CN104445160B - Method for preparing graphene through molten inorganic salt reaction bed - Google Patents
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- CN104445160B CN104445160B CN201410623638.0A CN201410623638A CN104445160B CN 104445160 B CN104445160 B CN 104445160B CN 201410623638 A CN201410623638 A CN 201410623638A CN 104445160 B CN104445160 B CN 104445160B
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Abstract
The invention discloses a method for preparing graphene through a molten inorganic salt reaction bed. The method comprises the following steps: with a phthalocyanine matter as a reaction raw material, uniformly mixing an inorganic salt with the phthalocyanine matter in the inorganic salt reaction bed, cracking the phthalocyanine matter into monatomic carbon, dissolving the monatomic carbon into the salt bed, separating out crystals on the surfaces of salts, washing out the salts through water to complete transfer, and finally obtaining a graphene material in an atmosphere furnace under a protective gas by adopting a program heating method. The method is simple, the process is environment-friendly, industrialized production can be achieved, and the obtained graphene has a highly plane orientation property.
Description
Technical field
The present invention relates to field of new material preparation, more particularly to a kind of method for preparing grapheme material.
Background technology
Geim in 2004 etc. has been peeled off since Graphene is obtained repeatedly using adhesive tape on native graphite, and Graphene is unique because of it
Monolayer lamellar hexagonal honeycomb lattice structure cause unprecedented sensation in scientific circles, its unique excellent properties and huge
Big potential using value is even more and causes whole world extensive concern.Chemically on bonding pattern, Graphene two-dimensional structure is constituted
Carbon atom with sp2Mode hydridization, this hybrid form causes carbon atom stable by σ bond formeds with three adjacent carbon atoms
C-C keys, impart the high mechanical property of Graphene.The π for providing in a large amount of carbon atoms on graphene planes simultaneously
Electron delocalization forms big π keys, and electronics can be moved freely wherein, therefore Graphene generally all has excellent electric conductivity.Than
If Graphene is a kind of zero gap semiconductor, electronics wherein movement velocity up to the 1/300 of the light velocity, Graphene carrier mobility
Speed is up to 2 × 105cm2·V-1·S-1Deng.Additionally, Graphene also has preferable thermal property and magnetic performance.Graphene
Higher specific surface area makes it have huge potential application in fields such as ultracapacitor, hydrogen storage, unimolecule chemical sensors.
At present, graphite oxide reducing process is the main method for preparing Graphene, and the method is graphite to be carried out at Strong oxdiative
Reason, obtains carrying out stripping to it again after graphene oxide preparing graphene oxide, eventually passes reduction treatment and obtains Graphene.By
In the structure of the meeting heavy damage graphene sheet layer during Strong oxdiative, although through reduction treatment, the electronics of graphene sheet layer
Conjugated structure obtains part recovery, and the property indices of gained grapheme material still exist larger with high-quality Graphene
Gap.Additionally, the oxidizing process of graphite generally needs substantial amounts of highly acid oxidant such as concentrated sulphuric acid, concentrated nitric acid and potassium permanganate
Deng, and also need to the toxic chemical substances such as hydrazine hydrate or sodium borohydride during reducing, not only energy consumption is big, inefficiency,
High cost and seriously polluted.Such as patent of invention CN102897756, CN102897757.Epitaxial growth method prepares Graphene and needs
At high temperature carbon-source gas (methane, ethane, acetylene etc.) are filled with, gas decomposes and forms Graphene in substrate, and the method is needed
More than 1000 degree of high temperature is wanted, and needs hydrogen as reducibility gas, strictly the response time is long is required to working condition, produced
Rate is low, and the use of a large amount of hazardous gases increased production cost and also limit further applying for Graphene.And Graphene
Peel off from substrate (such as copper, nickel, carborundum substrate) it is also very difficult, it is often extreme using strong acid burn into high-temperature gasification etc.
Method, not only high cost, environmental pollution has damaged greatly, also Graphene finished product.As patent of invention CN102903616,
CN102891074 etc..
This special structure of Graphene makes it have excellent physicochemical property, how to make it in macrostructure or function material
It is able in material using scientific circles' focus of attention now.But because Graphene disperses in the base bad, it is extremely difficult to homogeneous；Plus
Graphene be generally more difficult to form strong interface cohesion with matrix, so as to become puzzlement graphene composite material development a difficult problem.
As oriented growth, the Graphene being evenly distributed, can as needed design and be prepared into variously-shaped orientation stone
Black alkene array, can be prevented effectively from the application the difficult problem of dispersion, and can give full play to Graphene along the excellent property of plane
Can so as to have broad application prospects.
Therefore, in the urgent need to develop a kind of employing novel material, method it is simple, to equipment without particular/special requirement, into
This low, efficiency high, no pollution, zero-emission, easily promote the use of, can solve high cost present in existing graphene preparation technology,
Efficiency is low, of poor quality, poor dispersion, poor compatibility the problems such as, and can obtain with elevation plane orientation grapheme material side
Method.
The content of the invention
The present invention is directed to the deficiencies in the prior art, there is provided a kind of method that molten state inorganic salt reaction bed prepares Graphene.
For achieving the above object, the technical solution used in the present invention is：
A kind of method that molten state inorganic salt reaction bed prepares Graphene, with phthalocyanines material as reaction raw materials, inorganic
It is in reactant salt bed, inorganic salt and phthalocyanines material mixing is uniform, in atmosphere furnace, phthalocyanines material and inorganic salt are being heated up
Front mix homogeneously or inorganic salt melting after, phthalocyanines material is uniformly added in inorganic salt reaction bed, under a shielding gas, adopt
Use temperature programming method, crack and separate out obtain elevation plane orientation grapheme material.
Further, the phthalocyanines material includes nonmetal phthalocyanine class material, metal phthalocyanine class material, metal-oxide
Phthalocyanines material, the macromolecule containing phthalocyanine ring structure and the porphyrin polymer containing class phthalocyanine ring structure.
Further, the inorganic salt reaction bed is that resistant to elevated temperatures container loads inorganic salt；The inorganic salt is sodium salt, potassium
The mixing of one or more of salt, sulfate, hydrochlorate, nitrate.
Further, phthalocyanines reaction raw materials and the mass ratio of inorganic salt are 1:99-10:90.
Further, the protective gas is nitrogen, argon, argon/hydrogen mixed gas, argon/ammonia gas mixture, nitrogen
One of gas/hydrogen mixed gas, Nitrogen, Ammonia gaseous mixture, protective gas flow speed control is in 10-50cm3·min-1Between.
Further, the gaseous mixture volume ratio is 0.1:9.9-1:9.
Further, the cracking temperature is 800-1000 DEG C, and pyrolysis time is 4-24h.
Further, cracking reaction can carried out without catalyst or under having metal catalysis conditions, the metallic catalyst
For Copper Foil, copper mesh, nickel foil, nickel foam, copper alloy or nickel alloy.
Further, high-quality Graphene kind is added in inorganic salt or phthalocyanines material brilliant.
The method for preparing Graphene that the present invention is provided, using phthalocyanines material as raw material, using molten state inorganic salt as
Reaction bed, using cracking and the step of precipitation technology one graphite alkenes material is obtained.The present invention can be cracked in non-hydrogen environment and obtain stone
Black alkenes material, method is simple, environmental friendly, is capable of achieving industrialized production, and there is the graphite alkenes for obtaining elevation plane to be orientated
Property, can be applicable to single-molecule detection technology, field effect transistor and its integrated circuit, transparency conductive electrode, electrically conductive ink, field emission source
And its aspect such as vacuum electron device, ultracapacitor and biological devices.
Description of the drawings
Fig. 1 is Copper Phthalocyanine Molecule structural representation provided in an embodiment of the present invention.
Fig. 2 is the poly- phthalocyanine macromolecule schematic diagram of monolayer provided in an embodiment of the present invention.
Fig. 3 is the XRD spectrum of the orientation grapheme material obtained as medium with Sodium Chloride provided in an embodiment of the present invention.
Fig. 4 is the XRD spectrum of the orientation grapheme material obtained as medium with potassium chloride provided in an embodiment of the present invention.
Fig. 5 is the orientation grapheme material transmission electron microscope obtained as medium with Sodium Chloride provided in an embodiment of the present invention
(TEM) photo.
Fig. 6 is the orientation grapheme material transmission electron microscope obtained as medium with potassium chloride provided in an embodiment of the present invention
(TEM) photo.
Specific embodiment
A kind of method that molten state inorganic salt reaction bed prepares Graphene, (it is not done with phthalocyanines material as reaction raw materials
His feed purification is processed and directly used), in inorganic salt reaction bed, inorganic salt to be mixed homogeneously with reaction raw materials, phthalocyanines are former
Material is 1 with inorganic salt mixing quality ratio:99-10:90, it is under a shielding gas, special with reference to the heat chemistry of raw material in atmosphere furnace
Property, using temperature programming method, without catalyst or under having metallic catalyst effect, crack and analyse by the high temperature heat transfer of fused salt
Go out to obtain to be orientated graphite alkenes material with elevation plane.
The phthalocyanines material includes nonmetal phthalocyanine class material, metal phthalocyanine class material, metal-oxide phthalocyanines thing
Matter, the macromolecule containing phthalocyanine ring structure and the porphyrin polymer containing class phthalocyanine ring structure.It is preferred that magnesium-yttrium-transition metal phthalocyanines
Compound and its derivant are (such as Nickel Phthalocyanine, CuPc, FePC, phthalocyanine molybdenum, Cobalt Phthalocyanine, phthalocyanine gold, phthalocyanine silver and its derivant
One of Deng).
The inorganic salt reaction bed is that resistant to elevated temperatures container loads inorganic salt；The inorganic salt is sodium salt, potassium salt, sulphuric acid
The mixing of one or more of salt, hydrochlorate, nitrate.
Described that inorganic salt is mixed homogeneously with reaction raw materials, method is：Phthalocyanines material mixes with inorganic salt before intensification
Uniformly or after inorganic salt melting, phthalocyanines material is uniformly added in inorganic salt reaction bed.
The protective gas is nitrogen, argon, argon/hydrogen mixed gas, argon/ammonia gas mixture, nitrogen/hydrogen mixing
One of gas, Nitrogen, Ammonia gaseous mixture, the gaseous mixture volume ratio is 0.1:9.9-1:9, protective gas flow speed control is in 10-
50cm3·min-1Between.
Cracking temperature is different according to the heat chemistry characteristic of raw material, generally more than 800 degree, and preferred cracking temperature is
800-1000 DEG C, under preferred cracking temperature, the time for being cracked to form graphene sheet layer is 4-24 hours, shortens or extends and splits
The solution time has an impact to final grapheme material size, thickness and quality.Cracking reaction without catalyst or can have metal catalytic
Carry out under the conditions of agent, the metallic catalyst is Copper Foil, copper mesh, nickel foil, nickel foam, copper alloy or nickel alloy.
Add that high-quality Graphene kind is brilliant in inorganic salt or phthalocyanines material, can improve Graphene growth quality and
Speed.
By adjusting the experiment parameter energy effective control graphite alkenes materials such as cracking temperature, gas flow, gas flow rate
Size, thickness and quality；Different raw materials formulates different temperature programming schemes according to its heat chemistry characteristic；It is any containing phthalein
The compound and its derivant of cyanines ring all can be used as the raw material for obtaining azepine Graphene, metallic graphite carbon alkene and Graphene.
The acquisition of nitrogen itself nitrogen-atoms in phthalocyanine frame, higher if desired for obtaining in azepine graphite alkenes material
The nitrogen-atoms of content, can be passed through the gaseous mixture of ammonia and noble gases in cracking process；For improve material conductivity or its
His property, can increase the final nitrogen content of material by being passed through ammonia；Metal is received in graphite alkenes material containing metal nanoparticle
The acquisition of rice grain by taking CuPc as an example, is most obtained at last containing metallic copper nanoparticle from metal classification contained by raw material itself
The grapheme material of son.
Phthalocyanine is a class macrocyclic compound, and Phthalocyanine center is a 18- π system being made up of carbon nitrogen conjugated double bond,
There are a cavity, diameter about 2.7 × 10 in ring-10m.Two hydrogen atoms of center intracavity can be replaced by 70 multiple elements, including
Almost all of metallic element and a part of nonmetalloid (as shown in Figure 1), and metal-oxide etc..And phthalocyanine polymer
Refer to those macromolecules for containing phthalocyanine ring structure (such as Fig. 2).The present invention will be using such compound as raw material, with molten state salt
As reaction bed, the grapheme material with elevation plane orientation is obtained using cracking and the step of precipitation technology one；Using the method
CNT and fullerene can also be obtained.
Embodiment 1
Any purification process is done as raw material, not with 30.0 grams of commercially available CuPcs (CuPc), is mixed homogeneously with Sodium Chloride, raw material
It is 1 with the mass ratio of salt:99.In quartz tube furnace, under being protected with high-purity argon gas, argon flow speed control is in 50cm3·min-1,
The cracking under following intensification scheme obtains 20.7 grams of final metallic graphite carbon alkenes materials.It is i.e. per minute with 5 degree of slow programming rate
300 degree are warming up to, 300 degree are stablized 1 hour；With 5 degree it is per minute be warming up to 350 degree, 350 degree are stablized 1 hour；It is per minute with 5 degree
400 degree are warming up to, 400 degree are stablized 1 hour；With 3 degree it is per minute be warming up to 500 degree, 500 degree are stablized 4 hours；It is per minute with 2 degree
800 degree are warming up to, 800 degree are stablized 8 hours, are finally down to room temperature naturally, product is obtained with height-oriented with washing salt
Grapheme material, its XRD and transmission electron microscope collection of illustrative plates are shown in Fig. 3 and Fig. 5.
Embodiment 2
Any purification process is done as raw material, not with 30.0 grams of commercially available CuPcs (CuPc), is mixed homogeneously with potassium chloride, raw material
It is 1 with the mass ratio of salt:99.In quartz tube furnace, under being protected with high-purity argon gas, argon flow speed control is in 50cm3·min-1,
The cracking under following intensification scheme obtains 20.7 grams of final metallic graphite carbon alkenes materials.It is i.e. per minute with 5 degree of slow programming rate
300 degree are warming up to, 300 degree are stablized 1 hour；With 5 degree it is per minute be warming up to 350 degree, 350 degree are stablized 1 hour；It is per minute with 5 degree
400 degree are warming up to, 400 degree are stablized 1 hour；With 3 degree it is per minute be warming up to 500 degree, 500 degree are stablized 4 hours；It is per minute with 2 degree
800 degree are warming up to, 800 degree are stablized 8 hours, are finally down to room temperature naturally, product is obtained with height-oriented with washing salt
Grapheme material, its XRD and transmission electron microscope collection of illustrative plates are shown in Fig. 4 and Fig. 6.
Embodiment 3
Any purification process is done as raw material, not with 30.0 grams of commercially available CuPcs (CuPc), is mixed homogeneously with Sodium Chloride, raw material
It is 10 with the mass ratio of salt:90.In quartz tube furnace, under being protected with high-purity argon gas, argon flow speed control is in 50cm3·min-1, crack under following intensification scheme and obtain 20.7 grams of final metallic graphite carbon alkenes materials.I.e. with 5 degree of slow programming rate per point
Clock is warming up to 300 degree, and 300 degree are stablized 1 hour；With 5 degree it is per minute be warming up to 350 degree, 350 degree are stablized 1 hour；With 5 degree per point
Clock is warming up to 400 degree, and 400 degree are stablized 1 hour；With 3 degree it is per minute be warming up to 500 degree, 500 degree are stablized 4 hours；With 2 degree per point
Clock is warming up to 800 degree, and 800 degree are stablized 8 hours, and room temperature is finally down to naturally, and product obtains that there is height to take to wash salt
To grapheme material.
Embodiment 4
With 30.0 grams of commercially available CuPcs as (CuPc) raw material, any purification process is not done, mixed homogeneously with potassium chloride, raw material
It is 10 with the mass ratio of salt:90.In quartz tube furnace, under being protected with high-purity argon gas, argon flow speed control is in 50cm3·min-1, crack under following intensification scheme and obtain 20.7 grams of final metallic graphite carbon alkenes materials.I.e. with 5 degree of slow programming rate per point
Clock is warming up to 300 degree, and 300 degree are stablized 1 hour；With 5 degree it is per minute be warming up to 350 degree, 350 degree are stablized 1 hour；With 5 degree per point
Clock is warming up to 400 degree, and 400 degree are stablized 1 hour；With 3 degree it is per minute be warming up to 500 degree, 500 degree are stablized 4 hours；With 2 degree per point
Clock is warming up to 800 degree, and 800 degree are stablized 8 hours, and room temperature is finally down to naturally, and product obtains that there is height to take to wash salt
To grapheme material.
Under the different salt mediums of table 1, different salt obtain grapheme material specific surface area and compare with material rate
Embodiment 5
With 30.0 grams of laboratorys synthetic phthalocyanine nickel (NiPc) as raw material, mix homogeneously with Sodium Chloride, the quality of raw material and salt
Than for 1:99.In quartz tube furnace, under being protected with high-purity argon gas, argon flow speed control is in 50cm3·min-1, heating up as follows
Cracking under scheme obtains 20.7 grams of final metallic graphite carbon alkenes materials.It is warming up to 300 so that 5 degree of slow programming rate is per minute
Degree, 300 degree are stablized 1 hour；With 5 degree it is per minute be warming up to 350 degree, 350 degree are stablized 1 hour；Per minute 400 are warming up to 5 degree
Degree, 400 degree are stablized 1 hour；With 3 degree it is per minute be warming up to 500 degree, 500 degree are stablized 4 hours；Per minute 800 are warming up to 2 degree
Degree, 800 degree are stablized 8 hours, are finally down to room temperature naturally, and product is obtained with height-oriented Graphene with washing salt
Material.
Embodiment 6
With 30.0 grams of laboratorys synthetic phthalocyanine nickel (NiPc) as raw material, mix homogeneously with potassium chloride, the quality of raw material and salt
Than for 1:99.In quartz tube furnace, under being protected with high-purity argon gas, argon flow speed control is in 50cm3·min-1, heating up as follows
Cracking under scheme obtains 20.7 grams of final metallic graphite carbon alkenes materials.It is warming up to 300 so that 5 degree of slow programming rate is per minute
Degree, 300 degree are stablized 1 hour；With 5 degree it is per minute be warming up to 350 degree, 350 degree are stablized 1 hour；Per minute 400 are warming up to 5 degree
Degree, 400 degree are stablized 1 hour；With 3 degree it is per minute be warming up to 500 degree, 500 degree are stablized 4 hours；Per minute 800 are warming up to 2 degree
Degree, 800 degree are stablized 8 hours, are finally down to room temperature naturally, and product is obtained with height-oriented Graphene with washing salt
Material.
Embodiment 7
With 30.0 grams of laboratorys synthetic phthalocyanine nickel (NiPc) as raw material, mix homogeneously with Sodium Chloride, the quality of raw material and salt
Than for 10:90.In quartz tube furnace, under being protected with high-purity argon gas, argon flow speed control is in 50cm3·min-1, rising as follows
Cracking under warm scheme obtains 20.7 grams of final metallic graphite carbon alkenes materials.It is warming up to 300 so that 5 degree of slow programming rate is per minute
Degree, 300 degree are stablized 1 hour；With 5 degree it is per minute be warming up to 350 degree, 350 degree are stablized 1 hour；Per minute 400 are warming up to 5 degree
Degree, 400 degree are stablized 1 hour；With 3 degree it is per minute be warming up to 500 degree, 500 degree are stablized 4 hours；Per minute 800 are warming up to 2 degree
Degree, 800 degree are stablized 8 hours, are finally down to room temperature naturally, and product is obtained with height-oriented Graphene with washing salt
Material.
Embodiment 8
With 30.0 grams of laboratorys synthetic phthalocyanine nickel (NiPc) as raw material, mix homogeneously with potassium chloride, the quality of raw material and salt
Than for 10:90.In quartz tube furnace, under being protected with high-purity argon gas, argon flow speed control is in 50cm3·min-1, rising as follows
Cracking under warm scheme obtains 20.7 grams of final metallic graphite carbon alkenes materials.It is warming up to 300 so that 5 degree of slow programming rate is per minute
Degree, 300 degree are stablized 1 hour；With 5 degree it is per minute be warming up to 350 degree, 350 degree are stablized 1 hour；Per minute 400 are warming up to 5 degree
Degree, 400 degree are stablized 1 hour；With 3 degree it is per minute be warming up to 500 degree, 500 degree are stablized 4 hours；Per minute 800 are warming up to 2 degree
Degree, 800 degree are stablized 8 hours, are finally down to room temperature naturally, and product is obtained with height-oriented Graphene with washing salt
Material.
Under the different salt mediums of table 2, different salt obtain grapheme material specific surface area and compare with material rate
Embodiment 9
Any purification process is done as raw material, not with 30.0 grams of commercially available CuPcs (CuPc), is mixed homogeneously with Sodium Chloride, raw material
It is 1 with the mass ratio of salt:99.In quartz tube furnace, so that under high pure nitrogen protection, nitrogen flow rate control is in 50cm3·min-1,
The cracking under following intensification scheme obtains 20.7 grams of final metallic graphite carbon alkenes materials.It is i.e. per minute with 5 degree of slow programming rate
300 degree are warming up to, 300 degree are stablized 1 hour；With 5 degree it is per minute be warming up to 350 degree, 350 degree are stablized 1 hour；It is per minute with 5 degree
400 degree are warming up to, 400 degree are stablized 1 hour；With 3 degree it is per minute be warming up to 500 degree, 500 degree are stablized 4 hours；It is per minute with 2 degree
800 degree are warming up to, 800 degree are stablized 8 hours, are finally down to room temperature naturally, product is obtained with height-oriented with washing salt
Grapheme material.Its specific surface area is 197.8m2·g-1。
Embodiment 10
Any purification process is done as raw material, not with 30.0 grams of commercially available CuPcs (CuPc), adds small amounts Graphene brilliant
Kind, raw material is mixed homogeneously with graphene oxide with Sodium Chloride, and the mass ratio between three is 1:1:98.In quartz tube furnace,
Under with high-purity argon gas protection, argon flow speed control is in 50cm3·min-1, crack under following intensification scheme and obtain 20.7 grams finally
Metallic graphite carbon alkenes material.300 degree are warming up to so that 5 degree of slow programming rate is per minute, 300 degree are stablized 1 hour；It is every with 5 degree
Minute is warming up to 350 degree, and 350 degree are stablized 1 hour；With 5 degree it is per minute be warming up to 400 degree, 400 degree are stablized 1 hour；It is every with 3 degree
Minute is warming up to 500 degree, and 500 degree are stablized 4 hours；With 2 degree it is per minute be warming up to 800 degree, 800 degree are stablized 8 hours, last natural
Room temperature is down to, product is obtained with height-oriented grapheme material to wash salt.Its specific surface area is 210.8m2·g-1。
Reference examples
The step of synthetic method of the nitrogen-doped graphene of Chinese invention patent CN201110204957 is：First clean, be dried
Substrate；The solution containing catalyst is coated in substrate surface, the catalyst is water-soluble metal salt；Under anaerobic, will apply
The substrate temperature for being covered with catalyst rises to 500～1300oC, then reducing gas is passed through, reducing catalyst is then passed through gaseous state
Organic carbon source compound and gaseous nitrogen source compound reacted, obtain the nitrogen-doped graphene, its itrogen content of getter with nitrogen doped is
3.7%.
It should be noted last that, above specific embodiment only to illustrate technical scheme and unrestricted,
Although being described in detail to the present invention with reference to example, it will be understood by those within the art that, can be to the present invention
Technical scheme modify or equivalent, without deviating from the spirit and scope of technical solution of the present invention, it all should cover
In the middle of scope of the presently claimed invention.
Claims (9)
1. a kind of method that molten state inorganic salt reaction bed prepares Graphene, it is characterised in that：
It is in inorganic salt reaction bed, inorganic salt and phthalocyanines material mixing is uniform with phthalocyanines material as reaction raw materials, in gas
In atmosphere stove, phthalocyanines material and inorganic salt are mixed homogeneously or after inorganic salt melting before intensification, phthalocyanines material is uniform
Add inorganic salt reaction bed in, under a shielding gas, using temperature programming method, crack and separate out obtain elevation plane orientation stone
Black alkene material.
2. the method for claim 1, it is characterised in that：The phthalocyanines material includes nonmetal phthalocyanine class material, gold
Category phthalocyanines material, metal-oxide phthalocyanines material, the macromolecule containing phthalocyanine ring structure and the porphin containing class phthalocyanine ring structure
Quinoline is birdsed of the same feather flock together compound.
3. the method for claim 1, it is characterised in that：The inorganic salt reaction bed is that the filling of resistant to elevated temperatures container is inorganic
Salt；The inorganic salt is the mixing of one or more of sodium salt, potassium salt, sulfate, hydrochlorate, nitrate.
4. the method for claim 1, it is characterised in that：Phthalocyanines reaction raw materials are 1 with the mass ratio of inorganic salt:99-
10:90。
5. the method for claim 1, it is characterised in that：The protective gas is nitrogen, argon, argon/hydrogen mixing
One of gas, argon/ammonia gas mixture, nitrogen/hydrogen mixed gas, Nitrogen, Ammonia gaseous mixture, protective gas flow speed control is in 10-
50cm3·min-1Between.
6. method as claimed in claim 5, it is characterised in that：The gaseous mixture volume ratio is 0.1:9.9-1:9.
7. the method for claim 1, it is characterised in that：The cracking temperature is 800-1000 DEG C, and pyrolysis time is 4-
24h。
8. the method for claim 1, it is characterised in that：Cracking reaction without catalyst or can have metal catalysis conditions
Under carry out, the metallic catalyst be Copper Foil, copper mesh, nickel foil, nickel foam, copper alloy or nickel alloy.
9. the method for claim 1, it is characterised in that：Add high-quality in the inorganic salt or the phthalocyanines material
The Graphene kind of amount is brilliant.
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| US10392256B2 (en) * | 2014-11-07 | 2019-08-27 | Xuyang SUN | Method for preparing graphene by using molten inorganic salt reaction bed |
| CN104986757B (en) * | 2015-06-19 | 2018-02-13 | 电子科技大学 | A kind of method that graphene is prepared using pitch or kir as raw material |
| CN108069416B (en) * | 2016-11-14 | 2020-01-07 | 北京大学 | Ultra-clean graphene and preparation method thereof |
| CN109304478B (en) * | 2017-07-27 | 2022-06-21 | 哈尔滨工业大学 | Method for preparing graphene/copper composite powder by one-step method |
| CN108636438B (en) * | 2018-05-16 | 2021-10-26 | 成都理工大学 | Oxygen-nitrogen co-doped graphene photocatalyst and preparation method and application thereof |
| CN110003689A (en) * | 2019-04-05 | 2019-07-12 | 孙旭阳 | A method of directly growing graphene on carbon black |
| CN113460997B (en) * | 2021-06-01 | 2023-02-24 | 武汉理工大学 | Preparation method of three-dimensional grid-shaped graphene material |
| CN114180560A (en) * | 2021-12-21 | 2022-03-15 | 山西大学 | Preparation method of coal-based graphene in molten salt system |
| CN114735680B (en) * | 2022-04-27 | 2023-07-25 | 北京化工大学 | Graphene nanoribbon and preparation method thereof |
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| CN102491315A (en) * | 2011-12-08 | 2012-06-13 | 中国科学院化学研究所 | Method for preparing graphene |
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