CN106479175B - A kind of preparation method of self-supporting graphene-polyaniline nano-line composite material - Google Patents
A kind of preparation method of self-supporting graphene-polyaniline nano-line composite material Download PDFInfo
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Abstract
The present invention relates to a kind of preparation methods of self-supporting graphene-polyaniline nano-line composite material, graphite oxide is fully dispersed in water, film at self-supporting is filtered after reduction, goes out graphene-polyaniline nano-line composite material with the method growth in situ of three sections of electric currents in the electrolytic solution.Composite material is formed by with multi-level nano-structure.Greatly improve the specific surface area of material.This method simple and reliable process, effectively reduces cost, and is with a wide range of applications.
Description
Technical field
The invention belongs to the preparation field of graphene composite material, in particular to a kind of self-supporting graphene-polyaniline is received
The preparation method of rice noodles composite material.
Background technique
Graphene is studied by scientific circles extensively in recent years as a kind of novel two-dimension nano materials.As a kind of single former
Sub-pieces layer material, it is not only the basic structural unit of construction zero dimension fullerene quantum dot, one-dimensional carbon nanotube, and can be with structure
Make three-dimensional graphite.Due to its unique crystal structure, graphene has many excellent physicochemical properties, such as high mechanics
Performance, thermal conductivity, charge mobility, big specific surface area and unique quantum hall effect etc..Therefore, it is also applied to
Many aspects, including polymer composite, field effect transistor, liquid crystal display, energy stores etc..
Report that doped polyacetylene has metallic conductance (conductivity 10 for the first time from Shirakawa in 1977 etc.3~105S/
Cm since), various conductive high sons such as PPy, PTH, it is poly- to styrene (PPV) and polyaniline (Polyaniline, PANI) and he
Derivative come out one after another.Easy, stability is good because preparing by PANI, is the most organic conjugate conducting polymer of practical application
One of object.By a variety of synthetic technologys such as template synthesis method, self-assembly method, interfacial polymerization can prepare nanometer rods, nanotube,
The polyaniline nano material that nanofiber etc. comes in every shape.Wherein the method for Electrochemical self-assembly is simple, controllable, can be in no template
In the case where directly prepare polyaniline nano-line.With the development of nanosecond science and technology, a polyaniline nano structure especially wiener
The successful preparation of rice structure (such as nano wire, nanotube, nanometer rods) makes it was recognized that nano polyaniline is in electron-transport, light
Learn and unique size and dimensionality effect that mechanics etc. shows, imply polyaniline nano structure nano-sensor, point
The fields such as sub-conductor and the building of photoelectric nano device have wide potential application foreground.
Summary of the invention
Technical problem to be solved by the invention is to provide a kind of self-supporting graphene-polyaniline nano-line composite materials
Preparation method, method is easy, mild condition, is formed by composite material with multi-level nano-structure.Greatly improve material
Specific surface area.This method simple and reliable process, effectively reduces cost, and is with a wide range of applications.
A kind of preparation method of self-supporting graphene-polyaniline nano-line composite material of the invention, comprising:
(1) graphite oxide is added to the water, ultrasonic disperse, obtains graphite oxide dispersion, is then restored, and vacuum is taken out
Filter, obtains the graphene film of self-supporting；
(2) as working electrode after using lauryl sodium sulfate SDS solution to handle the graphene film of above-mentioned self-supporting,
Platinized platinum is used as to electrode, and in the electrolytic solution with the method for three sections of electric currents, growth in situ goes out polyaniline nano-line on graphene, i.e.,
Derived from support graphene-polyaniline nano-line composite material.
The concentration of graphite oxide dispersion is 0.01~1mg/mL in the step (1).
Reduction in the step (1) specifically: under the conditions of magnetic agitation, graphite oxide dispersion is added in hydrazine hydrate and ammonium hydroxide
In liquid, 70~100 DEG C are heated to, and keep 0.5~2h.
Graphene dispersing solution, hydrazine hydrate, ammonium hydroxide volume ratio be 1500~2500:0.5~5:3~7.
The mass percentage concentration of the hydrazine hydrate is 80~85%, the mass percentage concentration of ammonium hydroxide is 20~30%.
Vacuum filtration in the step (1) are as follows: filtered with the pvdf membrane in 0.22 μm of aperture.
The graphene film that self-supporting is obtained in step (1) is annealed reduction at high temperature, specifically: under an argon atmosphere,
0.5~3h, annealing are maintained at 200~500 DEG C of high temperature.
The mass percentage concentration of lauryl sodium sulfate SDS solution is 0.01~5% in the step (2).
Electrolyte is the mixed liquor of aniline and perchloric acid in the step (2), and wherein the concentration of aniline is 0.1 in electrolyte
~1M, perchloric acid concentration be 0.5~1.0M.
The method of three sections of electric currents in the step (2) are as follows: first with 0.1~0.05mA/cm20.1~1h is handled, then with 0.08
~0.03mA/cm22~5h is handled, finally with 0.03~0.01mA/cm2Handle 2~5h.
Self-supporting graphene-application of the polyaniline nano-line composite material in terms of gas sensing.
Beneficial effect
(1) preparation method of the invention is easy, and raw material is easy to get, mild condition；
(2) present invention grows the nano wire of polyaniline, structure-controllable, boundary by in-situ method on graphene-based bottom
Face, which combines, stablizes.
Detailed description of the invention
Fig. 1 is self-supporting graphene-polyaniline nano-line composite material surface scanning electron microscope (SEM) photograph prepared by embodiment 1；
Fig. 2 is self-supporting graphene-polyaniline nano-line composite material section surface sweeping electron microscope prepared by embodiment 1；
Fig. 3 is self-supporting graphene-polyaniline nano-line composite material surface surface sweeping electron microscope prepared by embodiment 3.
Specific embodiment
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate the present invention
Rather than it limits the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, those skilled in the art
Member can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims and limited
Range.
Embodiment 1
At room temperature, graphite oxide 20mg is weighed, is placed in 150mL beaker, then plus deionized water 80mL is made into
Beaker, is then placed in Ultrasound Instrument and is ultrasonically treated 6h by the graphite oxide dispersion of 0.25mg/mL, obtains graphite oxide dispersion
Liquid.
In the state of magnetic agitation, the ammonium hydroxide (25%) of the hydrazine hydrate (80%) and 280 μ L that take 40 μ L is added to oxidation
It is restored in graphite dispersing solution, places into oil bath pan and be heated to 95 DEG C, keep the temperature 1h.By graphite oxide dispersion 0.22nm
The pvdf membrane in aperture is filtered by vacuum, then is cleaned with deionized water, and removing obtains the graphene film of self-supporting.By graphite
Alkene film calcines 1h under argon gas state under the conditions of 400 DEG C, enhance reduction effect.
The graphene film of self-supporting is cleaned with the SDS solution that mass fraction is 1%, makes SDS molecule on area load.With
Stainless steel electrode collet, which is clamped to be put into electrolyte, serves as working electrode.There are 0.5M aniline and 1M perchloric acid in electrolyte.
With platinized platinum when work is to electrode.Use 0.08mA/cm2Current density handle 0.5h, then use 0.04mA/cm23h is handled, is finally used
0.02mA/cm2Processing 3h obtains graphene-polyaniline nano-line composite material.
Fig. 1 is the scanning electron microscope (SEM) photograph of the graphene/polyaniline nano wire of preparation, it will thus be seen that has diameter on graphene
The generation of the polyaniline nano-line of 100nm or so.
Embodiment 2
At room temperature, graphite oxide 20mg is weighed, is placed in 150mL beaker, then plus deionized water 80mL is made into
Beaker, is then placed in Ultrasound Instrument and is ultrasonically treated 6h by the graphite oxide dispersion of 0.25mg/mL, obtains graphite oxide dispersion
Liquid.
In the state of magnetic agitation, the ammonium hydroxide (25%) of the hydrazine hydrate (80%) and 280 μ L that take 40 μ L is added to oxidation
It is restored in graphite dispersing solution, places into oil bath pan and be heated to 95 DEG C, keep the temperature 1h.By graphite oxide dispersion 0.22nm
The pvdf membrane in aperture is filtered by vacuum, then is cleaned with deionized water, and removing obtains the graphene film of self-supporting.By graphite
Alkene film calcines 1h under argon gas state under the conditions of 400 DEG C, enhance reduction effect.
The graphene film of self-supporting is cleaned with the SDS solution that mass fraction is 1%, makes SDS molecule on area load.With
Stainless steel electrode collet, which is clamped to be put into electrolyte, serves as working electrode.There are 0.5M aniline and 1M perchloric acid in electrolyte.
With platinized platinum when work is to electrode.Use 0.04mA/cm2Current density handle 6.5h, as a result on graphene there is no polyaniline nano
The generation of line.
Embodiment 3
At room temperature, graphite oxide 20mg is weighed, is placed in 150mL beaker, then plus deionized water 80mL is made into
Beaker, is then placed in Ultrasound Instrument and is ultrasonically treated 6h by the graphite oxide dispersion of 0.25mg/mL, obtains graphite oxide dispersion
Liquid.
In the state of magnetic agitation, the ammonium hydroxide (25%) of the hydrazine hydrate (80%) and 280 μ L that take 40 μ L is added to oxidation
It is restored in graphite dispersing solution, places into oil bath pan and be heated to 95 DEG C, keep the temperature 1h.By graphite oxide dispersion 0.22nm
The pvdf membrane in aperture is filtered by vacuum, then is cleaned with deionized water, and removing obtains the graphene film of self-supporting.By graphite
Alkene film calcines 1h under argon gas state under the conditions of 400 DEG C, enhance reduction effect.
The graphene film of self-supporting is cleaned with the SDS solution that mass fraction is 1%, makes SDS molecule on area load.With
Stainless steel electrode collet, which is clamped to be put into electrolyte, serves as working electrode.There are 0.5M aniline and 1M hydrochloric acid in electrolyte.With
Platinized platinum is when work is to electrode.Use 0.08mA/cm2Current density handle 0.5h, then use 0.04mA/cm23h is handled, is finally used
0.02mA/cm2Processing 3h obtains graphene-polyaniline nano-line composite material.Fig. 3 is that the graphene/polyaniline of preparation is received
The scanning electron microscope (SEM) photograph of rice noodles, it will thus be seen that have the generation of the polyaniline nano-line of diameter 100nm or so on graphene.
Claims (3)
1. a kind of preparation method of self-supporting graphene-polyaniline nano-line composite material, comprising:
(1) graphite oxide is added to the water, ultrasonic disperse, obtains graphite oxide dispersion, is then restored, and vacuum filtration obtains
To the graphene film of self-supporting；The graphene film that self-supporting is wherein obtained in step (1) is annealed reduction at high temperature, specifically
Are as follows: under an argon atmosphere, 0.5 ~ 3 h, annealing are maintained at 200 ~ 500 DEG C of high temperature；Graphite oxide dispersion is dense in step (1)
Degree is 0.01 ~ 1 mg/mL；Reduction specifically: under the conditions of magnetic agitation, graphite oxide dispersion is added in hydrazine hydrate and ammonium hydroxide
In, 70 ~ 100 DEG C are heated to, and keep 0.5 ~ 2 h；Graphite oxide dispersion, hydrazine hydrate, ammonium hydroxide volume ratio be 1500 ~
2500: 0.5 ~ 5:3 ~ 7, hydrazine hydrate mass percentage concentration are 80 ~ 85%, and ammonium hydroxide mass percentage concentration is 20 ~ 30%；
(2) as working electrode, platinized platinum after using lauryl sodium sulfate SDS solution to handle the graphene film of above-mentioned self-supporting
As to electrode, in the electrolytic solution with the method for three sections of electric currents, growth in situ goes out polyaniline nano-line to get certainly on graphene
Support graphene-polyaniline nano-line composite material；Wherein the mass percentage concentration of lauryl sodium sulfate SDS solution is 0.01
~5 %；The wherein method of three sections of electric currents are as follows: first with 0.1 ~ 0.08 mA/cm20.1 ~ 1h is handled, then with 0.04 ~ 0.03 mA/cm2Place
2 ~ 5h is managed, finally with 0.02 ~ 0.01 mA/cm2Handle 2 ~ 5 h.
2. a kind of preparation method of self-supporting graphene-polyaniline nano-line composite material according to claim 1, special
Sign is: in the step (2) electrolyte be aniline and perchloric acid mixed liquor, wherein in electrolyte aniline concentration be 0.1 ~
1 M, perchloric acid concentration be 0.5 ~ 1.0 M.
3. prepared by a kind of preparation method of self-supporting graphene-polyaniline nano-line composite material according to claim 1
Obtained self-supporting graphene-application of the polyaniline nano-line composite material in terms of gas sensing.
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Inventor after: Li Linpeng Inventor after: Wang Hongzhi Inventor after: Hou Chengyi Inventor after: Li Yaogang Inventor after: Zhang Qinghong Inventor before: Wang Hongzhi Inventor before: Li Linpeng Inventor before: Hou Chengyi Inventor before: Li Yaogang Inventor before: Zhang Qinghong |
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