CN104071780A - Preparation method of controllable-layer-number graphene - Google Patents
Preparation method of controllable-layer-number graphene Download PDFInfo
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- CN104071780A CN104071780A CN201410289271.3A CN201410289271A CN104071780A CN 104071780 A CN104071780 A CN 104071780A CN 201410289271 A CN201410289271 A CN 201410289271A CN 104071780 A CN104071780 A CN 104071780A
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Abstract
The invention relates to a preparation method of controllable-layer-number graphene, which comprises the following steps: putting amorphous carbide in a heating furnace, introducing inert gas to expel air under ordinary pressure, starting quick heating, and introducing halogen gas or halogen-containing gas while keeping the inert gas flow rate when the temperature reaches 200-1400 DEG C, wherein the halogen gas or halogen-containing gas reacts with the non-carbon element in the carbide to form halide which is discharged, thereby leaving the carbon element material; and after the reaction is finished, on the premise of keeping the temperature constant, stopping introducing the halogen gas or halogen-containing gas, keeping introducing the inert gas to remove the remnant halide gas and reaction byproduct, and cooling room temperature in the inert gas atmosphere. The method can satisfy the requirements of different fields for different layer numbers of graphene; the adhesive force between the graphene and substrate is small, so that the graphene can be conveniently peeled from the substrate; and the reaction can be performed under ordinary pressure and milder conditions.
Description
Technical field
The present invention relates to the preparation method of the controlled Graphene of a kind of number of plies, be applicable to prepare on a large scale the Graphene that the number of plies can be controlled.
Technical background
Since within 2004, preparing Graphene by the method for mechanically peel [1], because Graphene has excellent electronic mobility, high theoretical specific surface area, high heat-conductivity conducting rate and high chemical stability, and become the focus of research.[2-5] these excellent and unique performances make Graphene aspect Energy conversion and storage, have huge application prospect, as fields such as fuel-cell catalyst, photochemical catalysis and solar cell materials.[4，5]
For these excellent character of Graphene being applied to practice, the controlled Graphene of the synthetic number of plies of large-scale low-cost is prerequisite.In recent years, researchist has proposed a lot of methods for the synthesis of Graphene.As first mechanically peel is put forward for the synthesis of Graphene, but this method hardly may expanding production [1]; By liquid phase, being disperseed and peeled off the method for graphene oxide also can be for the synthesis of Graphene [6-8], but the prepared Graphene number of plies of this method cannot accurately be controlled, and graphene sheet layer is easy to be stacked into 10 layers and forms above graphite linings, thereby lose the excellent properties of Graphene; On the surface of some transition metal (as copper sheet), can prepare individual layer or which floor Graphene by chemical Vapor deposition process, but this method energy consumption is very high.[9]; Under high temperature and ultrahigh vacuum(HHV), the particular crystal plane graphite with high directed crystal SiC can be turned to the controlled Graphene of the number of plies [10-15], this epitaxial growth method is brought Graphene growth into brand-new field, but this method needs the directed SiC of almost ideal height and very harsh synthesis condition (as 1250 degrees Celsius of above and high vacuum of high temperature) [10-16], in addition between synthetic Graphene and SiC substrate, have very strong bonding force, this has limited the further application of Graphene.In recent years, have been reported decolorizing carbon compound and can under low-temperature atmosphere-pressure, be halogenated and become Graphene [16], but there is no accurately controlled research of the number of plies.
Contriver finds in research process, adopts halogen process, and the temperature of reacting by adjusting, time, (decolorizing carbon compound is a-M to carbide composition
1-xc
xx value) or the concentration of reactant gases realize the object of the precision regulating Graphene number of plies.In addition, decolorizing carbon compound is isotropy, do not need as crystalline state SiC high directed, therefore reaction conditions can be normal pressure, minimum temperature can be low to moderate 200 ℃, reaction times can be controlled in 4 hours, and output can expand by the scale of simple expansion stove, and the synthetic number of plies that therefore can large-scale low-cost is adjustable Graphene accurately.At present, not yet there is the relevant report of synthesizing the Graphene that the number of plies can accuracy controlling with halogen process.
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[3].Novoselov,K.S.,et?al.Two-dimensional?gas?of?massless?Dirac?fermions?in?graphene.Nature438,197-200(2005).
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[5]Yin,Z.,et?al.Graphene-Based?Materials?for?Solar?Cell?Applications.Adv.Energy?Mater.2013,doi:10.1002/aenm.201300574
[6].Hernandez,Y.,et?al,High-yield?Production?of?graphene?by?liquid-phase?exfoliation.Nature?Nanotech.3,563-568(2008).
[7].Stankovich,S.,et?al.Graphene-based?composite?materials.Nature442,282–286(2006).
[8]Lotya,M.,et?al.Liquid?Phase?Production?of?Graphene?by?Exfoliation?of?Graphite?in?Surfactant/Water?Solutions.J.Am.Chem.Soc.131,3611(2009).
[9].Li,X.,et?al.Large-Area?Synthesis?of?High-Quality?and?Uniform?Graphene?Films?on?Copper?Foils.Science324,1312-1314(2009).
[10].Bolen,M.L.,et?al.Graphene?formation?mechanisms?on?4H-SiC(0001).Phys.Rev.B80,115433(2009).
[11].Forbeaux,I.,et?al.Heteroepitaxial?graphite?on6H-SiC(0001):Interface?formation?through?conduction-band?electronic?structure.Phys.Rev.B58,16396-16406(1998).
[12].Virojanadara,C.,et?al.Homogeneous?large-area?graphene?layer?growth?on6H-SiC(0001).Phys.Rev.B.78,245403(2008),.
[13].Kim,S.,et?al.Origins?of?anomalous?electronic?structures?of?epitaxial?graphene?on?silicon?carbide.Phys.Rev.Lett.100,176802(2008).
[14].Deng,D.,et?al.Freestanding?Graphene?by?Thermal?Splitting?of?Silicon?Carbide?Granules.Adv.Mater.22,2168–2171(2010),.
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Summary of the invention
A kind of method of decolorizing carbon compound being prepared under halogenation gas condition to the Graphene that the number of plies can accuracy controlling is provided herein.
The present invention solves the problems of the technologies described above adopted technical scheme: the preparation method of the controlled Graphene of a kind of number of plies, includes following steps:
(1) decolorizing carbon compound is put into process furnace, under normal pressure, pass into rare gas element with excluding air, then start rapid heating, when temperature reaches after 200～1400 ℃, under the condition of maintenance rare gas element gas flow, pass into the gas of halogen gas or halogen-containing element, it reacts formation halogenide and discharges with the non-carbon in carbide, thereby leaves carbon material;
(2) after question response completes, keep under temperature-resistant prerequisite, stop passing into the gas of halogen gas or halogen-containing element, what keep rare gas element passes into remove remaining halide gas and byproduct of reaction, then under inert gas atmosphere, temperature is cooled to room temperature, finally obtains the sample that contains Graphene.
Press such scheme, the general formula of described decolorizing carbon compound is a-M
1-xc
x, wherein M represents Si, Ti, Al, Mo, Ta, Zr, B or W element, and 0<x<1.
Press such scheme, described x span is 0.3～0.7.
Press such scheme, described halogen gas is F
2, Cl
2, Br
2and I
2any one in gas or their mixing.
Press such scheme, the gas of described halogen-containing element is HF or HCl gas.
Press such scheme, the described reaction times is 5 minutes～200 minutes.
Press such scheme, the flow range of described halogen gas or the gas of halogen-containing element is 20ml/min～500ml/min.
The concrete pattern of decolorizing carbon compound involved in the present invention does not require, film (comprising nanometer, micron and macroscopical film), particle (particle diameter is not required, comprise nanometer, micron and macroscopic particles), macroscopical block etc. all can react and prepare Graphene.
(changing decolorizing carbon compound is a-M for the temperature that the number of plies of the Graphene that the present invention is prepared can be reacted by adjusting, time, carbide composition
1-xc
xx value, 0<x<1) or the concentration of reactant gases or flow precisely controlled.
Compare with existing background technology, the present invention has the following advantages:
1, (decolorizing carbon compound is a-M for the temperature that the number of plies of Graphene can be reacted by adjusting, time, carbide composition
1-xc
xx value) or the concentration of reactant gases obtain accuracy controlling, can meet the requirement that different field is different to the Graphene number of plies.
2, decolorizing carbon compound is converted into after Graphene, and the sticking power between Graphene and substrate is less, is convenient to peel off from substrate.
3, can react under to gentle condition at Atmospheric Phase, and minimum temperature of reaction is 200 ℃ the shortest can being controlled in 4 hours of reaction times.
4, halogenation is the mode of production of a kind of economy and easy extension, and has had factory to produce carbide derivative by the method for halogenation, so halogenation is applied to produce Graphene, is easy to scale operation.
Accompanying drawing explanation
Fig. 1 is high-resolution-ration transmission electric-lens (HRTEM) picture of TiC in embodiment 1;
Fig. 2 is embodiment 1 gained Graphene HRTEM picture;
Fig. 3 is embodiment 1 gained Graphene HRTEM picture;
Fig. 4 is embodiment 3 gained Graphene HRTEM pictures;
Fig. 5 is embodiment 5 gained Graphene HRTEM pictures;
Fig. 6 is embodiment 5 gained Graphene HRTEM pictures;
Fig. 7 is Raman (Raman) spectrum of gained Graphene in embodiment 1 to 5;
Fig. 8 is the 2D peak of the Raman spectrum of gained Graphene in embodiment 1 to 5;
Fig. 9 is embodiment 9 gained Graphene HRTEM pictures;
Embodiment
Step 1: will contain decolorizing carbon compound and put into stove good seal, and check resistance to air loss, logical rare gas element (He, Ar etc.) half an hour is with excluding air under an atmospheric condition.Keep passing into rare gas element heating, after temperature reaches 200～1400 ℃ of desired reaction temperatures (temperature rise rate can be controlled arbitrarily), at the halogenation gas that keeps passing under the condition of certain inert gas flow given pace.
Step 2: after having reacted in step 1, keep under temperature-resistant prerequisite, the gas of turning off halogen gas or containing halogens, but to keep 0.5 hour or time that passes into of above rare gas element to go out remaining halogenation gas and byproduct of reaction.
Step 3: keep, under inert gas atmosphere, stove to be cooled to room temperature, rate of temperature fall can be controlled arbitrarily, finally obtains the sample of the Graphene that the number of plies can accuracy controlling.
Below in conjunction with embodiment, the present invention will be further described in detail, but this explanation can not be construed as limiting the invention.
Embodiment 1
Take 2g surface and there is amorphous nanoshell a-Ti
0.4c
0.6nano SiC, put it in silica tube after good seal, flow with 500ml/min passes into high-purity He gas 30 minutes to get rid of the air in silica tube, stove is heated to 200 degrees Celsius, keeping under the prerequisite that He gas flow is 100ml/min, the flow with 500ml/min during reaction passes into Cl
2gas, question response carries out stopping passing into Cl after one hour
2gas and keep He gas to pass into, keeps 200 ℃ of temperature of reaction to be down to room temperature after one hour and can obtain the nano particle that surface has the graphene-structured of 1 to 3 layer.Fig. 1 is the surperficial images of transmissive electron microscope (TEM) with the nano TiC of amorphous nano thin-film; If Fig. 2 is the images of transmissive electron microscope that in embodiment 1,200 ℃ of halogenation rear surfaces have the nano particle of 2 layer graphene structures, wherein the crystalline state TiC of nano-TiC particle inside still retains; Figure 3 shows that in embodiment 1 that 200 ℃ of halogenation rear surfaces have the images of transmissive electron microscope of the nano particle of 1-3 layer graphene structure, wherein the crystalline state TiC of nano-TiC particle inside is also converted into amorphous C.
Embodiment 2
Preparation process in the present embodiment and step are identical with above-described embodiment 1.Different: temperature of reaction is 400 ℃.Finally can obtain the nano particle that surface has the graphene-structured of layer 2-4.
Embodiment 3
Preparation process in the present embodiment and step are identical with above-described embodiment 1.Different: temperature of reaction is 600 ℃.Finally can obtain the nano particle that surface has the graphene-structured of 4-5 layer.Fig. 4 is that in embodiment 3,600 ℃ of halogenation surfaces have after the nano TiC of amorphous nanoshell, and surface has the images of transmissive electron microscope of the nano particle of 5 layer graphene structures;
Embodiment 4
Preparation process in the present embodiment and step are identical with above-described embodiment 1.Different: temperature of reaction is 800 ℃.Finally can obtain the nano particle that surface has the graphene-structured of 6-7 layer.
Embodiment 5
Preparation process in the present embodiment and step are identical with above-described embodiment 1.Different: temperature of reaction is 1000 ℃.Finally can obtain the nano particle that surface has the graphene-structured of 7-8 layer.Fig. 5 is that in embodiment 5,1000 ℃ of halogenation surfaces have after the nano TiC of amorphous nanoshell, and surface has the images of transmissive electron microscope of the nano particle of 8 layer graphene structures; Fig. 6 is that halogenation surface has the Graphene after the nano TiC of amorphous nano thin-film, the nano-graphene lamella after peeling off; Fig. 7 is at identical chlorine gas concentration and reaction times same sample, (embodiment 1-5) reacted Raman collection of illustrative plates under differing temps, and the enlarged view of the inside shows the variation at 2D peak, from 2673.3cm
-1(200 ℃), 2674.4cm
-1(400 ℃), 2679.1cm
-1(600 ℃), 2680.7cm
-1(800 ℃) are to 2686.5cm
-1(1000 ℃). the displacement at peak is that the increase due to the Graphene number of plies causes, and such variation and the variation of Fig. 2-5 are proved each other; Fig. 8 is that 2D peak enlarged view (embodiment 1-5) .2D is by two interior peak 2D
1(2670cm
-1) and 2D
2(2691cm
-1) form 2D
1(2670cm
-1) area percentage along with temperature of reaction increases and reduces, contrary 2D
2(2691cm
-1) area percentage along with temperature increase to increase, this surperficial Graphene number of plies increases along with temperature.
Embodiment 6
Preparation process in the present embodiment and step are identical with above-described embodiment 1.Different: temperature of reaction is 1200 ℃.Finally can obtain the nano particle that surface has the graphene-structured of 9-10 layer.
Embodiment 7
Preparation process in the present embodiment and step are identical with above-described embodiment 1.Different: to take 2g a-Zr
0.3c
0.7, temperature of reaction is 800 ℃.Finally can obtain the nano particle that surface has the graphene-structured of 6-8 layer.
Embodiment 8
Preparation process in the present embodiment and step are identical with above-described embodiment 1.Different: to take 2g surface and there is amorphous nanoshell a-Ti
0.4c
0.6micron TiC, temperature is 400 ℃, during reaction, the flow of He gas is 100ml/min, Cl
2the flow of gas is 300ml/min.Finally can obtain the micron particle of the graphene-structured that surperficial tool is of five storeys.
Embodiment 9
Preparation process in the present embodiment and step are identical with above-described embodiment 1.Different: to take 2g surface and there is amorphous nanoshell a-Ti
0.4c
0.6micron TiC, temperature is 600 ℃, during reaction, the flow of He gas is 100ml/min, Cl
2the flow of gas is 300ml/min.Finally can obtain the micron particle that surface has the graphene-structured of 8 layers.Fig. 9 is that in embodiment 9, halogenation surface has after the micron TiC of amorphous nano thin-film, on the micron particle surface obtaining, has 8 layer graphenes.
Embodiment 10
Preparation process in the present embodiment and step are identical with above-described embodiment 1.Different: to take 2g surface and there is amorphous nanoshell a-Ti
0.3c
0.7nano TiC, temperature is 800 ℃, during reaction, the flow of He gas is 100ml/min, Cl
2the flow of gas is 500ml/min.Finally can obtain the nano particle that surface has 8 layer graphene structures.
Embodiment 11
Preparation process in the present embodiment and step are identical with above-described embodiment 1.Different: to take 2g surface and there is amorphous nanoshell a-Ti
0.3c
0.7nano TiC, temperature is 800 ℃, during reaction, the flow of He gas is 100ml/min, Cl
2the flow of gas is 400ml/min.Finally can obtain the 6 layers of nano particle with graphene-structured in surface.
Embodiment 12
Preparation process in the present embodiment and step are identical with above-described embodiment 1.Different: to take 2g surface and there is amorphous nanoshell a-Ti
0.3c
0.7nano TiC, temperature is 800 ℃, during reaction, the flow of He gas is 100ml/min, Cl
2the flow of gas is 300ml/min.Finally can obtain the 6 layers of nano particle with graphene-structured in surface.
Embodiment 13
Preparation process in the present embodiment and step are identical with above-described embodiment 1.Different: to take 2g surface and there is amorphous nanoshell a-Ti
0.3c
0.7nano TiC, temperature is 800 ℃, during reaction, the flow of He gas is 100ml/min, Cl
2the flow of gas is 200ml/min.Finally can obtain the 4 layers of nano particle with graphene-structured in surface.
Embodiment 14
Preparation process in the present embodiment and step are identical with above-described embodiment 1.Different: to take 2g surface and there is amorphous nanoshell a-Ti
0.3c
0.7nano TiC, temperature is 800 ℃, during reaction, the flow of He gas is 100ml/min, Cl
2the flow of gas is 100ml/min.Finally can obtain the 2 layers of nano particle with graphene-structured in surface.
Embodiment 15
Preparation process in the present embodiment and step are identical with above-described embodiment 1.Different: to take 2g surface and there is amorphous nanoshell a-Ti
0.3c
0.7nano TiC, temperature is 800 ℃, during reaction, the flow of He gas is 100ml/min, Cl
2the flow of gas is 50ml/min.Finally can obtain the 1 layer of nano particle with graphene-structured in surface.
Embodiment 16
Preparation process in the present embodiment and step are identical with above-described embodiment 1.Different: to take 2g surface and there is amorphous nanoshell a-Ti
0.5c
0.5nano TiC, 800 ℃ of temperature of reaction.Finally can obtain the 5 layers of nano particle with graphene-structured in surface.
Embodiment 17
Preparation process in the present embodiment and step are identical with above-described embodiment 1.Different: to take 2g surface and there is amorphous nanoshell a-Ti
0.4c
0.6nano TiC, 800 ℃ of temperature of reaction, finally can obtain surface 3 layers of nano particle with graphene-structured.
Embodiment 18
Preparation process in the present embodiment and step are identical with above-described embodiment 1.Different: temperature of reaction is 600 ℃, the reaction times is 10min, finally can obtain the nano particle that surface has 1-2 layer graphene structure.
Embodiment 19
Preparation process in the present embodiment and step are identical with above-described embodiment 1.Different: temperature of reaction is 600 ℃, the reaction times is 30min, finally can obtain the nano particle that surface has 3 layer graphene structures.
Embodiment 20
Preparation process in the present embodiment and step are identical with above-described embodiment 1.Different: temperature of reaction is 600 ℃, the reaction times is 50min, finally can obtain the nano particle that surface has 4 layer graphene structures.
Embodiment 21
Preparation process in the present embodiment and step are identical with above-described embodiment 1.Different: temperature of reaction is 600 ℃, the reaction times is 90min, finally can obtain the nano particle that surface has 6 layer graphene structures.
Embodiment 22
Preparation process in the present embodiment and step are identical with above-described embodiment 1.Different: temperature of reaction is 600 ℃, the reaction times is 120min, finally can obtain the nano particle that surface has 7 layer graphene structures.
Embodiment 23
Preparation process in the present embodiment and step are identical with above-described embodiment 1.Different: with HCl and Cl
2mix other and replace Cl
2gas; Temperature is 1000 ℃, and during reaction, the flow of Ar gas is 100ml/min, Cl
2the flow of gas is 200ml/min, and the reaction times is controlled at 1h.Finally can obtain the nano particle that surface has 7 layer graphene structures.
Embodiment 24
Preparation process in the present embodiment and step are identical with above-described embodiment 1.Different: with thering is a-Ta
0.4c
0.6the nanometer Ta of film
4c replaces nanometer silicon carbide; Temperature is 1000 ℃, and the flow of He gas is 500ml/min, Cl
2the flow of gas is 200ml/min.Finally can obtain the nano particle that surface has 7 layer graphene structures.
Embodiment 25
Preparation process in the present embodiment and step are identical with above-described embodiment 1.Different: with thering is a-Zr
0.4c
0.6the nanometer ZrC of film replaces nanometer silicon carbide; Temperature is 1000 ℃, and the flow of He gas is 500ml/min, Cl
2the flow of gas is 200ml/min.Finally can obtain the nano particle that surface has 8 layer graphene structures.
Embodiment 26
Preparation process in the present embodiment and step are identical with above-described embodiment 1.Different: with thering is a-Zr
0.3c
0.7the nanometer ZrC of film replaces nanometer silicon carbide; Temperature is 1200 ℃, and the flow of He gas is 500ml/min, Cl
2the flow of gas is 200ml/min.Finally can obtain the nano particle that surface has 8 layer graphene structures.
Embodiment 27
Preparation process in the present embodiment and step are identical with above-described embodiment 1.Different: with thering is a-Si
0.3c
0.7the nano SiC of film replaces nanometer silicon carbide; Temperature is 1200 ℃, and the flow of He gas is 500ml/min, Cl
2the flow of gas is 200ml/min.Finally can obtain the nano particle that surface has 6 layer graphene structures.
Embodiment 28
Preparation process in the present embodiment and step are identical with above-described embodiment 1.Different: with thering is a-B
0.3c
0.7the nanometer BC of film replaces nanometer silicon carbide; Temperature is 1200 ℃, and the flow of He gas is 500ml/min, Cl
2the flow of gas is 200ml/min.Finally can obtain the nano particle that surface has 4 layer graphene structures.
Embodiment 29
Preparation process in the present embodiment and step are identical with above-described embodiment 1.Different: with thering is a-W
0.4c
0.6the nanometer WC of film replaces nanometer silicon carbide; Temperature is 800 ℃, and the flow of He gas is 500ml/min, Cl
2the flow of gas is 200ml/min.Finally can obtain the nano particle that surface has 5 layer graphene structures.
Embodiment 30
Preparation process in the present embodiment and step are identical with above-described embodiment 1.Different: with thering is a-Al
0.5c
0.5the nanometer Al of film
4c
3replace nanometer silicon carbide; Temperature is 1200 ℃, and the flow of He gas is 500ml/min, Cl
2the flow of gas is 200ml/min.Finally can obtain the nano particle that surface has 7 layer graphene structures.
Embodiment 31
Preparation process in the present embodiment and step are identical with above-described embodiment 1.Different: with thering is a-Mo
0.4c
0.6the nano SiC of film replaces nanometer silicon carbide; Temperature is 1200 ℃, and the flow of He gas is 500ml/min, Cl
2the flow of gas is 200ml/min.Finally can obtain the nano particle that surface has 8 layer graphene structures.
Embodiment 32
Preparation process in the present embodiment and step are identical with above-described embodiment 1.Different: reactant gases is HCl.Finally can obtain the nano particle that surface has the graphene-structured of 3-4 layer.
Embodiment 33
Preparation process in the present embodiment and step are identical with above-described embodiment 1.Different: reactant gases is F
2.Finally can obtain the nano particle of the graphene-structured that surperficial tool is of five storeys.
Embodiment 34
Preparation process in the present embodiment and step are identical with above-described embodiment 1.Different: reactant gases is Br
2, temperature of reaction is 1000 degrees Celsius.Finally can obtain the nano particle that surface has the graphene-structured of 4-5 layer.
Embodiment 35
Preparation process in the present embodiment and step are identical with above-described embodiment 1.Different: reactant gases is I
2, temperature of reaction is 1000 degrees Celsius.Finally can obtain the nano particle that surface has the graphene-structured of 3-4 layer.
Embodiment 36
Preparation process in the present embodiment and step are identical with above-described embodiment 1.Different: reactant gases is HF.Finally can obtain the nano particle that surface has the graphene-structured of 4-5 layer.
Embodiment 37
Preparation process in the present embodiment and step are identical with above-described embodiment 1.Different: reactant gases is Cl
2with HCl mixed gas.Finally can obtain the nano particle that surface has the graphene-structured of layer 2-3.
Embodiment 38
Preparation process in the present embodiment and step are identical with above-described embodiment 1.Different: reactant gases is Cl
2with HF mixed gas.Finally can obtain the nano particle that surface has the graphene-structured of 2 layers.
Claims (7)
1. a preparation method for the controlled Graphene of the number of plies, includes following steps:
(1) decolorizing carbon compound is put into process furnace, under normal pressure, pass into rare gas element with excluding air, then start rapid heating, when temperature reaches after 200～1400 ℃, under the condition of maintenance rare gas element gas flow, pass into the gas of halogen gas or halogen-containing element, it reacts formation halogenide and discharges with the non-carbon in carbide, thereby leaves carbon material;
(2) after question response completes, keep under temperature-resistant prerequisite, stop passing into the gas of halogen gas or halogen-containing element, what keep rare gas element passes into remove remaining halide gas and byproduct of reaction, then under inert gas atmosphere, temperature is cooled to room temperature, finally obtains the sample that contains Graphene.
2. by the preparation method of the controlled Graphene of the number of plies claimed in claim 1, it is characterized in that the general formula of described decolorizing carbon compound is a-M
1-xc
x, wherein M represents Si, Ti, Al, Mo, Ta, Zr, B or W element, and 0<x<1.
3. by the preparation method of the controlled Graphene of the number of plies claimed in claim 2, it is characterized in that described x span is 0.3～0.7.
4. the preparation method of the controlled Graphene of the number of plies according to claim 1, is characterized in that described halogen gas is F
2, Cl
2, Br
2and I
2any one in gas or their mixing.
5. the preparation method of the controlled Graphene of the number of plies according to claim 1, is characterized in that the gas of described halogen-containing element is HF or HCl gas.
6. the preparation method of the controlled Graphene of the number of plies according to claim 1, is characterized in that the described reaction times is 5 minutes～200 minutes.
7. the preparation method of the controlled Graphene of the number of plies according to claim 1, is characterized in that the flow range of the gas of described halogen gas or halogen-containing element is 20ml/min～500ml/min.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106672945A (en) * | 2016-12-23 | 2017-05-17 | 武汉理工大学 | Method for preparing metal self-doped graphene by performing partial chlorination on two-dimensional metal carbide crystal |
| CN106744844A (en) * | 2016-12-23 | 2017-05-31 | 武汉理工大学 | A kind of method by carrying out chlorination controlledly synthesis high-quality Graphene to two-dimentional carbide crystalline |
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| JPS5586075A (en) * | 1978-12-25 | 1980-06-28 | Showa Denko Kk | Concentration cell using graphite fiber inter layer compound |
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| CN101979315A (en) * | 2010-11-16 | 2011-02-23 | 中国科学院微电子研究所 | Preparation method of monoatomic-layer graphene film |
| CN102936746A (en) * | 2012-10-29 | 2013-02-20 | 武汉理工大学 | Method for directly converting amorphous carbide into graphene under low-temperature and normal-pressure halogenation conditions |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106672945A (en) * | 2016-12-23 | 2017-05-17 | 武汉理工大学 | Method for preparing metal self-doped graphene by performing partial chlorination on two-dimensional metal carbide crystal |
| CN106744844A (en) * | 2016-12-23 | 2017-05-31 | 武汉理工大学 | A kind of method by carrying out chlorination controlledly synthesis high-quality Graphene to two-dimentional carbide crystalline |
| CN106672945B (en) * | 2016-12-23 | 2019-05-24 | 武汉理工大学 | A method of metal auto-dope graphene is prepared by carrying out partial oxidation to two-dimensional metallic carbide crystalline |
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| CN104071780B (en) | 2016-08-17 |
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