CN103663441A - Method for preparing aza graphene and nanometer metal graphene through solid phase cracking method - Google Patents
Method for preparing aza graphene and nanometer metal graphene through solid phase cracking method Download PDFInfo
- Publication number
- CN103663441A CN103663441A CN201310652296.0A CN201310652296A CN103663441A CN 103663441 A CN103663441 A CN 103663441A CN 201310652296 A CN201310652296 A CN 201310652296A CN 103663441 A CN103663441 A CN 103663441A
- Authority
- CN
- China
- Prior art keywords
- graphene
- degree
- phthalocyanine
- cracking
- gas
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/184—Preparation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
Abstract
The invention relates to a method for preparing aza graphene and nanometer metal graphene by using a solid phase cracking technology, wherein a phthalocyanine compound, a phthalocyanine polymer and a derivative thereof are adopted as starting raw materials, and cracking is performed at a temperature of more than 700 DEG C under an atmosphere of high purity nitrogen gas, argon gas or argon/hydrogen mixed gas to obtain the nitrogen-containing graphene and nanometer metal graphene materials. The method is characterized in that 1, the method is simple, and the aza graphene and nanometer metal graphene materials can be obtained through one-time solid phase cracking; 2, the graphene materials can be obtained through cracking in a non-hydrogen environment; 3, with adjustment on the cracking temperature, the gas flow rate and other experiment parameters, the size, the thickness and the quality of the graphene materials can be effectively controlled; and 4, the graphene materials with the coil behavior can be obtained under the catalyst effect. The prepared graphene materials can be applied in the fields of single molecule detection technologies, field-effect transistors and integrated circuits thereof, transparent conductive electrodes, conductive inks, field emission sources and vacuum electron devices thereof, supercapacitors, biological devices and the like.
Description
Technical field
The present invention adopts a kind of solid phase cracking technique to prepare azepine Graphene and nano metal grapheme material, belongs to new high-tech material preparation field.
Background technology
Since Geim in 2004 etc. utilize adhesive tape repeatedly to peel off on natural graphite to make Graphene [1], Graphene causes unprecedented sensation in scientific circles because of its unique individual layer sheet hexagonal honeycomb crystalline network, and its unique excellent properties and huge potential using value have caused whole world extensive concern especially.Chemical bonding mode, form the carbon atom of Graphene two-dirnentional structure with sp
2mode hydridization, this hybrid form makes carbon atom and adjacent three carbon atoms form stable C-C key by σ key, has given Graphene high mechanical property [2].The π-electron delocalization that simultaneously a large amount of carbon atoms provide on perpendicular to Graphene plane forms large π key, and electronics can move freely therein, so Graphene all has excellent electroconductibility conventionally.Such as Graphene is a kind of zero gap semiconductor, electronics therein movement velocity can reach 1/300 of the light velocity, and Graphene carrier mobility speed is up to 2 * 10
5cm
2v
-1s
-1deng [3-8].In addition, Graphene also has good thermal property and magnetic performance [9,10].The specific surface area that Graphene is higher makes it at ultracapacitor, Chu Qing, and the fields such as unit molecule chemical sensor have huge potential application [11].
At present, graphite oxide reduction method is to prepare the main method of Graphene, and the method is that graphite is carried out to strong oxide treatment, obtains again it being peeled off and preparing graphene oxide after graphene oxide, finally by crossing reduction processing, obtains Graphene.Structure due to meeting havoc graphene sheet layer in strong oxidising process, although process through reduction, the electron conjugated structure of graphene sheet layer obtains part and recovers, and the property indices of gained grapheme material still exists larger gap with high-quality Graphene.In addition, the oxidising process of graphite needs a large amount of strongly-acid oxygenants as the vitriol oil, concentrated nitric acid and potassium permanganate etc. conventionally, and in reduction process, also need the toxic chemical substances such as hydrazine hydrate or sodium borohydride, not only energy consumption is large, inefficiency, cost is high but also seriously polluted.As patent of invention CN102897756, CN102897757 etc.
Epitaxial growth method is prepared Graphene needs at high temperature, be filled with carbon-source gas (methane, ethane, acetylene etc.), decomposing gas also forms Graphene in substrate, the method needs the above high temperature of 1000 degree, and need hydrogen as reducing gas, working condition is required strictly to long reaction time, productive rate is low, and the use of a large amount of hazardous gases has increased the further application that production cost has also limited Graphene.As patent of invention CN102903616, CN102891074 etc.
The characteristic electron of nitrating capable of regulating device in Graphene, conductivity and the electrochemical stability thereof of raising Graphene.Graphene nitrogen-doping method mainly contains (as patent of invention CN102887498, CN102745678, CN101708837 etc.) such as hydrothermal synthesis method, chemical synthesis, CVD method, plasma sputterings at present, and these method combined coefficienies and quality are generally lower.And in Graphene, mix the common way that metal nanoparticle is electrochemical device modification and electrode modification etc., at present main complex method has (as CN102174702A, CN102136306A etc.) such as oxidation reduction process, electrochemical reducings, the subject matter of these methods is to have a large amount of chemical waste fluids, and nanoparticle is easily assembled.
Therefore, in the urgent need to develop a kind of adopt novel material, method is simple, to equipment without particular requirement, cost is low, efficiency is high, zero pollution, zero release, easily promote the use of, can solve the problems such as the cost existing in existing Graphene technology of preparing is high, efficiency is low, of poor quality, and the azepine Graphene that can once produce from starting material without generation intermediates Graphene and the method for nano metal Graphene.
Phthalocyanine is a class macrocylc compound, and Phthalocyanine center is a 18-π system being comprised of carbon nitrogen conjugated double bond, has a cavity, diameter 2.7 * 10 in ring
-10m.Two hydrogen atoms in center cavity can be replaced by 70 multiple elements, comprise nearly all metallic element and a part of non-metallic element (as shown in Figure 1), and metal oxide etc.And phthalocyanine polymer is made a general reference those polymers that contains phthalocyanine ring structure (as Fig. 2).The present invention will be usingd this compounds as starting raw material, adopt Low Temperature Solid-Phase cracking technique to obtain Graphene class material.
Reference:
[1]Geim?A.K.;Novoselov?K.S.The?Rise?of?Graphene.Nature?Materials2007,6(3):183-191.
[2]Novoselov?K.S.;Jiang?Z.;Zhang?Y.;Room?temperature?quantum?hall?effect?in?graphene.Science,2007,315(5817):1379-1379.
[3]Rao,C.N.R.;Sood,A.K.;Voggu,R.;Subrahmanyam,K.S.Some?Novel?attributes?of?graphene.J.Phys.Chem.Lett.2010,1,572–580.
[4]Kamat,P.V.Graphene-Based?Nanoarchitectures.Anchoring?semiconductor?and?metal?nanoparticles?on?a?two-dimensional?carbon?support.J.Phys.Chem.Lett.2010,1,520–527.
[5]Green,A.A.;Hersam,M.C.Emerging?methods?for?producing?monodisperse?graphene?dispersions.J.Phys.Chem.Lett.2010,1,544–549.
[6]Li,L.S.;Yan,X.Colloidal?graphene?quantum?dots.J.Phys.Chem.Lett.2010,1,2572–2576.
[7]Du,A.;Smith,S.C.Electronic?Functionality?in?graphene-based?nanoarchitectures:discovery?and?design?via?first-Principles?modeling.J.Phys.Chem.Lett.2010,2,73–80.
[8]Kamat,P.V.Graphene-based?nanoassemblies?for?energy?conversion.J.Phys.Chem.Lett.2011,2,242–251.
[9]Balandin?A.A.;Ghosh?S.;Bao?W.;Calizo?I.;Teweldebrhan?D.;Miao?F.Superior?thermal?conductivity?of?single-layer?graphene.Nano.Lett.2008,8(3):902-907.
[10]Ghosh?S.;Calizo?I.;Teweldebrhan?D.;Pokatilov?E.P.;Nika?D.L.;Balandin?A.A.;Extremely?high?thermal?conductivity?of?graphene:prospects?for?thermal?management?applications?in?nanoelectronic?circuits.Applied?Physics?Letters,2008,92(15).
[11]Stoller?M.D.;Park?S.;Zhu?Y.;Graphene-based?ultracapacitors.Nano?Lett.;2008,8(10):3498-3502.
Summary of the invention
The invention provides a kind of method that adopts solid phase cracking technique to prepare azepine Graphene and metallic graphite carbon alkene.It relates to take phthalocyanine compound, phthalocyanine polymer and derivative thereof as starting raw material, under the conventional atmosphere such as nitrogen, argon gas, argon gas/hydrogen mixed gas, argon gas/ammonia gas mixture, nitrogen/hydrogen mixed gas, Nitrogen, Ammonia mixing, with reference to the thermochemistry characteristic of raw material, more than 700 degree, disposable cracking prepares nitrogenous Graphene and metallic graphite carbon alkene class material.Its method feature is as follows: with phthalocyanine compound, phthalocyanine polymer and derivative thereof, as unique starting raw material one step solid phase cracking, obtain azepine Graphene and nano metal Graphene class material 1.; 2. cracking temperature is low, energy efficient; 3. adopt protection of inert gas, can in non-nitrogen atmosphere environment, cracking obtain Graphene class material, safe; 4. regulate the experiment parameters such as cracking temperature and gas flow can effectively control the size of Graphene class material, thickness and quality; 5. as catalyzer, can also obtain having the grapheme material of curling behavior usining Copper Foil or nickel foil, its conductivity of raising that can material etc.The Graphene class material that the present invention makes will be applied to the aspects such as single-molecule detection technology, field effect transistor and unicircuit thereof, transparency conductive electrode, electrically conductive ink, field emission source and vacuum electron device thereof, absorbing material, super capacitor and biological device.
Technical solution of the present invention one is as follows:
Step 1: take phthalocyanine compound, phthalocyanine polymer and derivative thereof as starting raw material, do not do other raw materials and process directly use.
Step 2: in atmosphere furnace, under certain gas shield, with reference to the thermochemistry characteristic of raw material, adopt temperature programming method, once property cracking obtains azepine Graphene class and metallic graphite carbon alkene class material in catalyst-free condition.
Technical solution of the present invention two is as follows:
Step 1: take phthalocyanine compound, phthalocyanine polymer and derivative thereof as starting raw material, do not do other raw materials and process directly use.
Step 2: in atmosphere furnace, under certain gas shield, with reference to the thermochemistry characteristic of raw material, adopt temperature programming method, having in metal catalyst condition once property cracking obtain having azepine Graphene class and the metallic graphite carbon alkene class material of coiled structure.
Described starting raw material can be commercially available or self-control metallo phthalocyanine and derivative thereof.Preferably one of magnesium-yttrium-transition metal phthalocyanine-like compound and derivative thereof (as Nickel Phthalocyanine, CuPc, FePC, phthalocyanine molybdenum, Cobalt Phthalocyanine, phthalocyanine gold, phthalocyanine is silver-colored and derivative etc.).
Described starting raw material can also be one of nonmetal phthalocyanine class materials such as pure phthalocyanine compound.
Described starting raw material can also be one of containing metal oxide phthalocyanines material.
Described starting raw material can also be one of the polymer that contains phthalocyanine ring structure or the porphyrin polymkeric substance that contains class phthalocyanine ring structure.
Described gas shield refers at conventional shielding gas such as nitrogen, argon gas, argon gas/hydrogen mixed gas, argon gas/ammonia gas mixture, nitrogen/hydrogen mixed gas, Nitrogen, Ammonia gas mixtures; The concrete ratio of gas mixture is between volume ratio 0.1:9.9～1:9; Flow rate control is at 10～50cm
3min
-1between;
Described metal catalyst refers to the metal or alloy such as Copper Foil, copper mesh, nickel foil, nickel foam.
The cracking temperature of described cracking is different according to the thermochemistry characteristic of raw material, more than being generally 700 degree, is preferably 800～1000 degree.
Under preferred cracking temperature, the time that cracking autocatalysis generates graphene sheet layer is 4～24 hours, shortens or extend pyrolysis time to final grapheme material size, and thickness and quality have impact.
In azepine Graphene class material, the acquisition of nitrogen element, from self nitrogen-atoms in phthalocyanine frame, as needs obtain the more nitrogen-atoms of high-content, can pass into the gas mixture of ammonia and rare gas element in cracking process.
In the Graphene class material of containing metal nanoparticle, the acquisition of metal nanoparticle, from the contained metal classification of starting raw material self, be take CuPc as example, obtains the most at last the grapheme material that contains metallic copper nano particle.
The technology of the present invention feature: 1. any compound that contains phthalocyanine ring and derivative thereof all can be used as the starting raw material that obtains azepine Graphene and metallic graphite carbon alkene; 2. for improving material electroconductibility or other character, can increase the final nitrogen content of material by passing into ammonia; 3. regulate the experiment parameters such as cracking temperature, gas flow, gas flow rate can effectively control the size of Graphene class material, thickness and quality; 4. using Copper Foil or nickel foil etc. during as catalyzer, also can obtain having the grapheme material of curling behavior, can improve its conductivity etc.; 5. different raw materials is formulated different temperature programming schemes according to its thermochemistry characteristic; The present invention also provide a kind of in grapheme material disposable new technology of mixing nitrogen and stable metal nano particle.
Accompanying drawing explanation
Fig. 1 Copper Phthalocyanine Molecule structural representation
Fig. 2 individual layer gathers phthalocyanine polymer schematic diagram
The XRD figure spectrum of the grapheme material that contains metallic copper nano particle of Fig. 3 nitrogen atom doping
The grapheme material transmission electron microscope photo that contains metallic copper nano particle of Fig. 4 nitrogen atom doping
The grapheme material XRD figure spectrum of Fig. 5 nitrogen atom doping
The grapheme material transmission electron microscope photo of Fig. 6 nitrogen atom doping
Fig. 7 has the grapheme material transmission electron microscope photo of the nitrogen atom doping of coiled structure
Fig. 8 has the grapheme material stereoscan photograph of petal-like nitrogen atom doping
The grapheme material transmission electron microscope photo that contains metal nickel nano particle of Fig. 9 nitrogen atom doping
The XRD figure spectrum of the grapheme material that contains metal nickel nano particle of Figure 10 nitrogen atom doping
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail.Without departing from the idea case in the present invention described above, various replacements or the change according to ordinary skill knowledge and customary means, made, all within the scope of the present invention.
Embodiment 1:
The 30.0 grams of commercially available CuPcs of take are starting raw material, do not do any purification process.In quartz tube furnace, under high-purity argon gas protection, argon gas stream speed control is built in 50cm
3min
-1, under following intensification scheme, cracking obtains 20.7 grams of final metallic graphite carbon alkene class materials.With slow heat-up rate 5 degree per minutes, be warming up to 300 degree, 300 degree are stablized 1 hour; With 5 degree per minutes, be warming up to 350 degree, 350 degree are stablized 1 hour; With 5 degree per minutes, be warming up to 400 degree, 400 degree are stablized 1 hour; With 3 degree per minutes, be warming up to 500 degree, 500 degree are stablized 4 hours; With 2 degree per minutes, be warming up to 800 degree, 800 degree are stablized 8 hours, are finally naturally down to room temperature, obtain the Graphene that contains metallic copper nano particle, and its XRD and transmission electron microscope collection of illustrative plates are shown in Fig. 3 and Fig. 4.
Embodiment 2:
Take homemade CuPc as starting raw material, first as embodiment 1 prepares the Graphene that contains metallic copper nano particle, then use pure HCl, pure H
2sO
4deng strong acid, dissolve, stirring at room obtains the not grapheme material of containing metal particle after several hours, and its XRD, transmission electron microscope are shown in respectively Fig. 5 and Fig. 6.
Embodiment 3:
Take commercially available CuPc as starting raw material, do not do any purification process, in quartz tube furnace, take Copper Foil or nickel foil as base material, under high-purity argon gas protection, argon gas stream speed control is built in 30cm
3min
-1, its heating schedule is: with slow heat-up rate 5 degree per minutes, be warming up to 300 degree, 300 degree are stablized 1 hour; With 5 degree per minutes, be warming up to 350 degree, 350 degree are stablized 1 hour; With 5 degree per minutes, be warming up to 400 degree, 400 degree are stablized 1 hour; With 3 degree per minutes, be warming up to 700 degree, 700 degree are stablized 4 hours; With 2 degree per minutes, be warming up to 1000 degree, 1000 degree are stablized 8 hours, are finally naturally down to room temperature, obtain having the grapheme material of the nitrogen atom doping of coiled structure with acid treatment, and its shape appearance figure is shown in Fig. 7.
Embodiment 4:
Take commercially available CuPc as starting raw material, do not do any purification process, in quartz tube furnace, splitting gas is argon gas/hydrogen gas mixture, and the concrete ratio of gas mixture is volume ratio 0.8:9.2, and flow rate control is at 40cm
3min
-1, simultaneously as embodiment 1 cracking temperature, obtaining thering is the grapheme material that petal-like nitrogen-atoms mixes, its shape appearance figure is shown in Fig. 8.
Embodiment 5:
Take commercially available CuPc as starting raw material, do not do any purification process, in quartz tube furnace, as shown in embodiment mono-, splitting gas is argon gas/ammonia gas mixture body, and the concrete ratio of gas mixture is volume ratio 0.5:9.5, and flow rate control is at 30cm
3min
-1, simultaneously as embodiment 1 cracking temperature, obtaining the grapheme material of high nitrogen doped cupric, ultimate analysis shows that nitrogen content mass ratio is 14.05%.
Embodiment 6:
Take Nickel Phthalocyanine as starting raw material, do not do any purification process, in quartz tube furnace, under high-purity argon gas protection, argon gas stream speed control is built in 10cm
3min
-1, its heating schedule is as follows: with slow heat-up rate 5 degree per minutes, be warming up to 300 degree, 300 degree are stablized 1 hour; With 5 degree per minutes, be warming up to 350 degree, 350 degree are stablized 1 hour; With 5 degree per minutes, be warming up to 400 degree, 400 degree are stablized 1 hour; With 3 degree per minutes, be warming up to 500 degree, 500 degree are stablized 2 hours; With 2 degree per minutes, be warming up to 900 degree, 900 degree are stablized 12 hours, are finally naturally down to room temperature, obtain the Graphene that contains metal nickel nano particle of nitrogen atom doping, and its pattern is shown in Fig. 9, and Figure 10 is the XRD figure of the Graphene that contains metal nickel nano particle.
Embodiment 7:
The 10.0 grams of commercially available CuPcs of take are starting raw material, do not do any purification process.In box atmosphere furnace, under high-purity argon gas protection, argon gas stream speed control is built in 50cm
3min
-1, with slow heat-up rate 5 degree per minutes, being warming up to 300 degree, 300 degree are stablized 1 hour; With 5 degree per minutes, be warming up to 350 degree, 350 degree are stablized 1 hour; With 5 degree per minutes, be warming up to 400 degree, 400 degree are stablized 1 hour; With 3 degree per minutes, be warming up to 500 degree, 500 degree are stablized 4 hours; With 2 degree per minutes, be warming up to 700 degree, at 700 degree, stablize 12 hours, be finally naturally down to room temperature, under above-mentioned intensification scheme, cracking obtains 7.1 grams of metallic graphite carbon alkene class materials.
Embodiment 8:
Take and gather phthalocyanine as starting raw material, do not do any purification process, in quartz tube furnace, take Copper Foil as catalyzer, under high-purity argon gas protection, argon gas stream speed control is built in 30cm
3min
-1, its heating schedule is: with slow heat-up rate 5 degree per minutes, be warming up to 300 degree, 300 degree are stablized 1 hour; With 5 degree per minutes, be warming up to 350 degree, 350 degree are stablized 1 hour; With 5 degree per minutes, be warming up to 400 degree, 400 degree are stablized 1 hour; With 3 degree per minutes, be warming up to 700 degree, 700 degree are stablized 4 hours; With 2 degree per minutes, be warming up to 1000 degree, 1000 degree are stablized 8 hours, are finally naturally down to room temperature, obtain having the grapheme material of the nitrogen atom doping of coiled structure.
Embodiment 9:
The 20.0 grams of commercially available CuPcs of take are starting raw material, do not do any purification process.In box atmosphere furnace, under high-purity argon gas protection, argon gas stream speed control is built in 50cm
3min
-1, with slow heat-up rate 5 degree per minutes, being warming up to 300 degree, 300 degree are stablized 1 hour; With 5 degree per minutes, be warming up to 350 degree, 350 degree are stablized 1 hour; With 5 degree per minutes, be warming up to 400 degree, 400 degree are stablized 1 hour; With 3 degree per minutes, be warming up to 500 degree, 500 degree are stablized 4 hours; With 2 degree per minutes, be warming up to 1000 degree, 1000 degree are stablized 4 hours, are finally naturally down to room temperature, obtain 14.6 grams of Graphene class materials that contain metallic copper nano particle.
Reference examples:
The step of the synthetic method of the nitrating Graphene of Chinese invention patent CN201110204957 is: first clean, drying substrates; At substrate surface, apply the solution that contains catalyzer, this catalyzer is water-soluble metal salt; Under oxygen free condition, the substrate temperature that is coated with catalyzer is risen to 500～1300 ℃, then pass into reducing gas, reducing catalyst, then pass into the organic carbon source compound of gaseous state and the nitrogen source compound of gaseous state and react, obtain described nitrating Graphene, its itrogen content of getter with nitrogen doped is 3.7%.
Claims (11)
1. a method of preparing azepine Graphene and metallic graphite carbon alkene class material, the method comprises the following steps order:
A): take phthalocyanine-like compound, phthalocyanine polymer and derivative thereof as starting raw material, do not do other raw materials and process directly use;
B): in atmosphere furnace, under certain gas shield, with reference to the thermochemistry characteristic of raw material, adopt temperature programming method, at catalyst-free or there is cracking under metal catalyst effect to obtain final azepine Graphene class and nano metal Graphene class material.
2. method as claimed in claim 1, is characterized in that described starting raw material is commercially available or self-control metallo phthalocyanine and derivative thereof.
3. method as claimed in claim 2, preferably one of magnesium-yttrium-transition metal phthalocyanine-like compound and derivative thereof.
4. method as claimed in claim 1, is characterized in that described starting raw material is one of nonmetal phthalocyanine class materials such as pure phthalocyanine compound.
5. method as claimed in claim 1, is characterized in that described starting raw material is one of containing metal oxide phthalocyanines material.
6. method as claimed in claim 1, is characterized in that described starting raw material is the polymer that contains phthalocyanine ring structure or containing one of porphyrin polymkeric substance of class phthalocyanine ring structure.
7. method as claimed in claim 1, is characterized in that described metal catalyst refers to the metal or alloy such as Copper Foil, copper mesh, nickel foil, nickel foam.
8. method as claimed in claim 1, is characterized in that described reaction shielding gas can be one of nitrogen, argon gas, argon gas/hydrogen mixed gas, argon gas/ammonia gas mixture, nitrogen/hydrogen mixed gas, Nitrogen, Ammonia gas mixture; The concrete ratio of gas mixture is between volume ratio 0.1:9.9 ~ 1:9; Flow rate control is at 10 ~ 50 cm
3min
-1between.
9. method as claimed in claim 1, is characterized in that the autocatalysis temperature of described cracking is more than 700 degree.
10. method as claimed in claim 9, is characterized in that the preferred cracking autocatalysis of described cracking temperature temperature is 800 ~ 1000 degree.
11. described methods as claimed in claim 10, is characterized in that the time that described cracking autocatalysis generates graphene sheet layer is 4 ~ 24 hours.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310652296.0A CN103663441B (en) | 2013-12-04 | 2013-12-04 | A kind of solid phase cracking process prepares the method for azepine Graphene and nano metal Graphene |
| PCT/CN2014/077420 WO2015081663A1 (en) | 2013-12-04 | 2014-05-14 | Method for preparing aza graphene and nanometer metal graphene by using solid phase cracking method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310652296.0A CN103663441B (en) | 2013-12-04 | 2013-12-04 | A kind of solid phase cracking process prepares the method for azepine Graphene and nano metal Graphene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103663441A true CN103663441A (en) | 2014-03-26 |
| CN103663441B CN103663441B (en) | 2016-03-23 |
Family
ID=50302351
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310652296.0A Active CN103663441B (en) | 2013-12-04 | 2013-12-04 | A kind of solid phase cracking process prepares the method for azepine Graphene and nano metal Graphene |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN103663441B (en) |
| WO (1) | WO2015081663A1 (en) |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104449239A (en) * | 2014-12-18 | 2015-03-25 | 四川环碳科技有限公司 | Nitrogen-doped graphene composited electromagnetic shielding type electricity conductive primer and preparation method thereof |
| CN104445160A (en) * | 2014-11-07 | 2015-03-25 | 孙旭阳 | Method for preparing graphene through molten inorganic salt reaction bed |
| CN104477889A (en) * | 2014-12-03 | 2015-04-01 | 连丽君 | Method for directly growing graphene membrane on silicon substrate |
| WO2015081663A1 (en) * | 2013-12-04 | 2015-06-11 | 四川环碳科技有限公司 | Method for preparing aza graphene and nanometer metal graphene by using solid phase cracking method |
| CN104777207A (en) * | 2015-04-10 | 2015-07-15 | 武汉大学 | Three-dimensional nitrogen-doped graphene composite material as well as preparation method and application thereof |
| CN104860298A (en) * | 2015-03-25 | 2015-08-26 | 孙旭阳 | Method for preparing graphene by using molten state reaction bed |
| CN104952631A (en) * | 2015-06-15 | 2015-09-30 | 四川环碳科技有限公司 | Method for preparing graphene/carbon nano-tube composite material by adopting solid-phase cracking technology |
| WO2016070396A1 (en) * | 2014-11-07 | 2016-05-12 | 孙旭阳 | Method for preparing graphene by molten state inorganic salt reaction bed |
| CN105810945A (en) * | 2016-05-26 | 2016-07-27 | 江苏深苏电子科技有限公司 | Preparation method of lithium ion battery cathode material nitrogen-doped three-dimensional porous graphene |
| CN108636438A (en) * | 2018-05-16 | 2018-10-12 | 成都理工大学 | A kind of nitrogen co-doped graphene photo-catalyst of oxygen and its preparation method and application |
| CN109755519A (en) * | 2018-12-29 | 2019-05-14 | 湖南中科星城石墨有限公司 | A kind of Anode of lithium cell material and preparation method thereof with ductility carbon material cladding |
| CN109786698A (en) * | 2018-12-29 | 2019-05-21 | 湖南中科星城石墨有限公司 | A kind of nucleocapsid structure lithium ion battery cathode material and preparation method thereof coated using inorganic extending carbon material as shell |
| CN111874888A (en) * | 2020-08-06 | 2020-11-03 | 电子科技大学 | Preparation method of ultra-wideband wave absorber of micron-scale square carbon material |
| CN114733546A (en) * | 2022-03-28 | 2022-07-12 | 云南锡业集团（控股）有限责任公司研发中心 | Preparation method of nitrogen-doped carbon-loaded indium nanoparticles |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101289181A (en) * | 2008-05-29 | 2008-10-22 | 中国科学院化学研究所 | Doped graphene and method for preparing same |
| CN102134067A (en) * | 2011-04-18 | 2011-07-27 | 北京大学 | Method for preparing single-layer graphene |
| CN102491315A (en) * | 2011-12-08 | 2012-06-13 | 中国科学院化学研究所 | Method for preparing graphene |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101285175B (en) * | 2008-05-29 | 2010-07-21 | 中国科学院化学研究所 | Process for preparing graphenes by chemical vapour deposition method |
| CN102092710B (en) * | 2010-12-17 | 2013-01-23 | 中国科学院化学研究所 | Regular graphene and preparation method thereof |
| CN102229426B (en) * | 2011-05-25 | 2012-12-05 | 中国科学院化学研究所 | Preparation method of equiangular hexagonal graphene arranged in single layer sequentially |
| CN102344131B (en) * | 2011-07-06 | 2013-03-20 | 中国科学院上海微***与信息技术研究所 | Method for manufacturing graphene film on molybdenum-based substrate |
| CN103663441B (en) * | 2013-12-04 | 2016-03-23 | 四川环碳科技有限公司 | A kind of solid phase cracking process prepares the method for azepine Graphene and nano metal Graphene |
-
2013
- 2013-12-04 CN CN201310652296.0A patent/CN103663441B/en active Active
-
2014
- 2014-05-14 WO PCT/CN2014/077420 patent/WO2015081663A1/en active Application Filing
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101289181A (en) * | 2008-05-29 | 2008-10-22 | 中国科学院化学研究所 | Doped graphene and method for preparing same |
| CN102134067A (en) * | 2011-04-18 | 2011-07-27 | 北京大学 | Method for preparing single-layer graphene |
| CN102491315A (en) * | 2011-12-08 | 2012-06-13 | 中国科学院化学研究所 | Method for preparing graphene |
Cited By (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015081663A1 (en) * | 2013-12-04 | 2015-06-11 | 四川环碳科技有限公司 | Method for preparing aza graphene and nanometer metal graphene by using solid phase cracking method |
| US10392256B2 (en) * | 2014-11-07 | 2019-08-27 | Xuyang SUN | Method for preparing graphene by using molten inorganic salt reaction bed |
| CN104445160A (en) * | 2014-11-07 | 2015-03-25 | 孙旭阳 | Method for preparing graphene through molten inorganic salt reaction bed |
| WO2016070396A1 (en) * | 2014-11-07 | 2016-05-12 | 孙旭阳 | Method for preparing graphene by molten state inorganic salt reaction bed |
| EP3216757A4 (en) * | 2014-11-07 | 2018-04-04 | Sun, Xuyang | Method for preparing graphene by molten state inorganic salt reaction bed |
| CN104477889A (en) * | 2014-12-03 | 2015-04-01 | 连丽君 | Method for directly growing graphene membrane on silicon substrate |
| CN104449239A (en) * | 2014-12-18 | 2015-03-25 | 四川环碳科技有限公司 | Nitrogen-doped graphene composited electromagnetic shielding type electricity conductive primer and preparation method thereof |
| CN104860298A (en) * | 2015-03-25 | 2015-08-26 | 孙旭阳 | Method for preparing graphene by using molten state reaction bed |
| CN104777207A (en) * | 2015-04-10 | 2015-07-15 | 武汉大学 | Three-dimensional nitrogen-doped graphene composite material as well as preparation method and application thereof |
| CN104952631A (en) * | 2015-06-15 | 2015-09-30 | 四川环碳科技有限公司 | Method for preparing graphene/carbon nano-tube composite material by adopting solid-phase cracking technology |
| CN104952631B (en) * | 2015-06-15 | 2017-10-17 | 四川环碳科技有限公司 | The method that Graphene/carbon nanotube composite material is prepared using solid phase cracking technique |
| CN105810945A (en) * | 2016-05-26 | 2016-07-27 | 江苏深苏电子科技有限公司 | Preparation method of lithium ion battery cathode material nitrogen-doped three-dimensional porous graphene |
| CN108636438A (en) * | 2018-05-16 | 2018-10-12 | 成都理工大学 | A kind of nitrogen co-doped graphene photo-catalyst of oxygen and its preparation method and application |
| 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 |
| CN109755519A (en) * | 2018-12-29 | 2019-05-14 | 湖南中科星城石墨有限公司 | A kind of Anode of lithium cell material and preparation method thereof with ductility carbon material cladding |
| CN109786698A (en) * | 2018-12-29 | 2019-05-21 | 湖南中科星城石墨有限公司 | A kind of nucleocapsid structure lithium ion battery cathode material and preparation method thereof coated using inorganic extending carbon material as shell |
| CN111874888A (en) * | 2020-08-06 | 2020-11-03 | 电子科技大学 | Preparation method of ultra-wideband wave absorber of micron-scale square carbon material |
| CN111874888B (en) * | 2020-08-06 | 2021-09-14 | 电子科技大学 | Preparation method of ultra-wideband wave absorber of micron-scale square carbon material |
| CN114733546A (en) * | 2022-03-28 | 2022-07-12 | 云南锡业集团（控股）有限责任公司研发中心 | Preparation method of nitrogen-doped carbon-loaded indium nanoparticles |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2015081663A1 (en) | 2015-06-11 |
| CN103663441B (en) | 2016-03-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103663441B (en) | A kind of solid phase cracking process prepares the method for azepine Graphene and nano metal Graphene | |
| Liu et al. | Intermediate-mediated strategy to horn-like hollow mesoporous ultrathin g-C3N4 tube with spatial anisotropic charge separation for superior photocatalytic H2 evolution | |
| Zhou et al. | Semiconductor/boron nitride composites: Synthesis, properties, and photocatalysis applications | |
| Chen et al. | NiS and graphene as dual cocatalysts for the enhanced photocatalytic H2 production activity of g-C3N4 | |
| Chen et al. | Catalyst-free growth of three-dimensional graphene flakes and graphene/g-C3N4 composite for hydrocarbon oxidation | |
| Hu et al. | A brief review of graphene–metal oxide composites synthesis and applications in photocatalysis | |
| CN104445160B (en) | Method for preparing graphene through molten inorganic salt reaction bed | |
| Cai et al. | 3D graphene/ZnO composite with enhanced photocatalytic activity | |
| Agudosi et al. | A review of the graphene synthesis routes and its applications in electrochemical energy storage | |
| CN102176338B (en) | Graphene/copper nanowire composite electric-conducting material and preparation method thereof | |
| Guan et al. | Synthesis of sulfur doped g-C3N4 with enhanced photocatalytic activity in molten salt | |
| Zheng et al. | A new carbon allotrope: graphdiyne | |
| Agnoli et al. | Second generation graphene: Opportunities and challenges for surface science | |
| Guo et al. | Facile synthesis of VS4/graphene nanocomposites and their visible-light-driven photocatalytic water splitting activities | |
| CN102320597B (en) | Preparation method of graphene | |
| Atinafu et al. | Controllable synthesis and surface modification of molybdenum oxide nanowires: a short review | |
| Wang et al. | Preparation of Cu modified g-C3N4 nanorod bundles for efficiently photocatalytic CO2 reduction | |
| EP3216757B1 (en) | Method for preparing graphene by molten state inorganic salt reaction bed | |
| Rong et al. | Bi2Te3 sheet contributing to the formation of flower-like BiOCl composite and its N2 photofixation ability enhancement | |
| Jiao et al. | Sulfur/phosphorus doping-mediated morphology transformation of carbon nitride from rods to porous microtubes with superior photocatalytic activity | |
| Zhao et al. | Scalable one-pot synthesis of phosphorus-doped g-C3N4 nanosheets for enhanced visible-light photocatalytic hydrogen evolution | |
| Zhou et al. | Mesoporous anatase TiO2/reduced graphene oxide nanocomposites: A simple template-free synthesis and their high photocatalytic performance | |
| He et al. | Ultrafast synthetic strategies under extreme heating conditions toward single-atom catalysts | |
| Feng et al. | Graphene family for hydrogen peroxide production in electrochemical system | |
| CN103101909B (en) | Method for preparing nitrogen-doped graphene material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| ASS | Succession or assignment of patent right |
Free format text: FORMER OWNER: ZHAO RUI Effective date: 20140425 Owner name: SICHUAN HUANTAN TECHNOLOGY CO., LTD. Free format text: FORMER OWNER: XUE WEIDONG Effective date: 20140425 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| COR | Change of bibliographic data |
Free format text: CORRECT: ADDRESS; FROM: 610212 CHENGDU, SICHUAN PROVINCE TO: 610000 CHENGDU, SICHUAN PROVINCE |
|
| TA01 | Transfer of patent application right |
Effective date of registration: 20140425 Address after: High tech Zone Gaopeng road in Chengdu city of Sichuan province 610000 5 Building No. 2 No. 102 Applicant after: SICHUAN HUANTAN TECHNOLOGY CO., LTD. Address before: 610212, No. 90, middle and high road, hi tech Zone, Sichuan, Chengdu Applicant before: Xue Weidong Applicant before: Zhao Rui |
|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |