CN103663441B - A kind of solid phase cracking process prepares the method for azepine Graphene and nano metal Graphene - Google Patents
A kind of solid phase cracking process prepares the method for azepine Graphene and nano metal Graphene Download PDFInfo
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Abstract
A kind of method adopting solid phase cracking technique to prepare azepine Graphene and nano metal Graphene.It relates to phthalocyanine compound, phthalocyanine polymer and derivative thereof for starting raw material, at high pure nitrogen, under argon gas or argon gas/hydrogen mixed gas atmosphere, prepares nitrogenous Graphene and nano metal Graphene class material in more than 700 degree cracking.Its method feature is as follows: 1. method is simple, disposable solid phase cracking can obtain azepine Graphene and metallic graphite carbon alkene class material; 2. in non-hydrogen environment, cracking can obtain Graphene class material; 3. regulate the experiment parameter such as cracking temperature and gas flow effectively can control the size of Graphene class material, thickness and quality; 4. the grapheme material with curling behavior can be obtained under catalyst action.The Graphene class material that the present invention obtains can 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, ultracapacitor and biological devices.
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 obtained Graphene on natural graphite [1], Graphene causes unprecedented sensation in scientific circles because of the individual layer sheet hexagonal honeycomb lattice structure of its uniqueness, and its unique excellent properties and huge potential using value cause whole world extensive concern especially.Chemically on bonding pattern, 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, imparts the high mechanical property of Graphene [2].Form large π key in the π-electron delocalization provided perpendicular to carbon atom a large amount of on graphene planes, electronics can move freely wherein simultaneously, and therefore Graphene all has excellent electroconductibility usually.Such as Graphene is a kind of zero gap semiconductor, and electronics wherein 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 fields such as the specific surface area that Graphene is higher makes it at ultracapacitor, Chu Qing, unit molecule chemical sensor have huge potential application [11].
At present, graphite oxide reduction method is prepare the main method of Graphene, and the method is that graphite is carried out Strong oxdiative process, carries out stripping again and prepares graphene oxide, eventually pass reduction treatment and obtain Graphene after obtaining graphene oxide to it.Owing to the structure of havoc graphene sheet layer in Strong oxdiative process, although through reduction treatment, 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. usually, and also need the toxic chemical substance such as hydrazine hydrate or sodium borohydride in reduction process, not only energy consumption is large, inefficiency, cost are high but also seriously polluted.As patent of invention CN102897756, CN102897757 etc.
Epitaxial growth method prepares 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 high temperature of more than 1000 degree, and need hydrogen as reducing gas, working condition is required strict, long reaction time, low yield, and the use of a large amount of hazardous gas adds the further application that production cost also limit Graphene.As patent of invention CN102903616, CN102891074 etc.
The characteristic electron of nitrating adjustable device in Graphene, improves conductivity and the electrochemical stability thereof of Graphene.Current Graphene nitrogen-doping method mainly contains (as patent of invention CN102887498, CN102745678, CN101708837 etc.) such as hydrothermal synthesis method, chemical synthesis, CVD, plasma sputterings, and these method combined coefficienies and quality are general lower.And in Graphene, mix the usual way that metal nanoparticle is electrochemical device modification and electrode modification etc., main complex method has oxidation reduction process, electrochemical reducing etc. (as CN102174702A, CN102136306A etc.) at present, the subject matter of these methods has 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, no pollution, zero release, easily promote the use of, can solve the problems such as the cost existed in existing graphene preparation technology is high, efficiency is low, of poor quality, and can without the need to generating the method for azepine Graphene that intermediates Graphene once produces from starting material and nano metal Graphene.
Phthalocyanine is a class macrocylc compound, and Phthalocyanine center is a 18-π system be made up of carbon nitrogen conjugated double bond, has a cavity, diameter about 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 makes a general reference those polymers containing phthalocyanine ring structure (as Fig. 2).The present invention will, using this compounds as starting raw material, adopt Low Temperature Solid-Phase cracking technique to obtain Graphene class material.
Reference:
[1]GeimA.K.;NovoselovK.S.TheRiseofGraphene.NatureMaterials2007,6(3):183-191.
[2]NovoselovK.S.;JiangZ.;ZhangY.;Roomtemperaturequantumhalleffectingraphene.Science,2007,315(5817):1379-1379.
[3]Rao,C.N.R.;Sood,A.K.;Voggu,R.;Subrahmanyam,K.S.SomeNovelattributesofgraphene.J.Phys.Chem.Lett.2010,1,572–580.
[4]Kamat,P.V.Graphene-BasedNanoarchitectures.Anchoringsemiconductorandmetalnanoparticlesonatwo-dimensionalcarbonsupport.J.Phys.Chem.Lett.2010,1,520–527.
[5]Green,A.A.;Hersam,M.C.Emergingmethodsforproducingmonodispersegraphenedispersions.J.Phys.Chem.Lett.2010,1,544–549.
[6]Li,L.S.;Yan,X.Colloidalgraphenequantumdots.J.Phys.Chem.Lett.2010,1,2572–2576.
[7]Du,A.;Smith,S.C.ElectronicFunctionalityingraphene-basednanoarchitectures:discoveryanddesignviafirst-Principlesmodeling.J.Phys.Chem.Lett.2010,2,73–80.
[8]Kamat,P.V.Graphene-basednanoassembliesforenergyconversion.J.Phys.Chem.Lett.2011,2,242–251.
[9]BalandinA.A.;GhoshS.;BaoW.;CalizoI.;TeweldebrhanD.;MiaoF.Superiorthermalconductivityofsingle-layergraphene.Nano.Lett.2008,8(3):902-907.
[10]GhoshS.;CalizoI.;TeweldebrhanD.;PokatilovE.P.;NikaD.L.;BalandinA.A.;Extremelyhighthermalconductivityofgraphene:prospectsforthermalmanagementapplicationsinnanoelectroniccircuits.AppliedPhysicsLetters,2008,92(15).
[11]StollerM.D.;ParkS.;ZhuY.;Graphene-basedultracapacitors.NanoLett.;2008,8(10):3498-3502.
Summary of the invention
The invention provides a kind of method adopting solid phase cracking technique to prepare azepine Graphene and metallic graphite carbon alkene.It relates to phthalocyanine compound, phthalocyanine polymer and derivative thereof for 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, prepare nitrogenous Graphene and metallic graphite carbon alkene class material in more than 700 degree disposable cracking.Its method feature is as follows: 1. obtain azepine Graphene and nano metal Graphene class material with phthalocyanine compound, phthalocyanine polymer and derivative thereof as the cracking of unique starting raw material one step solid phase; 2. cracking temperature is low, energy efficient; 3. adopt protection of inert gas, in non-hydrogen atmosphere, cracking can obtain Graphene class material, security is high; 4. regulate the experiment parameter such as cracking temperature and gas flow effectively can control the size of Graphene class material, thickness and quality; 5. can also obtain the grapheme material with curling behavior using Copper Foil or nickel foil as catalyzer, can its conductivity of raising etc. of material.The Graphene class material that the present invention obtains 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, absorbing material, super capacitor and biological devices.
Technical solution of the present invention one is as follows:
Step one: with phthalocyanine compound, phthalocyanine polymer and derivative thereof for starting raw material, does not do other Feedstock treating and directly uses.
Step 2: in atmosphere furnace, with under certain gas shield, with reference to the thermochemistry characteristic of raw material, adopt temperature programming method, in catalyst-free condition, once property cracking obtains azepine Graphene class and metallic graphite carbon alkene class material.
Technical solution of the present invention two is as follows:
Step one: with phthalocyanine compound, phthalocyanine polymer and derivative thereof for starting raw material, does not do other Feedstock treating and directly uses.
Step 2: in atmosphere furnace, with under certain gas shield, with reference to the thermochemistry characteristic of raw material, adopts temperature programming method, obtains having azepine Graphene class and the metallic graphite carbon alkene class material of coiled structure there being on metal catalysis conditions once property cracking.
Described starting raw material can be commercially available or make metallo phthalocyanine and derivative thereof by oneself.One of preferred magnesium-yttrium-transition metal phthalocyanine-like compound and derivative thereof (as silver-colored in Nickel Phthalocyanine, CuPc, FePC, phthalocyanine molybdenum, Cobalt Phthalocyanine, phthalocyanine gold, phthalocyanine 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 polymer or the porphyrin polymkeric substance containing class phthalocyanine ring structure containing phthalocyanine ring structure.
Described gas shield refers at the 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 mixture; 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, is generally more than 700 degree, is preferably 800 ~ 1000 degree.
Under preferred cracking temperature, the time that cracking autocatalysis generates graphene sheet layer is 4 ~ 24 hours, and shorten or extend pyrolysis time to final grapheme material size, thickness and quality have impact.
In azepine Graphene class material, the acquisition of nitrogen element is from self nitrogen-atoms in phthalocyanine frame, obtaining the nitrogen-atoms of more high-content, can pass into the gas mixture of ammonia and rare gas element in cracking process as needed.
In the Graphene class material of containing metal nanoparticle, the acquisition of metal nanoparticle is from metal classification contained by starting raw material self, for CuPc, obtains the grapheme material containing metallic copper nano particle the most at last.
The technology of the present invention feature: 1. any compound containing phthalocyanine ring and derivative thereof all can be used as the starting raw material obtaining azepine Graphene and metallic graphite carbon alkene; 2., for improving material conductivity or other character, 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 effectively can control the size of Graphene class material, thickness and quality; 4., when using Copper Foil or nickel foil etc. as catalyzer, also can obtain the grapheme material with curling behavior, its conductivity etc. can be improved; 5. different raw materials formulates different temperature programming schemes according to its thermochemistry characteristic; 6. present invention also offers 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 containing metallic copper nano particle of Fig. 3 nitrogen atom doping
The grapheme material transmission electron microscope photo containing 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 containing metal nickel nano particle of Fig. 9 nitrogen atom doping
The XRD figure spectrum of the grapheme material containing 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, the various replacement made according to ordinary skill knowledge and customary means or change, all within the scope of the present invention.
Embodiment 1:
With 30.0 grams of commercially available CuPcs for starting raw material, do not do any purification process.In quartz tube furnace, with 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.Namely be warming up to 300 degree with slow heat-up rate 5 degree of per minutes, stablize 1 hour for 300 degree; Be warming up to 350 degree with 5 degree of per minutes, stablize 1 hour for 350 degree; Be warming up to 400 degree with 5 degree of per minutes, stablize 1 hour for 400 degree; Be warming up to 500 degree with 3 degree of per minutes, stablize 4 hours for 500 degree; Be warming up to 800 degree with 2 degree of per minutes, stablize 8 hours for 800 degree, be finally naturally down to room temperature, obtain the Graphene containing metallic copper nano particle, Fig. 3 and Fig. 4 be shown in by its XRD and transmission electron microscope collection of illustrative plates.
Embodiment 2:
With homemade CuPc for starting raw material, first as embodiment 1 prepares the Graphene containing metallic copper nano particle, then with pure HCl, pure H
2sO
4deng strong acid dissolution, stirring at room temperature obtains the grapheme material of not containing metal particle after several hours, and its XRD, transmission electron microscope are shown in Fig. 5 and Fig. 6 respectively.
Embodiment 3:
With commercially available CuPc for starting raw material, do not do any purification process, in quartz tube furnace, with Copper Foil or nickel foil for base material, under high-purity argon gas protection, argon gas stream speed control is built in 30cm
3min
-1, its heating schedule is: be warming up to 300 degree with slow heat-up rate 5 degree of per minutes, stablize 1 hour for 300 degree; Be warming up to 350 degree with 5 degree of per minutes, stablize 1 hour for 350 degree; Be warming up to 400 degree with 5 degree of per minutes, stablize 1 hour for 400 degree; Be warming up to 700 degree with 3 degree of per minutes, stablize 4 hours for 700 degree; Be warming up to 1000 degree with 2 degree of per minutes, stablize 8 hours for 1000 degree, be finally naturally down to room temperature, obtain the grapheme material of the nitrogen atom doping with coiled structure with acid treatment, its shape appearance figure is shown in Fig. 7.
Embodiment 4:
With commercially available CuPc for 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, obtain having the grapheme material that petal-like nitrogen-atoms mixes, its shape appearance figure is shown in Fig. 8.
Embodiment 5:
With commercially available CuPc for starting raw material, do not do any purification process, in quartz tube furnace, as shown in embodiment one, 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, obtain the grapheme material of high nitrogen doped cupric, ultimate analysis display 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, with under high-purity argon gas protection, argon gas stream speed control is built in 10cm
3min
-1, its heating schedule is as follows: be warming up to 300 degree with slow heat-up rate 5 degree of per minutes, stablize 1 hour for 300 degree; Be warming up to 350 degree with 5 degree of per minutes, stablize 1 hour for 350 degree; Be warming up to 400 degree with 5 degree of per minutes, stablize 1 hour for 400 degree; Be warming up to 500 degree with 3 degree of per minutes, stablize 2 hours for 500 degree; Be warming up to 900 degree with 2 degree of per minutes, stablize 12 hours for 900 degree, be finally naturally down to room temperature, obtain the Graphene containing metal nickel nano particle of nitrogen atom doping, its pattern is shown in Fig. 9, and Figure 10 is the XRD figure of the Graphene containing metal nickel nano particle.
Embodiment 7:
With 10.0 grams of commercially available CuPcs for starting raw material, do not do any purification process.In box atmosphere furnace, with under high-purity argon gas protection, argon gas stream speed control is built in 50cm
3min
-1, be warming up to 300 degree with slow heat-up rate 5 degree of per minutes, stablize 1 hour for 300 degree; Be warming up to 350 degree with 5 degree of per minutes, stablize 1 hour for 350 degree; Be warming up to 400 degree with 5 degree of per minutes, stablize 1 hour for 400 degree; Be warming up to 500 degree with 3 degree of per minutes, stablize 4 hours for 500 degree; Be warming up to 700 degree with 2 degree of per minutes, stablize 12 hours at 700 degree, 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:
With poly-phthalocyanine for starting raw material, not doing any purification process, in quartz tube furnace, take Copper Foil as catalyzer, and with under high-purity argon gas protection, argon gas stream speed control is built in 30cm
3min
-1, its heating schedule is: be warming up to 300 degree with slow heat-up rate 5 degree of per minutes, stablize 1 hour for 300 degree; Be warming up to 350 degree with 5 degree of per minutes, stablize 1 hour for 350 degree; Be warming up to 400 degree with 5 degree of per minutes, stablize 1 hour for 400 degree; Be warming up to 700 degree with 3 degree of per minutes, stablize 4 hours for 700 degree; Be warming up to 1000 degree with 2 degree of per minutes, stablize 8 hours for 1000 degree, be finally naturally down to room temperature, obtain the grapheme material of the nitrogen atom doping with coiled structure.
Embodiment 9:
With 20.0 grams of commercially available CuPcs for starting raw material, do not do any purification process.In box atmosphere furnace, with under high-purity argon gas protection, argon gas stream speed control is built in 50cm
3min
-1, be warming up to 300 degree with slow heat-up rate 5 degree of per minutes, stablize 1 hour for 300 degree; Be warming up to 350 degree with 5 degree of per minutes, stablize 1 hour for 350 degree; Be warming up to 400 degree with 5 degree of per minutes, stablize 1 hour for 400 degree; Be warming up to 500 degree with 3 degree of per minutes, stablize 4 hours for 500 degree; Be warming up to 1000 degree with 2 degree of per minutes, stablize 4 hours for 1000 degree, be finally naturally down to room temperature, obtain 14.6 grams of Graphene class materials containing metallic copper nano particle.
Reference examples:
The step of the synthetic method of the nitrating Graphene of Chinese invention patent CN201110204957 is: first cleaning, drying substrates; At the solution of substrate surface coating containing catalyzer, this catalyzer is water-soluble metal salt; Under anaerobic, the substrate temperature being coated with catalyzer is risen to 500 ~ 1300 DEG C, then passes into reducing gas, reducing catalyst, the nitrogen source compound of the organic carbon source compound and gaseous state that then pass into gaseous state reacts, and obtains described nitrating Graphene, and its itrogen content of getter with nitrogen doped is 3.7%.
Claims (9)
1. solid phase cracking process prepares a method for azepine Graphene and nano metal Graphene, and the method comprises the following steps order:
A): with phthalocyanine-like compound, phthalocyanine polymer for starting raw material, do not do other Feedstock treating and directly use;
B): in atmosphere furnace, under certain gas shield, with reference to the thermochemistry characteristic of raw material, adopt temperature programming method, catalyst-free or under having metal catalyst effect cracking obtain final azepine Graphene and nano metal Graphene class material;
The autocatalysis temperature of described cracking is more than 700 degree.
2. method as claimed in claim 1, is characterized in that described starting raw material is commercially available or self-control metallo phthalocyanine.
3. method as claimed in claim 2, is characterized in that described starting raw material is magnesium-yttrium-transition metal phthalocyanine-like compound.
4. method as claimed in claim 1, is characterized in that described starting raw material is nonmetal phthalocyanine class material.
5. method as claimed in claim 1, is characterized in that described starting raw material is containing metal oxide phthalocyanines material.
6. method as claimed in claim 1, is characterized in that described metal catalyst refers to Copper Foil, copper mesh, nickel foil or nickel foam.
7. method as claimed in claim 1, is characterized in that reaction shielding gas is 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 ~ 50cm
3min
-1between.
8. method as claimed in claim 1, is characterized in that the autocatalysis temperature of described cracking is 800 ~ 1000 degree.
9. method as claimed in claim 8, is characterized in that the time that the autocatalysis of described cracking generates graphene sheet layer is 4 ~ 24 hours.
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| 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 |
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| 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 |
| US10392256B2 (en) * | 2014-11-07 | 2019-08-27 | Xuyang SUN | Method for preparing graphene by using molten inorganic salt reaction bed |
| CN104445160B (en) * | 2014-11-07 | 2017-04-12 | 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 |
| 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 |
| CN104860298B (en) * | 2015-03-25 | 2018-02-16 | 孙旭阳 | The method that graphene is prepared using molten state reaction bed |
| CN104777207B (en) * | 2015-04-10 | 2017-11-28 | 武汉大学 | A kind of three-dimensional nitrogen-doped graphene composite and its preparation method and application |
| 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 |
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| 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 |
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| 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 |
| 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 |
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| 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 |
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| 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 |
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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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