CN103833024B - Graphene nanobelt and preparation method thereof - Google Patents
Graphene nanobelt and preparation method thereof Download PDFInfo
- Publication number
- CN103833024B CN103833024B CN201210490997.4A CN201210490997A CN103833024B CN 103833024 B CN103833024 B CN 103833024B CN 201210490997 A CN201210490997 A CN 201210490997A CN 103833024 B CN103833024 B CN 103833024B
- Authority
- CN
- China
- Prior art keywords
- preparation
- nanometer wall
- methylimidazole
- ethyl
- graphene nanobelt
- 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.)
- Active
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Landscapes
- Carbon And Carbon Compounds (AREA)
Abstract
The present invention relates to a kind of graphene nanobelt and preparation method thereof, comprise the steps: to prepare carbonoxide nanometer wall slurry; Prepare graphene nanobelt.In the preparation method of graphene nanobelt of the present invention, ionic liquid is heated to certain temperature, be conducive to increasing reduction effect, coordinate microwave can complete stripping fast again, and ionic liquid physical efficiency effectively prevents graphene nanobelt from again reuniting, then preparation process can be completed through simple separation, drying operation.
Description
Technical field
The present invention relates to chemical material synthesis field, particularly relate to a kind of graphene nanobelt and preparation method thereof.
Background technology
The kind of carbon material comprises the soccerballene (C of zero dimension
60deng), the carbon nanotube, carbon nanofiber etc. of one dimension, the Graphene of two dimension, three-dimensional graphite, diamond etc.Carbon nanometer wall (english abbreviation CNW) is the carbon nano structure with two-dimensional diffusion structure, its most typical shape characteristic can grow perpendicular to substrate material surface exactly, and be greater than the wall-like structure of Graphene for thickness, they are completely different from the feature of soccerballene, carbon nanotube, Graphene etc., can be used as the raw material of other carbon material of preparation.
Graphene nanobelt not only has the performance of Graphene, also possesses the performance that some are special, and such as its length-to-diameter ratio is very large, can up to thousands of times, can copper conductor be replaced at integrated circuit connection, to improve integrated level further, also can carry out modification to its structure and be prepared into switch device.But at present due to the problem that there is size control difficulty in graphene nanobelt preparation process, yield poorly, thus limit its application.
Summary of the invention
Goal of the invention of the present invention is to solve above-mentioned prior art Problems existing and deficiency, provides a kind of graphene nanobelt and preparation method thereof, and adopt hot reducing method to peel off carbonoxide nanometer wall, splitting time is short, and preparation efficiency is high, and technique is simple.
For reaching goal of the invention of the present invention, the technical solution used in the present invention is: a kind of preparation method of graphene nanobelt, comprise the steps: that (a) prepares carbonoxide nanometer wall slurry: get carbon nanometer wall and join in the vitriol oil, add potassium permanganate and stir, add deionized water again and carry out suction filtration, wash with hydrochloric acid afterwards, suction filtration in neutral, obtains carbonoxide nanometer wall slurry to filtrate.
B () prepares graphene nanobelt: after described carbonoxide nanometer wall slurry drying, by mass volume ratio 1g:(5 ~ 1000) ml, being joined by described carbonoxide nanometer wall and temperature is housed is Homogeneous phase mixing in the container of the ion liquid solvent of 150 ~ 300 DEG C, filter for the first time after microwave is peeled off, the filter residue obtained is filtered through organic solvent again, be filtered to filtrate in neutral with deionized water, finally by described filter residue and drying to constant weight graphene nanobelt.
In described step (a), the mass volume ratio of described carbon nanometer wall, the described vitriol oil, described potassium permanganate and described hydrogen peroxide is: 50g:1150ml:150g:250ml.
In described step (b), described microwave power is 1000 ~ 2000w, and the time of described microwave is 10 ~ 300 minutes, and described drying is carried out in vacuum drying oven, and the temperature of described drying is 60 ~ 100 DEG C.
In described step (b), described ionic liquid is 1-ethyl-3-methylimidazole Tetrafluoroboric acid, 1-ethyl-3-methylimidazole fluoroform sulfimide, 1-ethyl-3-methylimidazole trifluoromethanesulfonic acid, 1-ethyl-3-methylimidazole trifluoroacetic acid, 1-ethyl-3-methylimidazole fluoroform sulphonyl carbon, 1-ethyl-3-methylimidazole five acetyl fluoride imines, 1-ethyl-3-methylimidazole two cyaniding nitrogen, 1-ethyl-3, 5-methylimidazole fluoroform sulfimide, 1, 3-diethyl-4-methylimidazole fluoroform sulfimide, 1, at least one in 3-diethyl-5-Methylimidazole fluoroform sulfimide.
In described step (b), described organic solvent is 1-Methyl-2-Pyrrolidone or DMF.
In described step (a), the method preparing described carbon nanometer wall comprises the steps: (c) etched substrate: substrate etching cleaned up after 0.5 ~ 10 minute with the dilute acid soln of 0.01 ~ 1mol/L.
D () prepares carbon nanometer wall: described substrate is placed in oxygen-free environment and is heated to 600 ~ 900 DEG C; then substrate surface described in UV-irradiation is opened; pass into carbonaceous material and protective gas again and keep 30 ~ 300 minutes, obtaining carbon nanometer wall at described substrate surface.
In described step (c), described substrate is a kind of in iron foil, nickel foil, cobalt paper tinsel, and described dilute acid soln is the one in hydrochloric acid, nitric acid, sulfuric acid.
In described step (c), the concentration of described dilute acid soln is 0.1 ~ 0.5mol/L, and the time of described etching is 1 ~ 3 minute, and described substrate deionized water, ethanol, acetone clean successively.
In described step (d); described carbonaceous material is the one in methane, ethane, propane, acetylene, ethanol; described protective gas is the one in helium, nitrogen, argon gas; the flow velocity passing into described carbonaceous material is 10 ~ 1000sccm, and the volume ratio of described carbonaceous material and described protective gas is (2 ~ 10): 1.
The present invention also comprises the graphene nanobelt utilizing above-mentioned preparation method to obtain.
Compared with prior art, there is following advantage in graphene nanobelt of the present invention and preparation method thereof:
1. adopt etching method to prepare vertical carbon nanometer wall with photochemical catalysis chemical Vapor deposition process, its preparation technology is simple, condition is easily controlled, shorten etching time while improve production efficiency, and photochemical catalysis effectively can reduce temperature of reaction, reduce energy consumption, reduce production cost, and effectively can avoid produced problem in the plasma method preparation process in existing method, make the thickness of carbon nanometer wall evenly, structure is more complete.
2. ionic liquid is heated to certain temperature, be conducive to increasing reduction effect, then coordinate microwave can complete stripping fast, and ionic liquid physical efficiency effectively prevents graphene nanobelt from again reuniting, then can preparation process be completed through simple separation, drying operation.
3. prepare the high and good dispersity raw material of the productive rate of graphene nanobelt with carbonoxide nanometer wall for raw material can prepare voluntarily, lessen production cost like this.
4. equipment required in preparation process is all common chemical industry equipment, can save research and development equipment cost, is applicable to scale operation.
Accompanying drawing explanation
Fig. 1 is that the carbon nanometer wall SEM prepared by the embodiment of the present invention 1 schemes.
Fig. 2 is that the graphene nanobelt SEM prepared by the embodiment of the present invention 1 schemes.
Embodiment
Below in conjunction with embodiment, elaboration is further given to the present invention.
The preparation process of graphene nanobelt of the present invention is roughly divided into following steps: 1. etched substrate: substrate is put into the dilute acid soln etching 0.5 ~ 10 minute that concentration is 0.01 ~ 1mol/L, etch rear deionized water, ethanol, acetone cleans.
This step object is: by making metal liner end eclipse surface produce defect to metal substrate etching, effectively can improve the surface tissue of metal substrate, carbon nanometer wall energy is enough grown at this metal substrate surface.
Wherein, the preferred time etching this metal substrate is 60 ~ 180 seconds, and the preferred acid strength of etching metal substrate is 0.1 ~ 0.5mol/L.Preferred etching condition, can reach the effect of good etching above, improves the growth efficiency of carbon nanometer wall.
2. prepare carbon nanometer wall: cleaned substrate is put into reaction chamber and gets rid of the air of reaction chamber; then by silicon to 600 ~ 900 DEG C; open ultraviolet source equipment again; make UV-irradiation at substrate surface; then by volume (2 ~ 10): 1 passes into carbonaceous material (flow is 10 ~ 1000sccm) and protective gas, and keeps 30 ~ 300 minutes.
This step object is: the air got rid of in reaction chamber can remove the oxygen in reaction chamber, and avoid the participation of oxygen and affect the growth of carbon nanometer wall, the growth for carbon nanometer wall provides a stable environment.
After having reacted, stop passing into carbonaceous material, stop silicon; and close ultraviolet source equipment, stop after question response room is cooled to room temperature passing into protective gas, namely obtain carbon nanometer wall at substrate surface; it is scraped from substrate surface, just obtains pulverous carbon nanometer wall.
Wherein, substrate is a kind of in iron foil, nickel foil, cobalt paper tinsel, and dilute acid soln is the one in hydrochloric acid, nitric acid, sulfuric acid.Protective gas is the one in helium, nitrogen, argon gas, and carbonaceous material is the one in methane, ethane, propane, acetylene, ethanol.
3. prepare carbonoxide nanometer wall slurry: join in the vitriol oil of 0 DEG C by the pulverous carbon nanometer wall in above-mentioned steps 2, add potassium permanganate again, the temperature of mixture is kept to remain on less than 10 DEG C, after stirring 2h, 24h is stirred in room-temperature water bath, slowly deionized water is added again under condition of ice bath, after 15min, add the deionized water suction filtration containing 30% concentration hydrogen peroxide again, mixture color becomes glassy yellow afterwards, wash with the hydrochloric acid that concentration is 10% again, after suction filtration is neutrality to filtrate, namely obtain carbonoxide nanometer wall slurry.
Wherein, the mass volume ratio of carbon nanometer wall, the vitriol oil, potassium permanganate and hydrogen peroxide is: 50g:1150ml:150g:250ml.
4. prepare graphene nanobelt: after carbonoxide nanometer wall slurry drying, by mass volume ratio 1g:(5 ~ 1000) ml, being joined by carbonoxide nanometer wall and temperature is housed is Homogeneous phase mixing in the container of the ion liquid solvent of 150 ~ 300 DEG C, container microwave under the power of 1000 ~ 2000w is peeled off 10 ~ 300 minutes, then filter for the first time, by the filter residue that obtains again through organic solvent filter 23 ~ 6 time, filtrate is filtered in neutral with deionized water, finally the filter residue cleaned up is dried in the drying baker of 60 ~ 100 DEG C constant weight graphene nanobelt.
Wherein, organic solvent is 1-Methyl-2-Pyrrolidone (english abbreviation, NMP) or DMF (english abbreviation, DMF), effectively can remove ionic liquid.
Ionic liquid is 1-ethyl-3-methylimidazole Tetrafluoroboric acid (EtMeImBF
4), 1-ethyl-3-methylimidazole fluoroform sulfimide (EtMeImN (CF
3sO
2)
2), 1-ethyl-3-methylimidazole trifluoromethanesulfonic acid (EtMeImCF
3sO
3), 1-ethyl-3-methylimidazole trifluoroacetic acid (EtMeImCF
3cO
2), 1-ethyl-3-methylimidazole fluoroform sulphonyl carbon (EtMeImC (CF
3sO
2)
3), 1-ethyl-3-methylimidazole five acetyl fluoride imines (EtMeImN (C
2f
5sO
2)
2), 1-ethyl-3-methylimidazole two cyaniding nitrogen (EtMeImN (CN)
2), 1-ethyl-3,5-methylimidazole fluoroform sulfimide (1-Et-3,5-Me
2imN (CF
3sO
2)
2), 1,3-diethyl-4-methylimidazole fluoroform sulfimide (1,3-Et
2-4-MeImN (CF
3sO
2)
2), 1,3-diethyl-5-Methylimidazole fluoroform sulfimide (1,3-Et2-5-MeImN (CF
3sO
2)
2) at least one.
The present invention also comprises the graphene nanobelt utilizing above-mentioned preparation method to obtain.
Be specifically described with the preparation process of embodiment 1 to graphene nanobelt of the present invention below.
Embodiment 1
1. etched substrate: nickel foil is put into the dilute hydrochloric acid solution etching 0.5 minute that concentration is 1mol/L, the good rear deionized water of etching, ethanol, acetone clean.
2. prepare carbon nanometer wall: cleaned nickel foil put into reaction chamber and after getting rid of the air of described reaction chamber, nickel foil be heated to 900 DEG C; then ultraviolet source equipment is opened; make UV-irradiation on nickel foil surface; then carbonaceous material methane (flow is 200sccm) and protective gas nitrogen is passed into; the volume ratio of methane and nitrogen is 2:1, and keeps 100 minutes.
After having reacted, stop passing into carbonaceous material, stop nickel foil heating and close light source; stop after question response room is cooled to room temperature passing into protective gas; carbon nanometer wall can be obtained on nickel foil surface, it is scraped from nickel foil surface, just obtain carbon nanometer wall powder.
3. prepare carbonoxide nanometer wall slurry: prepare carbonoxide nanometer wall slurry: 50g carbon nanometer wall is added 0 DEG C, in the vitriol oil of 1.15L, add 150g potassium permanganate again, the temperature of mixture remains on less than 10 DEG C, stir 2h, then after room-temperature water bath stirs 24h, 4.6L deionized water is slowly added under condition of ice bath, after 15min, add 14L deionized water (wherein containing 250ml concentration is the hydrogen peroxide of 30%) again, mixture color becomes glassy yellow afterwards, suction filtration, wash with the hydrochloric acid that 2.5L concentration is 10% again, suction filtration, until filtrate is in neutral.
4. prepare graphene nanobelt: after carbonoxide nanometer wall slurry drying, get 1g carbonoxide nanometer wall, join and the 1-ethyl-3-methylimidazole Tetrafluoroboric acid (EtMeImBF that 50ml temperature is 150 DEG C is housed
4) ion liquid solvent container in Homogeneous phase mixing, container microwave under the power of 2000w is peeled off 30 minutes, then filter for the first time, the filter residue obtained is filtered 6 times through organic solvent 1-Methyl-2-Pyrrolidone (NMP) again, be filtered to filtrate in neutral with deionized water, finally the filter residue cleaned up is dried in the drying baker of 60 DEG C constant weight graphene nanobelt.
As can be seen from the carbon nanometer wall SEM figure in Fig. 1, the carbon nanometer wall thickness adopting photochemical catalysis chemical Vapor deposition process to prepare is even, is 20 ~ 40nm, and basic vertical substrates growth, high consistency is good.As shown in the graphene nanobelt SEM figure of Fig. 2, after carbon nanometer wall is stripped into graphene nanobelt, even width, is about 30 ~ 60nm, and length is about 5 ~ 10um.
Following table 1 is the design parameter of embodiment 2 ~ 11, and the processing step of each embodiment is identical with embodiment 1, and difference is processing parameter and processing condition, repeats no more its processing step at this.
Graphene nanobelt of the present invention and preparation method thereof, there is following advantage: 1. adopt etching method to prepare vertical carbon nanometer wall with photochemical catalysis chemical Vapor deposition process, its preparation technology is simple, condition is easily controlled, shorten etching time while improve production efficiency, and photochemical catalysis effectively can reduce temperature of reaction, reduce energy consumption, reduce production cost, and effectively can avoid produced problem in the plasma method preparation process in existing method, make the thickness of carbon nanometer wall evenly, structure is more complete.
2. ionic liquid is heated to certain temperature, be conducive to increasing reduction effect, then coordinate microwave can complete stripping fast, and ionic liquid physical efficiency effectively prevents graphene nanobelt from again reuniting, then can preparation process be completed through simple separation, drying operation.
3. prepare the high and good dispersity raw material of the productive rate of graphene nanobelt with carbonoxide nanometer wall for raw material can prepare voluntarily, lessen production cost like this.
4. equipment required in preparation process is all common chemical industry equipment, can save research and development equipment cost, is applicable to scale operation.
Foregoing; be only preferred embodiment of the present invention; not for limiting embodiment of the present invention; those of ordinary skill in the art are according to central scope of the present invention and spirit; can carry out corresponding flexible or amendment very easily, therefore protection scope of the present invention should be as the criterion with the protection domain required by claims.
Claims (9)
1. a preparation method for graphene nanobelt, is characterized in that, comprises the steps:
A () prepares carbonoxide nanometer wall slurry: get carbon nanometer wall and join in the vitriol oil, add potassium permanganate and stir, then adds deionized water and carry out suction filtration, washs afterwards with hydrochloric acid, and suction filtration in neutral, obtains carbonoxide nanometer wall slurry to filtrate; Wherein, described deionized water contains hydrogen peroxide;
B () prepares graphene nanobelt: after described carbonoxide nanometer wall slurry drying, by mass volume ratio 1g:(5 ~ 1000) ml, being joined by described carbonoxide nanometer wall and temperature is housed is Homogeneous phase mixing in the container of the ion liquid solvent of 150 ~ 300 DEG C, filter for the first time after microwave is peeled off, the filter residue obtained is filtered through organic solvent again, be filtered to filtrate in neutral with deionized water, finally by described filter residue and drying to constant weight graphene nanobelt.
2. preparation method according to claim 1, is characterized in that, in described step (a), the mass volume ratio of described carbon nanometer wall, the described vitriol oil, described potassium permanganate and described hydrogen peroxide is: 50g:1150ml:150g:250ml.
3. preparation method according to claim 1, is characterized in that, in described step (b), described microwave power is 1000 ~ 2000w, the time of described microwave is 10 ~ 300 minutes, and described drying is carried out in vacuum drying oven, and the temperature of described drying is 60 ~ 100 DEG C.
4. preparation method according to claim 1, it is characterized in that, in described step (b), described ionic liquid is 1-ethyl-3-methylimidazole Tetrafluoroboric acid, 1-ethyl-3-methylimidazole fluoroform sulfimide, 1-ethyl-3-methylimidazole trifluoromethanesulfonic acid, 1-ethyl-3-methylimidazole trifluoroacetic acid, 1-ethyl-3-methylimidazole fluoroform sulphonyl carbon, 1-ethyl-3-methylimidazole five acetyl fluoride imines, 1-ethyl-3-methylimidazole two cyaniding nitrogen, 1-ethyl-3, 5-methylimidazole fluoroform sulfimide, 1, 3-diethyl-4-methylimidazole fluoroform sulfimide, 1, at least one in 3-diethyl-5-Methylimidazole fluoroform sulfimide.
5. preparation method according to claim 1, is characterized in that, in described step (b), described organic solvent is 1-Methyl-2-Pyrrolidone or DMF.
6. preparation method according to claim 1, is characterized in that, in described step (a), the method preparing described carbon nanometer wall comprises the steps:
(c) etched substrate: substrate etching was cleaned up after 0.5 ~ 10 minute with the dilute acid soln of 0.01 ~ 1mol/L; Described substrate is a kind of in iron foil, nickel foil, cobalt paper tinsel;
D () prepares carbon nanometer wall: described substrate is placed in oxygen-free environment and is heated to 600 ~ 900 DEG C; then substrate surface described in UV-irradiation is opened; pass into carbonaceous material and protective gas again and keep 30 ~ 300 minutes, obtaining carbon nanometer wall at described substrate surface.
7. preparation method according to claim 6, is characterized in that, in described step (c), described dilute acid soln is the one in hydrochloric acid, nitric acid, sulfuric acid.
8. preparation method according to claim 6, it is characterized in that, in described step (c), the concentration of described dilute acid soln is 0.1 ~ 0.5mol/L, the time of described etching is 1 ~ 3 minute, and described substrate deionized water, ethanol, acetone clean successively.
9. preparation method according to claim 6; it is characterized in that; in described step (d); described carbonaceous material is the one in methane, ethane, propane, acetylene, ethanol; described protective gas is the one in helium, nitrogen, argon gas; the flow velocity passing into described carbonaceous material is 10 ~ 1000sccm, and the volume ratio of described carbonaceous material and described protective gas is (2 ~ 10): 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210490997.4A CN103833024B (en) | 2012-11-27 | 2012-11-27 | Graphene nanobelt and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210490997.4A CN103833024B (en) | 2012-11-27 | 2012-11-27 | Graphene nanobelt and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103833024A CN103833024A (en) | 2014-06-04 |
| CN103833024B true CN103833024B (en) | 2016-01-20 |
Family
ID=50796972
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210490997.4A Active CN103833024B (en) | 2012-11-27 | 2012-11-27 | Graphene nanobelt and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103833024B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103935976B (en) * | 2013-01-18 | 2016-05-18 | 海洋王照明科技股份有限公司 | Carbon nanometer wall and graphene nanobelt and preparation method |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101800302A (en) * | 2010-04-15 | 2010-08-11 | 上海交通大学 | Graphene nanometer sheet-cobaltous oxide composite negative electrode material of lithium ion battery and preparation method thereof |
| WO2012035551A1 (en) * | 2010-09-14 | 2012-03-22 | Council Of Scientific & Industrial Research | Electrochemical process for synthesis of graphene |
| CN102616768A (en) * | 2011-02-01 | 2012-08-01 | 长庚大学 | Graphene nanoribbon manufacturing method |
-
2012
- 2012-11-27 CN CN201210490997.4A patent/CN103833024B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101800302A (en) * | 2010-04-15 | 2010-08-11 | 上海交通大学 | Graphene nanometer sheet-cobaltous oxide composite negative electrode material of lithium ion battery and preparation method thereof |
| WO2012035551A1 (en) * | 2010-09-14 | 2012-03-22 | Council Of Scientific & Industrial Research | Electrochemical process for synthesis of graphene |
| CN102616768A (en) * | 2011-02-01 | 2012-08-01 | 长庚大学 | Graphene nanoribbon manufacturing method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103833024A (en) | 2014-06-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103833021B (en) | Nitrogen-doped graphene nano belt and preparation method thereof | |
| CN102757042B (en) | Method for preparing thin-layer graphene by liquid chemical method | |
| CN104370285A (en) | Method for macroscopically preparing high-quality graphene by using bio-mineralized material | |
| CN106554010A (en) | The method of preparation of industrialization big size graphene | |
| CN103935982B (en) | The preparation method of graphene nanobelt | |
| CN107032331B (en) | A kind of graphene preparation method based on dielectric base | |
| CN103569992A (en) | Preparation method of carbon nanotube | |
| CN103387223A (en) | Preparation method of graphite | |
| CN106744859A (en) | Graphene three-dimensional multistage pore structure powder prepared by a kind of low temperature polymer cracking | |
| CN103922318B (en) | Nitrogen-doped graphene nano belt and preparation method thereof | |
| CN103922319B (en) | Boron doped graphene nano belt and preparation method thereof | |
| CN103833024B (en) | Graphene nanobelt and preparation method thereof | |
| CN103833022B (en) | Graphene nanobelt and preparation method thereof | |
| CN103832999B (en) | Carbon nanometer wall and prepared the method for graphene nanobelt by it | |
| CN103738947A (en) | Preparation method for single-layer graphene ethylene glycol solution | |
| CN103879991B (en) | The preparation method of graphene nanobelt | |
| CN103879989B (en) | The preparation method of nitrogen-doped graphene nano belt | |
| CN103935975B (en) | The preparation method of carbon nanometer wall and graphene nanobelt | |
| CN103833023B (en) | Graphene nanobelt and preparation method thereof | |
| CN103924257A (en) | Graphene nanoribbons and preparation method thereof | |
| CN103935979B (en) | The preparation method of graphene nanobelt | |
| CN103879994B (en) | The preparation method of graphene nanobelt | |
| CN103935983B (en) | The preparation method of graphene nanobelt | |
| CN103879993B (en) | The preparation method of graphene nanobelt | |
| CN103935984B (en) | The preparation method of graphene nanobelt |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |