CN108316008A - A kind of vanadic sulfide/vanadium carbide composite nano plate assembly, it is prepared and application - Google Patents
A kind of vanadic sulfide/vanadium carbide composite nano plate assembly, it is prepared and application Download PDFInfo
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- CN108316008A CN108316008A CN201810033932.4A CN201810033932A CN108316008A CN 108316008 A CN108316008 A CN 108316008A CN 201810033932 A CN201810033932 A CN 201810033932A CN 108316008 A CN108316008 A CN 108316008A
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Abstract
The invention discloses a kind of synthesis fields belonging to nano material, and vanadic sulfide/vanadium carbide composite nano plate assembly, preparation method and application is coated more particularly, to a kind of nitrogen-doped carbon.This approach includes the following steps：(1) pass through the rose-shaped VS of Hydrothermal Growth by substrate of carbon fiber2, form vanadic sulfide nanometer sheet assembly；(2) it after drying vanadic sulfide nanometer sheet assembly in Tris and Dopamine hydrochloride mixed solution, is stirred continuously and its surface is coated on by dopamine autohemagglutination formation poly-dopamine；(3) high-temperature calcination can prepare NC claddings VS2VC composite nano plate assemblies.A kind of composite material with novel nano structure is prepared in the present invention, the material structure is similar to rose in nature, it can be supported in substrate material surface, it is not easy to cave in, with the active site that larger specific surface area and surface are abundant, have broad application prospects in catalysis, energy stores and conversion and optical electrical devices field.
Description
Technical field
The invention belongs to the synthesis fields of nano material, and vanadic sulfide/carbonization is coated more particularly, to a kind of nitrogen-doped carbon
Vanadium composite nano plate assembly, preparation method and application.
Background technology
Transient metal sulfide presents unique optical electrical property and catalytic property, thus in opto-electronic device and energy
It converts and there is great application potential in storage in source.Nanometer sheet assembly with special construction and composition combines a nanometer material
The physics and chemistry such as small-size effect, skin effect, quantum size effect, macro quanta tunnel effect and the Dielectric confinement effect of material
Matter often as active electrode material in optical electrical chemical device, but prepares the two-dimentional transition metal vulcanization of high surface area at present
Object nanometer sheet assembly is a technical barrier.There are chemical stability, electric conductivity and lifes for transient metal sulfide itself simultaneously
The shortcomings of object poor compatibility, also limits its application.
Invention content
For the disadvantages described above or Improvement requirement of the prior art, the present invention provides a kind of nitrogen-doped carbon cladding vanadic sulfide/
Vanadium carbide composite nano plate assembly, preparation method and application, fully in conjunction with the characteristics of transient metal sulfide nanometer sheet
With the demand of preparation, specific aim redesigns the preparation process of vanadic sulfide nanometer sheet assembly, and to crucial preparation process
Integrated artistic design, each step reaction condition (such as reactant concentration, reaction temperature, reaction time) optimize and select
It selects, a kind of nitrogen-doped carbon cladding vanadic sulfide/vanadium carbide composite nano plate assembly has finally been prepared, there is larger surface
Long-pending, special heterojunction characteristics and good stability, can be prepared as flexible electrode can be used for being catalyzed, energy stores with conversion and
Optical electrical device is led.
To achieve the above object, according to one aspect of the present invention, a kind of nitrogen-doped carbon cladding vanadic sulfide/carbonization is provided
The preparation method of vanadium composite nano plate assembly, includes the following steps：
(1) carbon fiber is placed in the mixed aqueous solution of sodium vanadate and thioacetamide and hydro-thermal reaction occurs, generate load
There are the carbon fiber of vanadic sulfide nanometer sheet, the vanadic sulfide nanometer sheet to be supported on carbon fiber surface in rose-shaped, formation vanadic sulfide
Nanometer sheet assembly；Wherein the concentration of sodium vanadate is not less than 20g/L, and the concentration of thioacetamide is not less than 30g/L；
(2) the vanadic sulfide nanometer sheet assembly drying that step (1) obtains is placed on to the mixing of Tris and Dopamine hydrochloride
In solution, Dopamine hydrochloride occurs self-polymeric reaction and forms poly-dopamine under stirring condition, and the poly-dopamine be coated on it is described
Vanadic sulfide nanometer sheet assembly surface obtains the nanometer sheet assembly of poly-dopamine cladding；
(3) the nanometer sheet assembly of the poly-dopamine cladding obtained step (2) is in the inert gas gas not less than 600 DEG C
It is calcined in atmosphere, obtains nitrogen-doped carbon cladding vanadic sulfide/vanadium carbide composite nano plate assembly.
Preferably, a concentration of 20~40g/L of step (1) sodium vanadate, a concentration of 30~60g/L of thioacetamide.
Preferably, a concentration of 25~35g/L of step (1) sodium vanadate, a concentration of 40~50g/L of thioacetamide.
Preferably, the temperature of step (1) described hydro-thermal reaction is 140~180 DEG C, and the reaction time is 20~30 hours.
Preferably, the temperature of step (1) described hydro-thermal reaction is 160~170 DEG C, and the reaction time is 24~26h.
Preferably, the pH of the mixed solution of step (2) Tris and Dopamine hydrochloride is 8.5.
Preferably, in step (3) Tris and Dopamine hydrochloride mixed solution Dopamine hydrochloride a concentration of 2~4mg/
ML, self-polymeric reaction time are 24~48h, 10~35 DEG C of reaction temperature.
Preferably, the flow of step (3) described inert gas is 80~120 standard milliliters/minute.
Preferably, step (3) described inert gas is argon gas or helium, and calcination temperature is 600~1000 DEG C, soaking time
For 1~3h.
Other side according to the invention provides a kind of nitrogen-doped carbon cladding vanadic sulfide/vanadium carbide composite nano plate
Assembly, using carbon fiber as matrix, to grow vanadic sulfide/vanadium carbide of lamellar structure in the carbon fiber substrate surface in situ
The assembly that hetero-junctions is formed, the assembly is in rose-shaped.
Preferably, the thickness of the lamella is 20~30nm, and length is 3~5 μm, and width is 4~6 μm.
Preferably, carbon content is 15.2~26.7wt% in the assembly, and nitrogen content is 0.5~2.3wt%, sulfur content
For 35.2~45.7wt%, surplus is vanadium.
It is compound to provide a kind of nitrogen-doped carbon cladding vanadic sulfide/vanadium carbide for other side according to the invention
The application of nanometer sheet assembly is used to prepare self-supporting flexible electrode.
In general, through the invention it is contemplated above technical scheme is compared with the prior art, can obtain down and show
Beneficial effect：
(1) the present invention provides a kind of rose-shaped nitrogen-doped carbon cladding vanadic sulfide/vanadium carbide composite nano plate assemblings
The preparation method of body is prepared based on hydro-thermal method assembling and high temperature cabonization processing, is first synthesized by hydro-thermal method rose-shaped
Vanadic sulfide assembly, then using dopamine D A autohemagglutinations formed poly-dopamine PDA be coated on vanadic sulfide assembly surface, finally
High-temperature calcination is carried out, forms the heterojunction structure of vanadic sulfide and vanadium carbide, on the other hand, the carbon-coating of N doping is coated on vulcanization
The surface of vanadium/vanadium carbide hetero-junctions, preparation method is simple, reproducible, and applicability is extensive, can be mass-produced.
(2) it is needed in the preparation process of nitrogen-doped carbon of the present invention cladding vanadic sulfide/vanadium carbide composite nano plate assembly pair
Integrated artistic design, reaction condition (such as reactant concentration, reaction temperature, reaction time) progress of each step of preparation process
Especially optimization and selection, each step coordinated could be made with high surface area, specific rose-shaped and heterojunction structure
Assembly materials.
(3) nitrogen-doped carbon provided by the invention coats vanadic sulfide/vanadium carbide composite nano plate assembly materials, nanoscale twins
Surface area is big, and being used as catalysis and energy storage material has good catalytic performance；The material has special heterojunction structure, stablizes
Property is strong；Carbon coating can significantly improve the poorly conductive of the transient metal sulfide nanometer sheet of the prior art, bio-compatible again simultaneously
Property difference defect.
(4) present invention can be prepared a kind of with new using simple reaction step and low-cost chemical raw material
The composite material of type nanostructure, the material structure are similar to rose in nature, can support, be not easy in substrate material surface
Cave in, with the abundant active site of larger specific surface area and surface, basis material be intensity it is high, it is flexible, flexible and
Length can be arbitrarily adjusted carbon fiber, and the assembly being prepared can be used for preparing self-supporting flexible electrode, be deposited in catalysis, energy
Storage has broad application prospects with conversion and optical electrical devices field.
Description of the drawings
Fig. 1 is the photo and scanning electron microscope diagram of the carbon fiber substrate material used in the embodiment of the present invention 2.
Fig. 2 is the rose-shaped NC claddings VS that embodiment 2 is grown in carbon fiber surface2/ VC nanometer sheet assemblies are swept
Retouch electron microscope picture.
Fig. 3 is the rose-shaped NC claddings VS that embodiment 2 is grown in carbon fiber surface2/ VC nanometer sheet assemblies are swept
Retouch electron microscope picture.
Fig. 4 is that NC prepared by the embodiment of the present invention 2 coats VS2/ VC composite nano plate transmission electron microscope figures.
Fig. 5 (A) is that NC prepared by the embodiment of the present invention 2 coats VS2The x-ray photoelectron spectroscopy figure of/VC composite nano plates；
Fig. 5 (B) is that NC prepared by the embodiment of the present invention 2 coats VS2The x-ray photoelectron spectroscopy figure of the V 2p of/VC composite nano plates；Figure
5 (C) are that NC prepared by the embodiment of the present invention 2 coats VS2The x-ray photoelectron spectroscopy figure of the S 2p of/VC composite nano plates；Fig. 5
(D) it is that NC prepared by the embodiment of the present invention 2 coats VS2The x-ray photoelectron spectroscopy figure of the C 1s of/VC composite nano plates.
Fig. 6 is that NC prepared by the embodiment of the present invention 2 coats VS2The X ray diffracting spectrum of/VC composite nano plates.
Fig. 7 is that NC prepared by the embodiment of the present invention 2 coats VS2/ VC composite nano plates are as electro-catalysis hydrogen peroxide sensor
Application effect figure.
Specific implementation mode
In order to make the purpose , technical scheme and advantage of the present invention be clearer, with reference to the accompanying drawings and embodiments, right
The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and
It is not used in the restriction present invention.As long as in addition, technical characteristic involved in the various embodiments of the present invention described below
It does not constitute a conflict with each other and can be combined with each other.
The present invention provides a kind of nitrogen-doped carbons ((nitrogen-doped carbon, NC, NC)) to coat vanadic sulfide
(VS2The preparation method of)/vanadium carbide (VC) composite nano plate assembly, includes the following steps：
(1) carbon fiber is placed in sodium vanadate Na3VO4With the mixed aqueous solution of thioacetamide (Thioacetamide, TAA)
Middle generation hydro-thermal reaction, generating load has the carbon fiber of vanadic sulfide nanometer sheet, the vanadic sulfide nanometer sheet to be supported on carbon fiber surface
Face is in rose-shaped, forms vanadic sulfide nanometer sheet assembly, the vanadic sulfide nanometer sheet is in rose-shaped.
Carbon fiber is placed in sodium vanadate Na3VO4With the mixed aqueous solution of thioacetamide (Thioacetamide, TAA), tool
Body modes of emplacement is that suspension is placed or other can be such that carbon fiber places vertically and the mode in mixed solution.Carbon fiber uses
The carbon fiber of Fuel Cell Earth, USA companies production, the carbon fiber strength is high, flexible, flexible, and length can be arbitrary
It adjusts, the present invention uses 2~5cm of length, the carbon fiber that 10 microns of diameter.The dense of sodium vanadate and thioacetamide is found in experiment
Degree cannot be too small, and the vanadic sulfide lamella otherwise formed is not only small but also accumulation is serious, cannot form ideal rose-shaped tool
There is the vanadic sulfide lamella of high surface area.For this purpose, sodium vanadate Na3VO4Concentration be not less than 20g/L, the concentration of thioacetamide is low
In 30g/L；Sodium vanadate Na3VO4A concentration of 20~40g/L, preferably 25~35g/L thioacetamides a concentration of 30~
60g/L, preferably 40~50g/L.The temperature of hydro-thermal reaction is 140~180 DEG C, and preferably 160~170 DEG C, the reaction time is
20~30 hours preferably 24~26h.
(2) the vanadic sulfide nanometer sheet assembly drying that step (1) obtains is placed on and (is specially soaked in) Tris (Tris
That is trishydroxymethylaminomethane) and the mixed solution of Dopamine hydrochloride in, under stirring condition Dopamine hydrochloride occur self-polymeric reaction
Poly-dopamine is formed, and the poly-dopamine is coated on the vanadic sulfide nanometer sheet assembly surface, obtains poly-dopamine cladding
Nanometer sheet assembly；Autohemagglutination formed poly-dopamine be in order to final assembly provide carbon source, the poly-dopamine formed here
On the one hand thickness can consume in next step is calcined to form the hetero-junctions of vanadium carbide and vanadic sulfide, another aspect carbon is also used for shape
Increase capacitance at the carbon coated shell of final assembly to improve the electric conductivity of assembly.For this purpose, the self-polymeric reaction time should not be too
It is short, and the concentration of dopamine cannot be below 2mg/mL, the carbon layers having thicknesses otherwise formed are small.The pH of Tris and Dopamine hydrochloride solution
It is 8.5.A concentration of 2~4mg/mL of Dopamine hydrochloride in Tris and Dopamine hydrochloride mixed solution, self-polymeric reaction time are 24
~48h, 10~35 DEG C of reaction temperature.
(3) the nanometer sheet assembly of the poly-dopamine cladding obtained step (2) is in the inert gas gas not less than 600 DEG C
It is calcined in atmosphere, obtains nitrogen-doped carbon cladding vanadic sulfide/vanadium carbide composite nano plate assembly.Inert gas is argon gas or helium
Gas, in order to ensure the formation of vanadium carbide and hetero-junctions, not preferably less than 600 DEG C of calcination temperature, ideal calcination temperature is 600~
1000 DEG C, the reaction time is 1~3h.The flow of inert gas is 80~120 standard milliliters/minute.
A kind of nitrogen-doped carbon provided by the invention coats vanadic sulfide/vanadium carbide composite nano plate assembly, according to above-mentioned side
Method is prepared, using carbon fiber as matrix, to grow vanadic sulfide/vanadium carbide of lamellar structure in carbon fiber substrate surface in situ
The assembly that hetero-junctions is formed, the assembly is in rose-shaped.Preferably, the thickness of the lamella is 20~30nm, length
It it is 3~5 μm, width is 4~6 μm.Carbon content is 15.2~26.7wt% in assembly, and nitrogen content is 0.5~2.3wt%, sulphur
Content is 35.2~45.7wt%, and surplus is vanadium.It is available that the nitrogen-doped carbon coats vanadic sulfide/vanadium carbide composite nano plate assembly
In the flexible electrode for preparing self-supporting, for catalysis, energy stores and conversion and optical electrical devices field.
The present invention is prepared for rose-shaped nitrogen-doped carbon cladding vulcanization in conjunction with carbonization using simple hydro-thermal method for the first time
Vanadium/vanadium carbide composite nano plate assembly, rose-shaped nanometer sheet assembly structure prepared by hydro-thermal method increase effectively material
The surface area of material, while N doping carbon-coating is formed using carbonization and is coated on vfanadium compound nanometer sheet surface, improve its electric conductivity
And stability, increase the active site on its surface.What is more important, in carbonisation, the surface meeting of vanadic sulfide nanometer sheet
Carbonization vanadium layers are converted into, special vanadic sulfide/vanadium carbide hetero-junctions is formed, which assembles bulk heterojunction by two different
Semiconductor single crystal material forms, and has a series of excellent physics, chemical property and unique architectural characteristic, such as rectification, light
Volt property and optical waveguide effect, can support much bigger current density, and the problems of electromigration of traditional integrated circuit is not present；It is different
The connection of matter knot is more reliable, of less demanding to lattice match, can build small size device etc..Therefore, this research and design and system
It is multiple that standby rose-shaped nitrogen-doped carbon cladding vanadic sulfide/vanadium carbide composite nano plate assembly will widen transition metal significantly
The application field and application mode for closing nanometer sheet, generate significant Social benefit and economic benefit.
It is embodiment below：
Embodiment 1
A kind of preparation method of rose-shaped nitrogen-doped carbon cladding vanadic sulfide/vanadium carbide composite nano plate assembly, packet
Include following steps：
(1) it is 2cm carbon fibers as the rose-shaped VS of matrix growth in situ using length2Nanometer sheet assembly materials.By carbon fiber
Dimension is placed in 20mg/mL Na3VO4In 30mg/mL TAA mixing precursor water solutions, it is evenly stirred until clarification, hangs on stainless
In steel reaction kettle, it is placed in 140 DEG C of baking ovens and hydro-thermal reaction occurs, reaction time 20h；
(2) the obtained load in step (1) there is into VS2Carbon fiber drying after be soaked in 2mg/mLTris hydrochloric acid DOPA
Amine mixed solution (pH 8.5), it is 10 DEG C to be stirred continuously in temperature, and for 24 hours, DA autohemagglutinations formation PDA is coated on rose-shaped for reaction
VS2Nanometer sheet surface；
(3) it is 80 standard milliliters/minute argon gas in throughput by PDA cladding nanometer sheet assemblies obtained in step (2)
600 DEG C of calcining 1h can prepare NC claddings VS in environment2- VC composite nano plate assemblies, VS2Hetero-junctions is formed with the interfaces VC.
Be prepared nitrogen-doped carbon cladding vanadic sulfide/vanadium carbide composite nano plate assembly be using carbon fiber as matrix,
The assembly that vanadic sulfide/vanadium carbide hetero-junctions of lamellar structure is formed is grown in carbon fiber substrate surface in situ, which is in
Rose-shaped, vanadic sulfide/vanadium carbide is in sheet；The thickness of lamella is 20~30nm, and length is 3~5 μm, and width is 4~6 μ
m.Carbon content is 15.2wt% in assembly, and nitrogen content 0.5wt%, sulfur content 45.7wt%, surplus is vanadium.The N doping
Carbon coating in rose-shaped VS2- VC hetero-junctions can be used for being catalyzed as the flexible electrode of self-supporting, energy stores and conversion and
Optical electrical devices field.
Embodiment 2
A kind of preparation method of rose-shaped nitrogen-doped carbon cladding vanadic sulfide/vanadium carbide composite nano plate assembly, packet
Include following steps：
(1) it is 2cm carbon fibers as the rose-shaped VS of matrix growth in situ using length2Nanometer sheet assembly materials.By carbon fiber
Dimension is placed in 30mg/mL Na3VO4In 40mg/mL TAA mixing precursor water solutions, it is evenly stirred until clarification, hangs on stainless
It in steel reaction kettle, is placed in 160 DEG C of baking ovens and reacts, the reaction time is for 24 hours；
(2) the obtained load in step (1) there is into VS2Carbon fiber drying after be soaked in 2mg/mLTris hydrochloric acid DOPA
Amine mixed solution (pH 8.5), it is 20 DEG C to be stirred continuously in temperature, and for 24 hours, DA autohemagglutinations formation PDA is coated on rose-shaped for reaction
VS2Nanometer sheet surface；
(3) it is 100 standard milliliters/minute argon gas in throughput by PDA cladding nanometer sheet assemblies obtained in step (2)
800 DEG C of calcining 2h can prepare NC claddings VS in environment2- VC composite nano plate assemblies, VS2Hetero-junctions is formed with the interfaces VC.
Be prepared nitrogen-doped carbon cladding vanadic sulfide/vanadium carbide composite nano plate assembly be using carbon fiber as matrix,
The assembly that vanadic sulfide/vanadium carbide hetero-junctions of lamellar structure is formed is grown in carbon fiber substrate surface in situ, which is in
It is rose-shaped；The thickness of lamella is 20~30nm, and length is 3~5 μm, and width is 4~6 μm.Carbon content is in assembly
16.8wt%, nitrogen content 0.8wt%, sulfur content 45.2wt%, surplus are vanadium.The carbon coating of N doping is rose-shaped
VS2- VC hetero-junctions can be used for being catalyzed as the flexible electrode of self-supporting, energy stores and conversion and optical electrical devices field.
Fig. 1 is the photo and scanning electron microscope diagram of the carbon fiber substrate material used in the embodiment of the present invention 2, from figure
1 as can be seen that carbon fiber smooth surface provides VS2 attachment sites, while a carbon fiber is formed by being permitted multi-beam carbon-fiber,
Upper left corner illustration shows that flexible carbon fiber can arbitrary degree of freedom bending.
Fig. 2 and Fig. 3 is the rose-shaped NC claddings VS that embodiment 2 is grown in carbon fiber surface2/ VC nanometer sheet assemblies
Different amplification scanning electron microscope diagram.It can be seen that rose-shaped NC coats VS2/ VC even compacts are supported on
In carbon fiber substrates.
Fig. 4 is that NC prepared by the embodiment of the present invention 2 coats VS2/ VC composite nano plate transmission electron microscope figures, from Fig. 4
It can be seen that VS2/VC spacings of lattice are respectively 0.264nm, the corresponding crystal faces of 0.240nm are respectively (111), (100).
Fig. 5 (A) is that NC prepared by the embodiment of the present invention 2 coats VS2The x-ray photoelectron spectroscopy figure of/VC composite nano plates；
Fig. 5 (B) is that NC prepared by the embodiment of the present invention 2 coats VS2The x-ray photoelectron spectroscopy figure of the V 2p of/VC composite nano plates；Figure
5 (C) are that NC prepared by the embodiment of the present invention 2 coats VS2The x-ray photoelectron spectroscopy figure of the S 2p of/VC composite nano plates；Fig. 5
(D) it is that NC prepared by the embodiment of the present invention 2 coats VS2The x-ray photoelectron spectroscopy figure of the C 1s of/VC composite nano plates.It can be with
Find out that NC coats VS2/ VC composite nano plates contain tetra- kinds of elements of C, N, S, V, and Fig. 5 (B) is it can be seen that V-C, V-S covalent bond
Presence, illustrate to form VS2/ VC hetero-junctions.
Fig. 6 is that NC prepared by the embodiment of the present invention 2 coats VS2The X ray diffracting spectrum of/VC composite nano plates.It can see
Go out VC crystal and is present in NC claddings VS2In/VC composite nano plates.
Obtained NC in step (3) is coated into VS2- VC composite nano plates assembly is immersed under the conditions of 0 DEG C of temperature
3h in 5mM potassium chloropalladates and potassium chloroplatinite precursor solution obtains the NC of the PtPd alloy nano particles modification of ultra-small grain size
Coat VS2/ VC composite nano plates, use it for electrochemical catalysis hydrogen peroxide.Fig. 7 is ultra-small grain size manufactured in the present embodiment
The NC of PtPd alloy nano particles modification coats VS2The application that/VC composite nano plates are sensed as electro-catalysis hydrogen peroxide ,-
0.15V applies the timing ampere phase for being continuously added to various concentration hydrogen peroxide under current potential to the PBS buffer solution (pH about 7.2) of 20ml
Answer curve (Amperometric i-t Curve) and corresponding linear fit curve；The curve shows the ladder-like of rule,
Illustrate response quickly (response time be less than 5s) of the electrode to hydrogen peroxide, sensitivity is 155.7 μ A cm-2mM-1。
Embodiment 3
A kind of preparation method of rose-shaped nitrogen-doped carbon cladding vanadic sulfide/vanadium carbide composite nano plate assembly, packet
Include following steps：
(1) it is 3cm carbon fibers as the rose-shaped VS of matrix growth in situ using length2Nanometer sheet assembly materials.By carbon fiber
Dimension is placed in 30mg/mL Na3VO4In 45mg/mL TAA mixing precursor water solutions, it is evenly stirred until clarification, hangs on stainless
It in steel reaction kettle, is placed in 160 DEG C of baking ovens and reacts, the reaction time is for 24 hours；
(2) the obtained load in step (1) there is into VS2Carbon fiber drying after be soaked in 2mg/mLTris hydrochloric acid DOPA
Amine mixed solution (pH 8.5), it is 10 DEG C to be stirred continuously in temperature, and for 24 hours, DA autohemagglutinations formation PDA is coated on rose-shaped for reaction
VS2Nanometer sheet surface；
(3) it is 100 standard milliliters/minute helium in throughput by PDA cladding nanometer sheet assemblies obtained in step (2)
800 DEG C of calcining 2h can prepare NC claddings VS in environment2- VC composite nano plate assemblies, VS2Hetero-junctions is formed with the interfaces VC.
Be prepared nitrogen-doped carbon cladding vanadic sulfide/vanadium carbide composite nano plate assembly be using carbon fiber as matrix,
The assembly that vanadic sulfide/vanadium carbide hetero-junctions of lamellar structure is formed is grown in carbon fiber substrate surface in situ, which is in
It is rose-shaped；The thickness of lamella is 20~30nm, and length is 3~5 μm, and width is 4~6 μm.Carbon content is in assembly
19.2wt%, nitrogen content 1.3wt%, sulfur content 40.3wt%, surplus are vanadium.The carbon coating of N doping is rose-shaped
VS2- VC hetero-junctions can be used for being catalyzed as the flexible electrode of self-supporting, energy stores and conversion and optical electrical devices field.
Embodiment 4
A kind of preparation method of rose-shaped nitrogen-doped carbon cladding vanadic sulfide/vanadium carbide composite nano plate assembly, packet
Include following steps：
(1) it is 3cm carbon fibers as the rose-shaped VS of matrix growth in situ using length2Nanometer sheet assembly materials.By carbon fiber
Dimension is placed in 40mg/mL Na3VO4In 60mg/mL TAA mixing precursor water solutions, it is evenly stirred until clarification, hangs on stainless
It in steel reaction kettle, is placed in 180 DEG C of baking ovens and reacts, the reaction time is for 24 hours；
(2) the obtained load in step (1) there is into VS2Carbon fiber drying after be soaked in 3mg/mLTris hydrochloric acid DOPA
Amine mixed solution (pH 8.5), it is 10 DEG C to be stirred continuously in temperature, and for 24 hours, DA autohemagglutinations formation PDA is coated on rose-shaped for reaction
VS2Nanometer sheet surface；
(3) it is 100 standard milliliters/minute argon gas in throughput by PDA cladding nanometer sheet assemblies obtained in step (2)
800 DEG C of calcining 2h can prepare NC claddings VS in environment2- VC composite nano plate assemblies, VS2Hetero-junctions is formed with the interfaces VC.
Be prepared nitrogen-doped carbon cladding vanadic sulfide/vanadium carbide composite nano plate assembly be using carbon fiber as matrix,
The assembly that vanadic sulfide/vanadium carbide hetero-junctions of lamellar structure is formed is grown in carbon fiber substrate surface in situ, which is in
It is rose-shaped；The thickness of lamella is 20~30nm, and length is 3~5 μm, and width is 4~6 μm.Carbon content is in assembly
18.6wt%, nitrogen content 1.2wt%, sulfur content 40.1wt%, surplus are vanadium.The carbon coating of N doping is rose-shaped
VS2- VC hetero-junctions can be used for being catalyzed as the flexible electrode of self-supporting, energy stores and conversion and optical electrical devices field.
Embodiment 5
A kind of preparation method of rose-shaped nitrogen-doped carbon cladding vanadic sulfide/vanadium carbide composite nano plate assembly, packet
Include following steps：
(1) it is 4cm carbon fibers as the rose-shaped VS of matrix growth in situ using length2Nanometer sheet assembly materials.By carbon fiber
Dimension is placed in 40mg/mL Na3VO4In 60mg/mL TAA mixing precursor water solutions, it is evenly stirred until clarification, hangs on stainless
In steel reaction kettle, it is placed in 180 DEG C of baking ovens and reacts, reaction time 30h；
(2) the obtained load in step (1) there is into VS2Carbon fiber drying after be soaked in 4mg/mLTris hydrochloric acid DOPA
Amine mixed solution (pH 8.5), it is 35 DEG C to be stirred continuously in temperature, reacts 48h, and DA autohemagglutinations formation DA is coated on rose-shaped
VS2Nanometer sheet surface；
(3) it is 80 standard milliliters/minute argon gas in throughput by PDA cladding nanometer sheet assemblies obtained in step (2)
1000 DEG C of calcining 3h can prepare NC claddings VS in environment2- VC composite nano plate assemblies, VS2Hetero-junctions is formed with the interfaces VC.
Be prepared nitrogen-doped carbon cladding vanadic sulfide/vanadium carbide composite nano plate assembly be using carbon fiber as matrix,
The assembly that vanadic sulfide/vanadium carbide hetero-junctions of lamellar structure is formed is grown in carbon fiber substrate surface in situ, which is in
It is rose-shaped；The thickness of lamella is 20~30nm, and length is 3~5 μm, and width is 4~6 μm.Carbon content is in assembly
20.4wt%, nitrogen content 2.3wt%, sulfur content 38.6wt%, surplus are vanadium.The carbon coating of N doping is rose-shaped
VS2- VC hetero-junctions can be used for being catalyzed as the flexible electrode of self-supporting, energy stores and conversion and optical electrical devices field.
Embodiment 6
A kind of preparation method of rose-shaped nitrogen-doped carbon cladding vanadic sulfide/vanadium carbide composite nano plate assembly, packet
Include following steps：
(1) it is 4cm carbon fibers as the rose-shaped VS of matrix growth in situ using length2Nanometer sheet assembly materials.By carbon fiber
Dimension is placed in 40mg/mL Na3VO4In 60mg/mL TAA mixing precursor water solutions, it is evenly stirred until clarification, is placed in 180 DEG C of bakings
It is reacted in case, reaction time 30h；
(2) the obtained load in step (1) there is into VS2Carbon fiber drying after be soaked in 3mg/mLTris hydrochloric acid DOPA
Amine mixed solution (pH 8.5), it is 25 DEG C to be stirred continuously in temperature, and for 24 hours, DA autohemagglutinations formation PDA is coated on rose-shaped for reaction
VS2Nanometer sheet surface；
(3) it is 120 standard milliliters/minute helium in throughput by PDA cladding nanometer sheet assemblies obtained in step (2)
1000 DEG C of calcining 2h can prepare NC claddings VS in environment2- VC composite nano plate assemblies, VS2Hetero-junctions is formed with the interfaces VC.
Be prepared nitrogen-doped carbon cladding vanadic sulfide/vanadium carbide composite nano plate assembly be using carbon fiber as matrix,
The assembly that vanadic sulfide/vanadium carbide hetero-junctions of lamellar structure is formed is grown in carbon fiber substrate surface in situ, which is in
It is rose-shaped；The thickness of lamella is 20~30nm, and length is 3~5 μm, and width is 4~6 μm.Carbon content is in assembly
18.3wt%, nitrogen content 1.1wt%, sulfur content 39.5wt%, surplus are vanadium.The carbon coating of N doping is rose-shaped
VS2- VC hetero-junctions can be used for being catalyzed as the flexible electrode of self-supporting, energy stores and conversion and optical electrical devices field.
As it will be easily appreciated by one skilled in the art that the foregoing is merely illustrative of the preferred embodiments of the present invention, not to
The limitation present invention, all within the spirits and principles of the present invention made by all any modification, equivalent and improvement etc., should all include
Within protection scope of the present invention.
Claims (10)
1. a kind of preparation method of nitrogen-doped carbon cladding vanadic sulfide/vanadium carbide composite nano plate assembly, which is characterized in that including
Following steps：
(1) carbon fiber is placed in the mixed aqueous solution of sodium vanadate and thioacetamide and hydro-thermal reaction occurs, generating load has sulphur
Change the carbon fiber of vanadium nanometer sheet, the vanadic sulfide nanometer sheet is supported on carbon fiber surface in rose-shaped, formation vanadic sulfide nanometer
Piece assembly；Wherein the concentration of sodium vanadate is not less than 20g/L, and the concentration of thioacetamide is not less than 30g/L；
(2) the vanadic sulfide nanometer sheet assembly drying that step (1) obtains is placed on to the mixed solution of Tris and Dopamine hydrochloride
In, Dopamine hydrochloride occurs self-polymeric reaction and forms poly-dopamine under stirring condition, and the poly-dopamine is coated on the vulcanization
Vanadium nanometer sheet assembly surface obtains the nanometer sheet assembly of poly-dopamine cladding；
(3) the nanometer sheet assembly of the poly-dopamine cladding obtained step (2) is in the inert gas atmosphere not less than 600 DEG C
It is calcined, obtains nitrogen-doped carbon cladding vanadic sulfide/vanadium carbide composite nano plate assembly.
2. preparation method as described in claim 1, which is characterized in that a concentration of 20~40g/L of step (1) sodium vanadate, sulphur
For a concentration of 30~60g/L of acetamide.
3. preparation method as described in claim 1, which is characterized in that the temperature of step (1) described hydro-thermal reaction be 140~
180 DEG C, the reaction time is 20~30 hours.
4. preparation method as described in claim 1, which is characterized in that the mixing of step (2) Tris and Dopamine hydrochloride
The pH of solution is 8.5.
5. preparation method as described in claim 1, which is characterized in that step (3) Tris and Dopamine hydrochloride mixing are molten
A concentration of 2~4mg/mL of Dopamine hydrochloride in liquid, self-polymeric reaction time are 24~48h, 10~35 DEG C of reaction temperature.
6. preparation method as described in claim 1, which is characterized in that the flow of step (3) described inert gas is 80~120
Standard milliliters/minute.
7. preparation method as described in claim 1, which is characterized in that step (3) described inert gas is argon gas or helium, is forged
It is 600~1000 DEG C to burn temperature, and soaking time is 1~3h.
8. a kind of nitrogen-doped carbon coats vanadic sulfide/vanadium carbide composite nano plate assembly, which is characterized in that it is to be with carbon fiber
Matrix grows the assembly that vanadic sulfide/vanadium carbide hetero-junctions of lamellar structure is formed, institute in the carbon fiber substrate surface in situ
Assembly is stated in rose-shaped；Preferably, the thickness of the lamella is 20~30nm, and length is 3~5 μm, and width is 4~6 μm.
9. assembly as claimed in claim 8, which is characterized in that carbon content is 15.2~26.7wt% in the assembly,
Nitrogen content is 0.5~2.3wt%, and sulfur content is 35.2~45.7wt%, and surplus is vanadium.
10. a kind of nitrogen-doped carbon cladding vanadic sulfide/vanadium carbide composite nano plate assembly as claimed in claim 8 or 9 is answered
With, which is characterized in that it is used to prepare self-supporting flexible electrode.
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| CN113925968A (en) * | 2021-10-18 | 2022-01-14 | 上海市第六人民医院 | Multifunctional vanadium carbide/polydopamine nanosheet and preparation method and application thereof |
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