CN102887502B - A kind of synthetic method of nitrating Graphene - Google Patents
A kind of synthetic method of nitrating Graphene Download PDFInfo
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Abstract
The invention provides a kind of synthetic method of nitrating Graphene, comprising step has: provide cleaning, dry substrate; 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.The synthetic method of nitrating Graphene of the present invention adopts water-soluble metal salt as catalyzer, effectively improve the homogeneity of catalyzer in the distribution of substrate surface, and by the synchronous charging of nitrogen source compound of the organic carbon source compound of gaseous state and gaseous state, one-step synthesis, simplify the production technique of nitrating Graphene, reduce production cost.Meanwhile, adopt the nitrating Graphene of chemical Vapor deposition process synthesis, make oxygen element content in nitrating Graphene low, electrochemical stability performance is high.
Description
Technical field
The invention belongs to the technical field of carbon material, be specifically related to a kind of synthetic method of nitrating Graphene.
Background technology
Graphene is a kind of Two-dimensional Carbon atomic crystal that strong K sea nurse (Andre K.Geim) of peace moral etc. of Univ Manchester UK in 2004 finds, is the very thin carbon material of single or multiple lift.Because the structure of its uniqueness and photoelectric property become the study hotspot in the fields such as carbon material, nanotechnology, Condensed Matter Physics and functional materials, many scientific workers are attracted.Single-layer graphene has large specific surface area, and excellent conduction, heat conductivility and low thermal expansivity, can be used for effect transistor, electrode materials, matrix material, liquid crystal display material, sensor.The method preparing Graphene at present mainly contains graphite breakaway, chemistry redox method, ultrasonic stripping method etc.But, prepared on a large scale in the process of Graphene by redox method at present, Graphene after reduction is also containing oxygen-containing functional groups such as-the OH ,-C-O-C-of small amount and-COOH, and these functional groups can reduce electrochemical stability and the electrochemical stability of Graphene.
At present, occurred the correlative study adopting process for preparing graphenes by chemical vapour deposition, but existing chemical Vapor deposition process generally needs to adopt metal or metallic compound to make catalyzer, but when being placed on substrate by this catalyzer, catalyst distribution can be caused uneven.In order to solve the problem of this catalyst distribution inequality, existing general chemical Vapor deposition process, physical vaporous deposition, vacuum thermal evaporation, magnetron sputtering method, plasma enhanced chemical vapor deposition method and print process by catalyst deposit to substrate, increase the homogeneity of above-mentioned catalyst distribution, but, which enhances the complicacy of operation and unnecessary equipment, cause high cost.
Summary of the invention
The object of the invention is to the above-mentioned deficiency overcoming prior art, provide that a kind of technique is simple, productive rate is high, production cost is low, the synthetic method of the nitrating Graphene be easy to operate and control.
In order to realize foregoing invention object, the technical scheme of the embodiment of the present invention is as follows:
A synthetic method for nitrating Graphene, comprises the steps:
Cleaning, drying substrates;
At the slurry of described substrate surface coating containing catalyzer, described catalyzer is water-soluble metal salt;
Under oxygen-free environment, vacuum condition, the described substrate being coated with catalyzer is warming up to 500 ~ 1300 DEG C, then passes into reducing gas, reduce described catalyzer, 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.
The synthetic method of above-mentioned nitrating Graphene adopts water-soluble metal salt as catalyzer, effectively improve the homogeneity of catalyzer in the distribution of substrate surface, and by the synchronous charging of nitrogen source compound of the organic carbon source compound of gaseous state and gaseous state, one-step synthesis, simplify the production technique of nitrating Graphene, reduce production cost.Meanwhile, adopt the nitrating Graphene of chemical Vapor deposition process synthesis, make oxygen element content in nitrating Graphene low, electrochemical stability performance is high.
Accompanying drawing explanation
Fig. 1 is the synthetic method craft schematic flow sheet of embodiment of the present invention nitrating Graphene;
Fig. 2 is the Electronic Speculum figure of the nitrating Graphene that the embodiment of the present invention 1 is synthesized;
Fig. 3 is the X-ray electronic spectrum of the nitrating Graphene that the embodiment of the present invention 1 is synthesized.
Embodiment
In order to make object of the present invention, technical scheme and advantage clearly understand, 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, be not intended to limit the present invention.
Embodiments provide that a kind of technique is simple, productive rate is high, production cost, the synthetic method of the nitrating Graphene be easy to operate and control.The technical process of the synthetic method of this nitrating Graphene as shown in Figure 1, comprises the steps:
S1: cleaning, drying substrates;
S2: at the slurry of this substrate surface coating containing catalyzer, this catalyzer is water-soluble metal salt;
S3: under oxygen-free environment, vacuum condition, the substrate this being coated with catalyzer is warming up 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 nitrating Graphene.
Particularly, in the synthetic method step S1 of above-mentioned nitrating Graphene, substrate should be high temperature resistant, namely has thermostability, and as the high temperature of 500 ~ 1300 DEG C in step S3, it preferably but be not only only one or more arbitrary combination in Copper Foil, iron foil, nickel foil.The substrate of this preferred material is high temperature resistant, and thermal stability is good.This substrate should premenarcheally clean, and to remove the foreign material sticking to substrate surface, reaches the object of clean substrate, to be conducive to the carrying out of following step S2.The cleaning in early stage of this substrate see the purging method in the step S11 in following embodiment 1.
In the synthetic method step S2 of above-mentioned nitrating Graphene, because catalyzer is water-soluble metal salt, therefore, catalyzer can directly be dissolved, be mixed with slurry, directly preferably adopt the mode of one or more arbitrary combination in spread coating, spin-coating method, infusion method to be coated in the surface of this substrate, thus reach the production technique simplifying synthesis nitrating Graphene, reduce the object of production cost.During catalyst preparation form slurry by this water-soluble metal salt, the volumetric molar concentration of this slurry preferably but be not only only 0.01mol/L ~ 1mol/L.This water-soluble metal salt preferably but be not limited to the water-soluble nitrate, villaumite etc. of metal.Wherein, metal water-soluble nitrate can but at least one be not limited in iron nitrate, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, nickelous nitrate etc.; Villaumite can but be not only only iron(ic) chloride, cobalt chloride and/or nickelous chloride etc.
In this step S2, the mol ratio of the gaseous state organic carbon source chemical combination that this catalyzer passes in the adhesive capacity and following step S3 of substrate surface preferably 1: 20 ~ 1000.The preferred consumption of this catalyzer can improve the reaction efficiency that in following step S3, nitrating Graphene is produced, and can reduce the content of catalyzer in nitrating Graphene product to greatest extent simultaneously.
In the synthetic method step S3 of above-mentioned nitrating Graphene, this oxygen free condition is to remove oxygen, and reducing gas and catalyzer can be carried out smoothly.This oxygen free condition is the oxygen-free atmosphere that rare gas element is formed, e.g., nitrogen atmosphere, argon gas atmosphere etc., preferred oxygen free condition is nitrogen atmosphere; Oxygen free condition also can be the oxygen free condition vacuumized, and the oxygen free condition of this vacuum effectively can not only remove oxygen, and can also remove impurity such as flying away aerial dust simultaneously, thus ensures the purity of nitrating Graphene.In addition, the condition of this vacuum can also promote the reaction of organic carbon source compound and nitrogen source compound, thus improves the productive rate of nitrating Graphene.Wherein, the oxygen free condition of this vacuum is preferably vacuum tightness and is less than 10
-3the condition of Pa vacuum anaerobic.Certainly, at oxygen free condition can be the oxygen free condition of normal pressure.
In this step S3, the flow that reducing gas passes into is preferably 10 ~ 200sccm; The time of reducing catalyst is 1 ~ 60 minute.Wherein, this reducing gas preferably but be not only only hydrogen, can also be the reducing gas such as CO gas certainly.The time of the above-mentioned preferred flow and reduction reaction that pass into reducing gas effectively can ensure that catalyzer and above-mentioned water-soluble metal salt fully reduce.In addition, the preferred kind of reducing gas can not disturb the generation of nitrating Graphene.
In this step S3, the organic carbon source compound passed into and the amount of nitrogen source compound are preferably: in organic carbon source compound, in carbon atom and nitrogen source compound, the mol ratio of nitrogen-atoms is 2 ~ 10: 1, and the time that this organic carbon source compound and nitrogen source compound carry out reacting is preferably 1 ~ 300 minute.Wherein, the flow that organic carbon source compound passes into is preferably 20 ~ 1000sccm, and this organic carbon source compound is preferably at least one in methane, ethane, acetylene, ethene, propylene; The flow that nitrogen source compound passes into is preferably 10 ~ 200sccm, and this nitrogen source compound is preferably at least one in nitrogen, ammonia, methylamine.The preferred proportion of this organic carbon source compound and nitrogen source compound consumption and flow, the content of nitrogen element in the nitrating Graphene generated can be made at a best content range, thus improve the electrochemical stability performance of this nitrating Graphene further, make organic carbon source compound and nitrogen source compound fully react simultaneously, improve the utilization ratio of reactant, thus further reduce production cost.Fully react both the preferred time that this organic carbon source compound and nitrogen source compound carry out reacting can ensure, the nitrating Graphene generated fully is deposited.
In this step S3, the lifting of underlayer temperature and organic carbon source compound, providing of nitrogen source compound temperature of reaction preferably adopt the method for one or more the combination in hot-wire chemical gas-phase deposition, radio-frequency plasma enhancing chemical vapour deposition, Microwave Plasma Torch Atomic Emission Spect rometry, laser chemical vapor deposition, low-pressure chemical vapor deposition, aumospheric pressure cvd to provide thermal source.According to the difference of aforementioned thermal source presentation mode, therefore, embodiment of the present invention chemical Vapor deposition process is also preferably one or more the combination in hot-wire chemical gas-phase deposition, radio-frequency plasma enhancing chemical vapour deposition, Microwave Plasma Torch Atomic Emission Spect rometry, laser chemical vapor deposition, low-pressure chemical vapor deposition, aumospheric pressure cvd accordingly.When providing thermal source namely to adopt laser induced chemical vapor depostion method to synthesize nitrating Graphene as adopted laser induced chemical vapor depostion method, because laser energy is concentrated, organic carbon source compound and nitrogen source compound reaction efficiency can be made to improve further, thus improve the production efficiency of nitrating Graphene.
In this step S3, after organic carbon source compound and nitrogen source compound reaction terminate, stop passing into reducing gas, organic carbon source compound and nitrogen source compound, stop the heating to substrate simultaneously, under the condition ensureing anaerobic, reaction system is cooled.
Further, as a preferably embodiment of the present invention, the synthetic method of above-mentioned nitrating Graphene also comprises the step of the purifying of the nitrating Graphene synthesized in step S3.The step of this nitrating Graphene purifying is preferably: cooled substrate is put into dilute acid soln and soak 0.1 ~ 24 hour, remove catalyst metal particles and other impurity, then clean with deionized water, then dry.Wherein, diluted acid kind can but at least one be not only only in hydrochloric acid, sulfuric acid, nitric acid.The concentration of this diluted acid is preferably greater than 0.01mol/L, is less than 1mol/L.
From the above mentioned, the synthetic method of above-mentioned nitrating Graphene adopts water-soluble metal salt as catalyzer, effectively improve the homogeneity of catalyzer in the distribution of substrate surface, and by organic carbon source compound and the synchronous charging of nitrogen source compound, one-step synthesis, simplify the production technique of nitrating Graphene, reduce production cost.Simultaneously, adopt the nitrating Graphene of chemical Vapor deposition process synthesis, make oxygen element content in nitrating Graphene low, electrochemical stability performance is high, wherein, by controlling the consumption of organic carbon source compound and nitrogenous source chemical combination, making the content of nitrogen element in the nitrating Graphene synthesized at a best content range, thus improving the electrochemical stability performance of this nitrating Graphene further.
Now for the synthetic method of concrete nitrating Graphene, the present invention is further elaborated.
Embodiment 1:
The synthetic method of nitrating Graphene, comprises the steps:
S11. by nickel foil substrate deionized water, ethanol, acetone ultrasonic cleaning post-drying, be that the iron nitrate of 1mol/L is spun on substrate surface by concentration;
S12. be that the substrate of the iron nitrate catalyzer of 1mol/L is put into reaction chamber by being coated with volumetric molar concentration, and enclosed reaction chamber, adopt mechanical pump, reaction chamber is evacuated to 10 by lobe pump and molecular pump step by step
-3below Pa, and after keeping 20 minutes, closure molecule pump, starts this silicon;
S13. when underlayer temperature reaches 1000 DEG C, keep temperature-resistant, pass into hydrogen 50sccm, keep 40 minutes, reducing catalyst;
S14. pass into methane and ammonia, methane flow is 1000sccm, and ammonia flow is 200sccm, and the intake of methane and ammonia is the mol ratio of C atom in ethane and nitrogen N atom is 5: 1, reacts 1 minute, generates nitrating Graphene; Wherein, the total amount of the methane passed into is 600: 1 with the mol ratio being coated in the iron nitrate on substrate.
S15., after having reacted, stop passing into hydrogen, methane, ammonia species and to silicon, and be cooled to room temperature, obtain nitrating Graphene;
S16. by surface deposition, the substrate of Graphene is put into 0.6mol/L dilute hydrochloric acid and is soaked 8 hours, removes ferrous metal particle and other impurity, then cleans with deionized water, dry.
The nitrating Graphene synthesized by the present embodiment 1 carries out Electronic Speculum (SEM) scanning analysis, and Electronic Speculum (SEM) scanned picture of this nitrating Graphene as shown in Figure 2.As shown in Figure 2, the nitrating Graphene that the present embodiment 1 synthesizes is two-dimensional film shape, and its size is 0.5 μm ~ 5 μm.
The nitrating Graphene synthesized by the present embodiment 1 carries out X-ray electronic spectrum (XPS) analysis, and its XPS result as shown in Figure 3.According to the result of Fig. 3, the nitrating Graphene nitrogen content that the present embodiment 1 synthesizes is about 5.7%.
Embodiment 2
The synthetic method of nitrating Graphene, comprises the steps:
S21. by Copper Foil substrate deionized water, ethanol, acetone ultrasonic cleaning post-drying, be that the Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES of 0.1mol/L is spun on substrate surface by concentration;
S22. be that the substrate of the Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES catalyzer of 0.1mol/L is put into reaction chamber by being coated with concentration, and enclosed reaction chamber, adopt mechanical pump, reaction chamber is evacuated to 10 by lobe pump and molecular pump step by step
-3below Pa, and after keeping 10 minutes, closure molecule pump, starts this silicon;
S23. when underlayer temperature reaches 1300 DEG C, keep temperature-resistant, pass into hydrogen 10sccm, make hydrogen and catalyst reaction, and keep 60 minutes, reducing catalyst;
S24. pass into ethane and nitrogen, ethane flow is 500sccm, and nitrogen flow is 50sccm, and the intake of ethane and nitrogen is the mol ratio of C atom in ethane and nitrogen N atom is 10: 1, reacts 100 minutes, generates nitrating Graphene; Wherein, the total amount of the ethane passed into is 20: 1 with the mol ratio being coated in the Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES on substrate.
S25., after having reacted, stop passing into hydrogen, ethane, nitrogen and to silicon, and be cooled to room temperature, obtain nitrating Graphene;
S26. by surface deposition, the substrate of Graphene puts into 0.3mol/L dilute sulphuric acid 16 hours, removes cobalt metallic particles and other impurity, then cleans with deionized water, dries.
Embodiment 3
The synthetic method of nitrating Graphene, comprises the steps:
S31. by iron foil substrate deionized water, ethanol, acetone ultrasonic cleaning post-drying, be that the nickelous nitrate of 0.01mol/L is spun on substrate surface by concentration;
S32. be that the substrate of the nickelous nitrate catalyzer of 0.01mol/L is put into reaction chamber by being coated with volumetric molar concentration, and enclosed reaction chamber, adopt mechanical pump, reaction chamber is evacuated to 10 by lobe pump and molecular pump step by step
-3below Pa, and after keeping 1 minute, closure molecule pump, starts this silicon;
S33. when underlayer temperature reaches 500 DEG C, keep temperature-resistant, pass into hydrogen 200sccm, keep 20 minutes, reducing catalyst;
S34. pass into acetylene and ammonia, acetylene flow is 100sccm, and ammonia flow is 100sccm, and the intake of acetylene and ammonia is the mol ratio of C atom in acetylene and ammonia atom N is 2: 1, reacts 300 minutes, generates nitrating Graphene; Wherein, the total amount of the acetylene passed into is 20: 1 with the mol ratio being coated in the nickelous nitrate on substrate;
S35., after having reacted, stop passing into hydrogen, methane, ammonia species and silicon, and be cooled to room temperature, obtain nitrating Graphene;
S36. by surface deposition, the substrate of Graphene is put into 0.1mol/L dilute hydrochloric acid and is soaked 24 hours, removes nickel metallic particles and other impurity, then cleans with deionized water, dry.
Embodiment 4
The synthetic method of nitrating Graphene, comprises the steps:
S41. Copper Foil and iron foil substrate being used deionized water, ethanol, acetone ultrasonic cleaning post-drying respectively, is that the ferric chloride Solution of 0.5mol/L is spun on Copper Foil and iron foil substrate surface by volumetric molar concentration;
S42. the substrate being coated with ferric chloride catalyst is put into reaction chamber, and enclosed reaction chamber, adopt mechanical pump, reaction chamber is evacuated to 10 by lobe pump and molecular pump step by step
-3below Pa, and after keeping 30 minutes, closure molecule pump, starts this silicon;
S43. when underlayer temperature reaches 800 DEG C, keep temperature-resistant, pass into hydrogen 100sccm, keep 1 minute, reducing catalyst;
S44. pass into methane and methylamine, methane flow is 20sccm, and methylamine flow is 10sccm, and the intake of methane and methylamine is the mol ratio of C atom in methane and methylamine and methylamine atom N is 2: 1, reacts 200 minutes, generates nitrating Graphene; Wherein, the total amount of the methane passed into is 1000: 1 with the mol ratio being coated in the iron(ic) chloride on substrate;
S45., after having reacted, stop passing into hydrogen, methane, methylamine material and silicon, and be cooled to room temperature, obtain nitrating Graphene;
S46. by surface deposition, the substrate of Graphene is put into 0.8mol/L dust technology and is soaked 0.1 hour, removes ferrous metal particle and other impurity, then cleans with deionized water, dry.
Embodiment 5
The synthetic method of nitrating Graphene, comprises the steps:
S51. Copper Foil and iron foil substrate being used deionized water, ethanol, acetone ultrasonic cleaning post-drying respectively, is that the ferric chloride Solution of 0.5mol/L is spun on Copper Foil and iron foil substrate surface by concentration;
S52. the substrate being coated with ferric chloride catalyst is put into reaction chamber, and enclosed reaction chamber, adopt mechanical pump, reaction chamber is evacuated to 10 by lobe pump and molecular pump step by step
-3below Pa, and after keeping 30 minutes, closure molecule pump, starts this silicon;
S53. when underlayer temperature reaches 800 DEG C, keep temperature-resistant, pass into hydrogen 100sccm, keep 1 minute, reducing catalyst;
S54. the methylamine of the methane of volume ratio 1: 1 and the mixed gas of ethene and volume ratio 1: 1 and the mixed gas of ammonia is passed into, the mixed gas flow of methane and ethene is 500sccm, the mixed gas flow of methylamine and ammonia is 100sccm, the mixed gas of methane and ethene and amine and ammonia mixed gas intake be the mol ratio of atom N in the mixed gas of C atom in the mixed gas of methane and ethene and methylamine and ammonia be 8: 1, react 200 minutes, generate nitrating Graphene; Wherein, the total amount of the methane passed into and the mixed gas of ethene is 700: 1 with the mol ratio being coated in the iron(ic) chloride on substrate;
S55., after having reacted, stop passing into hydrogen, methane, methylamine material and silicon, and be cooled to room temperature, obtain nitrating Graphene;
S56. by surface deposition, the substrate of Graphene is put into 0.8mol/L dust technology and is soaked 0.1 hour, removes ferrous metal particle and other impurity, then cleans with deionized water, dry.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any amendments done within the spirit and principles in the present invention, equivalent replacement and improvement etc., all should be included within protection scope of the present invention.
Claims (7)
1. a synthetic method for nitrating Graphene, comprises the steps:
Cleaning, drying substrates;
At the slurry of described substrate surface coating containing catalyzer, described catalyzer is water-soluble metal salt, and described coating method adopts at least one in spread coating, spin-coating method, infusion method; Described water-soluble metal salt is iron nitrate, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, nickelous nitrate or iron(ic) chloride;
Under oxygen-free environment, vacuum condition, the described substrate being coated with catalyzer is warming up to 500 ~ 1300 DEG C, then passes into reducing gas, reduce described catalyzer, 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;
Wherein, in described organic carbon source compound, in carbon atom and nitrogen source compound, the mol ratio of nitrogen-atoms is 2 ~ 10:1;
The flow that described organic carbon source compound passes into is 20 ~ 1000sccm; The flow that described nitrogen source compound passes into is 10 ~ 200sccm;
The flow that described reducing gas passes into is 10 ~ 200sccm; The time of reducing catalyst is 1 ~ 60 minute;
Described reducing gas is CO gas.
2. the synthetic method of nitrating Graphene according to claim 1, is characterized in that: the mol ratio of described catalyzer and described carbon-source cpd is 1:20 ~ 1000.
3. the synthetic method of nitrating Graphene according to claim 1, is characterized in that: the time that described organic carbon source compound and nitrogen source compound carry out reacting is 1 ~ 300 minute.
4., according to the synthetic method of the arbitrary described nitrating Graphene of claims 1 to 3, it is characterized in that: described organic carbon source compound is at least one in methane, ethane, acetylene, ethene, propylene.
5., according to the synthetic method of the arbitrary described nitrating Graphene of claims 1 to 3, it is characterized in that: described nitrogen source compound is at least one in nitrogen, ammonia, methylamine.
6. the synthetic method of nitrating Graphene according to claim 1, is characterized in that: described substrate is at least one in Copper Foil, iron foil, nickel foil.
7. the synthetic method of nitrating Graphene according to claim 1, is characterized in that: also comprise and described nitrating Graphene is put into concentration be greater than 0.01mol/L, be less than or equal to the step of carrying out purifying in the dilute acid soln of 1mol/L.
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| CN104465131B (en) * | 2014-12-24 | 2017-04-12 | 哈尔滨工业大学 | Preparing method of graphene nanoribbon and aluminum-based supercapacitor collector electrode |
| CN109534328B (en) * | 2017-09-22 | 2022-06-24 | 天津大学 | Two-dimensional nitrogen-doped graphene and preparation method thereof |
| CN112645313B (en) * | 2021-01-16 | 2022-05-27 | 大连理工大学 | Method for electrochemically rapidly preparing graphene-based monatomic catalyst in batch and application thereof |
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