000 claims description 27
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical compound Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 claims description 9
- 229960001149 dopamine hydrochloride Drugs 0.000 claims description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 7
- 239000002244 precipitate Substances 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 239000001307 helium Substances 0.000 claims description 4
- 229910052734 helium Inorganic materials 0.000 claims description 4
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 230000008569 process Effects 0.000 abstract description 13
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 3
- 239000002086 nanomaterial Substances 0.000 abstract description 2
- 230000003197 catalytic effect Effects 0.000 description 38
- 235000019441 ethanol Nutrition 0.000 description 33
- 238000004132 cross linking Methods 0.000 description 28
- 238000006116 polymerization reaction Methods 0.000 description 26
- 238000012360 testing method Methods 0.000 description 17
- 239000000463 material Substances 0.000 description 12
- 239000000243 solution Substances 0.000 description 11
- 230000000694 effects Effects 0.000 description 10
- 239000000126 substance Substances 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- 230000009286 beneficial effect Effects 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 230000009467 reduction Effects 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 2
- -1 ammonium ions Chemical class 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000005456 alcohol based solvent Substances 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000007327 hydrogenolysis reaction Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/20—Carbon compounds
- B01J27/22—Carbides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/51—Spheres
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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
- 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
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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
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- 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
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Abstract
The invention belongs to the technical field of preparation of nano materials, and particularly relates to a preparation method of a vanadium carbide/carbon sphere composite material, which comprises the following steps: obtaining a vanadium source and a carbon source, and dissolving the vanadium source and the carbon source in water to obtain a first mixed solution; adding an alcohol solvent into the first mixed solution, adjusting the pH value to 8.5-9.0, mixing, and separating to obtain a vanadium carbide/carbon sphere composite precursor; and calcining the vanadium carbide/carbon sphere composite precursor in the protective gas atmosphere to obtain the vanadium carbide/carbon sphere composite material. The preparation method of the vanadium carbide/carbon sphere composite material provided by the invention has the advantages that the process conditions are simple and easy to control, the strict conditions such as flammable gas and the like are not required, the generation process is safe and reliable, and the preparation method is suitable for industrial large-scale production and application.
Description
Technical Field
The invention belongs to the technical field of preparation of nano materials, and particularly relates to a preparation method of a vanadium carbide/carbon sphere composite material, namely the vanadium carbide/carbon sphere composite material.
Background
Noble metals such as platinum are widely used in catalytic processes in the fields of petrochemical industry, organic synthesis, fuel cells, automobiles, electronic industry, and the like because of their catalytic effects, but on the one hand, such noble metals are very small in reserves on the earth and are decreasing, and on the other hand, they are very expensive and have high application costs. Because of this, new catalytic materials that can replace noble metal catalysts such as platinum have been sought. Among a plurality of novel catalytic materials, Vanadium Carbide (VC) not only has excellent properties such as high hardness, high melting point, good electric conduction and heat conduction, but also has the common characteristics of transition metal carbide, and has wide application in the fields of physics, chemistry, materials and catalysis.
However, the existing preparation method of vanadium carbide materials has the problems of complex process, strict requirements on preparation conditions, low purity of the prepared vanadium carbide materials, large and non-uniform particle size, small effective comparison area, influence on catalytic efficiency and the like. Therefore, there is a need to search for and study a novel method for preparing vanadium carbide and its application as a water electrolysis catalyst.
Disclosure of Invention
The invention aims to provide a preparation method of a vanadium carbide material, and aims to solve the technical problems that the existing preparation method of the vanadium carbide material is complex in process, strict in preparation condition requirement, low in purity of the prepared vanadium carbide material, large and uneven in particle size, small in effective comparison area, influenced in catalytic efficiency and the like.
Another object of the present invention is to provide a vanadium carbide material.
In order to achieve the purpose of the invention, the technical scheme adopted by the invention is as follows:
a preparation method of vanadium carbide/carbon sphere composite material comprises the following steps:
obtaining a vanadium source and a carbon source, and dissolving the vanadium source and the carbon source in water to obtain a first mixed solution;
adding an alcohol solvent into the first mixed solution, adjusting the pH value to 8.5-9.0, mixing, and separating to obtain a vanadium carbide/carbon sphere composite precursor;
and calcining the vanadium carbide/carbon sphere composite precursor in the protective gas atmosphere to obtain the vanadium carbide/carbon sphere composite material.
Preferably, the carbon source comprises dopamine hydrochloride; and/or the presence of a gas in the gas,
the source of vanadium comprises ammonium metavanadate.
Preferably, in the first mixed solution, the mass ratio of the vanadium source to the carbon source is 1: (0.25-5).
Preferably, in the mixed system after the alcohol solvent is added to the first mixed solution, the volume ratio of water to the alcohol solvent is 1: (1-8); and/or the presence of a gas in the gas,
the alcohol solvent is selected from: at least one of ethanol and methanol.
Preferably, the step of subjecting the vanadium carbide/carbon sphere composite precursor to a calcination treatment comprises: heating the vanadium carbide/carbon sphere composite precursor to 700-1000 ℃ from a normal temperature state at a heating rate of 5-10 ℃/min in a protective gas atmosphere, and then calcining the vanadium carbide/carbon sphere composite precursor for 2-5 hours; and/or the presence of a gas in the gas,
the protective gas is selected from: at least one of nitrogen, argon, helium.
Preferably, the step of adding an alcohol solvent to the first mixed solution and then adjusting the pH value to 8.5 to 9.0 comprises: adding an alcohol solvent into the first mixed solution, and then adding ammonia water to adjust the pH value to 8.5-9.0; and/or the presence of a gas in the gas,
the mixing treatment time is 10-15 hours.
Preferably, the step of separating to obtain the vanadium carbide/carbon sphere composite precursor comprises: and centrifugally separating the mixed solution, and drying and separating to obtain a precipitate, wherein the precipitate is the vanadium carbide/carbon sphere composite precursor.
Preferably, the vanadium carbide/carbon sphere composite material is spherical, and the particle size is not more than 500 microns.
Accordingly, a vanadium carbide/carbon sphere composite material, in the shape of a sphere, comprising: the carbon sphere comprises a carbon sphere matrix and vanadium carbide uniformly distributed in the carbon sphere matrix.
Preferably, the particle size of the vanadium carbide/carbon sphere composite material is not more than 500 microns.
The preparation method of the vanadium carbide/carbon sphere composite material provided by the invention comprises the steps of dissolving the vanadium source and the carbon source in water to obtain a first mixed solution, adding an ethanol solution, adjusting the pH value of the solution to 8.5-9.0, carrying out polymerization crosslinking reaction on the carbon source and the vanadium source in an alkaline environment of the ethanol solution to obtain a vanadium carbide/carbon sphere composite precursor, and carrying out polymerization crosslinking on the vanadium source and the carbon source to avoid the phenomenon that the prepared vanadium carbide/carbon sphere composite precursor is too large in particle size due to large self-polymerization crosslinking of the carbon source, which is not beneficial to the subsequent preparation of the vanadium carbide/carbon sphere composite material with small particle size and large specific surface area. And then, calcining the vanadium carbide/carbon sphere composite precursor in a protective gas atmosphere, reducing a carbon source and a vanadium source which are polymerized and crosslinked in the vanadium carbide/carbon sphere composite precursor into vanadium carbide, and simultaneously forming a carbon sphere matrix, thereby obtaining the vanadium carbide/carbon sphere composite material which takes the carbon spheres as the matrix and uniformly distributes and combines the vanadium carbide on the surface of the carbon sphere matrix and in the internal pores. The preparation method of the vanadium carbide/carbon sphere composite material provided by the invention has the advantages that the process conditions are simple and easy to control, relatively strict conditions such as flammable gas and the like are not required, the generation process is safe and reliable, and the preparation method is suitable for industrial large-scale production and application; the prepared vanadium carbide/carbon sphere composite material is spherical, has high purity, controllable particle size, uniform particle size and appearance and large specific surface area, and effectively improves the catalytic contact area of the vanadium carbide/carbon sphere composite material, thereby improving the catalytic performance of the composite material.
The vanadium carbide/carbon sphere composite material provided by the invention is spherical and comprises the following components: the carbon sphere matrix provides a carrier for the vanadium carbide, so that the vanadium carbide is uniformly distributed and combined on the surface and inside of the carbon sphere matrix, and the catalytic stability of the vanadium carbide is improved; on the other hand, the carbon sphere matrix has the porous characteristic of litigation, which is beneficial to improving the loading capacity of the vanadium carbide catalyst in the vanadium carbide/carbon sphere composite material, thereby improving the catalytic effect of the composite material, and the carbon sphere matrix with the porous structure improves the catalytic contact area of the composite material, so that the catalytic performance of the composite material is more three-dimensional through the adsorption of the carbon sphere matrix on substances to be catalyzed, and the catalytic performance of the composite material is further improved.
Drawings
Fig. 1 is an X-ray powder diffraction graph of the vanadium carbide/carbon sphere composite material provided in example 1 of the present invention.
Fig. 2 is an SEM scanning electron microscope image of the vanadium carbide/carbon sphere composite material provided in example 1 of the present invention.
Fig. 3 is an EDS energy spectrum of vanadium element in the vanadium carbide/carbon sphere composite material provided in example 1 of the present invention.
Fig. 4 is an EDS energy spectrum of carbon element in the vanadium carbide/carbon sphere composite material provided in example 1 of the present invention.
Fig. 5 is a polarization curve of hydrogen evolution reaction of vanadium carbide/carbon sphere composite material as catalyst provided in example 1 of the present invention.
Detailed Description
In order to make the purpose, technical solution and technical effect of the embodiments of the present invention clearer, the technical solution in the embodiments of the present invention is clearly and completely described, and it is obvious that the described embodiments are a part of the embodiments of the present invention, but not all embodiments. All other embodiments obtained by a person of ordinary skill in the art without any inventive step in connection with the embodiments of the present invention shall fall within the scope of protection of the present invention.
In the description of the present invention, it is to be understood that the terms "first", "second" and the like are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implying any number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. In the description of the present invention, "a plurality" means two or more unless specifically defined otherwise.
The weight of the related components mentioned in the description of the embodiments of the present invention may not only refer to the specific content of each component, but also represent the proportional relationship of the weight among the components, and therefore, the content of the related components is scaled up or down within the scope disclosed in the description of the embodiments of the present invention as long as it is in accordance with the description of the embodiments of the present invention. Specifically, the weight described in the description of the embodiment of the present invention may be a unit of mass known in the chemical industry field, such as μ g, mg, g, and kg.
The embodiment of the invention provides a preparation method of a vanadium carbide/carbon sphere composite material, which comprises the following steps:
s10, obtaining a vanadium source and a carbon source, and dissolving the vanadium source and the carbon source in water to obtain a first mixed solution;
s20, adding an alcohol solvent into the first mixed solution, adjusting the pH value to 8.5-9.0, mixing, and separating to obtain a vanadium carbide/carbon sphere composite precursor;
and S30, calcining the vanadium carbide/carbon sphere composite precursor in the atmosphere of protective gas to obtain the vanadium carbide/carbon sphere composite material.
According to the preparation method of the vanadium carbide/carbon sphere composite material provided by the embodiment of the invention, after the vanadium source and the carbon source are dissolved in water to obtain a first mixed solution, an ethanol solution is added, the pH value of the solution is adjusted to 8.5-9.0, in an alkaline environment of the ethanol solution, the carbon source and the vanadium source are subjected to polymerization crosslinking reaction to obtain a vanadium carbide/carbon sphere composite precursor, and through the polymerization crosslinking of the vanadium source and the carbon source, the prepared vanadium carbide/carbon sphere composite precursor is prevented from being too large in particle size due to the self-polymerization crosslinking of a large amount of carbon source, and the subsequent preparation of the vanadium carbide/carbon sphere composite material with small particle size and large specific surface area is not facilitated. And then, calcining the vanadium carbide/carbon sphere composite precursor in a protective gas atmosphere, reducing a carbon source and a vanadium source which are polymerized and crosslinked in the vanadium carbide/carbon sphere composite precursor into vanadium carbide, and simultaneously forming a carbon sphere matrix, thereby obtaining the vanadium carbide/carbon sphere composite material which takes the carbon spheres as the matrix and uniformly distributes and combines the vanadium carbide on the surface of the carbon sphere matrix and in the internal pores. The preparation method of the vanadium carbide/carbon sphere composite material provided by the embodiment of the invention has the advantages of simple and easily-controlled process conditions, no need of strict conditions such as flammable gas and the like, safe and reliable generation process, and suitability for industrial large-scale production and application. The prepared vanadium carbide/carbon sphere composite material is spherical, has high purity, controllable particle size, uniform particle size and appearance and large specific surface area, and effectively improves the catalytic contact area of the vanadium carbide/carbon sphere composite material, thereby improving the catalytic performance of the composite material.
Specifically, in the step S10, a vanadium source and a carbon source are obtained, and the vanadium source and the carbon source are dissolved in water to obtain a first mixed solution. In the embodiment of the invention, a vanadium source and a carbon source are dissolved in water in advance to form a mixed solution, so that a material basis is provided for the subsequent preparation of the vanadium carbide/carbon sphere composite precursor and the vanadium carbide/carbon sphere composite material.
In further embodiments, the carbon source includes, but is not limited to, dopamine hydrochloride. According to the embodiment of the invention, dopamine hydrochloride is used as a carbon source, the carbon source has a good self-polymerization crosslinking effect in a subsequent alcohol mixed solvent, not only can be subjected to crosslinking polymerization with a vanadium source substance, but also provides a substance basis for forming a carbon sphere matrix in a subsequent composite material through the self-polymerization crosslinking effect of dopamine hydrochloride, and simultaneously, a vanadium source and a polymer crosslinking substance of the vanadium source and the carbon source can be combined into a self-polymerization substance of the carbon source in the self-polymerization crosslinking process of the carbon source, so that the vanadium source and the carbon source in the prepared vanadium carbide/carbon sphere composite precursor are stably combined and uniformly distributed.
In a further embodiment, the source of vanadium includes, but is not limited to, ammonium metavanadate. According to the embodiment of the invention, ammonium metavanadate is used as a vanadium source, the vanadium source has ammonium ions and is strong in reducibility, and after the ammonium metavanadate is combined with a carbon source to form a precursor, the vanadate combined on the carbon source can be reduced in the process of preparing the vanadium carbide/carbon sphere composite material by subsequent calcination, so that vanadium carbide is prepared and combined on the carbon spheres.
In some embodiments, the carbon source comprises dopamine hydrochloride; the source of vanadium comprises ammonium metavanadate.
In some embodiments, the step of dissolving the vanadium source and the carbon source in water comprises: firstly dissolving a vanadium source in water, then adding a carbon source for dissolving, wherein the dissolving mode can adopt stirring, ultrasonic oscillation and other modes, so that the carbon source and the vanadium source are fully dissolved in the water to form a uniform and stable mixed solution, and a favorable material basis is provided for the formation of a subsequent vanadium carbide/carbon sphere composite precursor.
In a further embodiment, in the first mixed solution, the mass ratio of the vanadium source to the carbon source is 1: (0.25-5). In the embodiment of the invention, the mass ratio of the vanadium source to the carbon source in the first mixed solution is 1: (0.25-5), the mass ratio not only effectively ensures that the amount of vanadium carbide combined in the formed composite material has the optimal catalytic effect, but also ensures that the formed vanadium carbide/carbon sphere composite material is spherical with uniform particles, small particle size and large specific surface area, the catalytic contact area of the vanadium carbide/carbon sphere composite material is increased, and the catalytic effect of the vanadium carbide/carbon sphere composite material is further improved. If the mass ratio of the vanadium source to the carbon source in the first mixed solution is too high or too low, the crosslinking effect of the carbon source and the vanadium source is affected, and the shape of the formed composite material is also affected. In some embodiments, the mass ratio of the vanadium source to the carbon source in the first mixed solution may be 1:0.5, 1:1, 1:2, 1:3, 1:4, or 1: 5.
Specifically, in step S20, an alcohol solvent is added to the first mixed solution, the pH value is adjusted to 8.5 to 9.0, and the mixture is mixed and separated to obtain a vanadium carbide/carbon sphere composite precursor. According to the embodiment of the invention, an alcohol solvent is added into the first mixed solution, the pH value is adjusted to 8.5-9.0, the mixture is treated, the carbon source and the vanadium source are subjected to polymerization crosslinking reaction in an alkaline environment of an ethanol solution to obtain the vanadium carbide/carbon sphere composite precursor, and the vanadium carbide/carbon sphere composite precursor prepared by polymerization crosslinking of the vanadium source and the carbon source is prevented from being too large in particle size due to self-polymerization crosslinking of a large amount of carbon source, which is not beneficial to the subsequent preparation of the vanadium carbide/carbon sphere composite material with small particle size and large specific surface area.
In a further embodiment, in the mixed system after the alcohol solvent is added to the first mixed solution, the volume ratio of water to the alcohol solvent is 1: (1-8). In the mixed system after the alcohol solvent is added in the embodiment of the invention, the volume ratio of water to the alcohol solvent is 1: (1-8), the volume ratio effectively regulates and controls the polymerization crosslinking effect of the carbon source and the vanadium source, and simultaneously reasonably regulates and controls the self-polymerization crosslinking degree of the carbon source, so that the carbon source and the vanadium source in a mixed system are crosslinked and polymerized to form a vanadium carbide/carbon sphere composite precursor with small and uniform particle size. If the content of the alcohol solvent in the mixed system is too small, the crosslinking effect of the carbon source and the vanadium source is poor, meanwhile, the self-polymerization crosslinking effect of the carbon source is poor, and the particle size of the formed vanadium carbide/carbon sphere composite precursor is too small, so that the subsequent calcination is not facilitated to prepare the vanadium carbide/carbon sphere composite material with uniform particle size and good catalytic effect; if the content of the alcohol solvent in the mixed system is too much, on the one hand, the uniform dispersion of the carbon source and the vanadium source in the mixed system is not facilitated, so that the polymerization crosslinking effect of the carbon source and the vanadium source is influenced; on the other hand, the excessive alcohol solvent causes the self-polymerization crosslinking degree of the carbon source to be increased, the vanadium source cannot be fully combined with the carbon source, the formed precursor particles are too large, the combination degree of the carbon source and the vanadium source is low, the vanadium source content is low, and the vanadium carbide/carbon sphere composite material with the expected particle size and catalytic effect cannot be prepared by calcination. In some embodiments, in the mixed system after the alcohol solvent is added to the first mixed solution, the volume ratio of water to the alcohol solvent may be 1:1, 1:2, 1:3, 1:4, 1:5, 1:6, 1:7, or 1: 8.
In a further embodiment, the alcoholic solvent is selected from: at least one of ethanol and methanol. In the embodiment of the invention, alcohol solvents such as ethanol and methanol can well promote the polymerization crosslinking reaction of the carbon source and the vanadium source.
In a further embodiment, the step of adding an alcohol solvent to the first mixed solution and then adjusting the pH value to 8.5-9.0 comprises: and adding an alcohol solvent into the first mixed solution, and then adding ammonia water to adjust the pH value to 8.5-9.0. According to the embodiment of the invention, as the polymerization crosslinking reaction of the carbon source and the vanadium source needs to be carried out in an alkaline environment, and an acidic environment is not beneficial to the polymerization crosslinking of the carbon source and the vanadium source, the pH value is adjusted to 8.5-9.0 by adding the ammonia water after the alcohol solvent is added into the first mixed solution, and the pH value in the mixed solution is adjusted by adopting the ammonia water, other impurity substances cannot be introduced into a reaction system, so that the purity of the prepared vanadium carbide/carbon sphere composite precursor and the composite material is ensured, the impurity content is low, and the catalytic effect of the composite material is ensured.
In a further embodiment, the mixing treatment time is 10-15 hours. According to the embodiment of the invention, an alcohol solvent is added into the first mixed solution, the pH value is adjusted to 8.5-9.0, and the mixture is mixed for 10-15 hours, so that a carbon source and a vanadium source are fully polymerized and crosslinked to form the vanadium carbide/carbon sphere composite precursor.
In some embodiments, dopamine hydrochloride is used as the carbon source, and the acidic carbon source is not beneficial to crosslinking polymerization of the carbon source and the vanadium source in an ethanol solvent, so that after the alcohol solvent is added into the first mixed solution, ammonia water is added to adjust the pH value to 8.5-9.0, and then mixing treatment is performed to fully polymerize and crosslink the carbon source and the vanadium source to form the vanadium carbide/carbon sphere composite precursor.
In a further embodiment, the step of separating to obtain the vanadium carbide/carbon sphere composite precursor comprises: and centrifugally separating the mixed solution, and drying and separating to obtain a precipitate, wherein the precipitate is the vanadium carbide/carbon sphere composite precursor. The solution after the mixing treatment is subjected to centrifugal separation, the precipitate obtained by separation is the vanadium carbide/carbon sphere composite precursor, and the vanadium carbide/carbon sphere composite precursor can be used for preparing the vanadium carbide/carbon sphere composite material after drying.
Specifically, in step S30, the vanadium carbide/carbon sphere composite precursor is calcined in a protective gas atmosphere to obtain a vanadium carbide/carbon sphere composite material. According to the embodiment of the invention, the vanadium carbide/carbon sphere composite precursor is calcined in a protective gas atmosphere, the vanadium carbide/carbon sphere composite precursor contains a carbon source, a vanadium source and a polymerization crosslinking substance of the carbon source and the vanadium source, and also contains a large amount of ammonium ions, so that the vanadium carbide/carbon sphere composite precursor has strong reducibility, in the high-temperature calcination treatment process in the protective gas atmosphere, the polymerization crosslinking carbon source and the vanadium source in the vanadium carbide/carbon sphere composite precursor are fully reduced into vanadium carbide, and the self-polymerization crosslinking carbon source is simultaneously reduced to form a carbon sphere matrix, so that the vanadium carbide/carbon sphere composite material which takes carbon spheres as the matrix and is uniformly distributed and combined on the surface of the carbon sphere matrix and in the internal pores is obtained.
In further embodiments, the shielding gas is selected from: at least one of nitrogen, argon, helium. According to the embodiment of the invention, the calcination treatment is carried out in at least one protective gas atmosphere of nitrogen, argon and helium, and the protective gas atmosphere can prevent a carbon source and a vanadium source in the vanadium carbide/carbon sphere composite precursor from being oxidized in a high-temperature environment.
In a further embodiment, the step of calcining the vanadium carbide/carbon sphere composite precursor comprises: and under the atmosphere of protective gas, heating the vanadium carbide/carbon sphere composite precursor from a normal temperature state to 700-1000 ℃ at a heating rate of 5-10 ℃/min, and then calcining the vanadium carbide/carbon sphere composite precursor for 2-5 hours. In the embodiment of the invention, under the atmosphere of protective gas, after the temperature is raised from a normal temperature state to 700-1000 ℃ at the temperature raising rate of 5-10 ℃/min, the vanadium carbide/carbon sphere composite precursor is calcined for 2-5 hours, so that the vanadium carbide/carbon sphere composite precursor is fully reduced into the vanadium carbide/carbon sphere composite material. Wherein the temperature rise rate of 5-10 ℃/min effectively regulates and controls the reduction rate of the vanadium carbide/carbon sphere composite precursor; heating to 700-1000 ℃, and then calcining for 2-5 hours, wherein the calcining temperature and the calcining time effectively ensure the reduction effect and the reduction sufficiency of the vanadium carbide/carbon sphere composite precursor, and if the calcining temperature is too high, the vanadium carbide/carbon sphere composite precursor is agglomerated, which is not beneficial to forming the nano-scale vanadium carbide/carbon sphere composite material; if the calcination temperature is too low, the reduction effect of the vanadium carbide/carbon sphere composite precursor is poor, and the catalytic performance of the vanadium carbide/carbon sphere composite material is affected. In some embodiments, the vanadium carbide/carbon sphere composite precursor is heated to 700 ℃, 800 ℃, 900 ℃ or 1000 ℃ at a heating rate of 5 ℃/min, 6 ℃/min, 7 ℃/min, 8 ℃/min, 9 ℃/min or 10 ℃/min under a protective gas atmosphere, and the calcination treatment time of the vanadium carbide/carbon sphere composite precursor can be 2 hours, 3 hours, 4 hours or 5 hours.
In a further embodiment, the vanadium carbide/carbon sphere composite material prepared in the embodiment of the invention is spherical, the carbon spheres are used as a matrix, and vanadium carbide is uniformly combined and distributed on the surfaces and inside of the carbon spheres, the vanadium carbide/carbon sphere composite material is small and uniform in particle size, the particle size is not more than 500 micrometers, the specific surface area is large, the catalytic contact area of the composite material is increased, so that the catalytic performance of the composite material is improved, the impurity content is low, the surface has the characteristics of micropores and the like, and the catalytic effect of the vanadium carbide/carbon sphere composite material is further improved.
Correspondingly, the embodiment of the invention also provides a vanadium carbide/carbon sphere composite material, which is spherical and comprises: the carbon sphere comprises a carbon sphere matrix and vanadium carbide uniformly distributed in the carbon sphere matrix.
The vanadium carbide/carbon sphere composite material provided by the embodiment of the invention is spherical and comprises the following components: the carbon sphere matrix provides a carrier for the vanadium carbide, so that the vanadium carbide is uniformly distributed and combined on the surface and inside of the carbon sphere matrix, and the catalytic stability of the vanadium carbide is improved; on the other hand, the carbon sphere matrix has the porous characteristic of litigation, which is beneficial to improving the loading capacity of the vanadium carbide catalyst in the vanadium carbide/carbon sphere composite material, thereby improving the catalytic effect of the composite material, and the carbon sphere matrix with the porous structure improves the catalytic contact area of the composite material, so that the catalytic performance of the composite material is more three-dimensional through the adsorption of the carbon sphere matrix on substances to be catalyzed, and the catalytic performance of the composite material is further improved.
In a further embodiment, the vanadium carbide/carbon sphere composite has a particle size of no greater than 500 microns. The vanadium carbide/carbon sphere composite material in the embodiment of the invention has small and uniform particle size, the particle size is not more than 500 micrometers, the specific surface area is large, and the catalytic contact area of the composite material is increased, so that the catalytic performance of the composite material is improved, the impurity content is low, the surface has the characteristics of micropores and the like, and the catalytic effect of the vanadium carbide/carbon sphere composite material is further improved.
The vanadium carbide/carbon sphere composite material prepared or provided by the embodiments of the invention has the characteristics, is an excellent catalytic material, can be used in the catalytic field of fuel cells, and can also be used in other catalytic fields such as hydrogen evolution, hydrogenation, hydrogenolysis, oxygen reduction, carriers and the like, and has wide application range and high practical value.
In order to make the above implementation details and operations of the present invention clearly understood by those skilled in the art and to make the progress of the vanadium carbide/carbon sphere composite material and the preparation method thereof obviously apparent, the above technical solutions are illustrated by a plurality of examples below.
Example 1
The embodiment provides a vanadium carbide/carbon sphere composite material, and the preparation method comprises the following steps:
s10, dissolving 160mg of ammonium metavanadate in 70mL of deionized water, and stirring until the ammonium metavanadate is completely dissolved for about 5 min; adding 300mg of dopamine hydrochloride, and continuously stirring until the dopamine hydrochloride is completely dissolved for about 15min to obtain a first mixed solution;
s20, adding 150mL of absolute ethyl alcohol into the first mixed solution, stirring uniformly, adding about 1mL of ammonia water into the first mixed solution, stirring uniformly, adjusting the pH value to about 9.0, and continuously stirring for about 12 hours; centrifuging the stirred mixed solution to obtain a precursor, and then placing the obtained precursor in a drying oven for drying at 60 ℃ for about 8 hours;
and S30, placing the dried precursor in a nitrogen atmosphere for calcination treatment, wherein the temperature rise rate of calcination is 5 ℃/min, raising the temperature to 900 ℃, carrying out constant-temperature calcination at 900 ℃ for 3h, and then naturally cooling to obtain the vanadium carbide/carbon sphere composite material.
Further, in order to verify the advancement of the vanadium carbide/carbon sphere composite material provided by the embodiment of the present invention, the embodiment of the present invention performs a performance test.
Test example 1
This test example carried out XRD testing on the vanadium carbide/carbon sphere composite material of example 1:
the final product obtained was tested according to the standard of the conventional XRD test, and the test results are shown in fig. 1, in which the abscissa is twice the incident angle of x-ray and the ordinate is the intensity after diffraction. Comparing the spectrum shown in the attached figure 1 with a vanadium carbide standard diffraction peak spectrum PDF #73-0476 (thin lines vertical to the abscissa in the attached figure 1 are positions corresponding to standard diffraction peaks), the XRD diffraction peak energy of the vanadium carbide synthesized by the method corresponds to the standard spectrum, and the final product obtained in the embodiment 1 of the invention is proved to be the vanadium carbide/carbon sphere composite material.
Further, this test example performed SEM tests on the vanadium carbide/carbon sphere composite material provided in example 1:
SEM scanning test of the vanadium carbide/carbon sphere composite material of example 1 was performed according to a conventional SEM scanning operation, and the specific test results are shown in FIG. 2. As shown in the attached figure 2, the vanadium carbide/carbon sphere composite material prepared in the embodiment 1 of the invention is a small sphere particle, has uniform appearance and particle size within 500 nanometers, and can be observed to have a large number of micropores on the surface of the small sphere particle. Combining the XRD test and the SEM scanning results, the vanadium carbide/carbon sphere composite material obtained in example 1 of the present invention is indeed in nanometer level, and the particle size is not greater than 500 nm.
Further, this test example performed EDS scan tests on the vanadium carbide/carbon sphere composite material provided in example 1, and the test results are shown in fig. 3 and 4. As can be seen from fig. 3, vanadium (V) is uniformly distributed in the carbon spheres; as can be seen from fig. 4, carbon (C) is uniformly distributed in the carbon spheres.
Test example 2
The test example tests the catalytic performance of the vanadium carbide/carbon sphere composite material of example 1:
according to a conventional method, the vanadium carbide/carbon sphere composite material obtained in example 1 is used for hydrogen evolution reaction, and a polarization curve of the vanadium carbide/carbon sphere composite material is tested, wherein a specific test result is shown in fig. 5, the abscissa is voltage, and the ordinate is current density.
As can be seen from FIG. 5, when the current density was 10mA cm-2In the process, the overpotential is only 0.161V, and it can be seen that the vanadium carbide/carbon sphere composite material obtained in example 1 of the present invention has excellent hydrogen evolution performance and shows catalytic performance similar to that of a noble metal catalyst.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (10)
1. The preparation method of the vanadium carbide/carbon sphere composite material is characterized by comprising the following steps:
obtaining a vanadium source and a carbon source, and dissolving the vanadium source and the carbon source in water to obtain a first mixed solution;
adding an alcohol solvent into the first mixed solution, adjusting the pH value to 8.5-9.0, mixing, and separating to obtain a vanadium carbide/carbon sphere composite precursor;
and calcining the vanadium carbide/carbon sphere composite precursor in the protective gas atmosphere to obtain the vanadium carbide/carbon sphere composite material.
2. The method of preparing a vanadium carbide/carbon sphere composite material according to claim 1, wherein the carbon source comprises dopamine hydrochloride; and/or the presence of a gas in the gas,
the source of vanadium comprises ammonium metavanadate.
3. The method for preparing the vanadium carbide/carbon sphere composite material according to claim 2, wherein the mass ratio of the vanadium source to the carbon source in the first mixed solution is 1: (0.25-5).
4. The method for preparing the vanadium carbide/carbon sphere composite material according to any one of claims 1 to 3, wherein in a mixed system obtained by adding an alcohol solvent to the first mixed solution, the volume ratio of water to the alcohol solvent is 1: (1-8); and/or the presence of a gas in the gas,
the alcohol solvent is selected from: at least one of ethanol and methanol.
5. The method for preparing the vanadium carbide/carbon sphere composite material according to claim 4, wherein the step of subjecting the vanadium carbide/carbon sphere composite precursor to calcination treatment comprises: heating the vanadium carbide/carbon sphere composite precursor to 700-1000 ℃ from a normal temperature state at a heating rate of 5-10 ℃/min in a protective gas atmosphere, and then calcining the vanadium carbide/carbon sphere composite precursor for 2-5 hours; and/or the presence of a gas in the gas,
the protective gas is selected from: at least one of nitrogen, argon, helium.
6. The preparation method of the vanadium carbide/carbon sphere composite material according to claim 5, wherein the step of adjusting the pH value to 8.5 to 9.0 after adding the alcohol solvent to the first mixed solution comprises: adding an alcohol solvent into the first mixed solution, and then adding ammonia water to adjust the pH value to 8.5-9.0; and/or the presence of a gas in the gas,
the mixing treatment time is 10-15 hours.
7. The method for preparing the vanadium carbide/carbon sphere composite material according to claim 6, wherein the step of separating the vanadium carbide/carbon sphere composite precursor comprises: and centrifugally separating the mixed solution, and drying and separating to obtain a precipitate, wherein the precipitate is the vanadium carbide/carbon sphere composite precursor.
8. The method for preparing the vanadium carbide/carbon sphere composite material according to any one of claims 1 to 3 and 5 to 7, wherein the vanadium carbide/carbon sphere composite material is spherical and has a particle size of not more than 500 μm.
9. A vanadium carbide/carbon sphere composite material, wherein the vanadium carbide/carbon sphere composite material is spherical, comprising: the carbon sphere comprises a carbon sphere matrix and vanadium carbide uniformly distributed in the carbon sphere matrix.
10. The vanadium carbide/carbon sphere composite material of claim 9, wherein the particle size of the vanadium carbide/carbon sphere composite material is not greater than 500 microns.
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