CN106744844A

CN106744844A - A kind of method by carrying out chlorination controlledly synthesis high-quality Graphene to two-dimentional carbide crystalline

Info

Publication number: CN106744844A
Application number: CN201611208447.3A
Authority: CN
Inventors: 木士春; 寇宗魁; 郭贝贝; 孟天
Original assignee: Wuhan University of Technology WUT
Current assignee: Wuhan University of Technology WUT
Priority date: 2016-12-23
Filing date: 2016-12-23
Publication date: 2017-05-31

Abstract

The present invention relates to a kind of method by carrying out chlorination controlledly synthesis high-quality Graphene to two-dimentional carbide crystalline.Specific preparation method is as follows：At a certain temperature to chlorine is introduced in two-dimentional carbide crystalline, obtained with the etching reaction of two-dimentional carbide using chlorine.This method being capable of controlledly synthesis individual layer, two-layer and few layer, I_D/I_GLess than 0.5, in-plane defects negligible amounts, or even the Graphene without in-plane defects.And the presoma two dimension carbide used in the present invention, raw material sources are extensively, with low cost, while required synthesis condition is gentle, the cost of synthesizing graphite alkene is relatively low, and it is Graphene that two-dimentional carbide can be chlorinated completely.

Description

One kind is by carrying out chlorination controlledly synthesis high-quality Graphene to two-dimentional carbide crystalline Method

Technical field

The present invention relates to a kind of method by carrying out chlorination controlledly synthesis high-quality Graphene to two-dimentional carbide, belong to Graphene controllable preparation technical field.

Background technology

Graphene is a kind of carbon material of bi-dimensional cellular shape, from 04 year by Hai Mu and Nuo Woxiao loves (Science, 2004, 306,666-669) since finding, due to its unique electricity, mechanics, optics, thermal property, and its in electronic device, biology With the extensive use in the field such as chemical sensor, energy storage device and composite, and the concern of theoretical and experimental science man is enjoyed. Preferable grapheme material should be individual layer, without in-plane defects, so just can greatly retain its theoretical electricity, light Etc. characteristic.Recently, the high-quality graphene of the specific number of plies such as two-layer and few layer also result in researcher due to its special nature Interest.However, how controllably the homogeneous high-quality Graphene of the batch synthesis number of plies is faced with many challenges.Mesh Before, following several method can be expected to solve this problem：1) chemical vapour deposition technique (CVD), the method is controllable preparation industry The Perfected process of level high-quality graphene product, but the method preparation condition is extremely harsh, it is costly, and the stone for preparing Black alkene transfer is difficult, hinders its industrialization development；2) liquid phase or gas phase stripping method, the method production Graphene have cost Low, simple to operate, the advantages of Graphene quality is high, but to there is also that single-layer graphene yield is high, lamella is reunited serious, need to enter one Step sloughs the defects such as stabilizer, causes to show weak in terms of controlledly synthesis Graphene；3) oxidation-reduction method, this method is high Effect, cost is relatively low, and energy large-scale industrial production, has a disadvantage in that the electronics knot of strong oxidizer meeting heavy damage Graphene Structure and perfection of crystal, influence electronic property, thus limit it to a certain extent in accurate microelectronic Using.

Clarie Berger etc. prepare individual layer (Journal Physical using epitaxial growth method first Chemistry B, 2004,108,19912-19916) and multilayer (Science, 2006,312,1191-1196) high-quality graphite Alkene thin slice simultaneously have studied its performance.By heating, Si systems are removed on Si-terminated (00001) face of monocrystalline 6H-SiC Take Graphene.Graphite flake on Si surfaces is slow-growing and terminates growth quickly after reaching a high temperature, and in the stone of C Surface Black thin slice is not limited, and its thickness is up to 5 to 100 layers.The graphene platelet thickness of formation is determined by heating-up temperature.This method Two kinds of Graphenes can be obtained：A kind of is the Graphene being grown on Si layers, due to Si layers of contact, the electric conductivity of this Graphene Can be a greater impact；Another kind is the Graphene being grown on C layers, and quality is high, with excellent conductive capability.Although the party Method seems have the prospect of light on controllable preparation high-quality Graphene, but this method condition harshness (high temperature, Gao Zhen It is empty) and obtained Graphene be difficult to be separated from substrate, it is difficult to carry out industrialization promotion.Therefore, bag is believed and is waited at high temperature Reason business glomerocryst carborundum has obtained self-supporting graphene film (Advanced Materials, 2010,22,2168-2171).With The fracture of Si-C keys and the evaporation of Si atoms, self assembly is graphene nanometer sheet to C atoms at high temperature.The synthesis of this method is simple, week Phase is short, it is not necessary to substrate with high costs, reduces the production cost of technical grade high-quality Graphene to a certain extent, but by In the limitation for not breaking away from high temperature high vacuum synthesis condition, thus synthesis cost is still very high.Meanwhile, the stone of the method production The size and the number of plies of black alkene are difficult to control to, thus limit its development in following controlledly synthesis high-quality Graphene.

Thus, study that a kind of with low cost, synthesis is simple, be capable of controlledly synthesis single-layer graphene and few layer graphene piece Method tool is of great significance.

The content of the invention

The present invention is intended to provide a kind of by carrying out chlorination controlledly synthesis high-quality Graphene to two-dimentional carbide crystalline Method, this method being capable of controlledly synthesis individual layer, two-layer and few layer, I_D/I_GLess than 0.5, in-plane defects negligible amounts, or even without in face The Graphene of defect.

To achieve the above object, technical scheme：

A kind of method by carrying out chlorination controlledly synthesis high-quality Graphene to two-dimentional carbide crystalline, its feature exists In：At a certain temperature to chlorine is introduced in two-dimentional carbide crystalline, obtained with the etching reaction of two-dimentional carbide using chlorine Graphene.

By such scheme, the two-dimentional carbide mentioned in technical solution of the present invention refers to the horizontal structure axle of two-dimentional carbide The big order of magnitude of vertical stratification axle unit at least one of unit, by horizontal direction full-size point, can be divided into nano-scale two-dimensional carbonization Thing, micron order two dimension carbide, Centimeter Level and above two dimension carbide.

By such scheme, the two-dimentional carbide crystalline mentioned in technical solution of the present invention is monocrystalline two dimension carbide and polycrystalline Two-dimentional carbide.

By such scheme, the two-dimentional carbide mentioned in technical solution of the present invention include beryllium carbide, boron carbide, magnesium carbide, Aluminium carbide, carborundum, calcium carbide, scandium carbide, titanium carbide, vanadium carbide, chromium carbide, manganess carbide, cementite, cobalt carbide, carbonization nickel, Carbonization copper, carbon zinc, carbonization gallium, carbonization germanium, strontium carbide, yttrium carbide, zirconium carbide, niobium carbide, molybdenum carbide, carbonization ruthenium, barium carbide, One or more mixing in lanthanum carbide, hafnium carbide, carbonization thallium, tungsten carbide, ramet, thorium carbide, uranium carbide, or Two-dimentional carbide such as aluminium-titanium carbonate that two kinds and two or more above-mentioned metals are combined to form with carbon etc..

By such scheme, chlorination temperature is 200-2000 DEG C, specific chlorination temperature root in technical solution of the present invention Depending on according to the sublimation temperature of chloride and the quality of Graphene of generation, 1500 DEG C are usually no more than.

By such scheme, the time of chlorinating mentioned in technical solution of the present invention is 15min-8h, time of chlorinating according to The number of plies and size of the species of two-dimentional carbide, size, quantity and required generation Graphene determine typically to be not less than 15min.

By such scheme, the chlorine flow velocity mentioned in technical solution of the present invention is 1-100sccm, is usually no more than 80sccm, specifically depending on the species and amount of the number of plies according to Graphene and two-dimentional carbide.

By such scheme, the technology specifically comprises the steps of：Two-dimentional carbide presoma is put into heating furnace, in starvation Under the conditions of be warming up to chlorination temperature, be passed through chlorine, carry out chlorination, chlorine gas source is closed after the completion of chlorination, under this chlorination temperature lead to Enter inert gas to continue to be obtained with stove natural cooling after being incubated a period of time.

By such scheme, described starvation condition is to be passed through inert gas to exclude air or vacuumize acquisition.

By such scheme, described inert gas is high pure nitrogen or argon gas.

By such scheme, before chlorination temperature is warming up to, 80 DEG C -200 DEG C are first warming up to, are incubated a period of time to remove sample Product surface adsorbed molecules and group, soaking time are usually no more than 4h, are specifically chosen as 1-4h；

By such scheme, the soaking time after the chlorination is 15min-12h.

By such scheme, the above method more specifically, is comprised the following steps：

1) a certain amount of two-dimentional carbide crystalline precursor samples are weighed, is placed in porcelain boat, vibration makes two-dimentional carbide equal It is laid in porcelain boat evenly；

2) porcelain boat that will be equipped with two-dimentional carbide precursor is put into the centre of quartz ampoule on tube furnace, is passed through a period of time High pure nitrogen or argon gas exclude quartzy air in tube, or below 0.1Pa is evacuated in vacuum tube furnace；

3) 80 DEG C -200 DEG C are warming up to, typically not greater than 150 DEG C, insulation a period of time, 4h is usually no more than, it is specific optional It is 1-4h；

4) continue to be usually no more than 40 DEG C/min with given pace and be warming up to 200-2000 DEG C, treat temperature reach setting value with 1-100sccm, the speed for being usually no more than 80sccm is passed through chlorine, is passed through the basis of time two dimension carbide precursor of chlorine Depending on the number of plies of amount and generation Graphene, 15min is typically not less than, is chosen as 15min-8h, close chlorine gas source, be passed through high-purity argon Gas or nitrogen, continue to be incubated a period of time at this temperature；

5) continue to be passed through high-purity argon gas or nitrogen, after tubular type furnace temperature is down to room temperature naturally, take out sample, be put into weighing In bottle, in case using.

The two-dimentional carbide mentioned in technical solution of the present invention can be by selective etch method, ball milling block carbide method Or CVD is obtained.

The present invention creatively carries out chlorination with two-dimentional carbide crystalline, is given birth to two-dimentional carbide etching reaction using chlorine Into chloride, with generation and the evaporation of chloride, carbon atom is reset, and controlledly synthesis has obtained in-plane defects negligible amounts, Even without in-plane defects, I_D/I_GFew layer even Graphene of double-deck and individual layer less than 0.5.Can be applied to high-quality Graphene Controlledly synthesis, while the synthesis to graphene-based material and other carbon materials equally has very strong reference.

Compared with background technology, the present invention has advantage following prominent：

1) the presoma two dimension carbide used in the present invention, raw material sources are extensively, with low cost, while required Synthesis condition is gentle, and the cost of synthesizing graphite alkene is relatively low, and it is Graphene that two-dimentional carbide can be chlorinated completely.Present invention synthesis The graphene-based material of high-quality has a wide range of applications in the field such as energy conversion and storage, precise electronic, transistor.

2) the Graphene defect for synthesizing in the present invention is less, and quality is high, and the number of plies can be regulated and controled according to reaction condition.Pass through The thickness of regulation and control time of chlorinating, chlorine flow velocity and presoma two dimension carbide, can adjust to the number of plies of prepared Graphene Control, obtains the Graphene of double-deck even individual layer.And the size of Graphene can control to close by regulating and controlling the size of two-dimentional carbide Into.The method is a kind of potential selection of controlledly synthesis high-quality graphene product.

3) preparation method uses two-dimentional carbide range of choice wide, including beryllium carbide, boron carbide, magnesium carbide, carbonization Aluminium, carborundum, calcium carbide, scandium carbide, titanium carbide, vanadium carbide, chromium carbide, manganess carbide, cementite, cobalt carbide, carbonization nickel, carbonization Copper, carbon zinc, carbonization gallium, carbonization germanium, strontium carbide, yttrium carbide, zirconium carbide, niobium carbide, molybdenum carbide, carbonization ruthenium, barium carbide, carbonization Lanthanum, hafnium carbide, carbonization thallium, tungsten carbide, ramet, thorium carbide, uranium carbide etc. or binary metal carbide, such as aluminium-titanium carbonate.

Brief description of the drawings：

Fig. 1 is the TEM figures of platy-monocrystal chromium carbide and prepared Graphene.A) two-dimentional carbide chromium TEM figures；B) two The corresponding high power TEM figures of dimension carbide chromium；C) the layer graphene piece TEM of product three figures；D) the corresponding high power of three layer graphene pieces TEM schemes.

Fig. 2 is the AFM figures of prepared Graphene.A) the AFM figures of product Graphene；B) corresponding linear height section Figure.

The XRD of Fig. 3 platy-monocrystals chromium carbide and prepared Graphene.

The Raman spectrograms of Fig. 4 platy-monocrystals chromium carbide and prepared Graphene.

Specific embodiment

Below by embodiment in detail the present invention is described in detail.

Embodiment 1

Weigh 2g two dimension carbide chromium nanometer sheets to be placed in small porcelain boat, vibration makes sample be laid in porcelain boat；

Silica gel sealing experimental provision is used, checks that air-tightness ensures well；

High-purity argon gas 1h is passed through at room temperature, with the air in remover；

In high-purity argon atmosphere, 80 DEG C are warming up to 5 DEG C/min, are incubated 2h, remove the moisture in sample；

1000 DEG C are warming up to 10 DEG C/min, after temperature is constant, high-purity argon gas is closed and chlorine is passed through with 15sccm flow velocitys Gas, time 20min；

After the completion of question response, high-purity argon gas are passed through, at 1000 DEG C, continue to be incubated 4h, then naturally cool to room temperature.

Fig. 1 is the TEM figures of two-dimentional carbide chromium and prepared Graphene, and wherein chromium carbide is the nanometer of two-dimentional monocrystalline Chip architecture, synthesized Graphene is two to three layers, and size is up to micron order.

Fig. 2 is the AFM figures of prepared Graphene.Prepared Graphene contains a small amount of defect, and the number of plies observes layer with TEM Number is consistent.

Fig. 3 is the XRD of platy-monocrystal chromium carbide and prepared Graphene, and carbide chromium used is tongbaite knot Structure, the non-single layer structure of Graphene of synthesis, 26 ° or so of peak is (002) crystallographic plane diffraction peak.

The Raman spectrograms of Fig. 4 two dimension carbide chromium and prepared Graphene.From the observation of its Raman figure, sheet list Brilliant chromium carbide is in 546cm^-1And 604cm^-1There are two Raman vibration peaks, its optical branch lattice wave long and Acoustic Branch lattice wave are corresponded to respectively The vibration peak for causing.And sample is typical graphite Raman spectrum, including 1323cm after chlorination^-1The D peaks at place, 1573cm^-1Place G peaks and 2649cm^-1The 2D peaks at place, 2D peaks can only be divided into four peaks or six sub- peaks, illustrate that Graphene has bilayer or three Rotating fields.I_D/I_GIt is 0.42, prepared Graphene is illustrated containing a small amount of defect, while I_2D/I_GIt is 1.20 (between 1-1.5), Illustrate that the prepared Graphene number of plies is 2~3 layers.

Embodiment 2

Weigh 2g two dimension carbide chromium micron films to be placed in small porcelain boat, vibration makes sample be laid in porcelain boat；

High-purity argon gas 2h is passed through at room temperature, with the air in remover；

1050 DEG C are warming up to 10 DEG C/min, after temperature is constant, high-purity argon gas is closed and chlorine is passed through with 10sccm flow velocitys Gas, time 40min；

After the completion of question response, high-purity argon gas are passed through, at 1050 DEG C, continue to be incubated 2h, then naturally cool to room temperature.

High power TEM schemes and XRD shows that the chromium carbide for being used is the micron film of two-dimentional monocrystalline, and synthesized Graphene is Two-layer, size is up to micron order.And AFM schemes, then the Graphene of generation is illustrated containing a small amount of defect, and there are about two atomic layers thicks Degree.

From the observation of its Raman figure, carbide chromium micron film is in 548cm^-1And 608cm^-1There are two Raman vibration peaks, respectively The vibration peak that corresponding its optical branch lattice wave long and Acoustic Branch lattice wave cause.And sample is typical graphite Raman light after chlorination Spectrum, including 1323cm^-1The D peaks at place, 1574cm^-1The G peaks and 2650cm at place^-1The 2D peaks at place, 2D peaks can only be divided into four peaks Peak, illustrates that Graphene has double-decker.I_D/I_GIt is 0.32, prepared Graphene is illustrated containing a small amount of defect, while I_2D/I_GFor 1.6 (between 1.5-2), illustrate that the prepared Graphene number of plies is 2 layers.

Embodiment 3

Weigh 2g two dimensions carbide chromium centimetre piece (3cm*5cm) to be placed in small porcelain boat, during sample lain in into porcelain boat；

High pure nitrogen 2h is passed through at room temperature, with the air in remover；

In High Purity Nitrogen atmosphere, 100 DEG C are warming up to 8 DEG C/min, are incubated 2h, remove the moisture in sample；

1200 DEG C are warming up to 10 DEG C/min, after temperature is constant, high pure nitrogen is closed and chlorine is passed through with 12sccm flow velocitys Gas, time 30min；

After the completion of question response, high pure nitrogen is passed through, at 1200 DEG C, continues to be incubated 4h, then naturally cool to room temperature.

High power TEM schemes and XRD shows that the chromium carbide for being used is centimetre piece of two-dimentional monocrystalline, and synthesized Graphene is 6-7 layers, size is up to Centimeter Level.The Graphene of AFM figure explanation generations contains a small amount of defect, and has about 7 atomic layer level thickness.

From the observation of its Raman figure, two-dimentional carbide chromium centimetre piece is in 550cm^-1And 610cm^-1There are two Raman vibration peaks, The vibration peak that its optical branch lattice wave long and Acoustic Branch lattice wave cause is corresponded to respectively.And sample is typical graphite Raman after chlorination Spectrum, including 1325cm^-1The D peaks at place, 1576cm^-1The G peaks and 2652cm at place^-1The 2D peaks at place, 2D peaks only have big halfwidth (>80cm^-1)。I_D/I_GIt is 0.42, prepared Graphene is illustrated containing a small amount of defect, while I_2D/I_GIt is 0.6, illustrates prepared stone The black alkene number of plies is few layer, about 6-7 layers.

Embodiment 4

Weigh 2g two dimension polycrystalline chromium carbide nanometer sheets to be placed in small porcelain boat, vibration makes sample be laid in porcelain boat；

In high-purity argon atmosphere, 90 DEG C are warming up to 6 DEG C/min, are incubated 3h, remove the moisture in sample；

900 DEG C are warming up to 15 DEG C/min, after temperature is constant, high-purity argon gas is closed and chlorine gas is passed through with 8sccm flow velocitys Body, time 1h；

After the completion of question response, high-purity argon gas are passed through, at 900 DEG C, continue to be incubated 3h, then naturally cool to room temperature.

High power TEM schemes and XRD shows, the chromium carbide for being used is two-dimentional polycrystalline nanometer sheet, and synthesized Graphene is Individual layer, size is up to hundreds of nanometers.The Graphene of AFM figure explanation generations contains a small amount of defect, and has about 1 atomic layer level thickness.

From the observation of its Raman figure, two-dimentional polycrystalline chromium carbide nanometer sheet is in 546cm^-1And 604cm^-1There are two Raman vibration peaks, The vibration peak that its optical branch lattice wave long and Acoustic Branch lattice wave cause is corresponded to respectively, peak type broadens, illustrate that chromium carbide crystallization degree drops It is low.And sample is typical graphite Raman spectrum, including 1322cm after chlorination^-1The D peaks at place, 1572cm^-1The G peaks at place and 2649cm^-1The 2D peaks at place, 2D peaks are a sharp peak, halfwidth 18cm^-1, illustrate that Graphene has monoatomic layer structure.I_D/ I_GIt is 0.12, prepared Graphene is illustrated containing a small amount of defect, while I_2D/I_GIt is 2.8, illustrates that the prepared Graphene number of plies is list Layer.

Comparative example 1

Weigh 2g two dimension amorphous silicon carbide chromium nanometer sheets to be placed in small porcelain boat, vibration makes sample be laid in porcelain boat；

High power TEM schemes and XRD shows, the chromium carbide for being used is two-dimentional unbodied nanometer sheet, synthesized Graphene It is individual layer, size is up to hundreds of nanometers.The Graphene of AFM figure explanation generations contains more defect, and has about 1 atomic layers thick Degree.

From the observation of its Raman figure, two-dimentional amorphous silicon carbide chromium nanometer sheet is in 500-800cm^-1There is a bulge at place, illustrates carbon Change chromium is amorphous state.And sample is typical graphite Raman spectrum, including 1320cm after chlorination^-1The D peaks at place, 1570cm^-1Place G peaks and 2646cm^-1The 2D peaks at place, 2D peaks are a sharp peak, halfwidth 22cm^-1, illustrate that Graphene has monoatomic layer Structure.I_D/I_GIt is 0.81, prepared Graphene is illustrated containing more defect, while I_2D/I_GIt is 2.45, illustrates prepared Graphene The number of plies is individual layer.

Embodiment 5

Weigh 3g two dimension carbide beryllium micron films to be placed in small porcelain boat, vibration makes sample be laid in porcelain boat；

Below 0.1Pa is evacuated to, with the air in remover；

In under the vacuum of below 0.1Pa, 100 DEG C are warming up to 7 DEG C/min, are incubated 2h, remove the moisture in sample；

800 DEG C are warming up to 10 DEG C/min, after temperature is constant, chlorine gas, time are passed through with 10sccm flow velocitys 30min；

After the completion of question response, high pure nitrogen is passed through, at 800 DEG C, continues to be incubated 1h, then naturally cool to room temperature.

High power TEM schemes and XRD shows that the beryllium carbide for being used is the micron film of two-dimentional monocrystalline, and synthesized Graphene is Three layers, size is up to micron order.The Graphene of AFM figure explanation generations contains a small amount of defect, and has about 3 atomic layer level thickness.

From the observation of its Raman figure, two-dimentional carbide beryllium micron film is in 500-800cm^-1There are two sharp vibration peaks at place. And sample is typical graphite Raman spectrum, including 1325cm after chlorination^-1The D peaks at place, 1574cm^-1The G peaks and 2651cm at place^-1The 2D peaks at place, 2D peaks are a peak for wideization, halfwidth 62cm^-1, illustrate that Graphene has few Rotating fields.I_D/I_GIt is 0.32, Prepared Graphene is illustrated containing a small amount of defect, while I_2D/I_GIt is 1.3, illustrates that the prepared Graphene number of plies is three layers.

Embodiment 6

Weigh 2g two dimension carbide boron micron films to be placed in small porcelain boat, vibration makes sample be laid in porcelain boat；

Below 0.1Pa is evacuated to, with the air in remover；

In under the vacuum of below 0.1Pa, 100 DEG C are warming up to 10 DEG C/min, are incubated 2h, remove the moisture in sample；

400 DEG C are warming up to 10 DEG C/min, after temperature is constant, chlorine gas, time 1h are passed through with 7sccm flow velocitys；

After the completion of question response, high pure nitrogen is passed through, at 400 DEG C, continues to be incubated 1h, then naturally cool to room temperature.

High power TEM schemes and XRD shows that the boron carbide for being used is the micron film of two-dimentional monocrystalline, and synthesized Graphene is Two-layer, size is up to micron order.The Graphene of AFM figure explanation generations contains a small amount of defect, and has about 2 atomic layer level thickness.

From the observation of its Raman figure, two-dimentional carbide boron micron film is in 500-800cm^-1There are two sharp vibration peaks at place. And sample is typical graphite Raman spectrum, including 1326cm after chlorination^-1The D peaks at place, 1576cm^-1The G peaks and 2652cm at place^-1The 2D peaks at place, 2D peaks are a peak for wideization, halfwidth 52cm^-1, illustrate that Graphene does not have monoatomic layer structure.I_D/I_GFor 0.32, prepared Graphene is illustrated containing a small amount of defect, while I_2D/I_GIt is 1.7, illustrates that the prepared Graphene number of plies is two-layer.

Embodiment 7

Weigh 2g two dimension carbide magnesium micron films to be placed in small porcelain boat, vibration makes sample be laid in porcelain boat；

In high-purity argon atmosphere, 80 DEG C are warming up to 8 DEG C/min, are incubated 2h, remove the moisture in sample；

900 DEG C are warming up to 10 DEG C/min, after temperature is constant, high-purity argon gas is closed and chlorine gas is passed through with 8sccm flow velocitys Body, time 50min；

After the completion of question response, high-purity argon gas are passed through, at 900 DEG C, continue to be incubated 2h, then naturally cool to room temperature.

High power TEM schemes and XRD shows that the magnesium carbide for being used is the micron film of two-dimentional monocrystalline, and synthesized Graphene is 2 ~3 layers, size is up to micron order.The Graphene of AFM figure explanation generations contains a small amount of defect, and has about 2-3 atomic layer level thickness.

From the observation of its Raman figure, two-dimentional carbide magnesium micron film is in 500-800cm^-1There are two sharp vibration peaks at place. And sample is typical graphite Raman spectrum, including 1324cm after chlorination^-1The D peaks at place, 1575cm^-1The G peaks and 2649cm at place^-1The 2D peaks at place, 2D peaks are a peak for wideization, halfwidth 61cm^-1, illustrate that Graphene does not have monoatomic layer structure.I_D/I_GFor 042, prepared Graphene is illustrated containing a small amount of defect, while I_2D/I_GIt is 1.2, illustrates that the prepared Graphene number of plies is layer 2-3.

Embodiment 8

Weigh 2g two dimension polycrystalline aluminum carbide nano pieces to be placed in small porcelain boat, vibration makes sample be laid in porcelain boat；

In High Purity Nitrogen atmosphere, 90 DEG C are warming up to 5 DEG C/min, are incubated 1h, remove the moisture in sample；

1200 DEG C are warming up to 10 DEG C/min, after temperature is constant, high pure nitrogen is closed and chlorine gas is passed through with 9sccm flow velocitys Body, time 40min；

After the completion of question response, high pure nitrogen is passed through, at 1200 DEG C, continues to be incubated 2h, then naturally cool to room temperature.

High power TEM schemes and XRD shows, the aluminium carbide for being used is two-dimentional polycrystalline nanometer sheet, and synthesized Graphene is Individual layer, size is up to nanoscale.The Graphene of AFM figure explanation generations contains a small amount of defect, and has about 1 atomic layer level thickness.

From the observation of its Raman figure, two-dimentional polycrystalline aluminum carbide nano piece is in 500-800cm^-1There are two sharp vibration peaks at place. And sample is typical graphite Raman spectrum, including 1323cm after chlorination^-1The D peaks at place, 1572cm^-1The G peaks and 2649cm at place^-1The 2D peaks at place, 2D peaks are a sharp peak, halfwidth 15cm^-1, illustrate that Graphene has monoatomic layer structure.I_D/I_GFor 0.12, prepared Graphene is illustrated containing a small amount of defect, while I_2D/I_GIt is 2.7, illustrates that the prepared Graphene number of plies is individual layer.

Embodiment 9

Weigh 2g two dimension monocrystalline silicon carbide nanometer sheets to be placed in small porcelain boat, vibration makes sample be laid in porcelain boat；

In high-purity argon atmosphere, 100 DEG C are warming up to 10 DEG C/min, are incubated 1h, remove the moisture in sample；

800 DEG C are warming up to 10 DEG C/min, after temperature is constant, high-purity argon gas is closed and chlorine gas is passed through with 10sccm flow velocitys Body, time 1h；

After the completion of question response, high-purity argon gas are passed through, at 800 DEG C, continue to be incubated 2h, then naturally cool to room temperature.

High power TEM schemes and XRD shows that the carborundum for being used is the nanometer sheet of two-dimentional monocrystalline, and synthesized Graphene is Individual layer, size is up to hundreds of nanometers.The Graphene of AFM figure explanation generations contains a small amount of defect, and has about 1 atomic layer level thickness.

From the observation of its Raman figure, two-dimentional monocrystalline silicon carbide nanometer sheet is in 500-900cm^-1There are two sharp vibration peaks at place. And sample is typical graphite Raman spectrum, including 1324cm after chlorination^-1The D peaks at place, 1571cm^-1The G peaks and 2650cm at place^-1The 2D peaks at place, 2D peaks are a sharp peak, halfwidth 16cm^-1, illustrate that Graphene has monoatomic layer structure.I_D/I_GFor 0.12, prepared Graphene is illustrated containing a small amount of defect, while I_2D/I_GIt is 2.9, illustrates that the prepared Graphene number of plies is individual layer.

Comparative example 2

Weigh 2g two dimension amorphous carborundum nanometer sheets to be placed in small porcelain boat, vibration makes sample be laid in porcelain boat；

High power TEM schemes and XRD shows, the carborundum for being used is two-dimentional unbodied nanometer sheet, synthesized Graphene It is individual layer, size is up to hundreds of nanometers.The Graphene of AFM figure explanation generations contains a large amount of defects, and has about 1 atomic layers thick Degree.

From the observation of its Raman figure, two-dimentional amorphous carborundum nanometer sheet is in 500-3500cm^-1There is a wideization peak at place.And chlorine Sample is typical graphite Raman spectrum, including 1324cm after change^-1The D peaks at place, 1571cm^-1The G peaks and 2650cm at place^-1Place 2D peaks, 2D peaks are a sharp peak, halfwidth 18cm^-1, illustrate that Graphene has monoatomic layer structure.I_D/I_GIt is 1.2, Prepared Graphene is illustrated containing a large amount of defects, while I_2D/I_GIt is 2.8, illustrates that the prepared Graphene number of plies is individual layer.

Embodiment 10

Weigh 2g two dimension carbide calcium micron films to be placed in small porcelain boat, vibration makes sample be laid in porcelain boat；

In high-purity argon atmosphere, 100 DEG C are warming up to 8 DEG C/min, are incubated 1h, remove the moisture in sample；

1300 DEG C are warming up to 10 DEG C/min, after temperature is constant, high-purity argon gas is closed and chlorine is passed through with 12sccm flow velocitys Gas, time 2h；

After the completion of question response, high-purity argon gas are passed through, at 1300 DEG C, continue to be incubated 2h, then naturally cool to room temperature.

High power TEM schemes and XRD shows, the calcium carbide for being used is two-dimentional monocrystalline, and synthesized Graphene is three layers, size Up to micron order.The Graphene of AFM figure explanation generations contains a small amount of defect, and has about 3 atomic layer level thickness.

From the observation of its Raman figure, two-dimentional carbide calcium nanometer sheet is in 500-800cm^-1There are two sharp vibration peaks at place. And sample is typical graphite Raman spectrum, including 1326cm after chlorination^-1The D peaks at place, 1574cm^-1The G peaks and 2653cm at place^-1The 2D peaks at place, 2D peaks are a peak for wideization, halfwidth 68cm^-1, illustrate that Graphene is non-monoatomic layer structure.I_D/I_GFor 0.42, prepared Graphene is illustrated containing a small amount of defect, while I_2D/I_GIt is 1.1, illustrates that the prepared Graphene number of plies is 3 layers.

Embodiment 11

Weigh 2g monocrystalline two dimension scandium carbide nanometer sheet to be placed in small porcelain boat, vibration makes sample be laid in porcelain boat；

In high-purity argon atmosphere, 90 DEG C are warming up to 8 DEG C/min, are incubated 2h, remove the moisture in sample；

1400 DEG C are warming up to 10 DEG C/min, after temperature is constant, high-purity argon gas is closed and chlorine gas is passed through with 6sccm flow velocitys Body, time 3h；

After the completion of question response, high-purity argon gas are passed through, at 1400 DEG C, continue to be incubated 2h, then naturally cool to room temperature.

High power TEM schemes and XRD shows, the scandium carbide for being used is two-dimentional carbide scandium, and synthesized Graphene is 2 Layer, size is up to micron order.The Graphene of AFM figure explanation generations contains a small amount of defect, and has about 2 atomic layer level thickness.

From the observation of its Raman figure, two-dimentional carbide scandium nanometer sheet is in 500-800cm^-1There are two sharp vibration peaks at place. And sample is typical graphite Raman spectrum, including 1325cm after chlorination^-1The D peaks at place, 1573cm^-1The G peaks and 2651cm at place^-1The 2D peaks at place, 2D peaks are a peak for wideization, halfwidth 42cm^-1, illustrate that Graphene is non-monoatomic layer structure.I_D/I_GFor 0.32, prepared Graphene is illustrated containing a small amount of defect, while I_2D/I_GIt is 1.6, illustrates that the prepared Graphene number of plies is 2 layers.

Embodiment 12

Weigh 4g two dimension polycrystalline titanium carbide nanometer sheets to be placed in small porcelain boat, vibration makes sample be laid in porcelain boat；

In High Purity Nitrogen atmosphere, 100 DEG C are warming up to 5 DEG C/min, are incubated 2h, remove the moisture in sample；

200 DEG C are warming up to 5 DEG C/min, after temperature is constant, high pure nitrogen is closed and chlorine gas is passed through with 10sccm flow velocitys Body, time 2h；

After the completion of question response, high pure nitrogen is passed through, at 200 DEG C, continues to be incubated 2h, then naturally cool to room temperature.

High power TEM schemes and XRD shows that the titanium carbide for being used is the nanometer sheet of two-dimentional monocrystalline, and synthesized Graphene is 3 Layer, size is up to nanoscale.The Graphene of AFM figure explanation generations contains a small amount of defect, and has about 3 atomic layer level thickness.From it Raman figure is observed, and two-dimentional carbide titanium nanometer sheet is in 500-3500cm^-1There is a wideization peak at place.And sample is typical case after chlorination Graphite Raman spectrum, including 1324cm^-1The D peaks at place, 1574cm^-1The G peaks and 2652cm at place^-1The 2D peaks at place, 2D peaks are one The peak of individual wideization, halfwidth 64cm^-1, illustrate that Graphene is non-monoatomic layer structure.I_D/I_GIt is 0.38, illustrates prepared stone Black alkene contains a small amount of defect, while I_2D/I_GIt is 1.09, illustrates that the prepared Graphene number of plies is 3 layers.

Embodiment 13

Weigh 4g two dimension carbide vanadium nanometer sheets to be placed in small porcelain boat, vibration makes sample be laid in porcelain boat；

Below 0.1Pa is evacuated to, with the air in remover；

In under the vacuum of below 0.1Pa, 90 DEG C are warming up to 5 DEG C/min, are incubated 2h, remove the moisture in sample；

700 DEG C are warming up to 10 DEG C/min, after temperature is constant, chlorine gas, time 4h are passed through with 7sccm flow velocitys；

After the completion of question response, high pure nitrogen is passed through, at 700 DEG C, continues to be incubated 1h, then naturally cool to room temperature.

High power TEM schemes and XRD shows that the vanadium carbide for being used is the micron film of two-dimentional monocrystalline, and synthesized Graphene is Two-layer, size is up to micron order.The Graphene of AFM figure explanation generations contains a small amount of defect, and has about 2 atomic layer level thickness.

From the observation of its Raman figure, two-dimentional carbide vanadium nanometer sheet is in 500-800cm^-1There are two sharp vibration peaks at place. And sample is typical graphite Raman spectrum, including 1323cm after chlorination^-1The D peaks at place, 1572cm^-1The G peaks and 2651cm at place^-1The 2D peaks at place, 2D peaks are a peak for wideization, halfwidth 42cm^-1, illustrate that Graphene does not have monoatomic layer structure.I_D/I_GFor 0.22, prepared Graphene is illustrated containing a small amount of defect, while I_2D/I_GIt is 1.8, illustrates that the prepared Graphene number of plies is two-layer.

Embodiment 14

Weigh 2g two dimension carbide manganese nanometer sheets to be placed in small porcelain boat, vibration makes sample be laid in porcelain boat；

High-purity argon gas 3h is passed through at room temperature, with the air in remover；

In high-purity argon atmosphere, 100 DEG C are warming up to 9 DEG C/min, are incubated 3h, remove the moisture in sample；

1500 DEG C are warming up to 10 DEG C/min, after temperature is constant, high-purity argon gas is closed and chlorine gas is passed through with 5sccm flow velocitys Body, time 4h；

After the completion of question response, high-purity argon gas are passed through, at 1500 DEG C, continue to be incubated 3h, then naturally cool to room temperature.

High power TEM schemes and XRD shows that the manganess carbide for being used is the nanometer sheet of two-dimentional monocrystalline, and synthesized Graphene is Individual layer, size is up to nanoscale.The Graphene of AFM figure explanation generations contains a small amount of defect, and has about 1 atomic layer level thickness.

From the observation of its Raman figure, two-dimentional carbide manganese nanometer sheet is in 500-800cm^-1There are two sharp vibration peaks at place. And sample is typical graphite Raman spectrum, including 1324cm after chlorination^-1The D peaks at place, 1572cm^-1The G peaks and 2650cm at place^-1The 2D peaks at place, 2D peaks are a sharp peak, halfwidth 12cm^-1, illustrate that Graphene is monoatomic layer structure.I_D/I_GFor 0.22, prepared Graphene is illustrated containing a small amount of defect, while I_2D/I_GIt is 2.8, illustrates that the prepared Graphene number of plies is individual layer.

Embodiment 15

Weigh 4g two dimension polycrystalline cementite micron films to be placed in small porcelain boat, vibration makes sample be laid in porcelain boat；

High pure nitrogen 1h is passed through at room temperature, with the air in remover；

In High Purity Nitrogen atmosphere, 110 DEG C are warming up to 6 DEG C/min, are incubated 2h, remove the moisture in sample；

1000 DEG C are warming up to 8 DEG C/min, after temperature is constant, high pure nitrogen is closed and chlorine gas is passed through with 8sccm flow velocitys Body, time 3h；

After the completion of question response, high pure nitrogen is passed through, at 1000 DEG C, continues to be incubated 2h, then naturally cool to room temperature.

High power TEM schemes and XRD shows, the cementite for being used is two-dimentional polycrystalline micron film, and synthesized Graphene is 2 Layer, size is up to micron order.The Graphene of AFM figure explanation generations contains a small amount of defect, and has about 2 atomic layer level thickness.From it Raman figure is observed, and two-dimentional polycrystalline cementite micron film is in 500-800cm^-1There are two sharp vibration peaks at place.And sample after chlorination It is typical graphite Raman spectrum, including 1322cm^-1The D peaks at place, 1572cm^-1The G peaks and 2649cm at place^-1The 2D peaks at place, 2D Peak is a peak for wideization, halfwidth 34cm^-1, illustrate that Graphene is non-monoatomic layer structure.I_D/I_GIt is 0.28, illustrates made Standby Graphene contains a small amount of defect, while I_2D/I_GIt is 1.9, illustrates that the prepared Graphene number of plies is 2 layers.

Embodiment 16

Weigh 4g two dimension carbide cobalt micron films to be placed in small porcelain boat, vibration makes sample be laid in porcelain boat；

Below 0.1Pa is evacuated to, with the air in remover；

In under the vacuum of below 0.1Pa, 100 DEG C are warming up to 5 DEG C/min, are incubated 2h, remove the moisture in sample；

1100 DEG C are warming up to 10 DEG C/min, after temperature is constant, chlorine gas, time 2h are passed through with 8sccm flow velocitys；

After the completion of question response, high pure nitrogen is passed through, at 1100 DEG C, continues to be incubated 2h, then naturally cool to room temperature.

High power TEM schemes and XRD shows that the cobalt carbide for being used is the micron film of two-dimentional monocrystalline, and synthesized Graphene is Two-layer, size is up to micron order.The Graphene of AFM figure explanation generations contains a small amount of defect, and has about 2 atomic layer level thickness.

From the observation of its Raman figure, two-dimentional carbide cobalt micron film is in 500-800cm^-1There are two sharp vibration peaks at place. And sample is typical graphite Raman spectrum, including 1322cm after chlorination^-1The D peaks at place, 1571cm^-1The G peaks and 2650cm at place^-1The 2D peaks at place, 2D peaks are a peak for wideization, halfwidth 42cm^-1, illustrate that Graphene does not have monoatomic layer structure.I_D/I_GFor 0.32, prepared Graphene is illustrated containing a small amount of defect, while I_2D/I_GIt is 1.7, illustrates that the prepared Graphene number of plies is two-layer.

Embodiment 17

Weigh 2g two dimension carbide nickel nano films to be placed in small porcelain boat, vibration makes sample be laid in porcelain boat；

High power TEM schemes and XRD shows that the carbonization nickel for being used is the nanometer sheet of two-dimentional monocrystalline, and synthesized Graphene is Individual layer, size is up to micron order.The Graphene of AFM figure explanation generations contains a small amount of defect, and has about 1 atomic layer level thickness.

From the observation of its Raman figure, two-dimentional carbide nickel nano film is in 500-800cm^-1There are two sharp vibration peaks at place. And sample is typical graphite Raman spectrum, including 1320cm after chlorination^-1The D peaks at place, 1571cm^-1The G peaks and 2651cm at place^-1The 2D peaks at place, 2D peaks are a sharp peak, halfwidth 14cm^-1, illustrate that Graphene is monoatomic layer structure.I_D/I_GFor 0.09, prepared Graphene is illustrated containing a small amount of defect, while I_2D/I_GIt is 2.9, illustrates that the prepared Graphene number of plies is individual layer.

Embodiment 18

Weigh 4g two dimension polycrystalline carbonization copper micron films to be placed in small porcelain boat, vibration makes sample be laid in porcelain boat；

In High Purity Nitrogen atmosphere, 120 DEG C are warming up to 7 DEG C/min, are incubated 2h, remove the moisture in sample；

1500 DEG C are warming up to 10 DEG C/min, after temperature is constant, high pure nitrogen is closed and chlorine is passed through with 10sccm flow velocitys Gas, time 4h；

After the completion of question response, high pure nitrogen is passed through, at 1500 DEG C, continues to be incubated 3h, then naturally cool to room temperature.

High power TEM schemes and XRD shows, the carbonization copper for being used is two-dimentional polycrystalline micron film, and synthesized Graphene is Individual layer, size is up to micron order.The Graphene of AFM figure explanation generations contains a small amount of defect, and has about 1 atomic layer level thickness.

From the observation of its Raman figure, two-dimentional polycrystalline is carbonized copper micron film in 500-800cm^-1There are two sharp vibration peaks at place. And sample is typical graphite Raman spectrum, including 1321cm after chlorination^-1The D peaks at place, 1571cm^-1The G peaks and 2649cm at place^-1The 2D peaks at place, 2D peaks are a sharp peak, halfwidth 16cm^-1, illustrate that Graphene is monoatomic layer structure.I_D/I_GFor 0.18, prepared Graphene is illustrated containing a small amount of defect, while I_2D/I_GIt is 2.9, illustrates that the prepared Graphene number of plies is individual layer.

Embodiment 19

Weigh 4g two dimension carbide zinc nanometer sheets to be placed in small porcelain boat, vibration makes sample be laid in porcelain boat；

Below 0.1Pa is evacuated to, with the air in remover；

In under the vacuum of below 0.1Pa, 100 DEG C are warming up to 6 DEG C/min, are incubated 1h, remove the moisture in sample；

1600 DEG C are warming up to 10 DEG C/min, after temperature is constant, chlorine gas, time 3h are passed through with 8sccm flow velocitys；

After the completion of question response, high pure nitrogen is passed through, at 1600 DEG C, continues to be incubated 2h, then naturally cool to room temperature.

High power TEM schemes and XRD shows that the carbon zinc for being used is the nanometer sheet of two-dimentional monocrystalline, and synthesized Graphene is Individual layer, size is up to nanoscale.The Graphene of AFM figure explanation generations contains a small amount of defect, and has about 1 atomic layer level thickness.

From the observation of its Raman figure, two-dimentional carbide zinc nanometer sheet is in 500-800cm^-1There are two sharp vibration peaks at place. And sample is typical graphite Raman spectrum, including 1321cm after chlorination^-1The D peaks at place, 1572cm^-1The G peaks and 2651cm at place^-1The 2D peaks at place, 2D peaks are a sharp peak, halfwidth 12cm^-1, illustrate that Graphene has monoatomic layer structure.I_D/I_GFor 0.12, prepared Graphene is illustrated containing a small amount of defect, while I_2D/I_GIt is 2.7, illustrates that the prepared Graphene number of plies is individual layer.

Embodiment 20

Weigh 2g two dimension carbide gallium nanometer sheets to be placed in small porcelain boat, vibration makes sample be laid in porcelain boat；

1700 DEG C are warming up to 10 DEG C/min, after temperature is constant, high-purity argon gas is closed and chlorine gas is passed through with 8sccm flow velocitys Body, time 3h；

After the completion of question response, high-purity argon gas are passed through, at 1700 DEG C, continue to be incubated 3h, then naturally cool to room temperature.

High power TEM schemes and XRD shows that the carbonization gallium for being used is the nanometer sheet of two-dimentional monocrystalline, and synthesized Graphene is Individual layer, size is up to nanoscale.The Graphene of AFM figure explanation generations contains a small amount of defect, and has about 1 atomic layer level thickness.

From the observation of its Raman figure, two-dimentional carbide gallium nanometer sheet is in 500-800cm^-1There are two sharp vibration peaks at place. And sample is typical graphite Raman spectrum, including 1321cm after chlorination^-1The D peaks at place, 1572cm^-1The G peaks and 2650cm at place^-1The 2D peaks at place, 2D peaks are a sharp peak, halfwidth 11cm^-1, illustrate that Graphene is monoatomic layer structure.I_D/I_GIt is 0.1, Prepared Graphene is illustrated containing a small amount of defect, while I_2D/I_GIt is 2.6, illustrates that the prepared Graphene number of plies is individual layer.

Embodiment 21

Weigh 4g two dimension polycrystalline carbonization germanium micron films to be placed in small porcelain boat, vibration makes sample be laid in porcelain boat；

In High Purity Nitrogen atmosphere, 110 DEG C are warming up to 7 DEG C/min, are incubated 2h, remove the moisture in sample；

1800 DEG C are warming up to 10 DEG C/min, after temperature is constant, high pure nitrogen is closed and chlorine is passed through with 10sccm flow velocitys Gas, time 2h；

After the completion of question response, high pure nitrogen is passed through, at 1800 DEG C, continues to be incubated 3h, then naturally cool to room temperature.

High power TEM schemes and XRD shows, the carbonization germanium for being used is two-dimentional polycrystalline micron film, and synthesized Graphene is Individual layer, size is up to micron order.The Graphene of AFM figure explanation generations contains a small amount of defect, and has about 1 atomic layer level thickness.

From the observation of its Raman figure, two-dimentional polycrystalline is carbonized germanium micron film in 500-800cm^-1There are two sharp vibration peaks at place. And sample is typical graphite Raman spectrum, including 1320cm after chlorination^-1The D peaks at place, 1572cm^-1The G peaks and 2648cm at place^-1The 2D peaks at place, 2D peaks are a sharp peak, halfwidth 13cm^-1, illustrate that Graphene is monoatomic layer structure.I_D/I_GFor 0.19, prepared Graphene is illustrated containing a small amount of defect, while I_2D/I_GIt is 2.4, illustrates that the prepared Graphene number of plies is individual layer.

Embodiment 22

Weigh 3.8g two dimension polycrystalline strontium carbide centimetre pieces to be placed in small porcelain boat, vibration makes sample be laid in porcelain boat；

Below 0.1Pa is evacuated to, with the air in remover；

In under the vacuum of below 0.1Pa, 110 DEG C are warming up to 7 DEG C/min, are incubated 1h, remove the moisture in sample；

1200 DEG C are warming up to 10 DEG C/min, after temperature is constant, chlorine gas, time 3h are passed through with 8sccm flow velocitys；

High power TEM schemes and XRD shows, the strontium carbide for being used is two-dimentional polycrystalline centimetre piece, and synthesized Graphene is single Layer, size is up to several centimetres.The Graphene of AFM figure explanation generations contains a small amount of defect, and has about 1 atomic layer level thickness.

From the observation of its Raman figure, two-dimentional polycrystalline strontium carbide centimetre piece is in 500-3500cm^-1There is a wideization peak at place.And chlorination Sample is typical graphite Raman spectrum, including 1321cm afterwards^-1The D peaks at place, 1572cm^-1The G peaks and 2650cm at place^-1Place 2D peaks, 2D peaks are a sharp peak, halfwidth 14cm^-1, illustrate that Graphene has monoatomic layer structure.I_D/I_GIt is 0.11, says Bright prepared Graphene contains a small amount of defect, while I_2D/I_GIt is 2.8, illustrates that the prepared Graphene number of plies is individual layer.

Embodiment 23

Weigh 2g two dimension carbide yttrium nanometer sheets to be placed in small porcelain boat, vibration makes sample be laid in porcelain boat；

1800 DEG C are warming up to 10 DEG C/min, after temperature is constant, high-purity argon gas is closed and chlorine gas is passed through with 9sccm flow velocitys Body, time 4h；

After the completion of question response, high-purity argon gas are passed through, at 1800 DEG C, continue to be incubated 3h, then naturally cool to room temperature.

High power TEM schemes and XRD shows that the yttrium carbide for being used is the nanometer sheet of two-dimentional monocrystalline, and synthesized Graphene is Individual layer, size is up to nanoscale.The Graphene of AFM figure explanation generations contains a small amount of defect, and has about 1 atomic layer level thickness.

From the observation of its Raman figure, two-dimentional carbide yttrium nanometer sheet is in 500-800cm^-1There are two sharp vibration peaks at place. And sample is typical graphite Raman spectrum, including 1322cm after chlorination^-1The D peaks at place, 1571cm^-1The G peaks and 2651cm at place^-1The 2D peaks at place, 2D peaks are a sharp peak, halfwidth 12cm^-1, illustrate that Graphene is monoatomic layer structure.I_D/I_GFor 0.15, prepared Graphene is illustrated containing a small amount of defect, while I_2D/I_GIt is 2.7, illustrates that the prepared Graphene number of plies is individual layer.

Embodiment 24

Weigh 4g two dimension polycrystalline zirconium carbide micron films to be placed in small porcelain boat, vibration makes sample be laid in porcelain boat；

In High Purity Nitrogen atmosphere, 110 DEG C are warming up to 10 DEG C/min, are incubated 2h, remove the moisture in sample；

1200 DEG C are warming up to 10 DEG C/min, after temperature is constant, high pure nitrogen is closed and chlorine is passed through with 11sccm flow velocitys Gas, time 1h；

After the completion of question response, high pure nitrogen is passed through, at 1200 DEG C, continues to be incubated 3h, then naturally cool to room temperature.

High power TEM schemes and XRD shows, the zirconium carbide for being used is two-dimentional polycrystalline micron film, and synthesized Graphene is Individual layer, size is up to micron order.The Graphene of AFM figure explanation generations contains a small amount of defect, and has about 1 atomic layer level thickness.

From the observation of its Raman figure, two-dimentional polycrystalline zirconium carbide micron film is in 500-800cm^-1There are two sharp vibration peaks at place. And sample is typical graphite Raman spectrum, including 1321cm after chlorination^-1The D peaks at place, 1571cm^-1The G peaks and 2649cm at place^-1The 2D peaks at place, 2D peaks are a sharp peak, halfwidth 16cm^-1, illustrate that Graphene is monoatomic layer structure.I_D/I_GFor 0.14, prepared Graphene is illustrated containing a small amount of defect, while I_2D/I_GIt is 2.5, illustrates that the prepared Graphene number of plies is individual layer.

Embodiment 25

Weigh 3.4g two dimension carbide niobium centimetre pieces to be placed in small porcelain boat, vibration makes sample be laid in porcelain boat；

Below 0.1Pa is evacuated to, with the air in remover；

In under the vacuum of below 0.1Pa, 110 DEG C are warming up to 10 DEG C/min, are incubated 1h, remove the moisture in sample；

1300 DEG C are warming up to 10 DEG C/min, after temperature is constant, chlorine gas, time 2h are passed through with 10sccm flow velocitys；

After the completion of question response, high pure nitrogen is passed through, at 1300 DEG C, continues to be incubated 2h, then naturally cool to room temperature.

High power TEM schemes and XRD shows, the niobium carbide for being used is two-dimentional monocrystalline centimetre piece, and synthesized Graphene is single Layer, size is up to Centimeter Level.The Graphene of AFM figure explanation generations contains a small amount of defect, and has about 1 atomic layer level thickness.

From the observation of its Raman figure, two-dimentional carbide niobium centimetre piece is in 500-3500cm^-1There is a wideization peak at place.And chlorination Sample is typical graphite Raman spectrum, including 1322cm afterwards^-1The D peaks at place, 1571cm^-1The G peaks and 2651cm at place^-1Place 2D peaks, 2D peaks are a sharp peak, halfwidth 16cm^-1, illustrate that Graphene has monoatomic layer structure.I_D/I_GIt is 0.13, says Bright prepared Graphene contains a small amount of defect, while I_2D/I_GIt is 2.9, illustrates that the prepared Graphene number of plies is individual layer.

Embodiment 26

Weigh 2g two dimension carbide molybdenum nanometer sheets to be placed in small porcelain boat, vibration makes sample be laid in porcelain boat；

In high-purity argon atmosphere, 120 DEG C are warming up to 10 DEG C/min, are incubated 1h, remove the moisture in sample；

900 DEG C are warming up to 10 DEG C/min, after temperature is constant, high-purity argon gas is closed and chlorine gas is passed through with 10sccm flow velocitys Body, time 2h；

High power TEM schemes and XRD shows that the molybdenum carbide for being used is the nanometer sheet of two-dimentional monocrystalline, and synthesized Graphene is 2 Layer, size is up to nanoscale.The Graphene of AFM figure explanation generations contains a small amount of defect, and has about 2 atomic layer level thickness.

From the observation of its Raman figure, two-dimentional carbide zirconium nanometer sheet is in 500-800cm^-1There are two sharp vibration peaks at place. And sample is typical graphite Raman spectrum, including 1323cm after chlorination^-1The D peaks at place, 1572cm^-1The G peaks and 2652cm at place^-1The 2D peaks at place, 2D peaks are a peak for wideizationr, halfwidth 32cm^-1, illustrate that Graphene is non-monoatomic layer structure.I_D/I_GFor 0.32, prepared Graphene is illustrated containing a small amount of defect, while I_2D/I_GIt is 1.8, illustrates that the prepared Graphene number of plies is 2 layers.

Embodiment 27

Weigh 4g two dimension polycrystalline carbonization ruthenium micron films to be placed in small porcelain boat, vibration makes sample be laid in porcelain boat；

High pure nitrogen 3h is passed through at room temperature, with the air in remover；

In High Purity Nitrogen atmosphere, 120 DEG C are warming up to 10 DEG C/min, are incubated 1h, remove the moisture in sample；

1300 DEG C are warming up to 10 DEG C/min, after temperature is constant, high pure nitrogen is closed and chlorine gas is passed through with 8sccm flow velocitys Body, time 2h；

High power TEM schemes and XRD shows, the carbonization ruthenium for being used is two-dimentional polycrystalline micron film, and synthesized Graphene is 3 Layer, size is up to micron order.The Graphene of AFM figure explanation generations contains a small amount of defect, and has about 3 atomic layer level thickness.

From the observation of its Raman figure, polycrystalline is carbonized ruthenium micron film in 500-800cm^-1There are two sharp vibration peaks at place.And chlorine Sample is typical graphite Raman spectrum, including 1322cm after change^-1The D peaks at place, 1573cm^-1The G peaks and 2650cm at place^-1Place 2D peaks, 2D peaks are a peak for wideization, halfwidth 62cm^-1, illustrate that Graphene is non-monoatomic layer structure.I_D/I_GIt is 0.44, Prepared Graphene is illustrated containing a small amount of defect, while I_2D/I_GIt is 1.2, illustrates that the prepared Graphene number of plies is 3 layers.

Embodiment 28

Weigh 3.6g two dimension carbide barium centimetre pieces to be placed in small porcelain boat, vibration makes sample be laid in porcelain boat；

Below 0.1Pa is evacuated to, with the air in remover；

In under the vacuum of below 0.1Pa, 100 DEG C are warming up to 10 DEG C/min, are incubated 1h, remove the moisture in sample；

1200 DEG C are warming up to 10 DEG C/min, after temperature is constant, chlorine gas, time 1h are passed through with 10sccm flow velocitys；

High power TEM schemes and XRD shows, the barium carbide for being used is two-dimentional monocrystalline centimetre piece, and synthesized Graphene is single Layer, size is up to Centimeter Level.The Graphene of AFM figure explanation generations contains a small amount of defect, and has about 1 atomic layer level thickness.

From the observation of its Raman figure, two-dimentional carbide barium centimetre piece is in 500-3500cm^-1There is a wideization peak at place.And chlorination Sample is typical graphite Raman spectrum, including 1321cm afterwards^-1The D peaks at place, 1572cm^-1The G peaks and 2652cm at place^-1Place 2D peaks, 2D peaks are a sharp peak, halfwidth 16cm^-1, illustrate that Graphene has monoatomic layer structure.I_D/I_GIt is 0.14, says Bright prepared Graphene contains a small amount of defect, while I_2D/I_GIt is 2.8, illustrates that the prepared Graphene number of plies is individual layer.

Embodiment 29

Weigh 2g two dimension carbide lanthanum nanometer sheets to be placed in small porcelain boat, vibration makes sample be laid in porcelain boat；

In high-purity argon atmosphere, 100 DEG C are warming up to 10 DEG C/min, are incubated 2h, remove the moisture in sample；

1500 DEG C are warming up to 10 DEG C/min, after temperature is constant, high-purity argon gas is closed and chlorine is passed through with 10sccm flow velocitys Gas, time 1h；

After the completion of question response, high-purity argon gas are passed through, at 1500 DEG C, continue to be incubated 2h, then naturally cool to room temperature.

High power TEM schemes and XRD shows that the lanthanum carbide for being used is the nanometer sheet of two-dimentional monocrystalline, and synthesized Graphene is 2 Layer, size is up to nanoscale.The Graphene of AFM figure explanation generations contains a small amount of defect, and has about 2 atomic layer level thickness.

From the observation of its Raman figure, two-dimentional carbide lanthanum nanometer sheet is in 500-800cm^-1There are two sharp vibration peaks at place. And sample is typical graphite Raman spectrum, including 1322cm after chlorination^-1The D peaks at place, 1571cm^-1The G peaks and 2653cm at place^-1The 2D peaks at place, 2D peaks are a peak for wideizationr, halfwidth 34cm^-1, illustrate that Graphene is non-monoatomic layer structure.I_D/I_GFor 0.22, prepared Graphene is illustrated containing a small amount of defect, while I_2D/I_GIt is 1.7, illustrates that the prepared Graphene number of plies is 2 layers.

Embodiment 30

Weigh 3g two dimension polycrystalline hafnium carbide micron films to be placed in small porcelain boat, vibration makes sample be laid in porcelain boat；

In High Purity Nitrogen atmosphere, 100 DEG C are warming up to 10 DEG C/min, are incubated 2h, remove the moisture in sample；

1600 DEG C are warming up to 10 DEG C/min, after temperature is constant, high pure nitrogen is closed and chlorine is passed through with 10sccm flow velocitys Gas, time 2h；

High power TEM schemes and XRD shows, the hafnium carbide for being used is two-dimentional polycrystalline micron film, and synthesized Graphene is 3 Layer, size is up to micron order.Scheme from AFM as can be seen that the Graphene of generation contains a small amount of defect, and there are about 3 atomic layers thicks Degree.

From the observation of its Raman figure, two-dimentional polycrystalline hafnium carbide micron film is in 500-800cm^-1There are two sharp vibration peaks at place. And sample is typical graphite Raman spectrum, including 1321cm after chlorination^-1The D peaks at place, 1572cm^-1The G peaks and 2653cm at place^-1The 2D peaks at place, 2D peaks are a peak for wideization, halfwidth 52cm^-1, illustrate that Graphene is non-monoatomic layer structure.I_D/I_GFor 0.46, prepared Graphene is illustrated containing a small amount of defect, while I_2D/I_GIt is 1.1, illustrates that the prepared Graphene number of plies is 3 layers.

Embodiment 31

Weigh 3.6g two dimension polycrystalline carbonization thallium centimetre pieces to be placed in small porcelain boat, vibration makes sample be laid in porcelain boat；

Below 0.1Pa is evacuated to, with the air in remover；

In under the vacuum of below 0.1Pa, 120 DEG C are warming up to 10 DEG C/min, are incubated 2h, remove the moisture in sample；

600 DEG C are warming up to 10 DEG C/min, after temperature is constant, chlorine gas, time 2h are passed through with 10sccm flow velocitys；

After the completion of question response, high pure nitrogen is passed through, at 600 DEG C, continues to be incubated 2h, then naturally cool to room temperature.

High power TEM schemes and XRD shows, the carbonization thallium for being used is two-dimentional polycrystalline centimetre piece, and synthesized Graphene is single Layer, size is up to Centimeter Level.Can be observed from AFM figures, the Graphene of generation contains a small amount of defect, and has about 1 atomic layers thick Degree.

From the observation of its Raman figure, two-dimentional polycrystalline is carbonized thallium centimetre piece in 500-3500cm^-1There is a wideization peak at place.And chlorination Sample is typical graphite Raman spectrum, including 1320cm afterwards^-1The D peaks at place, 1571cm^-1The G peaks and 2650cm at place^-1Place 2D peaks, 2D peaks are a sharp peak, halfwidth 12cm^-1, illustrate that Graphene has monoatomic layer structure.I_D/I_GIt is 0.11, says Bright prepared Graphene contains a small amount of defect, while I_2D/I_GIt is 2.9, illustrates that the prepared Graphene number of plies is individual layer.

Embodiment 32

Weigh 2g two dimension monocrystalline tungsten carbide nanometer sheets to be placed in small porcelain boat, vibration makes sample be laid in porcelain boat；

In high-purity argon atmosphere, 110 DEG C are warming up to 10 DEG C/min, are incubated 2h, remove the moisture in sample；

500 DEG C are warming up to 10 DEG C/min, after temperature is constant, high-purity argon gas is closed and chlorine gas is passed through with 10sccm flow velocitys Body, time 2h；

After the completion of question response, high-purity argon gas are passed through, at 500 DEG C, continue to be incubated 2h, then naturally cool to room temperature.

High power TEM schemes and XRD shows that the tungsten carbide for being used is the nanometer sheet of two-dimentional monocrystalline, and synthesized Graphene is 2 Layer, size is up to nanoscale.Can be observed from AFM figures, the Graphene of generation contains a small amount of defect, and there are about 2 atomic layers thicks Degree.

From the observation of its Raman figure, two-dimentional monocrystalline tungsten carbide nanometer sheet is in 500-800cm^-1There are two sharp vibration peaks at place. And sample is typical graphite Raman spectrum, including 1321cm after chlorination^-1The D peaks at place, 1572cm^-1The G peaks and 2651cm at place^-1The 2D peaks at place, 2D peaks are a peak for wideizationr, halfwidth 31cm^-1, illustrate that Graphene is non-monoatomic layer structure.I_D/I_GFor 0.21, prepared Graphene is illustrated containing a small amount of defect, while I_2D/I_GIt is 1.8, illustrates that the prepared Graphene number of plies is 2 layers.

Embodiment 33

Weigh 3g two dimension polycrystalline ramet micron films to be placed in small porcelain boat, vibration makes sample be laid in porcelain boat；

In High Purity Nitrogen atmosphere, 80 DEG C are warming up to 10 DEG C/min, are incubated 3h, remove the moisture in sample；

1800 DEG C are warming up to 10 DEG C/min, after temperature is constant, high pure nitrogen is closed and chlorine is passed through with 10sccm flow velocitys Gas, time 1h；

After the completion of question response, high pure nitrogen is passed through, at 1800 DEG C, continues to be incubated 2h, then naturally cool to room temperature.

High power TEM schemes and XRD shows, the ramet for being used is two-dimentional polycrystalline micron film, and synthesized Graphene is 3 Layer, size is up to micron order.Scheme from AFM as can be seen that the Graphene of generation contains a small amount of defect, and there are about 3 atomic layers thicks Degree.

From the observation of its Raman figure, two-dimentional polycrystalline ramet micron film is in 500-800cm^-1There are two sharp vibration peaks at place. And sample is typical graphite Raman spectrum, including 1320cm after chlorination^-1The D peaks at place, 1571cm^-1The G peaks and 2651cm at place^-1The 2D peaks at place, 2D peaks are a peak for wideization, halfwidth 42cm^-1, illustrate that Graphene is non-monoatomic layer structure.I_D/I_GFor 0.32, prepared Graphene is illustrated containing a small amount of defect, while I_2D/I_GIt is 1.2, illustrates that the prepared Graphene number of plies is 3 layers.

Embodiment 34

Weigh 2.9g two dimension carbide thorium centimetre pieces to be placed in small porcelain boat, vibration makes sample be laid in porcelain boat；

Below 0.1Pa is evacuated to, with the air in remover；

800 DEG C are warming up to 10 DEG C/min, after temperature is constant, chlorine gas, time 1h are passed through with 12sccm flow velocitys；

After the completion of question response, high pure nitrogen is passed through, at 800 DEG C, continues to be incubated 2h, then naturally cool to room temperature.

High power TEM schemes and XRD shows, the thorium carbide for being used is two-dimentional monocrystalline centimetre piece, and synthesized Graphene is single Layer, size is up to Centimeter Level.Can be observed from AFM figures, the Graphene of generation contains a small amount of defect, and has about 1 atomic layers thick Degree.

From the observation of its Raman figure, two-dimentional carbide thorium centimetre piece is in 500-3500cm^-1There is a wideization peak at place.And chlorination Sample is typical graphite Raman spectrum, including 1321cm afterwards^-1The D peaks at place, 1572cm^-1The G peaks and 2651cm at place^-1Place 2D peaks, 2D peaks are a sharp peak, halfwidth 13cm^-1, illustrate that Graphene has monoatomic layer structure.I_D/I_GIt is 0.12, says Bright prepared Graphene contains a small amount of defect, while I_2D/I_GIt is 2.6, illustrates that the prepared Graphene number of plies is individual layer.

Embodiment 35

Weigh 2g two dimension carbide uranium nanometer sheets to be placed in small porcelain boat, vibration makes sample be laid in porcelain boat；

In high-purity argon atmosphere, 90 DEG C are warming up to 10 DEG C/min, are incubated 2h, remove the moisture in sample；

1200 DEG C are warming up to 10 DEG C/min, after temperature is constant, high-purity argon gas is closed and chlorine is passed through with 10sccm flow velocitys Gas, time 1h；

After the completion of question response, high-purity argon gas are passed through, at 1200 DEG C, continue to be incubated 2h, then naturally cool to room temperature.

High power TEM schemes and XRD shows that the uranium carbide for being used is the nanometer sheet of two-dimentional monocrystalline, and synthesized Graphene is 2 Layer, size is up to nanoscale.Can be observed from AFM figures, the Graphene of generation contains a small amount of defect, and there are about 2 atomic layers thicks Degree.

From the observation of its Raman figure, two-dimentional carbide uranium nanometer sheet is in 500-800cm^-1There are two sharp vibration peaks at place. And sample is typical graphite Raman spectrum, including 1320cm after chlorination^-1The D peaks at place, 1570cm^-1The G peaks and 2649cm at place^-1The 2D peaks at place, 2D peaks are a peak for wideizationr, halfwidth 36cm^-1, illustrate that Graphene is non-monoatomic layer structure.I_D/I_GFor 0.28, prepared Graphene is illustrated containing a small amount of defect, while I_2D/I_GIt is 1.5, illustrates that the prepared Graphene number of plies is 2 layers.

Embodiment 36

Weigh 3g two dimension polycrystalline boron carbide nanometer sheets to be placed in small porcelain boat with carbide molybdenum micron film, vibration puts down sample It is layered in porcelain boat；

In High Purity Nitrogen atmosphere, 120 DEG C are warming up to 10 DEG C/min, are incubated 3h, remove the moisture in sample；

900 DEG C are warming up to 10 DEG C/min, after temperature is constant, high pure nitrogen is closed and chlorine gas is passed through with 10sccm flow velocitys Body, time 2h；

After the completion of question response, high pure nitrogen is passed through, at 900 DEG C, continues to be incubated 2h, then naturally cool to room temperature.

High power TEM schemes and XRD shows that the molybdenum carbide for being used is the micron film of two-dimentional monocrystalline, and boron carbide is more for two dimension Brilliant nanometer sheet, two-dimentional carbide is completely converted into Graphene, and synthesized Graphene is 2 layers, and size is up to Centimeter Level.From AFM Figure is as can be seen that the Graphene of generation contains a small amount of defect, and has about 2 atomic layer level thickness.

From the observation of its Raman figure, the mixture of two-dimentional boron carbide and two-dimentional molybdenum carbide is in 500-800cm^-1Place has four sharply Vibration peak.And sample is typical graphite Raman spectrum, including 1321cm after chlorination^-1The D peaks at place, 1572cm^-1The G at place Peak and 2652cm^-1The 2D peaks at place, 2D peaks are a peak for wideization, halfwidth 48cm^-1, illustrate that Graphene is non-monoatomic layer knot Structure.I_D/I_GIt is 0.42, prepared Graphene is illustrated containing a small amount of defect, while I_2D/I_GIt is 1.6, illustrates prepared graphene layer Number is 2 layers.

Embodiment 37

Weigh 2.9g two dimension carbide aluminium titanium centimetre pieces to be placed in small porcelain boat, vibration makes sample be laid in porcelain boat；

Below 0.1Pa is evacuated to, with the air in remover；

700 DEG C are warming up to 10 DEG C/min, after temperature is constant, chlorine gas, time 1h are passed through with 8sccm flow velocitys；

After the completion of question response, high pure nitrogen is passed through, at 700 DEG C, continues to be incubated 2h, then naturally cool to room temperature.

High power TEM schemes and XRD shows, the aluminium-titanium carbonate for being used is two-dimentional monocrystalline centimetre piece, and synthesized Graphene is Individual layer, size is up to Centimeter Level.Can be observed from AFM figures, the Graphene of generation contains a small amount of defect, and has about 1 atomic layer Thickness.

From the observation of its Raman figure, two-dimentional carbide aluminium titanium centimetre piece is in 500-3500cm^-1There is a wideization peak at place.And chlorine Sample is typical graphite Raman spectrum, including 1322cm after change^-1The D peaks at place, 1571cm^-1The G peaks and 2652cm at place^-1Place 2D peaks, 2D peaks are a sharp peak, halfwidth 11cm^-1, illustrate that Graphene has monoatomic layer structure.I_D/I_GIt is 0.14, Prepared Graphene is illustrated containing a small amount of defect, while I_2D/I_GIt is 2.7, illustrates that the prepared Graphene number of plies is individual layer.

Claims

1. a kind of method by carrying out chlorination controlledly synthesis high-quality Graphene to two-dimentional carbide crystalline, it is characterised in that： At a certain temperature to chlorine is introduced in two-dimentional carbide crystalline, graphite is obtained with the etching reaction of two-dimentional carbide using chlorine Alkene.

2. method according to claim 1, it is characterised in that：Described two-dimentional carbide refers to the level of two-dimentional carbide The big order of magnitude of vertical stratification axle unit at least one of axis of no-feathering unit, by horizontal direction full-size point, can be divided into nanoscale two Dimension carbide, micron order two dimension carbide, Centimeter Level and above two dimension carbide.

3. method according to claim 1, it is characterised in that：Described two-dimentional carbide crystalline is monocrystalline two dimension carbonization Thing and polycrystalline two dimension carbide.

4. method according to claim 1, it is characterised in that：Described two-dimentional carbide include beryllium carbide, boron carbide, Magnesium carbide, aluminium carbide, carborundum, calcium carbide, scandium carbide, titanium carbide, vanadium carbide, chromium carbide, manganess carbide, cementite, cobalt carbide, Carbonization nickel, carbonization copper, carbon zinc, carbonization gallium, carbonization germanium, strontium carbide, yttrium carbide, zirconium carbide, niobium carbide, molybdenum carbide, carbonization ruthenium, Barium carbide, lanthanum carbide, hafnium carbide, carbonization thallium, tungsten carbide, ramet, thorium carbide, one or more mixed in uranium carbide Close, or the two-dimentional carbide such as aluminium-titanium carbonate that combines to form of two kinds and two or more above-mentioned metals and carbon etc..

5. method according to claim 1, it is characterised in that：Described chlorination temperature is 200-2000 DEG C.

6. method according to claim 1, it is characterised in that：Described time of chlorinating is 15min-8h.

7. method according to claim 1, it is characterised in that：Described chlorine flow velocity is 1-100sccm.

8. method according to claim 1, it is characterised in that：Two-dimentional carbide presoma is put into heating furnace, every Chlorination temperature is warming up under exhausted Oxygen Condition, chlorine is passed through, chlorination is carried out, chlorine gas source is closed after the completion of chlorination, in this chlorination temperature Inert gas is passed through under degree to continue to be obtained with stove natural cooling after being incubated a period of time.

9. method according to claim 1, it is characterised in that：Before chlorination temperature is warming up to, 80 DEG C -200 is first warming up to DEG C, insulation a period of time, soaking time was usually no more than 4h to remove sample surfaces binding molecule and group.

10. method according to claim 1, it is characterised in that：Soaking time after the chlorination is 15min-12h.