CN102887501A - Method for preparing nitrating graphene - Google Patents
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Abstract
The invention provides a method for preparing nitrating graphene by adopting a chemical vapor deposition process. The method comprises the steps of: providing a high-temperature resistant substrate, a solid/or liquid organic carbon source compound and a solid and/or liquid organic nitrogen source compound; mixing the organic carbon source compound with the organic nitrogen source compound to obtain a mixture solution or suspension solution; coating the mixture solution or suspension solution on the surface of the substrate; and under the anaerobic condition, raising the temperature of the substrate coated with the mixture to 500-1300 DEG C so that the mixture react to generate nitrating graphene. The method for preparing nitrating graphene has the advantages of effectively simplifying the production process of the nitrating graphene and lowering the production cost without additionally adding a catalyst, easily controlling nitrating quantity in nitrating graphene, ensuring uniform doping effect and high electrochemical stability.
Description
Technical field
The invention belongs to the technical field of carbon material, be specifically related to a kind of preparation method of nitrating Graphene.
Background technology
Graphene is a kind of Two-dimensional Carbon atomic crystal that the strong K of the peace moral of Univ Manchester UK in 2004 sea nurse (Andre K.Geim) etc. is found, is the carbon material as thin as a wafer of single or multiple lift.Because its unique structure and photoelectric property make it become the study hotspot in the fields such as carbon material, nanotechnology, Condensed Matter Physics and functional materials, have attracted many scientific workers.Single-layer graphene has large specific surface area, and good conduction, heat conductivility and low thermal expansivity can be used for effect transistor, electrode materials, matrix material, liquid crystal display material, sensor.The method for preparing at present Graphene mainly contains graphite breakaway, chemistry redox method, ultrasonic stripping method etc.Yet, prepare on a large scale in the process of Graphene by redox method at present, reduction Graphene later also contain small amount-OH ,-C-O-C-and-oxygen-containing functional groups such as COOH, these functional groups can reduce electrochemical stability and the electrochemical stability of Graphene.
At present, the correlative study of process for preparing graphenes by chemical vapour deposition has appearred adopting, still, existing chemical Vapor deposition process need to utilize catalyzer, and this catalyzer is that metal or metallic compound are made catalyzer, but when being placed on this catalyzer on the substrate, can cause catalyst distribution inhomogeneous.In order to solve the problem of this catalyst distribution inequality, existing general using chemical Vapor deposition process, physical vaporous deposition, vacuum thermal evaporation method, magnetron sputtering method, plasma enhanced chemical vapor deposition method and print process to substrate, increase the homogeneity of above-mentioned catalyst distribution with catalyst deposit.Therefore, existing employing process for preparing graphenes by chemical vapour deposition needs to add in addition catalyzer, and high to equipment requirements, and complicated operation causes high cost.
Summary of the invention
The object of the invention is to overcome the above-mentioned deficiency of prior art, provide that a kind of technique is simple, productive rate is high, production cost is low, the preparation method of the nitrating Graphene that is easy to operate and control.
In order to realize the foregoing invention purpose, the technical scheme of the embodiment of the invention is as follows:
A kind of preparation method of nitrating Graphene comprises the steps:
Substrate, solid-state and/or liquid organic carbon source compound and solid-state and/or liquid organic nitrogen source compound are provided;
With described organic carbon source compound and organic nitrogen source compound, and be mixed with mixture solution or suspension liquid;
Described mixture solution or suspension liquid are coated in described substrate surface;
Under oxygen-free environment, vacuum condition, the described substrate that is coated with mixture solution or suspension liquid is warming up to 500～1300 ℃ makes mixture reaction, generate described nitrating Graphene.
The preparation method of above-mentioned nitrating Graphene is with solid-state and/or liquid organic carbon source compound, solid-state and/or liquid organic nitrogen source compound, be mixed with solution or suspension liquid, and directly be coated in the surface of substrate, make organic carbon source compound and organic nitrogen source compound direct reaction, do not need to add in addition catalyzer, effectively simplified the production technique of nitrating Graphene, reduced production cost, simultaneously, adopt the synthetic nitrating Graphene of chemical Vapor deposition process, so that easy to control, the uniform doping of itrogen content of getter with nitrogen doped in the nitrating Graphene, the electrochemical stability performance is high.
Description of drawings
Fig. 1 is preparation method's process flow diagram of embodiment of the invention nitrating Graphene;
Fig. 2 is the Electronic Speculum figure of the nitrating Graphene of the embodiment of the invention 1 preparation;
Fig. 3 is the X ray electronic spectrum of the nitrating Graphene of the embodiment of the invention 1 preparation.
Embodiment
In order to make purpose of the present invention, technical scheme and advantage clearer, below in conjunction with drawings and Examples, the present invention is described in further detail.Should be appreciated that specific embodiment described herein only in order to explain the present invention, is not intended to limit the present invention.
The embodiment of the invention provides that a kind of technique is simple, productive rate is high, production cost, the preparation method of the nitrating Graphene that is easy to operate and control.The preparation method's of this nitrating Graphene technical process comprises the steps: as shown in Figure 1
S1: substrate, solid-state and/or liquid organic carbon source compound and solid-state and/or liquid organic nitrogen source compound are provided;
S2: with organic carbon source compound and organic nitrogen source compound, and be mixed with mixture solution or suspension liquid;
S3: mixture solution or suspension liquid are coated in substrate surface;
S4: under oxygen-free environment, vacuum condition, the substrate that is coated with mixture solution or suspension liquid is warming up to 500～1300 ℃ makes mixture reaction, generate described nitrating Graphene.
Particularly, among preparation method's step S1 of above-mentioned nitrating Graphene, substrate should be high temperature resistant, and such as 500～1300 ℃ high temperature among the step S4, it is preferably one or more arbitrary combination in Copper Foil, iron foil, the nickel foil.The substrate of this preferred material is high temperature resistant, and thermal stability is good.
Above-mentioned organic carbon source compound is preferably at least a in ferrocene, dicyclopentadienylcobalt, nickelocene, the two luxuriant manganese, and the organic nitrogen source compound is preferably at least a in urea, aniline, the N-methyl-p-nitroaniline.This preferred organic carbon source compound and organic nitrogen source compound have the good solubility energy, can be mixed with uniform solution, and can be coated in uniformly the surface of substrate, form even and thin rete, thereby effectively reduce the thickness of the nitrating Graphene of surviving among the following step S4.Wherein, contain metal ion in this preferred organic carbon source compound, the existence of this metal ion is conducive to the generation of nitrating Graphene, to improve the productive rate of nitrating Graphene.Certain above-mentioned organic carbon source compound and organic nitrogen source compound also can substitute with other solid-state and/or liquid organic carbon source compounds and solid-state and/or liquid organic nitrogen source compound.When selected organic carbon source compound and/or organic nitrogen source compound are the organic carbon source compound of non-dissolubility and/or organic nitrogen source compound, it can be ground (such as ball milling) and prepare uniform suspension liquid.
Among preparation method's step S2 of above-mentioned nitrating Graphene, the mode of this organic carbon source compound and organic nitrogen source compound can adopt ultrasonic mixing, mixes, one or more arbitrary combination in the ball grinding stirring.Reached and made both well-mixed purposes.In order evenly to be coated to mixed organic carbon source compound and organic nitrogen source compound on the substrate, this mixture should be mixed with solution or suspension liquid, the mode of preparation can be first with after organic carbon source compound and the organic nitrogen source compound, and solubilizing agent (such as deionized water etc.) is uniformly dispersed organic carbon source compound and organic nitrogen source compound in solvent again; Also can in mixing process, add solvent (such as deionized water etc.), with this organic carbon source compound, organic nitrogen source compound and solvent preferably adopt ultrasonic mixing, mix, the mode of one or more arbitrary combination in the ball grinding stirring mixes, and is preferably 5～30% mixture solution or suspension liquid thereby form mass percentage concentration.The not strict restriction of this mixture solution concentration is as preparing saturated mixture solution etc.
Among preparation method's step S3 of above-mentioned nitrating Graphene, the method that mixture solution or suspension liquid are coated to substrate surface preferably adopts one or more arbitrary combination in spread coating, spin-coating method, the infusion method, thereby reach the production technique of simplifying preparation nitrating Graphene, reduced the purpose of production cost.
Among this step S3, before substrate surface application of mixture solution or suspension liquid, preferably in advance this substrate is cleaned, the mode of cleaning is preferably and adopts successively ionized water, ethanol, acetone ultrasonic cleaning post-drying, and is stand-by.Clean this substrate to remove the foreign material that stick to substrate surface, reach the purpose of clean substrate, to be conducive to the coating of mixture solution or suspension liquid.This substrate in earlier stage clean referring to the purging method among the step S11 among the following embodiment 1.
Among preparation method's step S4 of above-mentioned nitrating Graphene, this oxygen free condition is in order to remove oxygen, so that the production of nitrating Graphene can be carried out smoothly, to prevent that under hot conditions, the Graphene of generation is oxidized.This oxygen free condition is the oxygen-free atmosphere that rare gas element consists of, as, nitrogen atmosphere, argon gas atmosphere etc., preferred oxygen free condition is nitrogen atmosphere; Oxygen free condition also can be the condition that vacuumizes, and the condition of this vacuum can not only effectively be removed oxygen, and can also remove simultaneously impurity such as flying away aerial dust, thereby further guarantees the purity of nitrating Graphene.In addition, the condition of this vacuum can also promote the reaction of above-mentioned organic carbon source compound and organic nitrogen source compound, thereby improves the productive rate of nitrating Graphene.Wherein, the condition optimization of this vacuum is that vacuum tightness is less than 10
-3The vacuum condition of Pa.Certainly, at oxygen free condition can be the oxygen free condition of normal pressure.
Among this step S4, the carbon and nitrogen atoms mol ratio of this organic carbon source compound and organic nitrogen source compound is preferably 2～20: 1, and the time that this organic carbon source compound and organic nitrogen source compound react is preferably 1～300 minute.The preferred proportion of this organic carbon source compound and organic nitrogen source compound amount, can so that in the nitrating Graphene that generates the content of nitrogen element at the content range an of the best, thereby further improve the electrochemical stability performance of this nitrating Graphene, simultaneously so that organic carbon source compound and organic nitrogen source compound fully react, improve the utilization ratio of reactant, thereby further reduce production costs.The preferred time that this organic carbon source compound and organic nitrogen source compound react can guarantee that both fully react, so that the nitrating Graphene that generates fully deposits.
Among this step S4, one or more the method for combination that provides preferred employing hot-wire chemical gas-phase deposition, radio-frequency plasma to strengthen in chemical vapour deposition, microwave plasma enhanced chemical vapour deposition, laser chemical vapor deposition, low-pressure chemical vapor deposition, the aumospheric pressure cvd of the lifting of underlayer temperature and this organic carbon source compound, organic nitrogen source compound temperature of reaction provides thermal source.Difference according to aforementioned thermal source presentation mode, therefore, embodiment of the invention chemical Vapor deposition process also is preferably accordingly hot-wire chemical gas-phase deposition, radio-frequency plasma and strengthens one or more combination in chemical vapour deposition, microwave plasma enhanced chemical vapour deposition, laser chemical vapor deposition, low-pressure chemical vapor deposition, the aumospheric pressure cvd.As when adopting the laser chemical vapor deposition method to provide thermal source namely to adopt the synthetic nitrating Graphene of laser chemical vapor deposition method, because laser energy is concentrated, can so that organic carbon source compound and organic nitrogen source compound reaction efficiency further improve, thereby improve the production efficiency of nitrating Graphene.
Among this step S4, after the reaction of organic carbon source compound and organic nitrogen source compound contact, stop the heating to substrate, under the condition that guarantees anaerobic, so that reaction system is cooled off.
Further, in a preferred embodiment of the present invention, the preparation method of above-mentioned nitrating Graphene also comprises the step with the purifying of nitrating Graphene synthetic among the step S4.The step of this nitrating Graphene purifying is preferably: cooled substrate is put into dilute acid soln soaked 0.1～24 hour, remove the reactant that does not participate in reaction fully, by product and other impurity of production, clean with deionized water, then oven dry.Wherein, the kind of diluted acid can but not only be at least a in hydrochloric acid, sulfuric acid, the nitric acid.The concentration of this diluted acid is preferably more than 0.01mol/L, less than 1mol/L.
From the above mentioned, the preparation method of above-mentioned nitrating Graphene is with solid-state and/or liquid organic carbon source compound, solid-state and/or liquid organic nitrogen source compound, be mixed with solution or suspension liquid, and directly be coated in the surface of substrate, make organic carbon source compound and organic nitrogen source compound direct reaction, do not need to add in addition catalyzer, Effective Raise simplified the production technique of nitrating Graphene, reduced production cost, simultaneously, adopt the synthetic nitrating Graphene of chemical Vapor deposition process, so that itrogen content of getter with nitrogen doped is easy to control in the nitrating Graphene, uniform doping, the electrochemical stability performance is high.Wherein, by the consumption of control organic carbon source compound and nitrogenous source chemical combination so that in the synthetic nitrating Graphene content of nitrogen element at the content range an of the best, thereby further improve the electrochemical stability performance of this nitrating Graphene.
Now take the preparation method of concrete nitrating Graphene as example, the present invention is further elaborated.
Embodiment 1:
The preparation method of nitrating Graphene comprises the steps:
S11. with nickel foil substrate deionized water, ethanol, acetone ultrasonic cleaning post-drying, and adopt that to mix method ground mode be that 5: 1 ferrocene and urea mixes with the carbon and nitrogen atoms mol ratio, in the process that mixes, add deionized water, it is the 20wt% mixing solutions that ferrocene and urea are mixed with mass percentage concentration, then is spun on substrate surface;
The substrate that S12. will be coated with mixing solutions is put into reaction chamber, and enclosed reaction chamber, adopts mechanical pump, and lobe pump and molecular pump are evacuated to 10 with reaction chamber step by step
-3Below the Pa, and after keeping 10 minutes, the closure molecule pump begins heating;
S13. when underlayer temperature reaches 500 ℃, keep temperature-resistant, begin to generate the nitrating Graphene;
S14. question response stopped the substrate heating, and is cooled to room temperature after 300 minutes, obtained the nitrating Graphene;
S15. with surface deposition the substrate of nitrating Graphene put into rare nitric acid dousing 0.1 hour of 0.7mol/L, remove the reactant, ferrous metal particle and other impurity that participate in reaction fully, then clean with deionized water, this nitrating Graphene is collected in oven dry.
Present embodiment 1 synthetic nitrating Graphene is carried out Electronic Speculum (SEM) scanning analysis, and the Electronic Speculum of this nitrating Graphene (SEM) scanned picture as shown in Figure 2.As shown in Figure 2, present embodiment 1 synthetic nitrating Graphene is the two-dimensional film shape, and its size is about 0.5～5 μ m.
Present embodiment 1 synthetic nitrating Graphene is carried out X ray electronic spectrum (XPS) analysis, and its XPS result as shown in Figure 3.According to the result of Fig. 3 as can be known, present embodiment 1 synthetic nitrating Graphene nitrogen content is about 8.3%.
Embodiment 2
The preparation method of nitrating Graphene comprises the steps:
S21. with nickel foil substrate deionized water, ethanol, acetone ultrasonic cleaning post-drying, and to adopt ball milling hybrid system ground mode be that 10: 1 nickelocene and aniline mixes with the carbon and nitrogen atoms mol ratio, in the process that mixes, add deionized water, it is the 5wt% mixing solutions that nickelocene and aniline are mixed with mass percentage concentration, then is spun on substrate surface;
The substrate that S22. will be coated with mixing solutions is put into reaction chamber, and enclosed reaction chamber, adopts mechanical pump, and lobe pump and molecular pump are evacuated to 10 with reaction chamber step by step
-3Below the Pa, and after keeping 30 minutes, the closure molecule pump begins heating;
S23. when underlayer temperature reaches 1300 ℃, keep temperature-resistant, begin to generate the nitrating Graphene;
S24. question response stopped the substrate heating, and is cooled to room temperature after 1 minute, obtained the nitrating Graphene;
S25. with surface deposition the substrate of nitrating Graphene put into rare nitric acid dousing 8 hours of 0.4mol/L, remove the reactant, nickel metallic particles and other impurity that participate in reaction fully, then clean with deionized water, this nitrating Graphene is collected in oven dry.
Embodiment 3
The preparation method of nitrating Graphene comprises the steps:
S31. with iron foil substrate deionized water, ethanol, acetone ultrasonic cleaning post-drying, and adopt that to mix method ground mode be that 2: 1 dicyclopentadienylcobalt and urea mixes with the carbon and nitrogen atoms mol ratio, in the process that mixes, add deionized water, it is the 30wt% mixing solutions that dicyclopentadienylcobalt and urea are mixed with mass percentage concentration, and then blade coating is in substrate surface;
The substrate that S32. will be coated with mixing solutions is put into reaction chamber, and enclosed reaction chamber, adopts mechanical pump, and lobe pump and molecular pump are evacuated to 10 with reaction chamber step by step
-3Below the Pa, and after keeping 1 minute, the closure molecule pump begins heating;
S33. when underlayer temperature reaches 1000 ℃, keep temperature-resistant, begin to generate the nitrating Graphene;
S34. question response stopped the substrate heating, and is cooled to room temperature after 100 minutes, obtained the nitrating Graphene;
S35. with surface deposition the substrate of nitrating Graphene put into rare nitric acid dousing 16 hours of 0.2mol/L, remove the reactant, cobalt metallic particles and other impurity that participate in reaction fully, then clean with deionized water, this nitrating Graphene is collected in oven dry.
Embodiment 4
The preparation method of nitrating Graphene comprises the steps:
S41. with iron foil substrate deionized water, ethanol, acetone ultrasonic cleaning post-drying, and adopt that to mix method ground mode be that 20: 1 two luxuriant manganese and urea mixes with the carbon and nitrogen atoms mol ratio, in the process that mixes, add deionized water, it is the 10wt% mixing solutions that dicyclopentadienylcobalt and urea are mixed with mass percentage concentration, then is spun on substrate surface;
The substrate that S42. will be coated with mixing solutions is put into reaction chamber, and enclosed reaction chamber, adopts mechanical pump, and lobe pump and molecular pump are evacuated to 10 with reaction chamber step by step
-3Below the Pa, and after keeping 20 minutes, the closure molecule pump begins heating;
S43. when underlayer temperature reaches 700 ℃, keep temperature-resistant, begin to generate the nitrating Graphene;
S44. question response stopped the substrate heating, and is cooled to room temperature after 200 minutes, obtained the nitrating Graphene;
S45. with surface deposition the substrate of nitrating Graphene put into rare nitric acid dousing 24 hours of 0.08mol/L, remove the reactant, manganese metallic particles and other impurity that participate in reaction fully, then clean with deionized water, this nitrating Graphene is collected in oven dry.
Embodiment 5
The preparation method of nitrating Graphene comprises the steps:
S51. with iron foil substrate deionized water, ethanol, acetone ultrasonic cleaning post-drying, and adopt that to mix method ground mode be that 20: 1 two luxuriant manganese, ferrocene, urea and aniline mixes with the carbon and nitrogen atoms mol ratio, in the process that mixes, add deionized water, being mixed with mass percentage concentration is the 15wt% mixing solutions, then is spun on substrate surface; Wherein, the mol ratio of two luxuriant manganese and ferrocene is 1: 2, and the mol ratio of urea and aniline is 1: 1;
The substrate that S52. will be coated with mixing solutions is put into reaction chamber, and enclosed reaction chamber, adopts mechanical pump, and lobe pump and molecular pump are evacuated to 10 with reaction chamber step by step
-3Below the Pa, and after keeping 20 minutes, the closure molecule pump begins heating;
S53. when underlayer temperature reaches 1200 ℃, keep temperature-resistant, begin to generate the nitrating Graphene;
S54. question response stopped the substrate heating, and is cooled to room temperature after 200 minutes, obtained the nitrating Graphene;
S55. with surface deposition the substrate of nitrating Graphene put into rare nitric acid dousing 24 hours of 0.08mol/L, remove the reactant, manganese metallic particles and other impurity that participate in reaction fully, then clean with deionized water, this nitrating Graphene is collected in oven dry.
The above only is preferred embodiment of the present invention, not in order to limiting the present invention, all any modifications of doing within the spirit and principles in the present invention, is equal to and replaces and improvement etc., all should be included within protection scope of the present invention.
Claims (10)
1. the preparation method of a nitrating Graphene comprises the steps:
Substrate, solid-state and/or liquid organic carbon source compound and solid-state and/or liquid organic nitrogen source compound are provided;
With described organic carbon source compound and organic nitrogen source compound, and be mixed with mixture solution or suspension liquid;
Described mixture solution or suspension liquid are coated in described substrate surface;
Under oxygen-free environment, vacuum condition, the described substrate that is coated with mixture solution or suspension liquid is warming up to 500～1300 ℃ makes mixture reaction, generate described nitrating Graphene.
2. the preparation method of nitrating Graphene according to claim 1, it is characterized in that: the carbon and nitrogen atoms mol ratio of described organic carbon source compound and organic nitrogen source compound is 2～20: 1.
3. the preparation method of nitrating Graphene according to claim 1, it is characterized in that: the mass percent concentration of described mixture solution or suspension liquid is 5～30%.
4. the preparation method of arbitrary described nitrating Graphene according to claim 1～3 is characterized in that: described organic carbon source compound is at least a in ferrocene, dicyclopentadienylcobalt, nickelocene, the two luxuriant manganese.
5. the preparation method of arbitrary described nitrating Graphene according to claim 1～3 is characterized in that: described organic nitrogen source compound is at least a in urea, aniline, the N-methyl-p-nitroaniline.
6. the preparation method of nitrating Graphene according to claim 1 is characterized in that: described substrate is at least a in Copper Foil, iron foil, the nickel foil.
7. the preparation method of nitrating Graphene according to claim 1 is characterized in that: be that vacuum tightness is less than 10 under the described oxygen free condition
-3The vacuum condition of Pa.
8. the preparation method of nitrating Graphene according to claim 1 is characterized in that: described substrate is at least a in Copper Foil, iron foil, the nickel foil.
9. the preparation method of nitrating Graphene according to claim 1 is characterized in that: also comprise the step of described nitrating Graphene being carried out purifying.
10. the preparation method of nitrating Graphene according to claim 9, it is characterized in that: the step that described nitrating Graphene carries out purifying is for to put into concentration greater than 0.01mol/L with the nitrating Graphene, less than soaking in the 1mol/L dilute acid soln 0.1～24 hour.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103265023A (en) * | 2013-06-07 | 2013-08-28 | 新疆师范大学 | Preparation method of nitrogen-doped graphene |
| CN103265024A (en) * | 2013-06-08 | 2013-08-28 | 新疆师范大学 | Method for preparing graphene compound |
| CN103407991A (en) * | 2013-07-10 | 2013-11-27 | 西北工业大学 | Preparation method of nickel/nickel oxide-decorated nitrogen-doped graphene material |
| WO2015049624A1 (en) * | 2013-10-02 | 2015-04-09 | Basf Se | Amine precursors for depositing graphene |
| CN106145101A (en) * | 2016-07-06 | 2016-11-23 | 北京光科博冶科技有限责任公司 | A kind of bigger serface nitrogen-doped graphene and preparation method thereof |
| CN106276911A (en) * | 2015-06-22 | 2017-01-04 | 中原大学 | Manufacturing method of nitrogen-doped graphene and manufacturing method of composite radiating fin thereof |
| CN106517133A (en) * | 2016-10-09 | 2017-03-22 | 华中科技大学 | Nitrogen-doped three-dimensional bicontinuous porous structure ultrathin carbon layer and preparation method and application thereof |
| CN109911887A (en) * | 2017-12-13 | 2019-06-21 | 宁波杉杉新材料科技有限公司 | A kind of preparation method of N doping porous graphene |
| CN114349060A (en) * | 2021-12-29 | 2022-04-15 | 山西大学 | Preparation method of carbon-supported magnetic nanoparticle nitrogen-doped magnetic graphene |
Citations (2)
| 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 |
| CN101696491A (en) * | 2009-10-22 | 2010-04-21 | 清华大学 | In-situ method for preparing graphene/carbon nanotube composite film |
-
2011
- 2011-07-21 CN CN201110204967.8A patent/CN102887501B/en active Active
Patent Citations (2)
| 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 |
| CN101696491A (en) * | 2009-10-22 | 2010-04-21 | 清华大学 | In-situ method for preparing graphene/carbon nanotube composite film |
Non-Patent Citations (1)
| Title |
|---|
| ZHENGZONG SUN ET AL.: "Growth of graphene from solid carbon sources", 《NATURE》 * |
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| CN103265023A (en) * | 2013-06-07 | 2013-08-28 | 新疆师范大学 | Preparation method of nitrogen-doped graphene |
| CN103265024A (en) * | 2013-06-08 | 2013-08-28 | 新疆师范大学 | Method for preparing graphene compound |
| CN103407991A (en) * | 2013-07-10 | 2013-11-27 | 西北工业大学 | Preparation method of nickel/nickel oxide-decorated nitrogen-doped graphene material |
| WO2015049624A1 (en) * | 2013-10-02 | 2015-04-09 | Basf Se | Amine precursors for depositing graphene |
| CN105636932A (en) * | 2013-10-02 | 2016-06-01 | 巴斯夫欧洲公司 | Amine precursors for depositing graphene |
| CN106276911A (en) * | 2015-06-22 | 2017-01-04 | 中原大学 | Manufacturing method of nitrogen-doped graphene and manufacturing method of composite radiating fin thereof |
| CN106145101A (en) * | 2016-07-06 | 2016-11-23 | 北京光科博冶科技有限责任公司 | A kind of bigger serface nitrogen-doped graphene and preparation method thereof |
| CN106145101B (en) * | 2016-07-06 | 2018-08-10 | 北京光科博冶科技有限责任公司 | A kind of bigger serface nitrogen-doped graphene and preparation method thereof |
| CN106517133A (en) * | 2016-10-09 | 2017-03-22 | 华中科技大学 | Nitrogen-doped three-dimensional bicontinuous porous structure ultrathin carbon layer and preparation method and application thereof |
| CN109911887A (en) * | 2017-12-13 | 2019-06-21 | 宁波杉杉新材料科技有限公司 | A kind of preparation method of N doping porous graphene |
| CN114349060A (en) * | 2021-12-29 | 2022-04-15 | 山西大学 | Preparation method of carbon-supported magnetic nanoparticle nitrogen-doped magnetic graphene |
| CN114349060B (en) * | 2021-12-29 | 2024-03-12 | 山西大学 | Preparation method of carbon-coated magnetic nanoparticle nitrogen-doped magnetic graphene |
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