CN110681409A - Carbon tube supported ultra-small VN hydrogen production electrocatalyst, synthesis method and application - Google Patents
Carbon tube supported ultra-small VN hydrogen production electrocatalyst, synthesis method and application Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 39
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 29
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 239000001257 hydrogen Substances 0.000 title claims abstract description 28
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 28
- 239000010411 electrocatalyst Substances 0.000 title claims abstract description 22
- 238000001308 synthesis method Methods 0.000 title claims abstract description 12
- SKKMWRVAJNPLFY-UHFFFAOYSA-N azanylidynevanadium Chemical compound [V]#N SKKMWRVAJNPLFY-UHFFFAOYSA-N 0.000 claims abstract description 31
- 238000001035 drying Methods 0.000 claims abstract description 14
- 238000000227 grinding Methods 0.000 claims abstract description 13
- GFHNAMRJFCEERV-UHFFFAOYSA-L cobalt chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Co+2] GFHNAMRJFCEERV-UHFFFAOYSA-L 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 9
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims abstract description 8
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 6
- 239000000376 reactant Substances 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 239000000843 powder Substances 0.000 claims abstract description 4
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- 238000004140 cleaning Methods 0.000 claims abstract description 3
- 238000001816 cooling Methods 0.000 claims abstract description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- 239000013589 supplement Substances 0.000 claims description 8
- 238000000605 extraction Methods 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 239000003054 catalyst Substances 0.000 claims description 6
- 229910017052 cobalt Inorganic materials 0.000 claims description 6
- 239000010941 cobalt Substances 0.000 claims description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 5
- 239000011261 inert gas Substances 0.000 claims description 5
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 4
- 238000005868 electrolysis reaction Methods 0.000 claims description 4
- 229920000877 Melamine resin Polymers 0.000 claims description 3
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 2
- 239000004202 carbamide Substances 0.000 claims description 2
- 238000005086 pumping Methods 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims 2
- 230000000630 rising effect Effects 0.000 claims 2
- 229910021529 ammonia Inorganic materials 0.000 claims 1
- ALTWGIIQPLQAAM-UHFFFAOYSA-N metavanadate Chemical compound [O-][V](=O)=O ALTWGIIQPLQAAM-UHFFFAOYSA-N 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
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- 229910052573 porcelain Inorganic materials 0.000 description 6
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000007772 electrode material Substances 0.000 description 4
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- 230000008901 benefit Effects 0.000 description 3
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 229910021642 ultra pure water Inorganic materials 0.000 description 3
- 239000012498 ultrapure water Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
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- 235000019441 ethanol Nutrition 0.000 description 1
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- 150000004767 nitrides Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- -1 transition metal sulfide Chemical class 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-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
- B01J27/24—Nitrogen compounds
-
- B01J35/23—
-
- B01J35/33—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0027—Powdering
- B01J37/0036—Grinding
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
-
- 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
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention discloses a carbon tube supported ultra-small VN hydrogen production electrocatalyst, a synthesis method and application, and belongs to the technical field of electrocatalyst synthesis. Mixing and grinding a nitrogen-containing carbon source, cobalt chloride hexahydrate and ammonium metavanadate to obtain a reactant raw material; the method comprises the steps of keeping the reactant raw materials at the temperature of 600-900 ℃ for 2-5h in the argon atmosphere, cleaning, drying and grinding the powder obtained after cooling to obtain the carbon tube-loaded vanadium nitride.
Description
Technical Field
The invention relates to the technical field of electrocatalyst synthesis, in particular to a carbon tube supported ultra-small VN hydrogen production electrocatalyst, a synthesis method and application.
Background
In recent years, due to the non-renewable property of fossil energy, the new energy direction is always a hot topic, and in renewable energy, hydrogen energy occupies a great position in new energy due to the unique advantages thereof, and industrial hydrogen production methods mainly include hydrogen production by methane reforming and hydrogen production by water electrolysis. The water resource is rich in the whole world, so that the advantage of hydrogen production by electrolyzing water is established. The electrode material is selected to determine the efficiency of water electrolysis, and the electrode material with the highest efficiency is a noble metal at present, but the noble metal is too expensive to popularize in a large area, so that an electrode material with low price is required to produce hydrogen. At present, transition metal sulfide and nitride are used as electrode materials to produce hydrogen.
Vanadium Nitride (VN) has the advantages of high mechanical strength, high electron transfer rate, high corrosion resistance and the like, has wide application in the fields of chemistry, batteries and the like, and is a potential electro-catalytic material.
In the prior art, the preparation process for preparing vanadium nitride is complex, the manufacturing cost is high, and the electrochemical performance of the prepared vanadium nitride needs to be further improved.
Disclosure of Invention
The invention aims to overcome the problems in the prior art and provides a carbon tube supported ultra-small VN hydrogen production electrocatalyst, a synthesis method and application.
One of the purposes of the invention is to provide a synthesis method of a carbon tube supported ultra-small VN hydrogen production electrocatalyst, which comprises the following steps:
s1, mixing and grinding a nitrogen-containing carbon source, cobalt chloride hexahydrate and ammonium metavanadate to obtain a reactant raw material;
s2, keeping the temperature of the reactant raw materials at 900 ℃ for 2-5h under the argon atmosphere, and cleaning, drying and grinding the powder obtained after cooling to obtain the carbon tube-loaded vanadium nitride.
Preferably, the nitrogen-containing carbon source is urea, dicyandiamide or melamine.
Preferably, in the step S1, the nitrogen-containing carbon source, cobalt chloride hexahydrate and ammonium metavanadate are mixed according to a mass ratio of 60: 4: 0.5-2 mixing.
Preferably, the mixed material in the step S1 is ground for 15-25 min.
Preferably, the washing in step S2 is specifically washing with water and washing with alcohol alternately three times each.
Preferably, the drying temperature in step S2 is 55-65 ℃, and the drying time is 2.5-3.5 h.
Preferably, the grinding time in step S2 is 8-12 min.
Preferably, step S2 is performed in a tube furnace, in which an inert gas, argon, is first introduced into the tube furnace, then air is pumped and supplied for 3 times, the vacuum pump pumps the air pressure in the tube to-0.1 MPa during air pumping, and the air pressure in the tube is controlled to 0MPa during air supplying; under the condition that the air pressure is 0MPa, the temperature is increased to 500 ℃ at the heating rate of 10 ℃/min, the temperature is kept for 2h, then the temperature is increased to 600-900 ℃ at the heating rate of 5 ℃/min, and the temperature is kept for 2 h.
The second purpose of the invention is to provide a carbon tube supported cobalt-doped ultra-small VN hydrogen production electrocatalyst synthesized by the synthesis method of the carbon tube supported ultra-small VN hydrogen production electrocatalyst.
The invention also aims to provide the application of the carbon tube supported cobalt-doped ultra-small VN hydrogen production electrocatalyst as a hydrogen production catalyst for electrolysis of water.
Compared with the prior art, the invention has the beneficial effects that: the method adopted by the invention is a one-step pressure-free pyrolysis method to obtain the ultra-small VN particles supported by the carbon nano tubes, the synthesis method is simple, the structure is unique, and the conductivity of the catalyst is improved by doping the cobalt simple substance in the synthesized catalyst, so that the catalyst has better electrochemical performance, and the synthesis cost is low, thus being suitable for industrial production.
The invention takes nitrogen-containing carbon source as nitrogen source and carbon source, ammonium metavanadate as vanadium source, cobalt chloride hexahydrate as cobalt source, and cobalt source as carbon tube inducer and dopant, the carbon tube bears a large amount of vanadium nitride particles, because the carbon tube can transmit electrons to vanadium nitride periphery fast, thus make the efficiency improve, the vanadium nitride of the invention is about 5nm ultra-small nanoparticle, make the quantity of vanadium nitride particle that unit area of carbon tube load more, therefore the electrochemical activity area is also bigger, the catalyst electrochemistry is better.
Drawings
Fig. 1 is an XRD pattern of VN prepared in example 1.
FIG. 2 is a 2K Scanning Electron Microscope (SEM) photograph of ultra-small VN supported by carbon tubes prepared in example 1.
FIG. 3 is a Transmission Electron Microscope (TEM) photograph of ultra-small VN supported by carbon tubes prepared in example 1.
Fig. 4 is an LSV hydrogen production performance curve of the carbon tube supported ultra-small VN electrocatalyst prepared in this example 1 under an alkaline environment.
Detailed Description
The following detailed description of the present invention will be described in conjunction with the accompanying drawings and examples, but it should be understood that the scope of the present invention is not limited to the specific embodiments. All other examples, which can be obtained by a person skilled in the art without inventive step based on the examples of the present invention, are within the scope of the present invention, and the test methods without specifying the specific conditions in the following examples are generally performed according to the conventional conditions or according to the conditions suggested by the respective manufacturers.
Example 1
The synthesis method of the carbon tube supported cobalt-doped ultra-small VN hydrogen production electrocatalyst comprises the following steps:
s1, placing 1500mg of dicyandiamide, 100mg of cobalt chloride hexahydrate and 0.025g of ammonium metavanadate in a mortar for grinding for 20 minutes to uniformly mix the raw materials, placing the obtained mixture in a porcelain boat, placing the porcelain boat in a tubular atmosphere furnace, and placing two furnace plugs at two ends of a quartz tube respectively.
S2, introducing inert gas argon into the tube, then performing air extraction and air supplement for three times respectively, wherein the air pressure in the tube is pumped to-0.1 MPa by a vacuum pump during air extraction, and the air supplement is controlled to-0 MPa; under the condition that the air pressure is 0MPa, the temperature is increased to 500 ℃ at the heating rate of 10 ℃/min, the temperature is kept for 2h, then the temperature is increased to 900 ℃ at the heating rate of 5 ℃/min, and the temperature is kept for 2 h.
S3, taking out the sample when the sample is cooled to room temperature, grinding for 20min, and then using 1mol/L H2SO4And (5) pickling for 12 h. And washing and centrifuging the acid-washed sample for three times by using ultrapure water and absolute ethyl alcohol alternately, and drying the washed sample in a constant-temperature drying box at the temperature of 60 ℃. After drying, the sample was ground for 10 min.
Example 2
The synthesis method of the carbon tube supported cobalt-doped ultra-small VN hydrogen production electrocatalyst comprises the following steps:
s1, putting 1500mg of melamine, 0.75mg of cobalt chloride hexahydrate and 0.025g of ammonium metavanadate in a mortar for grinding for 20 minutes to uniformly mix the raw materials, putting the obtained mixture into a porcelain boat, putting the porcelain boat into a tubular atmosphere furnace, and putting two furnace plugs at two ends of a quartz tube respectively.
S2, introducing inert gas argon into the tube, then performing air extraction and air supplement for three times respectively, wherein the air pressure in the tube is pumped to-0.1 MPa by a vacuum pump during air extraction, and the air supplement is controlled to-0 MPa; under the condition that the air pressure is 0MPa, the temperature is increased to 500 ℃ at the heating rate of 10 ℃/min, the temperature is kept for 2h, then the temperature is increased to 800 ℃ at the heating rate of 5 ℃/min, and the temperature is kept for 2 h.
S3, taking out the sample when the sample is cooled to room temperature, grinding for 20min, and then pickling for 12H by using 1mol/L H2SO 4. And washing and centrifuging the acid-washed sample for three times by using ultrapure water and absolute ethyl alcohol alternately, and drying the washed sample in a constant-temperature drying box at the temperature of 60 ℃. After drying, the sample was ground for 10 min.
Example 3
The synthesis method of the carbon tube supported cobalt-doped ultra-small VN hydrogen production electrocatalyst comprises the following steps:
s1, placing 1500mg of dicyandiamide, 100mg of cobalt chloride hexahydrate and 0.05g of ammonium metavanadate in a mortar for grinding for 20 minutes to uniformly mix the raw materials, placing the obtained mixture in a porcelain boat, placing the porcelain boat in a tubular atmosphere furnace, and placing two furnace plugs at two ends of a quartz tube respectively.
S2, introducing inert gas argon into the tube, then performing air extraction and air supplement for three times respectively, wherein the air pressure in the tube is pumped to-0.1 MPa by a vacuum pump during air extraction, and the air supplement is controlled to-0 MPa; under the condition that the air pressure is 0MPa, the temperature is increased to 500 ℃ at the heating rate of 10 ℃/min, the temperature is kept for 2h, then the temperature is increased to 900 ℃ at the heating rate of 5 ℃/min, and the temperature is kept for 2 h.
S3, taking out the sample when the sample is cooled to room temperature, grinding for 20min, and then using 1mol/L H2SO4And (5) pickling for 12 h. And washing and centrifuging the acid-washed sample for three times by using ultrapure water and absolute ethyl alcohol alternately, and drying the washed sample in a constant-temperature drying box at the temperature of 60 ℃. After drying, the sample was ground for 10 min.
In addition, in the above examples 1-3, the SEM images and the transmission electron microscope images of the prepared samples are plotted on the LSV hydrogen production performance curve under the alkaline environment, and the results show that VN size synthesized in the above examples is about 5nm, and the lattice fringes show that VN is the (111) crystal plane, and the attached figure of the specification is the relevant test chart of example 1.
From FIG. 1, we can see that the X-ray powder diffraction peaks can be indicated by VN and that there is also cobalt present therein;
the formation of carbon tubes is clearly seen in the Scanning Electron Microscope (SEM) photograph of FIG. 2.
From the projection electron microscope (TEM) of fig. 3, it can be clearly seen that VN is about 5nm in size, and the lattice fringes indicate that it is the (111) crystal plane of VN;
FIG. 4 is the LSV hydrogen production performance curve of a carbon tube supported ultra-small VN electrocatalyst at a pH of about 14, from which it can be seen that the hydrogen production performance curve is 10mA/cm2When the scanning speed is 5mV/s under the current density, the overpotential of the sample is 210mV, and the sample has good electrochemical performance.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (6)
1. A synthesis method of a carbon tube supported ultra-small VN hydrogen production electrocatalyst is characterized by comprising the following steps:
s1, mixing and grinding a nitrogen-containing carbon source, cobalt chloride hexahydrate and ammonium metavanadate to obtain a reactant raw material;
s2, keeping the temperature of the reactant raw materials at 900 ℃ for 2-5h under the argon atmosphere, cooling to obtain powder, and cleaning, drying and grinding the powder to obtain the carbon tube-loaded vanadium nitride.
2. The method for synthesizing the carbon tube-supported cobalt-doped ultra-small VN hydrogen-production electrocatalyst according to claim 1, wherein the nitrogen-containing carbon source in step S1 is urea, dicyandiamide or melamine.
3. The method for synthesizing the carbon tube-supported cobalt-doped ultra-small VN hydrogen-production electrocatalyst according to claim 1, wherein the nitrogen-containing carbon source, cobalt chloride hexahydrate and ammonia metavanadate in the step S1 are mixed in a mass ratio of 60: 4: 0.5-2 mixing.
4. The method for synthesizing the carbon tube-supported cobalt-doped ultra-small VN hydrogen-production electrocatalyst according to claim 1, wherein the step S2 is performed in a tube furnace, specifically, inert gas argon is firstly introduced into the tube furnace, then air extraction and air supplement are performed for 3 times, the vacuum pump is used for pumping until the pressure in the tube is-0.1 MPa, and the air pressure in the air supplement control tube is 0 MPa; under the condition that the air pressure is 0MPa, the temperature is increased to 500 ℃ at the temperature rising rate of 15-20 ℃/min, the temperature is kept for 2h, then the temperature is increased to 900 ℃ at the temperature rising rate of 5 ℃/min, and the temperature is kept for 2 h.
5. The carbon tube supported cobalt doped ultra small VN hydrogen production electrocatalyst synthesized according to any one of claims 1-4.
6. Use of a carbon tube supported cobalt doped ultra-small VN hydrogen production electrocatalyst according to claim 5 as a hydrogen production catalyst for electrolysis of water.
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CN113215614A (en) * | 2021-04-26 | 2021-08-06 | 陕西科技大学 | Carbon-layer-loaded tungsten-doped vanadium nitride nanoparticle composite electrocatalyst and preparation method and application thereof |
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CN113231107A (en) * | 2021-04-29 | 2021-08-10 | 陕西科技大学 | Carbon nanotube-coated vanadium nitride/iron carbide composite electrocatalyst and preparation method and application thereof |
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CN114308104A (en) * | 2021-12-27 | 2022-04-12 | 华南理工大学 | Preparation method and application of nitrogen-doped carbon material loaded bimetallic cobalt and vanadium catalyst |
CN114645283A (en) * | 2020-12-15 | 2022-06-21 | 陕西科技大学 | High-efficiency vanadium nitride/molybdenum carbide heterojunction hydrogen production electrocatalyst and preparation method and application thereof |
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CN114645283B (en) * | 2020-12-15 | 2024-02-09 | 陕西科技大学 | High-efficiency vanadium nitride/molybdenum carbide heterojunction hydrogen-producing electrocatalyst and preparation method and application thereof |
CN113215614A (en) * | 2021-04-26 | 2021-08-06 | 陕西科技大学 | Carbon-layer-loaded tungsten-doped vanadium nitride nanoparticle composite electrocatalyst and preparation method and application thereof |
CN113235129A (en) * | 2021-04-26 | 2021-08-10 | 陕西科技大学 | Vanadium nitride/tungsten carbide composite electrocatalyst and preparation method and application thereof |
CN113235129B (en) * | 2021-04-26 | 2022-02-11 | 陕西科技大学 | Vanadium nitride/tungsten carbide composite electrocatalyst and preparation method and application thereof |
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CN113441165A (en) * | 2021-07-30 | 2021-09-28 | 陕西科技大学 | VN/g-C3N4Composite photocatalyst and preparation method thereof |
CN114308104A (en) * | 2021-12-27 | 2022-04-12 | 华南理工大学 | Preparation method and application of nitrogen-doped carbon material loaded bimetallic cobalt and vanadium catalyst |
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