CN103879992A - Preparation method of graphene nanobelt - Google Patents
Preparation method of graphene nanobelt Download PDFInfo
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- CN103879992A CN103879992A CN201210558228.3A CN201210558228A CN103879992A CN 103879992 A CN103879992 A CN 103879992A CN 201210558228 A CN201210558228 A CN 201210558228A CN 103879992 A CN103879992 A CN 103879992A
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Abstract
A preparation method of a graphene nanobelt comprises the following steps: carrying out a photocatalytic chemical vapor deposition reaction on a carbon source under the action of ultraviolet light as a photocatalyst in order to generate a carbon nanowall on an etched metal substrate, scrapping off the carbon nanowall to obtain carbon nanowall powder, carrying out a three-electrode system reaction on the carbon nanowall powder as a raw material to prepare an intercalation carbon nanowall, dispersing the intercalation carbon nanowall in an ionic liquid according to a solid-to-liquid ratio of 1g:10-100ml in order to obtain a dispersion, carrying out heating peeling of the dispersion in a fast medium wave radiator with the power of 40-100w/cm, filtering, washing filter residues, and drying to obtain the graphene nanobelt. The graphene nanobelt with a high dimension homogeneity can be obtained by using the carbon nanowall powder as a raw material for preparing the graphene nanobelt and carrying out heating peeling in the fast medium wave radiator, the method makes no oxygen-containing groups introduced into the finally obtained graphene nanobelt, and the graphene nanobelt with a good quality can be prepared through the method.
Description
Technical field
The present invention relates to the synthetic field of nano-carbon material, particularly relate to a kind of preparation method of graphene nanobelt.
Background technology
Graphene nanobelt is on the basis of two-dimentional Graphene plane, the zonal structure forming through certain shearing.Graphene nanobelt not only has the performance of Graphene, also possesses some special performances, and for example its length-to-diameter ratio is larger, can be up to thousands of times, can replace copper conductor at integrated circuit connection, further improve integrated level, also can carry out modification to its structure and be prepared into switch device.
At present, the preparation method of graphene nanobelt adopts cutting carbon nanotubes method conventionally, first this method is immersed in carbon nanotube in sulfuric acid, heats after adding strong oxidizer, utilizes strong oxidizer to make carbon nanotube open loop and obtain graphene nanobelt under high temperature action.The graphene nanobelt that this side prepares conventionally can introduce oxygen-containing functional group and the conductivity of graphene nanobelt, and the homogeneity of size is difficult to control, and makes the poor of the graphene nanobelt quality that finally obtains, is difficult to practical requirement.
Summary of the invention
Based on this, be necessary to provide a kind of preparation method of graphene nanobelt, with the good graphene nanobelt of preparation quality.
A preparation method for graphene nanobelt, comprises the steps:
Use dilute acid soln to carry out etching to metal substrate;
Under the atmosphere of anaerobic and shielding gas, described metal substrate is heated to 600 DEG C ~ 900 DEG C;
Under the irradiation of UV-light, pass into the one in methane, ethane, propane, acetylene and ethanol to described metal substrate surface, process photochemical catalysis chemical vapour deposition reaction 30 minutes ~ 300 minutes, at described metal substrate Surface Creation carbon nanometer wall;
After having reacted, under the atmosphere of described shielding gas, the metal substrate with carbon nanometer wall is cooled to room temperature, then described carbon nanometer wall is scraped from the surface of described metal substrate, obtain carbon nanometer wall powder;
Described carbon nanometer wall powder is positioned on collector and is pressed into carbon nanometer wall lamella and obtain working electrode;
To jointly be soaked in electrolytic solution, at 5mA/cm electrode, reference electrode and described working electrode
2~ 100mA/cm
2current density, room temperature under react after 1 hour ~ 20 hours, reacted electrolytic solution is filtered, washs filter residue the dry intercalation carbon nanometer wall that obtains; And
Being 1g:10 ~ 100ml by solid-to-liquid ratio is scattered in described intercalation carbon nanometer wall in ionic liquid, to obtain dispersion liquid, during to be 40 ~ 100w/cm by described dispersion liquid at power fast, in wave emitter, heating is filtered after peeling off, and washing filter residue is also dried and obtains graphene nanobelt.
In an embodiment, the step that described use dilute acid soln carries out etching to metal substrate is specially therein: described metal substrate is put into the dilute acid soln etching 0.5 minute ~ 10 minutes that concentration is 0.01mol/L ~ 1mol/L.
In an embodiment, described use dilute acid soln carries out etch step to metal substrate and is specially therein: described metal substrate is put into the dilute acid soln etching 1 minute ~ 3 minutes that concentration is 0.1mol/L ~ 0.5mol/L.
In an embodiment, described ultraviolet light wavelength is 200 ~ 400nm therein.
In an embodiment, a kind of flow in described methane, ethane, propane, acetylene and ethanol is 10sccm ~ 1000sccm therein.
In an embodiment, the volume ratio of a kind of and described shielding gas in described methane, ethane, propane, acetylene and ethanol is 2 ~ 10:1 therein.
In an embodiment, described electrolytic solution is selected from least one in formic acid, acetic acid, propionic acid, nitric acid, Nitromethane 99Min. therein.
In an embodiment, described washing filter residue the dry step that obtains intercalation carbon nanometer wall are specially therein: with filter residue described in deionized water wash, and in 60 DEG C ~ 80 DEG C vacuum-dryings 12 hours ~ 24 hours.
Therein in an embodiment, described ionic liquid is selected from 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 and 1, one in 3-diethyl-5-Methylimidazole fluoroform sulfimide.
Therein in an embodiment, described washing filter residue the dry step that obtains graphene nanobelt are specially described filter residue 1-Methyl-2-Pyrrolidone or N, dinethylformamide washing 3 ~ 6 times, use successively ethanol, acetone and deionized water wash, then at 60 DEG C ~ 100 DEG C, vacuum-drying to constant weight obtains graphene nanobelt again.
First the preparation method of above-mentioned graphene nanobelt utilizes photochemical catalysis chemical vapour deposition to prepare structural integrity, carbon nanometer wall powder that dimensional homogeneity is higher, raw material using this carbon nanometer wall powder as graphene nanobelt, carry out heating and peeling off in fast middle wave emitter, be heated concentrated, efficiency is high, obtain the graphene nanobelt that dimensional homogeneity is higher, and this method, not preparing in process and can introducing oxy radical at the graphene nanobelt finally obtaining, prepare the good graphene nanobelt of quality.
Brief description of the drawings
Fig. 1 is preparation method's schema of the graphene nanobelt of an embodiment;
Fig. 2 is the SEM figure of the carbon nanometer wall prepared of embodiment 1;
Fig. 3 is the SEM figure of the graphene nanobelt prepared of embodiment 1.
Embodiment
For above-mentioned purpose of the present invention, feature and advantage can be become apparent more, below in conjunction with accompanying drawing, the specific embodiment of the present invention is described in detail.A lot of details are set forth in the following description so that fully understand the present invention.But the present invention can implement to be much different from alternate manner described here, and those skilled in the art can do similar improvement without prejudice to intension of the present invention in the situation that, and therefore the present invention is not subject to the restriction of following public concrete enforcement.
Refer to Fig. 1, the preparation method of the graphene nanobelt of an embodiment, comprises the steps:
Step S110: use dilute acid soln to carry out etching to metal substrate.
Metal substrate is preferably the one in iron foil, nickel foil and cobalt paper tinsel.
Use dilute acid soln step that metal substrate is carried out to etching to be specially: metal substrate is put into the dilute acid soln etching 0.5 minute ~ 10 minutes that concentration is 0.01mol/L ~ 1mol/L.
Dilute acid soln is dilute hydrochloric acid solution, dilution heat of sulfuric acid or dilute nitric acid solution.
Preferably, the concentration of dilute acid soln is 0.1mol/L ~ 0.5mol/L, and the time of etching is 1 minute ~ 3 minutes.
Metal substrate is carried out to etching, make metal substrate surface produce defect, can effectively improve the surface tissue of metal substrate, think that carbon nanometer wall provides a favourable growth substrate, make the enough surface growths in metal substrate of carbon nanometer wall energy.
A kind of metal substrate in iron foil, nickel foil and cobalt paper tinsel is put into the dilute acid soln etching 1 minute ~ 3 minutes that concentration is 0.1mol/L ~ 0.5mol/L, can reach good etching effect, be conducive to improve the growth efficiency of carbon nanometer wall.
Step S120: under the atmosphere of anaerobic and shielding gas, metal substrate is heated to 600 DEG C ~ 900 DEG C.
First the metal substrate through over etching is cleaned up and is dried with deionized water, ethanol and acetone successively, for subsequent use.
The metal substrate through over etching after cleaning-drying is put into reaction chamber.The air of getting rid of in reaction chamber also passes into shielding gas, makes reaction chamber completely in anaerobic state, avoids the participation of oxygen and affects the growth of carbon nanometer wall, for the growth of carbon nanometer wall provides a stable environment.
Metal substrate is heated to 600 DEG C ~ 900 DEG C, and insulation to reaction finishes.
Shielding gas is preferably at least one in helium, nitrogen, argon gas.
Step S130: under the irradiation of UV-light, pass into the one in methane, ethane, propane, acetylene and ethanol to metal substrate surface, process photochemical catalysis chemical vapour deposition reaction 30 minutes ~ 300 minutes, at metal substrate Surface Creation carbon nanometer wall.
Ultraviolet source equipment and metal substrate are just right.Open ultraviolet source equipment, make the surface of UV-irradiation in metal substrate.
UV-light is as photocatalyst.Ultraviolet light wavelength is preferably 200 ~ 400nm.
Under the irradiation of UV-light, in reaction chamber, pass into carbon source, make in the atmosphere of metal substrate in carbon source.Carbon source is selected from the one in methane, ethane, propane, acetylene and ethanol.
The flow of carbon source is 10sccm ~ 1000sccm.
Preferably, the volume ratio of carbon source and shielding gas is 2 ~ 10:1.
Under UV-irradiation and in shielding gas atmosphere, the one process photochemical catalysis chemical vapour deposition reaction in methane, ethane, propane, acetylene and ethanol 30 minutes ~ 300 minutes, Formed nanometer wall in metal substrate.
Step S140: after having reacted, under the atmosphere of shielding gas, the metal substrate with carbon nanometer wall is cooled to room temperature, then carbon nanometer wall is scraped from the surface of metal substrate, obtain carbon nanometer wall powder.
React after 30 minutes ~ 300 minutes; stop passing into carbon source, close heating installation and close ultraviolet source equipment, after question response chamber and the metal substrate with carbon nanometer wall are cooled to room temperature, stop passing into shielding gas; the carbon nanometer wall on metal substrate surface is scraped, obtain carbon nanometer wall powder.
Question response chamber and be cooled to room temperature with the metal substrate of carbon nanometer wall after stop again passing into shielding gas, prevent that the carbon nanometer wall generating is at high temperature oxidized, and further ensures to obtain the quality of carbon nanometer wall powder.
Step S150: carbon nanometer wall powder is positioned on collector and is pressed into carbon nanometer wall lamella and obtain working electrode.
Carbon nanometer wall powder and binding agent are positioned on collector, then, with mould compacting, make to form carbon nanometer wall lamella on collector, obtain the working electrode of three-electrode system.Collector preferably adopts stainless steel collector.
Carbon nanometer wall lamella is of a size of 75*40*7mm
3.
Step S160: will jointly be soaked in electrolytic solution, at 5mA/cm electrode, reference electrode and working electrode
2~ 100mA/cm
2current density, room temperature under react after 1 hour ~ 20 hours, reacted electrolytic solution is filtered, washs filter residue the dry intercalation carbon nanometer wall that obtains.
Adopt stereotype as to electrode, Hg/Hg
2sO
4as reference electrode.
Electrolytic solution is selected from least one in formic acid, acetic acid, propionic acid, nitric acid, Nitromethane 99Min..Electrolytic solution also plays the effect of intercalator simultaneously, and under electric field action, electrolytic solution forms potential difference at working electrode surface, constantly overcomes the reactive force between carbon nanowall layer under the driving of potential difference, is inserted between carbon nanowall layer, obtains intercalation carbon nanometer wall.
React after 1 hour ~ 20 hours, reacted electrolytic solution filtered, then by the filter residue deionized water wash obtaining, then by the vacuum-drying 12 hours ~ 24 hours at 60 DEG C ~ 80 DEG C of the filter residue after washing, be dried, pure intercalation carbon nanometer wall.
Step S170: being 1g:10 ~ 100ml by solid-to-liquid ratio is scattered in intercalation carbon nanometer wall to obtain dispersion liquid in ionic liquid, during to be 40 ~ 100w/cm by dispersion liquid at power fast, in wave emitter, heating is filtered after peeling off, and washing filter residue is also dried and obtains graphene nanobelt.
Intercalation carbon nanometer wall is scattered in to be convenient to rapid heating in ionic liquid and to peel off, and the graphene nanobelt obtaining after peeling off is also scattered in ionic liquid.Can prevent that as dispersion liquid graphene nanobelt from reuniting with ionic liquid, thereby improve the productive rate of graphene nanobelt.
In order to reach good dispersion effect, to improve the productive rate of charge stripping efficiency and graphene nanobelt, the solid-to-liquid ratio of intercalation carbon nanometer wall and ionic liquid is preferably 1g:10 ~ 100ml.
Ionic liquid is selected from 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-Me2ImN (CF
3sO
2)
2), 1,3-diethyl-4-methylimidazole fluoroform sulfimide (1,3-Et
2-4-MeImN (CF
3sO
2)
2) and 1,3-diethyl-5-Methylimidazole fluoroform sulfimide (1,3-Et
2-5-MeImN (CF
3sO
2)
2) in one.
Above-mentioned ionic liquid is liquid at normal temperatures, so that intercalated graphite is scattered in ionic liquid, peels off to carry out at normal temperatures fast middle wave emitter heating, and heating is fast, and energy consumption is low, and preparation cost is low.
Dispersion liquid is 40 ~ 100w/cm at power heats to peel off after 1 minute ~ 30 minutes in wave emitter in fast and filters for the first time, again by 1-Methyl-2-Pyrrolidone for filter residue (NMP) or N, dinethylformamide (DMF) washing 3 ~ 6 times, fully to remove the ionic liquid in filter residue.Then, use successively ethanol, acetone and deionized water wash, then vacuum-drying to constant weight obtains graphene nanobelt at 60 DEG C ~ 100 DEG C.
During to be 40 ~ 100w/cm at power fast, in wave emitter, heat and peel off, can realize rapid heating, to ensure certain charge stripping efficiency, make splitting time shorter, production efficiency is higher; On the other hand, avoid the power of microwave too high, to the structure generation destruction of graphene nanobelt.
Heat stripping process in wave emitter in fast in, do not introduce impurity, the filtrate obtaining of filtration, ionic liquid can reclaim and reuse, and is conducive to reduce preparation cost.
The preparation method of above-mentioned graphene nanobelt, first utilize UV-light as photocatalyst, carbon source is through photochemical catalysis chemical vapour deposition reaction Formed nanometer wall in the metal substrate through over etching, this carbon nanometer wall is scraped and obtains carbon nanometer wall powder, using this carbon nanometer wall powder as raw material, adopt three-electrode system reaction to prepare intercalation carbon nanometer wall, to this intercalation carbon nanometer wall carry out fast in wave emitter heating peel off and obtain graphene nano wall.
Utilize UV-light as photocatalyst, carbon source has been avoided the traditional destruction of preparation method's applying plasma to carbon nanometer wall in plasma atmosphere through the method for photochemical catalysis chemical vapour deposition reaction Formed nanometer wall in the metal substrate through over etching, carbon nanometer wall that can generating structure is comparatively complete, dimensional homogeneity is higher.
The graphene nanobelt that the method adopts the carbon nanometer wall powder of preparation voluntarily to prepare as raw material, the preparation of carbon nanometer wall powder is using a kind of as carbon source in methane, ethane, propane, acetylene and ethanol, these several carbon sources are comparatively cheap, with respect to the raw material that adopts commercially available carbon nanotube as graphene nanobelt, its cost is relatively low, and photochemical catalysis can effectively reduce temperature of reaction, reduce energy consumption, reduce production cost.
Preparation method's technique of this graphene nanobelt is simple, and condition is easily controlled, and heats charge stripping efficiency high in fast middle wave emitter, has improved production efficiency.
Preparation method's equipment used of this graphene nanobelt is all common chemical industry equipment, and lower to the requirement of equipment, technique is simple, and condition is easily controlled, and is applicable to scale operation.
It is below specific embodiment.
Embodiment 1
1. the dilute hydrochloric acid solution etching 0.5 minute of nickel foil being put into concentration and be 1mol/L, etching is well cleaned and is dried with deionized water, ethanol, acetone afterwards;
2. get rid of the air in reaction chamber and pass into nitrogen, nickel foil after cleaning-drying is put into the reaction chamber that is connected with nitrogen, and nickel foil is heated to 900 DEG C and insulation, then open ultraviolet source equipment, make UV-irradiation on nickel foil surface, ultraviolet light wavelength is 250nm, then passes into methane 200sccm, the volume ratio of methane and nitrogen is 2:1, keeps 100 minutes;
3. after having reacted, stop passing into methane, stop nickel foil heating and close ultraviolet source equipment, question response chamber stops passing into nitrogen after being cooled to room temperature, and nickel foil Surface Creation carbon nanometer wall, scrapes it from nickel foil surface, just obtain carbon nanometer wall powder;
4. the preparation of intercalation carbon nanometer wall: adopt stainless steel substrates as collector, the above-mentioned carbon nanometer wall powder preparing is put on collector, being pressed into specification on collector is 75*40*7mm
3the carbon nanometer wall lamella of (about 2g) is as working electrode, using stereotype as to electrode, and Hg/Hg
2sO
4as reference electrode, formic acid, as electrolytic solution, is put into three electrodes electrolyzer and is fully immersed in electrolytic solution, at 5mA/cm
2current density, room temperature under react 20 hours, then reacted electrolytic solution is filtered, the filter residue obtaining is placed in vacuum drying oven in 60 DEG C and can obtains pure, dry intercalation carbon nanometer wall after dry 24 hours by washed with de-ionized water;
5. getting intercalation carbon nanometer wall, is that 1g:10ml joins EtMeImBF is housed by mass volume ratio
4in the container of ionic liquid, in the fast middle wave emitter that is 80w/cm by this container placement power, heat and peel off 10 minutes, then filter for the first time, the filter residue obtaining NMP filtration washing 6 times, use successively again ethanol, acetone, deionized water wash, filter, the filter residue of collecting is dried to constant weight at vacuum drying oven at 60 DEG C and obtains graphene nanobelt.
Fig. 2 and Fig. 3 are respectively the carbon nanometer wall of embodiment 1 and the SEM of graphene nanobelt figure.
As can be seen from Figures 2 and 3, carbon nanometer wall is perpendicular to the intensive growth of substrate, even thickness, being about 30 ~ 60nm, is that the prepared graphene nanobelt width distribution of raw material is concentrated by carbon nanometer wall, is about 20 ~ 40nm, length is about 2 ~ 20um, and length-to-diameter ratio is about 50 ~ 1000.
This graphene nanobelt do not introduce oxygen-containing functional group, width distribution is comparatively even, and in stripping process, can keep to greatest extent the integrity of graphene nano band structure, the quality of the graphene nanobelt preparing is better.
Embodiment 2
1. adopt iron foil as substrate, iron foil is put into the dilution heat of sulfuric acid etching 4 minutes that concentration is 0.5mol/L, etching is well cleaned and is dried with deionized water, ethanol, acetone afterwards;
2. the air in eliminating reaction chamber pass into argon gas, iron foil after cleaning-drying is put into the reaction chamber that is connected with argon gas, and iron foil is heated to 600 DEG C and insulation, then open ultraviolet source equipment, make UV-irradiation on iron foil surface, ultraviolet light wavelength is 200nm, then passes into ethane 100sccm, the volume ratio of ethane and argon gas is 5:1, keeps 200 minutes;
3. after having reacted, stop passing into ethane, stop iron foil heating and close ultraviolet source equipment, question response chamber stops passing into argon gas after being cooled to room temperature, and iron foil Surface Creation carbon nanometer wall, scrapes it from iron foil surface, just obtain carbon nanometer wall powder;
4. the preparation of intercalation carbon nanometer wall: adopt stainless steel substrates as collector, the above-mentioned carbon nanometer wall powder preparing is put on collector, being pressed into specification on collector is 75*40*7mm
3the carbon nanometer wall lamella of (about 2g) is as working electrode, using stereotype as to electrode, and Hg/Hg
2sO
4as reference electrode, acetic acid, as electrolytic solution, is put into three electrodes electrolyzer and is fully immersed in electrolytic solution, at 20mA/cm
2current density, room temperature under react 1 hour, then reacted electrolytic solution is filtered, the filter residue obtaining is placed in vacuum drying oven in 70 DEG C and can obtains pure, dry intercalation carbon nanometer wall after dry 20 hours by washed with de-ionized water;
5. getting intercalation carbon nanometer wall, is that 1g:100ml joins EtMeImN (CF is housed by mass volume ratio
3sO
2)
2in the container of ionic liquid, this container is placed in the fast middle wave emitter that power is 40w/cm and heats and peel off 30 minutes, then filter for the first time, the filter residue obtaining DMF filtration washing 3 times, use successively again ethanol, acetone, deionized water wash, filter, the filter residue of collecting is dried to constant weight at vacuum drying oven at 80 DEG C and obtains graphene nanobelt.
Embodiment 3
1. adopt cobalt paper tinsel as substrate, cobalt paper tinsel is put into the dilute nitric acid solution etching 10 minutes that concentration is 0.01mol/L, etching is well cleaned and is dried with deionized water, ethanol, acetone afterwards;
2. the air in eliminating reaction chamber pass into helium, cobalt paper tinsel after cleaning-drying is put into the reaction chamber that is connected with helium, and cobalt paper tinsel is heated to 700 DEG C of insulations, then open ultraviolet source equipment, make UV-irradiation on cobalt paper tinsel surface, ultraviolet light wavelength is 350nm, then passes into acetylene 10sccm, the volume ratio of acetylene and helium is 8:1, keeps 300 minutes;
3. after having reacted, stop passing into acetylene, stop the heating of cobalt paper tinsel and close ultraviolet source equipment, question response chamber stops passing into helium after being cooled to room temperature, and cobalt paper tinsel Surface Creation carbon nanometer wall, scrapes it from cobalt paper tinsel surface, just obtain carbon nanometer wall powder;
4. the preparation of intercalation carbon nanometer wall: adopt stainless steel substrates as collector, the above-mentioned carbon nanometer wall powder preparing is put on collector, being pressed into specification on collector is 75*40*7mm
3the carbon nanometer wall lamella of (about 2g) is as working electrode, using stereotype as to electrode, and Hg/Hg
2sO
4as reference electrode, propionic acid, as electrolytic solution, is put into three electrodes electrolyzer and is fully immersed in electrolytic solution, at 50mA/cm
2current density, room temperature under react 2 hours, then reacted electrolytic solution is filtered, the filter residue obtaining is placed in vacuum drying oven in 80 DEG C and can obtains pure, dry intercalation carbon nanometer wall after dry 12 hours by washed with de-ionized water;
5. getting intercalation carbon nanometer wall, is that 1g:50ml joins EtMeImCF is housed by mass volume ratio
3sO
3in the container of ionic liquid, this container is placed in the fast middle wave emitter that power is 100w/cm and heats and peel off 1 minute, then filter for the first time, the filter residue obtaining NMP filtration washing 5 times, use successively again ethanol, acetone, deionized water wash, filter, the filter residue of collecting is dried to constant weight at vacuum drying oven at 100 DEG C and obtains graphene nanobelt.
Embodiment 4
1. adopt nickel foil as substrate, nickel foil is put into the dilute hydrochloric acid solution etching 2 minutes that concentration is 0.2mol/L, etching is well cleaned and is dried with deionized water, ethanol, acetone afterwards;
2. the air in eliminating reaction chamber pass into nitrogen, nickel foil after cleaning-drying is put into the reaction chamber that is connected with nitrogen, and nickel foil is heated to 750 DEG C and insulation, then open ultraviolet source equipment, make UV-irradiation on nickel foil surface, ultraviolet light wavelength is 400nm, then passes into propane 1000sccm, the volume ratio of propane and nitrogen is 10:1, keeps 30 minutes;
3. after having reacted, stop passing into propane, stop nickel foil heating and close ultraviolet source equipment, question response chamber stops passing into nitrogen after being cooled to room temperature, and nickel foil Surface Creation carbon nanometer wall, scrapes it from nickel foil surface, just obtain carbon nanometer wall powder;
4. the preparation of intercalation carbon nanometer wall: adopt stainless steel substrates as collector, the above-mentioned carbon nanometer wall powder preparing is put on collector, being pressed into specification on collector is 75*40*7mm
3the carbon nanometer wall lamella of (about 2g) is as working electrode, using stereotype as to electrode, and Hg/Hg
2sO
4as reference electrode, the nitric acid that massfraction is 68%, as electrolytic solution, is put into three electrodes electrolyzer and is fully immersed in electrolytic solution, at 100mA/cm
2current density, room temperature under react 5 hours, then reacted electrolytic solution is filtered, the filter residue obtaining is placed in vacuum drying oven in 75 DEG C and can obtains pure, dry intercalation carbon nanometer wall after dry 15 hours by washed with de-ionized water;
5. getting intercalation carbon nanometer wall, is that 1g:20ml joins EtMeImCF is housed by mass volume ratio
3cO
3in the container of ionic liquid, this container is placed in the fast middle wave emitter that power is 50w/cm and heats and peel off 5 minutes, then filter for the first time, the filter residue obtaining DMF filtration washing 3 times, use successively again ethanol, acetone, deionized water wash, filter, the filter residue of collecting is dried to constant weight at vacuum drying oven at 90 DEG C and obtains graphene nanobelt.
Embodiment 5
1. adopt iron foil as substrate, iron foil is put into the dilution heat of sulfuric acid etching 5 minutes that concentration is 0.1mol/L, etching is well cleaned and is dried with deionized water, ethanol, acetone afterwards;
2. the air in eliminating reaction chamber pass into argon gas, iron foil after cleaning-drying is put into the reaction chamber that is connected with argon gas, and iron foil is heated to 800 DEG C and insulation, then open ultraviolet source equipment, make UV-irradiation on iron foil surface, ultraviolet light wavelength is 300nm, then passes into ethanol 500sccm, the volume ratio of ethanol and argon gas is 6:1, keeps 50 minutes;
3. after having reacted, stop passing into ethanol, stop iron foil heating and close ultraviolet source equipment, question response chamber stops passing into argon gas after being cooled to room temperature, and iron foil Surface Creation carbon nanometer wall, scrapes it from iron foil surface, just obtain carbon nanometer wall powder;
4. the preparation of intercalation carbon nanometer wall: adopt stainless steel substrates as collector, the above-mentioned carbon nanometer wall powder preparing is put on collector, being pressed into specification on collector is 75*40*7mm
3the carbon nanometer wall lamella of (about 2g) is as working electrode, using stereotype as to electrode, and Hg/Hg
2sO
4as reference electrode, formic acid, as electrolytic solution, is put into three electrodes electrolyzer and is fully immersed in electrolytic solution, at 80mA/cm
2current density, room temperature under react 10 hours, then reacted electrolytic solution is filtered, the filter residue obtaining is placed in vacuum drying oven in 65 DEG C and can obtains pure, dry intercalation carbon nanometer wall after dry 18 hours by washed with de-ionized water;
5. getting intercalation carbon nanometer wall, is that 1g:80ml joins EtMeImC (CF is housed by mass volume ratio
3sO
2)
3in the container of ionic liquid, this container is placed in the fast middle wave emitter that power is 90w/cm and heats and peel off 3 minutes, then filter for the first time, the filter residue obtaining NMP filtration washing 4 times, use successively again ethanol, acetone, deionized water wash, filter, the filter residue of collecting is dried to constant weight at vacuum drying oven at 70 DEG C and obtains graphene nanobelt.
Embodiment 6
1. adopt cobalt paper tinsel as substrate, cobalt paper tinsel is put into the dilute nitric acid solution etching 8 minutes that concentration is 0.4mol/L, etching is well cleaned and is dried with deionized water, ethanol, acetone afterwards;
2. the air in eliminating reaction chamber pass into helium, cobalt paper tinsel after cleaning-drying is put into the reaction chamber that is connected with helium, and cobalt paper tinsel is heated to 850 DEG C and insulation, then open ultraviolet source equipment, make UV-irradiation on cobalt paper tinsel surface, ultraviolet light wavelength is 230nm, then passes into methane 800sccm, the volume ratio of methane and helium is 4:1, keeps 90 minutes;
3. after having reacted, stop passing into methane, stop the heating of cobalt paper tinsel and close ultraviolet source equipment, question response chamber stops passing into helium after being cooled to room temperature, and cobalt paper tinsel Surface Creation carbon nanometer wall, scrapes it from cobalt paper tinsel surface, just obtain carbon nanometer wall powder;
4. the preparation of intercalation carbon nanometer wall: adopt stainless steel substrates as collector, the above-mentioned carbon nanometer wall powder preparing is put on collector, being pressed into specification on collector is 75*40*7mm
3the carbon nanometer wall lamella of (about 2g) is as working electrode, using stereotype as to electrode, and Hg/Hg
2sO
4as reference electrode, Nitromethane 99Min., as electrolytic solution, is put into three electrodes electrolyzer and is fully immersed in electrolytic solution, at 40mA/cm
2current density, room temperature under react 15 hours, then reacted electrolytic solution is filtered, the filter residue obtaining is placed in vacuum drying oven in 60 DEG C and can obtains pure, dry intercalation carbon nanometer wall after dry 20 hours by washed with de-ionized water;
5. getting intercalation carbon nanometer wall, is that 1g:60ml joins EtMeImN (C is housed by mass volume ratio
2f
5sO
2)
2in the container of ionic liquid, this container is placed in the fast middle wave emitter that power is 75w/cm and heats and peel off 8 minutes, then filter for the first time, the filter residue obtaining DMF filtration washing 5 times, use successively again ethanol, acetone, deionized water wash, filter, the filter residue of collecting is dried to constant weight at vacuum drying oven at 60 DEG C and obtains graphene nanobelt.
Embodiment 7
1. adopt nickel foil as substrate, nickel foil is put into the dilute hydrochloric acid solution etching 3 minutes that concentration is 0.25mol/L, etching is well cleaned and is dried with deionized water, ethanol, acetone afterwards;
2. the air in eliminating reaction chamber pass into nitrogen, nickel foil after cleaning-drying is put into the reaction chamber that is connected with nitrogen, and nickel foil is heated to 900 DEG C and insulation, then open ultraviolet source equipment, make UV-irradiation on nickel foil surface, ultraviolet light wavelength is 380nm, then passes into ethane 300sccm, the volume ratio of ethane and nitrogen is 3:1, keeps 120 minutes;
3. after having reacted, stop passing into ethane, stop nickel foil heating and close ultraviolet source equipment, question response chamber stops passing into nitrogen after being cooled to room temperature, and nickel foil Surface Creation carbon nanometer wall, scrapes it from nickel foil surface, just obtain carbon nanometer wall powder;
4. the preparation of intercalation carbon nanometer wall: adopt stainless steel substrates as collector, the above-mentioned carbon nanometer wall powder preparing is put on collector, being pressed into specification on collector is 75*40*7mm
3the carbon nanometer wall lamella of (about 2g) is as working electrode, using stereotype as to electrode, and Hg/Hg
2sO
4as reference electrode, acetic acid and the Nitromethane 99Min. mixed solution that 1:1 mixes by volume, as electrolytic solution, is put into three electrodes electrolyzer and is fully immersed in electrolytic solution, at 10mA/cm
2current density, room temperature under react 6 hours, then reacted electrolytic solution is filtered, the filter residue obtaining is placed in vacuum drying oven in 80 DEG C and can obtains pure, dry intercalation carbon nanometer wall after dry 12 hours by washed with de-ionized water;
5. getting intercalation carbon nanometer wall, is that 1g:40ml joins EtMeImN (CN) is housed by mass volume ratio
2in the container of ionic liquid, this container is placed in the fast middle wave emitter that power is 60w/cm and heats and peel off 20 minutes, then filter for the first time, the filter residue obtaining NMP filtration washing 3 times, use successively again ethanol, acetone, deionized water wash, filter, the filter residue of collecting is dried to constant weight at vacuum drying oven at 100 DEG C and obtains graphene nanobelt.
Embodiment 8
1. adopt iron foil as substrate, iron foil is put into the dilute hydrochloric acid solution etching 4 minutes that concentration is 1mol/L, etching is well cleaned and is dried with deionized water, ethanol, acetone afterwards;
2. the air in eliminating reaction chamber pass into argon gas, iron foil after cleaning-drying is put into the reaction chamber that is connected with argon gas, and iron foil is heated to 650 DEG C and insulation, then open ultraviolet source equipment, make UV-irradiation on iron foil surface, ultraviolet light wavelength is 200nm, then passes into acetylene 200sccm, the volume ratio of acetylene and argon gas is 2:1, keeps 180 minutes;
3. after having reacted, stop passing into acetylene, stop iron foil heating and close ultraviolet source equipment, question response chamber stops passing into argon gas after being cooled to room temperature, and iron foil Surface Creation carbon nanometer wall, scrapes it from iron foil surface, just obtain carbon nanometer wall powder;
4. the preparation of intercalation carbon nanometer wall: adopt stainless steel substrates as collector, the above-mentioned carbon nanometer wall powder preparing is put on collector, being pressed into specification on collector is 75*40*7mm
3the carbon nanometer wall lamella of (about 2g) is as working electrode, using stereotype as to electrode, and Hg/Hg
2sO
4as reference electrode, the nitric acid that formic acid and massfraction are 68% mixed solution that 4:1 mixes by volume, as electrolytic solution, is put into three electrodes electrolyzer and is fully immersed in electrolytic solution, at 30mA/cm
2current density, room temperature under react 8 hours, then reacted electrolytic solution is filtered, the filter residue obtaining is placed in vacuum drying oven in 70 DEG C and can obtains pure, dry intercalation carbon nanometer wall after dry 15 hours by washed with de-ionized water;
5. getting intercalation carbon nanometer wall, is that 1g:30ml joins and 1-Et-3 is housed, 5-Me by mass volume ratio
2imN (CF
3sO
2)
2in the container of ionic liquid, this container is placed in the fast middle wave emitter that power is 70w/cm and heats and peel off 25 minutes, then filter for the first time, the filter residue obtaining DMF filtration washing 6 times, use successively again ethanol, acetone, deionized water wash, filter, the filter residue of collecting is dried to constant weight at vacuum drying oven at 80 DEG C and obtains graphene nanobelt.
Embodiment 9
1. adopt cobalt paper tinsel as substrate, cobalt paper tinsel is put into the dilution heat of sulfuric acid etching 2 minutes that concentration is 0.3mol/L, etching is well cleaned and is dried with deionized water, ethanol, acetone afterwards;
2. the air in eliminating reaction chamber pass into argon gas, cobalt paper tinsel after cleaning-drying is put into the reaction chamber that is connected with helium, and cobalt paper tinsel is heated to 700 DEG C and insulation, then open ultraviolet source equipment, make UV-irradiation on cobalt paper tinsel surface, ultraviolet light wavelength is 330nm, then passes into propane 50sccm, the volume ratio of propane and helium is 5:1, keeps 240 minutes;
3. after having reacted, stop passing into propane, stop the heating of cobalt paper tinsel and close ultraviolet source equipment, question response chamber stops passing into helium after being cooled to room temperature, and cobalt paper tinsel Surface Creation carbon nanometer wall, scrapes it from cobalt paper tinsel surface, just obtain carbon nanometer wall powder.
4. the preparation of intercalation carbon nanometer wall: adopt stainless steel substrates as collector, the above-mentioned carbon nanometer wall powder preparing is put on collector, being pressed into specification on collector is 75*40*7mm
3the carbon nanometer wall lamella of (about 2g) is as working electrode, using stereotype as to electrode, and Hg/Hg
2sO
4as reference electrode, the nitric acid that propionic acid and massfraction are 68% mixed solution that 1:2 mixes by volume, as electrolytic solution, is put into three electrodes electrolyzer and is fully immersed in electrolytic solution, at 5mA/cm
2current density, room temperature under react 15 hours, then reacted electrolytic solution is filtered, the filter residue obtaining is placed in vacuum drying oven in 80 DEG C and can obtains pure, dry intercalation carbon nanometer wall after dry 20 hours by washed with de-ionized water;
5. getting intercalation carbon nanometer wall, is that 1g:100ml joins 1,3-Et is housed by mass volume ratio
2-4-MeImN (CF
3sO
2)
2in the container of ionic liquid, this container is placed in the fast middle wave emitter that power is 65w/cm and heats and peel off 15 minutes, then filter for the first time, the filter residue obtaining NMP filtration washing 3 times, use successively again ethanol, acetone, deionized water wash, filter, the filter residue of collecting is dried to constant weight at vacuum drying oven at 90 DEG C and obtains graphene nanobelt.
Embodiment 10
1. adopt nickel foil as substrate, nickel foil is put into the dilute nitric acid solution etching 5 minutes that concentration is 0.5mol/L, etching is well cleaned and is dried with deionized water, ethanol, acetone afterwards;
2. the air in eliminating reaction chamber pass into nitrogen, nickel foil after cleaning-drying is put into the reaction chamber that is connected with nitrogen, and nickel foil is heated to 800 DEG C and insulation, then open ultraviolet source equipment, make UV-irradiation on nickel foil surface, ultraviolet light wavelength is 400nm, then passes into ethanol 20sccm, the volume ratio of ethanol and nitrogen is 8:1, keeps 300 minutes;
3. after having reacted, stop passing into ethanol, stop nickel foil heating and close ultraviolet source equipment, question response chamber stops passing into nitrogen after being cooled to room temperature, and nickel foil Surface Creation carbon nanometer wall, scrapes it from nickel foil surface, just obtain carbon nanometer wall powder;
4. the preparation of intercalation carbon nanometer wall: adopt stainless steel substrates as collector, the above-mentioned carbon nanometer wall powder preparing is put on collector, being pressed into specification on collector is 75*40*7mm
3the carbon nanometer wall lamella of (about 2g) is as working electrode, using stereotype as to electrode, and Hg/Hg
2sO
4as reference electrode, acetic acid, as electrolytic solution, is put into three electrodes electrolyzer and is fully immersed in electrolytic solution, at 100mA/cm
2current density, room temperature under react 2 hours, then reacted electrolytic solution is filtered, the filter residue obtaining is placed in vacuum drying oven in 60 DEG C and can obtains pure, dry intercalation carbon nanometer wall after dry 18 hours by washed with de-ionized water;
5. getting intercalation carbon nanometer wall, is that 1g:10ml joins 1,3-Et is housed by mass volume ratio
2-5-MeImN (CF
3sO
2)
2in the container of ionic liquid, this container is placed in the fast middle wave emitter that power is 40w/cm and heats and peel off 10 minutes, then filter for the first time, the filter residue obtaining DMF filtration washing 4 times, use successively again ethanol, acetone, deionized water wash, filter, the filter residue of collecting is dried to constant weight at vacuum drying oven at 70 DEG C and obtains graphene nanobelt.
Embodiment 11
1. adopt cobalt paper tinsel as substrate, cobalt paper tinsel is put into the dilute hydrochloric acid solution etching 1 minute that concentration is 0.05mol/L, etching is well cleaned and is dried with deionized water, ethanol, acetone afterwards;
2. the air in eliminating reaction chamber pass into argon gas, cobalt paper tinsel after cleaning-drying is put into the reaction chamber that is connected with argon gas, and cobalt paper tinsel is heated to 900 DEG C and insulation, then open ultraviolet source equipment, make UV-irradiation on cobalt paper tinsel surface, ultraviolet light wavelength is 250nm, then passes into methane 100sccm, the volume ratio of methane and argon gas is 10:1, keeps 30 minutes;
3. after having reacted, stop passing into methane, stop the heating of cobalt paper tinsel and close ultraviolet source equipment, question response chamber stops passing into argon gas after being cooled to room temperature, and cobalt paper tinsel Surface Creation carbon nanometer wall, scrapes it from cobalt paper tinsel surface, just obtain carbon nanometer wall powder;
4. the preparation of intercalation carbon nanometer wall: adopt stainless steel substrates as collector, the above-mentioned carbon nanometer wall powder preparing is put on collector, being pressed into specification on collector is 75*40*7mm
3the carbon nanometer wall lamella of (about 2g) is as working electrode, using stereotype as to electrode, and Hg/Hg
2sO
4as reference electrode, Nitromethane 99Min., as electrolytic solution, is put into three electrodes electrolyzer and is fully immersed in electrolytic solution, at 50mA/cm
2current density, room temperature under react 1 hour, then reacted electrolytic solution is filtered, the filter residue obtaining is placed in vacuum drying oven in 80 DEG C and can obtains pure, dry intercalation carbon nanometer wall after dry 20 hours by washed with de-ionized water;
5. getting intercalation carbon nanometer wall, is that 1g:50ml joins EtMeImBF is housed by mass volume ratio
4in the container of ionic liquid, this container is placed in the fast middle wave emitter that power is 100w/cm and heats and peel off 2 minutes, then filter for the first time, the filter residue obtaining NMP filtration washing 5 times, use successively again ethanol, acetone, deionized water wash, filter, the filter residue of collecting is dried to constant weight at vacuum drying oven at 100 DEG C and obtains graphene nanobelt.
The processing parameter of embodiment 1 ~ 11 is in table 1.
The processing parameter of table 1 embodiment 1 ~ 11
The above embodiment has only expressed several embodiment of the present invention, and it describes comparatively concrete and detailed, but can not therefore be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection domain of patent of the present invention should be as the criterion with claims.
Claims (10)
1. a preparation method for graphene nanobelt, is characterized in that, comprises the steps:
Use dilute acid soln to carry out etching to metal substrate;
Under the atmosphere of anaerobic and shielding gas, described metal substrate is heated to 600 DEG C ~ 900 DEG C;
Under the irradiation of UV-light, pass into the one in methane, ethane, propane, acetylene and ethanol to described metal substrate surface, process photochemical catalysis chemical vapour deposition reaction 30 minutes ~ 300 minutes, at described metal substrate Surface Creation carbon nanometer wall;
After having reacted, under the atmosphere of described shielding gas, the metal substrate with carbon nanometer wall is cooled to room temperature, then described carbon nanometer wall is scraped from the surface of described metal substrate, obtain carbon nanometer wall powder;
Described carbon nanometer wall powder is positioned on collector and is pressed into carbon nanometer wall lamella and obtain working electrode;
To jointly be soaked in electrolytic solution, at 5mA/cm electrode, reference electrode and described working electrode
2~ 100mA/cm
2current density, room temperature under react after 1 hour ~ 20 hours, reacted electrolytic solution is filtered, washs filter residue the dry intercalation carbon nanometer wall that obtains; And
Being 1g:10 ~ 100ml by solid-to-liquid ratio is scattered in described intercalation carbon nanometer wall in ionic liquid, to obtain dispersion liquid, during to be 40 ~ 100w/cm by described dispersion liquid at power fast, in wave emitter, heating is filtered after peeling off, and washing filter residue is also dried and obtains graphene nanobelt.
2. the preparation method of graphene nanobelt according to claim 1, it is characterized in that, the step that described use dilute acid soln carries out etching to metal substrate is specially: described metal substrate is put into the dilute acid soln etching 0.5 minute ~ 10 minutes that concentration is 0.01mol/L ~ 1mol/L.
3. the preparation method of graphene nanobelt according to claim 2, it is characterized in that, described use dilute acid soln carries out etch step to metal substrate and is specially: described metal substrate is put into the dilute acid soln etching 1 minute ~ 3 minutes that concentration is 0.1mol/L ~ 0.5mol/L.
4. the preparation method of graphene nanobelt according to claim 1, is characterized in that, described ultraviolet light wavelength is 200 ~ 400nm.
5. the preparation method of graphene nanobelt according to claim 1, is characterized in that, a kind of flow in described methane, ethane, propane, acetylene and ethanol is 10sccm ~ 1000sccm.
6. the preparation method of graphene nanobelt according to claim 1, is characterized in that, the volume ratio of a kind of and described shielding gas in described methane, ethane, propane, acetylene and ethanol is 2 ~ 10:1.
7. the preparation method of graphene nanobelt according to claim 1, is characterized in that, described electrolytic solution is selected from least one in formic acid, acetic acid, propionic acid, nitric acid, Nitromethane 99Min..
8. the preparation method of graphene nanobelt according to claim 1, it is characterized in that, described washing filter residue the dry step that obtains intercalation carbon nanometer wall are specially: with filter residue described in deionized water wash, and in 60 DEG C ~ 80 DEG C vacuum-dryings 12 hours ~ 24 hours.
9. the preparation method of graphene nanobelt according to claim 1, it is characterized in that, described ionic liquid is selected from 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 and 1, one in 3-diethyl-5-Methylimidazole fluoroform sulfimide.
10. the preparation method of graphene nanobelt according to claim 1, it is characterized in that, described washing filter residue the dry step that obtains graphene nanobelt are specially: by described filter residue 1-Methyl-2-Pyrrolidone or N, dinethylformamide washing 3 ~ 6 times, use successively ethanol, acetone and deionized water wash, then at 60 DEG C ~ 100 DEG C, vacuum-drying to constant weight obtains graphene nanobelt again.
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| JPH04193953A (en) * | 1990-11-27 | 1992-07-14 | Shimadzu Corp | Method and device for forming hard carbon film |
| CN1277145A (en) * | 1999-06-11 | 2000-12-20 | 李铁真 | Method for synthetizing vertical arrangement high-purity carbon nanometre tube in large-scale on large size substrate using hot CVD method |
| WO2012035551A1 (en) * | 2010-09-14 | 2012-03-22 | Council Of Scientific & Industrial Research | Electrochemical process for synthesis of graphene |
| CN102807213A (en) * | 2012-08-30 | 2012-12-05 | 中国科学院苏州纳米技术与纳米仿生研究所 | Method for electrochemically preparing graphene |
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| JPH04193953A (en) * | 1990-11-27 | 1992-07-14 | Shimadzu Corp | Method and device for forming hard carbon film |
| CN1277145A (en) * | 1999-06-11 | 2000-12-20 | 李铁真 | Method for synthetizing vertical arrangement high-purity carbon nanometre tube in large-scale on large size substrate using hot CVD method |
| WO2012035551A1 (en) * | 2010-09-14 | 2012-03-22 | Council Of Scientific & Industrial Research | Electrochemical process for synthesis of graphene |
| CN102807213A (en) * | 2012-08-30 | 2012-12-05 | 中国科学院苏州纳米技术与纳米仿生研究所 | Method for electrochemically preparing graphene |
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