CN108837838A - A kind of extra small vanadium carbide insertion carbon nano-tube material, preparation method and its application in terms of water-splitting produces hydrogen - Google Patents
A kind of extra small vanadium carbide insertion carbon nano-tube material, preparation method and its application in terms of water-splitting produces hydrogen Download PDFInfo
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- CN108837838A CN108837838A CN201810435322.7A CN201810435322A CN108837838A CN 108837838 A CN108837838 A CN 108837838A CN 201810435322 A CN201810435322 A CN 201810435322A CN 108837838 A CN108837838 A CN 108837838A
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- vanadium carbide
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- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 51
- 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 37
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 239000001257 hydrogen Substances 0.000 title claims abstract description 28
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 28
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 24
- 239000000463 material Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 238000003780 insertion Methods 0.000 title claims abstract description 15
- 230000037431 insertion Effects 0.000 title claims abstract description 15
- 238000010438 heat treatment Methods 0.000 claims abstract description 17
- 238000000227 grinding Methods 0.000 claims abstract description 16
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims abstract description 12
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims abstract description 11
- 239000003863 metallic catalyst Substances 0.000 claims abstract description 7
- 239000013078 crystal Substances 0.000 claims abstract description 4
- 230000002378 acidificating effect Effects 0.000 claims abstract 3
- 239000012535 impurity Substances 0.000 claims abstract 3
- 239000000203 mixture Substances 0.000 claims abstract 3
- SKKMWRVAJNPLFY-UHFFFAOYSA-N azanylidynevanadium Chemical compound [V]#N SKKMWRVAJNPLFY-UHFFFAOYSA-N 0.000 claims abstract 2
- 238000004140 cleaning Methods 0.000 claims abstract 2
- 238000001035 drying Methods 0.000 claims abstract 2
- 239000000843 powder Substances 0.000 claims description 21
- 229910052751 metal Inorganic materials 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 11
- 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
- 229910052573 porcelain Inorganic materials 0.000 claims description 8
- OQUOOEBLAKQCOP-UHFFFAOYSA-N nitric acid;hexahydrate Chemical compound O.O.O.O.O.O.O[N+]([O-])=O OQUOOEBLAKQCOP-UHFFFAOYSA-N 0.000 claims description 5
- 229910016874 Fe(NO3) Inorganic materials 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 239000000376 reactant Substances 0.000 claims description 4
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims 1
- 238000013021 overheating Methods 0.000 claims 1
- 235000011149 sulphuric acid Nutrition 0.000 claims 1
- 238000001291 vacuum drying Methods 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 27
- 238000000034 method Methods 0.000 abstract description 18
- 230000015572 biosynthetic process Effects 0.000 abstract description 5
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 238000003786 synthesis reaction Methods 0.000 abstract description 5
- 239000003792 electrolyte Substances 0.000 abstract description 3
- 230000035484 reaction time Effects 0.000 abstract description 3
- 238000001354 calcination Methods 0.000 abstract description 2
- ZLANVVMKMCTKMT-UHFFFAOYSA-N methanidylidynevanadium(1+) Chemical class [V+]#[C-] ZLANVVMKMCTKMT-UHFFFAOYSA-N 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 description 11
- 239000002994 raw material Substances 0.000 description 11
- 229910052799 carbon Inorganic materials 0.000 description 10
- 238000006555 catalytic reaction Methods 0.000 description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 229910017052 cobalt Inorganic materials 0.000 description 6
- 239000010941 cobalt Substances 0.000 description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 6
- 238000007654 immersion Methods 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 238000010792 warming Methods 0.000 description 6
- 239000002245 particle Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 2
- 229930006000 Sucrose Natural products 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 239000011554 ferrofluid Substances 0.000 description 2
- 239000005720 sucrose Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- QIJNJJZPYXGIQM-UHFFFAOYSA-N 1lambda4,2lambda4-dimolybdacyclopropa-1,2,3-triene Chemical compound [Mo]=C=[Mo] QIJNJJZPYXGIQM-UHFFFAOYSA-N 0.000 description 1
- 241001672694 Citrus reticulata Species 0.000 description 1
- 229910039444 MoC Inorganic materials 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 239000010431 corundum Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000000713 high-energy ball milling Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- XDBSEZHMWGHVIL-UHFFFAOYSA-M hydroxy(dioxo)vanadium Chemical compound O[V](=O)=O XDBSEZHMWGHVIL-UHFFFAOYSA-M 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000011553 magnetic fluid Substances 0.000 description 1
- 239000006249 magnetic particle Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
- -1 transition metal carbides Chemical class 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 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
Classifications
-
- 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
-
- 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
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
-
- 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
- B01J37/084—Decomposition of carbon-containing compounds into carbon
-
- 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
-
- 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 kind of extra small vanadium carbides to be embedded in carbon nano-tube material, its structure includes the extra small crystal grain of vanadium nitride that pipe thickness is no more than the carbon nanotube of 3nm and is dispersed in carbon nanotube tube wall, and the extra small vanadium carbide insertion carbon nano-tube material has the tubular morphology of nano-scale.The preparation method of extra small vanadium carbide insertion carbon nano-tube material is：It is fully ground after dicyandiamide, ammonium metavanadate and metallic catalyst are mixed；Then mixture is heat-treated under atmosphere protection, with 500-1200 DEG C；After the completion of heat treatment, place the product in remove impurity under acidic environment；Grinding obtains target product after cleaning, drying.The present invention also provides application of this material in terms of water-splitting produces hydrogen.The present invention obtains that synthesis temperature is low, reaction time is short, materials chemistry forms the uniform VC/CNTs that electro catalytic activity, stability are high in full pH electrolyte environment of uniform, appearance and size and produces hydrogen elctro-catalyst by one-step calcination method.
Description
Technical field
The present invention relates to the synthesis of catalyst and applied technical fields, and in particular to a kind of extra small vanadium carbide insertion carbon nanometer
Tube material, preparation method and its application in terms of cracking aquatic products hydrogen catalyst as electro-catalysis.
Background technique
Hydrogen Energy is considered as promising energy carrier due to its high energy density.Inexpensive, efficient Hydrogen Energy is from can
From the perspective of sustainable development, scientific and technical support is needed, this is also a challenge.It is an economic production hydrogen that water-splitting, which produces hydrogen,
Means, and discharge of the process without carbon dioxide.And this process needs to reduce the catalyst that hydrogen forms activation energy.Many institute's weeks
Know, noble metal（Pt, Rh, Pd etc.）Low overpotential and fast electronic mechanism when due to their drive responses, it is considered to be outstanding
Production hydrogen catalyst.But high cost, content lower limit their widespread adoptions.Some nonmetallic materials are by extensive
Research, such as transient metal sulfide, carbide, composite material or alloy.Wherein transition metal, such as tungsten carbide, molybdenum carbide,
It is shown to be similar to platinum group metal property by report, becomes the selection good instead of platinum group metal.
Vanadium carbide high rigidity, high-melting-point, the general characteristic with transition metal carbides, while there is good lead
Electricity, thermally conductive, catalytic performance have a wide range of applications in physics, chemistry, Material Field, and vanadium carbide answering in electro-catalysis field
It is seldom with going back, therefore prepare nano vanadium carbide power applications and have great importance in electro-catalysis field.Application No. is
CN103606428A Chinese patent " a kind of nano vanadium carbide ferrofluid and preparation method thereof, use partial size for one high energy ball
Nano-magnetic vanadium carbide is ground as the magnetic particle in magnetic fluid, presoma is prepared using aqueous solution dosing method, barium oxide is straight
It connects after carbonizatin method prepares nano vanadium carbide high-energy ball milling and nano-magnetic vanadium carbide is made, it is then that nano-magnetic vanadium carbide particle is pre-
It is scattered in base fluid, surface is modified to obtain nano vanadium carbide ferrofluid." this method the step of it is simple, but obtain carbonization
The size of vanadium is still bigger, it is difficult to meet the requirement of elctro-catalyst.Chinese patent " the preparation of Publication No. CN101891193
The method of nano vanadium carbide is using metavanadic acid hinge and sucrose as raw material, first by raw material heat in corundum mandarin orange pot under the conditions of 800 DEG C
It is molten to be prepared as Gel Precursor, then presoma is dried in a hydrogen atmosphere, obtain the vanadic anhydride elder generation body of sucrose cladding
Powder, first body powder obtain nanometer powder by 1000-1200 DEG C of high-temperature heat treatment." this method preparation vanadium carbide close
It is excessively high at temperature, it is unfavorable for industrialized production.
The above method prepares vanadium carbide powder complex process, higher cost, the application in no electro-catalysis field.Therefore, having must
A kind of at low cost, preparation method of the nano vanadium carbide of simple process is explored, to better meet vanadium carbide in electro-catalysis
The application in agent field.
Summary of the invention
The purpose of the present invention is to provide a kind of extra small vanadium carbides to be embedded in carbon nanotube（VC/CNTs）Material, preparation method
And its application in terms of cracking aquatic products hydrogen catalyst as electro-catalysis.With overcome preparation method of the existing technology it is complicated,
VC partial size is big, pattern is single, few disadvantage is applied in electro-catalysis field.The present invention by one-step calcination method obtain synthesis temperature it is low,
Reaction time is short, materials chemistry forms uniform, the uniform electro catalytic activity, stability in full pH electrolyte environment of appearance and size
High VC/CNTs produces hydrogen elctro-catalyst.Metallic atom in raw material（Cobalt, iron, nickel）Introducing not only promote carbon pipe generation and
Crystallization, and VC crystal grain is inhibited to grow up, so that generating extra small VC particle（No more than 3 nm）.
In order to achieve the above object, the present invention adopts the following technical scheme that：
A kind of VC/CNTs produces the preparation method of hydrogen elctro-catalyst, includes the following steps：
Step 1：By dicyandiamide, ammonium metavanadate, metallic catalyst is sufficiently mixed according to a certain percentage, and ratio is（10-20）：（2-
4）：（1-3）, it is fully ground 20~50min, obtains reactant feed, wherein the ratio of raw material is counted in mortar in mass ratio；
Step 2：Reactant feed prepared by step 1 is placed in porcelain boat, is reacted in tube furnace under certain atmosphere, temperature model
Enclosing is 500-1200 DEG C, soaking time 1-5h, and heating rate is 5-10 DEG C/min, obtains black powder.
Step 3：In order to remove the metal simple-substance in powder, 0.5M H is placed it in2SO4Middle 10-24h is dried in vacuo 6h
Grinding obtains VC/CNTs and produces hydrogen elctro-catalyst afterwards.
Metallic catalyst in above-mentioned steps one refers to Nickelous nitrate hexahydrate, Fe(NO3)39H2O, in cabaltous nitrate hexahydrate
Any one.
Certain atmosphere in above-mentioned steps two refers to argon gas, nitrogen, any one in vacuum.
Metal simple-substance in above-mentioned steps three refers to nickel, iron, any one in cobalt.
And a kind of VC/CNTs prepared by the above method produces hydrogen elctro-catalyst, VC/CNTs prepared by the present invention produces hydrogen
Elctro-catalyst, VC are embedded in carbon tube wall, and partial size is less than 3nm, and carbon pipe is mutually wound, and the pipe thickness of crystallization is about 2-3nm, sample shape
Looks are uniform, good dispersion.
Compared with prior art, the invention has the following beneficial technical effects：
1）Step sintering process used in the present invention, reaction time is short, and synthesis temperature is low（700 DEG C can synthesize）, overcome biography
System method prepares vanadium carbide complex steps, needs higher synthesis temperature（At least 1000 DEG C）Defect；
2）Dicyandiamide contains N element, so that the VC/CNTs of preparation is rich in N defect, so that the activity for being conducive to catalyst improves；
3）Metallic atom in raw material（Iron, cobalt, nickel）Introducing be the structure（Carbon nanotube, extra small vanadium carbide）The key of generation,
Also the catalytic activity of catalyst is improved to a certain extent；
4）Carbon pipe in VC/CNTs is that a step is generated in-situ, and the good conductivity of one-dimensional carbon pipe, tube wall is thin, is conducive to electronics biography
It is defeated, while effectively having dispersed vanadium carbide crystal grain, inhibit growing up for vanadium carbide, so that the more active sites of sample exposure, moreover it is possible to
Vanadium carbide is protected in catalytic process, prevents its corrosion by electrolyte；
5）It reacts VC partial size in obtained VC/CNTs production hydrogen elctro-catalyst and is less than 3nm, much smaller than VC particle on the document reported
Size, and its pattern is uniform, good dispersion；
6）The VC/CNTs of this method preparation, which produces hydrogen elctro-catalyst, can be used for the full pH value production hydrogen electricity of the water-splitting in electro-catalysis field
Catalyst.
Detailed description of the invention
Fig. 1 is the XRD diagram of the VC/CNTs prepared in embodiment 1；
The SEM figure that Fig. 2 is the VC/CNTs prepared in embodiment 3；
The TEM figure that Fig. 3 is the VC/CNTs prepared in embodiment 3；
The LSV figure that Fig. 4 is the VC/CNTs prepared in embodiment 4；
The i-t figure that Fig. 5 is the VC/CNTs prepared in embodiment 6.
Specific embodiment
With reference to the accompanying drawing and embodiment invention is further described in detail, it should be appreciated that these embodiments are only used
In illustrating rather than limit the scope of the invention.Here it will be understood that this field after having read the content of the invention authorized
Technical staff can make any change or modification to the present invention, these equivalences equally fall within the application the appended claims and limited
Fixed range.
Embodiment 1
Step 1：1.5g dicyandiamide, 0.3g ammonium metavanadate are weighed, 0.2g cabaltous nitrate hexahydrate is sufficiently mixed grinding 40min；
Step 2：The resulting raw material of step 1 is put into porcelain boat, is reacted in the tube furnace using vacuum as atmosphere, heating rate is
5 DEG C/min, 500 DEG C are first warming up to, keeps the temperature 2h, is continuously heating to 800 DEG C, 2h is kept the temperature, is cooled to room temperature and obtains black powder；
Step 3：By obtained black powder in 0.5M H2SO4Middle immersion 10h, this is to remove the metal list in sample
Matter, grinding obtains VC/CNTs production hydrogen elctro-catalyst after being dried in vacuo 6h.
Fig. 1 is the XRD spectrum of VC/CNTs elctro-catalyst prepared by the present embodiment, it can be seen that VC/CNTs from map
Contain graphited carbon, VC and cobalt in sample（The cobalt being embedded in carbon pipe）Presence, three's characteristic peak is obvious, illustrates crystallinity
It is good.
Embodiment 2
Step 1：2g dicyandiamide, 0.2g ammonium metavanadate are weighed, 0.3g cabaltous nitrate hexahydrate is sufficiently mixed grinding 30min；
Step 2：The resulting raw material of step 1 is put into porcelain boat, is reacted in the tube furnace using vacuum as atmosphere, heating rate is
10 DEG C/min, 500 DEG C are first warming up to, keeps the temperature 2h, is continuously heating to 700 DEG C, 2h is kept the temperature, is cooled to room temperature and obtains black powder；
Step 3：By obtained black powder in 0.5M H2SO4Middle immersion 10h, this is to remove the metal list in sample
Matter, grinding obtains VC/CNTs production hydrogen elctro-catalyst after being dried in vacuo 6h.
Fig. 2,3 be VC/CNTs elctro-catalyst prepared by the present embodiment SEM and TEM map, can from SEM figure
Carbon nanotube pattern is complete out, is uniformly dispersed, it can be seen that the presence of cobalt from TEM figure（Black particles region）, vanadium carbide grain
Diameter (grey particle region) is less than 3 nm, and carbon pipe thickness is about 2-3nm, and lattice fringe is obvious, illustrates for graphitic carbon, with XRD
As a result consistent.
Embodiment 3
Step 1：1g dicyandiamide, 0.2g ammonium metavanadate are weighed, 0.1g Nickelous nitrate hexahydrate is sufficiently mixed grinding 50min；
Step 2：The resulting raw material of step 1 is put into porcelain boat, is reacted in the tube furnace using nitrogen as atmosphere, heating rate is
7 DEG C/min, 500 DEG C are first warming up to, keeps the temperature 2h, is continuously heating to 1000 DEG C, 2h is kept the temperature, is cooled to room temperature and obtains black powder；
Step 3：By obtained black powder in 0.5M H2SO4Middle immersion 20h, this is to remove the metal list in sample
Matter, grinding obtains VC/CNTs production hydrogen elctro-catalyst after being dried in vacuo 6h.
Embodiment 4
Step 1：1.5g dicyandiamide, 0.3g ammonium metavanadate are weighed, 0.3g cabaltous nitrate hexahydrate is sufficiently mixed grinding 20min；
Step 2：The resulting raw material of step 1 is put into porcelain boat, is reacted in the tube furnace using nitrogen as atmosphere, heating rate is
8 DEG C/min, 500 DEG C are first warming up to, keeps the temperature 2h, is continuously heating to 900 DEG C, 2h is kept the temperature, is cooled to room temperature and obtains black powder；
Step 3：By obtained black powder in 0.5M H2SO4For 24 hours, this is to remove the metal list in sample for middle immersion
Matter, grinding obtains VC/CNTs production hydrogen elctro-catalyst after being dried in vacuo 6h.
Fig. 4 is the LSV figure of VC/CNTs elctro-catalyst prepared by the present embodiment, indicates to work as electric current under 0 test condition of pH
Density is 10mA/cm2, when sweep speed is 3 mV/s, which is 160mV, illustrates that sample catalysis produces hydrogen activity
It is excellent.
Embodiment 5
Step 1：1g dicyandiamide, 0.4g ammonium metavanadate are weighed, 0.1g Fe(NO3)39H2O is sufficiently mixed grinding 30min；
Step 2：The resulting raw material of step 1 is put into porcelain boat, is reacted in the tube furnace using argon gas as atmosphere, heating rate is
10 DEG C/min, 500 DEG C are first warming up to, keeps the temperature 2h, is continuously heating to 1100 DEG C, 2h is kept the temperature, is cooled to room temperature and obtains black powder；
Step 3：By obtained black powder in 0.5M H2SO4Middle immersion 20h, this is to remove the metal list in sample
Matter, grinding obtains VC/CNTs production hydrogen elctro-catalyst after being dried in vacuo 6h.
Embodiment 6
Step 1：1.5g dicyandiamide, 0.4g ammonium metavanadate are weighed, 0.2g Fe(NO3)39H2O is sufficiently mixed grinding 40min；
Step 2：The resulting raw material of step 1 is put into porcelain boat, is reacted in the tube furnace using argon gas as atmosphere, heating rate is
6 DEG C/min, 500 DEG C are first warming up to, keeps the temperature 2h, is continuously heating to 1200 DEG C, 2h is kept the temperature, is cooled to room temperature and obtains black powder；
Step 3：By obtained black powder in 0.5M H2SO4Middle immersion 12h, this is to remove the metal list in sample
Matter, grinding obtains VC/CNTs production hydrogen elctro-catalyst after being dried in vacuo 6h.
Fig. 5 is the i-t figure of VC/CNTs elctro-catalyst prepared by the present embodiment, indicates to have served as under 14 test condition of pH
When potential is 340mV, current density is about 10mA/cm2, and at least stable 15h, current density illustrate sample without obvious decaying
Excellent in stability.
Claims (9)
1. a kind of extra small vanadium carbide is embedded in carbon nano-tube material, it is characterised in that：Its structure includes that pipe thickness is no more than 3nm
Carbon nanotube and the extra small crystal grain of the vanadium nitride being dispersed in carbon nanotube tube wall, the extra small vanadium carbide are embedded in carbon nanotube material
Expect the tubular morphology with nano-scale.
2. a kind of preparation method of extra small vanadium carbide insertion carbon nano-tube material, which is characterized in that include the following steps：
It is fully ground after dicyandiamide, ammonium metavanadate and metallic catalyst are mixed；Then under atmosphere protection, with 500-1200
DEG C mixture is heat-treated；After the completion of heat treatment, place the product in remove impurity under acidic environment；It is ground after cleaning, drying
Mill obtains extra small vanadium carbide insertion carbon nano-tube material.
3. a kind of preparation method of extra small vanadium carbide insertion carbon nano-tube material according to claim 2, it is characterised in that：
The metallic catalyst is one or more of Nickelous nitrate hexahydrate, Fe(NO3)39H2O, cabaltous nitrate hexahydrate.
4. a kind of preparation method of extra small vanadium carbide insertion carbon nano-tube material according to claim 2, it is characterised in that：
Dicyandiamide, ammonium metavanadate and metallic catalyst are according to mass ratio（10-20）：（2-4）：（1-3）Mixing.
5. a kind of preparation method of extra small vanadium carbide insertion carbon nano-tube material according to claim 2, it is characterised in that：
The atmosphere protection is using any one in argon gas, nitrogen, vacuum.
6. a kind of preparation method of extra small vanadium carbide insertion carbon nano-tube material according to claim 2, it is characterised in that：
The 500-1200 DEG C of soaking time being heat-treated to mixture is 1-5h.
7. a kind of preparation method of extra small vanadium carbide insertion carbon nano-tube material according to claim 2, it is characterised in that：
Product through Overheating Treatment is placed under acidic environment and removes impurity, using the H of 0.5M2SO410-24h is impregnated to product.
8. a kind of preparation method of extra small vanadium carbide insertion carbon nano-tube material according to claim 2, which is characterized in that
The step specifically includes：
Step 1：By dicyandiamide, ammonium metavanadate and metallic catalyst according to mass ratio（10-20）：（2-4）：（1-3）Mixing, fills
Divide grinding 20~50min, obtains reactant feed；
Step 2：Reactant feed prepared by step 1 is placed in porcelain boat, is reacted in tube furnace under atmosphere protection, temperature model
Enclosing is 500-1200 DEG C, soaking time 1-5h, and heating rate is 5-10 DEG C/min, obtains black powder；
Step 3：In order to remove the metal simple-substance in black powder, black powder is placed in 0.5M H2SO4 and impregnates 10-24h,
Grinding obtains extra small vanadium carbide insertion carbon nano-tube material after vacuum drying 6h.
9. application of the extra small vanadium carbide insertion carbon nano-tube material in terms of water-splitting produces hydrogen described in claim 1.
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