CN103879993A - Preparation method of graphene nanobelt - Google Patents
Preparation method of graphene nanobelt Download PDFInfo
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- CN103879993A CN103879993A CN201210558229.8A CN201210558229A CN103879993A CN 103879993 A CN103879993 A CN 103879993A CN 201210558229 A CN201210558229 A CN 201210558229A CN 103879993 A CN103879993 A CN 103879993A
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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, using the carbon nanowall powder as a raw material for preparing the graphene nanobelt, and peeling through an instant huge intercalation carbon nanowall temperature difference caused by alternated cooling and heating in order to obtain the graphene nanobelt with a high dimensional homogeneity. The method can maximally maintain the structural integrity of the graphene nanobelt, and 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 the first shielding gas, described metal substrate is heated to 600 ℃ ~ 900 ℃;
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 the first 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 electrode, reference electrode and described working electrode, under the current density of 5mA/cm2 ~ 100mA/cm2, room temperature, react after 1 hour ~ 20 hours, reacted electrolytic solution is filtered, washs filter residue the dry intercalation carbon nanometer wall that obtains;
Described intercalation carbon nanometer wall is soaked in the one in liquid nitrogen, liquid argon and liquid hydrogen to cooling 0.5 minute ~ 30 minutes; And
Cooled intercalation carbon nanometer wall in the second shielding gas atmosphere, process 30 minutes ~ 300 minutes in 800 ℃ ~ 1000 ℃, is obtained to graphene nanobelt after cooling.
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 the first shielding gas in described methane, ethane, propane, acetylene and ethanol is 2 ~ 10:1 therein.
In an embodiment, described substrate is the one in iron foil, nickel foil and cobalt paper tinsel 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 ℃ ~ 80 ℃ vacuum-dryings 12 hours ~ 24 hours.
In an embodiment, described the first shielding gas and the second shielding gas are the one in helium, nitrogen and argon gas therein.First the preparation method of above-mentioned graphene nanobelt utilizes photochemical catalysis chemical vapour deposition to prepare structural integrity, the carbon nanometer wall powder that dimensional homogeneity is higher, raw material using this carbon nanometer wall powder as graphene nanobelt, utilization colds and heat succeed each other and makes intercalation carbon nanometer wall moment be subject to the huge temperature difference and peel off to obtain the graphene nanobelt that dimensional homogeneity is higher, this method can at utmost keep graphene nanobelt structural integrity, and can not introduce oxy radical at the graphene nanobelt finally obtaining in preparation process, prepare the good graphene nanobelt of quality.
Accompanying drawing explanation
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 nano 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 the first shielding gas, metal substrate is heated to 600 ℃ ~ 900 ℃.
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 the first 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 ℃ ~ 900 ℃, and insulation to reaction finishes.
The first 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 the first shielding gas is 2 ~ 10:1.
Under UV-irradiation and in the first 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 the first 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 the first 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 the first shielding gas, prevent that the carbon nanometer wall generating is at high temperature oxidized, and further guarantees 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 ℃ ~ 80 ℃ of the filter residue after washing, be dried, pure intercalation carbon nanometer wall.
Step S170: intercalation carbon nanometer wall is soaked in the one in liquid nitrogen, liquid argon and liquid hydrogen to cooling 0.5 minute ~ 30 minutes.
Intercalation carbon nanometer wall is entered in small vessels, and the one that this small vessels is placed in to liquid nitrogen, liquid argon and liquid hydrogen is soaked and within 0.5 minute ~ 30 minutes, is made intercalation carbon nanometer wall fully cooling.
Under normal pressure, the temperature of liquid nitrogen is-196 ℃, and the temperature of liquid argon is-185.7 ℃, and the temperature of liquid hydrogen is-252.7 ℃, can make intercalation carbon nanometer wall cooling rapidly.
Step S180: cooled intercalation carbon nanometer wall in the second shielding gas atmosphere, process 30 minutes ~ 300 minutes in 800 ℃ ~ 1000 ℃, is obtained to graphene nanobelt after cooling.
Cooled intercalation carbon nanometer wall is put into the muffle furnace that is filled with the second shielding gas fast, in 800 ℃ ~ 1000 ℃ processing 30 minutes ~ 300 minutes, make intercalation carbon nanometer wall moment be subject to the huge temperature difference and peel off, be cooled to room temperature, obtain graphene nanobelt.
The second shielding gas is preferably the one in helium, nitrogen, argon gas.In the second shielding gas atmosphere, heat-treat, avoid intercalation carbon nanometer wall and graphene nanobelt to be at high temperature oxidized, be conducive to prepare the graphene nanobelt of structural integrity.
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, utilizing colds and heat succeed each other makes intercalation carbon nanometer wall moment be subject to the huge temperature difference and peels off and obtain the graphene nanobelt that dimensional homogeneity is higher.
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.
Adopt cold and hot moment alternately to peel off intercalation carbon nanometer wall and obtain graphene nanobelt, stripping process, without using chemical reagent, has been realized green non-pollution and has been peeled off, and after having peeled off, naturally cooled to room temperature, without separating again.
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 ℃ 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 ℃ and can obtains pure, dry intercalation carbon nanometer wall after dry 24 hours by washed with de-ionized water;
5. get the dried intercalation carbon nanometer wall of 100g and enter in small vessels, and this small vessels is put in the container that liquid nitrogen is housed and soaked 5 minutes, make the cooling rear taking-up completely of intercalation carbon nanometer wall;
6. cooled intercalation carbon nanometer wall to be put into furnace body temperature be fast 1100 ℃, be filled with in the retort furnace of nitrogen, makes intercalation carbon nanometer wall moment be subject to the huge temperature difference and peel off, and is finally cooled to greenhouse, 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 ℃ 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 ℃ and can obtains pure, dry intercalation carbon nanometer wall after dry 20 hours by washed with de-ionized water;
5. get the dried intercalation carbon nanometer wall of 100g and enter in small vessels, and this small vessels is put in the container that liquid argon is housed and soaked 30 minutes, make the cooling rear taking-up completely of intercalation carbon nanometer wall;
6. cooled intercalation carbon nanometer wall to be put into furnace body temperature be fast 1000 ℃, be filled with in the retort furnace of argon gas, makes intercalation carbon nanometer wall moment be subject to the huge temperature difference and peel off, and is finally cooled to greenhouse, 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 ℃ of insulations, then open ultraviolet source equipment, make UV-irradiation on cobalt paper tinsel surface, ultraviolet light wavelength is 400nm, 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 ℃ and can obtains pure, dry intercalation carbon nanometer wall after dry 12 hours by washed with de-ionized water;
5. get the dried intercalation carbon nanometer wall of 100g and enter in small vessels, and this small vessels is put in the container that liquid hydrogen is housed and soaked 10 minutes, make the cooling rear taking-up completely of intercalation carbon nanometer wall;
6. cooling intercalation carbon nanometer wall to be put into furnace body temperature be fast 900 ℃, be filled with in the retort furnace of helium, makes intercalation carbon nanometer wall moment be subject to the huge temperature difference and peel off, and is finally cooled to greenhouse, 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 ℃ and insulation, then open ultraviolet source equipment, make UV-irradiation on nickel foil surface, ultraviolet light wavelength is 350nm, 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 ℃ and can obtains pure, dry intercalation carbon nanometer wall after dry 15 hours by washed with de-ionized water;
5. get the dried intercalation carbon nanometer wall of 100g and enter in small vessels, and this small vessels is put in the container that liquid argon is housed and soaked 0.5 minute, make the cooling rear taking-up completely of intercalation carbon nanometer wall;
6. cooling intercalation carbon nanometer wall to be put into furnace body temperature be fast 800 ℃, be filled with in the retort furnace of nitrogen, makes intercalation carbon nanometer wall moment be subject to the huge temperature difference and peel off, and is finally cooled to greenhouse, 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 ℃ 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 ℃ and can obtains pure, dry intercalation carbon nanometer wall after dry 18 hours by washed with de-ionized water;
5. get the dried intercalation carbon nanometer wall of 100g and enter in small vessels, and this small vessels is put in the container that liquid nitrogen is housed and soaked 1 minute, make the cooling rear taking-up completely of intercalation carbon nanometer wall;
6. cooling intercalation carbon nanometer wall to be put into furnace body temperature be fast 850 ℃, be filled with in the retort furnace of argon gas, makes intercalation carbon nanometer wall moment be subject to the huge temperature difference and peel off, and is finally cooled to greenhouse, 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 ℃ and insulation, then open ultraviolet source equipment, make UV-irradiation on cobalt paper tinsel surface, ultraviolet light wavelength is 280nm, 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 ℃ and can obtains pure, dry intercalation carbon nanometer wall after dry 20 hours by washed with de-ionized water;
5. get the dried intercalation carbon nanometer wall of 100g and enter in small vessels, and this small vessels is put in the container that liquid argon is housed and soaked 20 minutes, make the cooling rear taking-up completely of intercalation carbon nanometer wall;
6. cooling intercalation carbon nanometer wall to be put into furnace body temperature be fast 950 ℃, be filled with in the retort furnace of helium, makes intercalation carbon nanometer wall moment be subject to the huge temperature difference and peel off, and is finally cooled to greenhouse, 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 ℃ 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 ℃ and can obtains pure, dry intercalation carbon nanometer wall after dry 12 hours by washed with de-ionized water;
5. get the dried intercalation carbon nanometer wall of 100g and enter in small vessels, and this small vessels is put in the container that liquid hydrogen is housed and soaked 4 minutes, make the cooling rear taking-up completely of intercalation carbon nanometer wall;
6. cooling intercalation carbon nanometer wall to be put into furnace body temperature be fast 1050 ℃, be filled with in the retort furnace of nitrogen, makes intercalation carbon nanometer wall moment be subject to the huge temperature difference and peel off, and is finally cooled to greenhouse, 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 ℃ and insulation, then open ultraviolet source equipment, make UV-irradiation on iron foil surface, ultraviolet light wavelength is 330nm, 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 ℃ and can obtains pure, dry intercalation carbon nanometer wall after dry 15 hours by washed with de-ionized water;
5. get the dried intercalation carbon nanometer wall of 100g and enter in small vessels, and this small vessels is put in the container that liquid argon is housed and soaked 15 minutes, make the cooling rear taking-up completely of intercalation carbon nanometer wall;
6. cooling intercalation carbon nanometer wall to be put into furnace body temperature be fast 1000 ℃, be filled with in the retort furnace of argon gas, makes intercalation carbon nanometer wall moment be subject to the huge temperature difference and peel off, and is finally cooled to greenhouse, 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 ℃ and insulation, then open ultraviolet source equipment, make UV-irradiation on cobalt paper tinsel surface, ultraviolet light wavelength is 250nm, 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 ℃ and can obtains pure, dry intercalation carbon nanometer wall after dry 20 hours by washed with de-ionized water;
5. get the dried intercalation carbon nanometer wall of 100g and enter in small vessels, and this small vessels is put in the container that liquid nitrogen is housed and soaked 30 minutes, make the cooling rear taking-up completely of intercalation carbon nanometer wall;
6. cooling intercalation carbon nanometer wall to be put into furnace body temperature be fast 1100 ℃, be filled with in the retort furnace of helium, makes intercalation carbon nanometer wall moment be subject to the huge temperature difference and peel off, and is finally cooled to greenhouse, 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 ℃ 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 ℃ and can obtains pure, dry intercalation carbon nanometer wall after dry 18 hours by washed with de-ionized water;
5. get the dried intercalation carbon nanometer wall of 100g and enter in small vessels, and this small vessels is put in the container that liquid argon is housed and soaked 2 minutes, make the cooling rear taking-up completely of intercalation carbon nanometer wall;
6. cooling intercalation carbon nanometer wall to be put into furnace body temperature be fast 900 ℃, be filled with in the retort furnace of nitrogen, makes intercalation carbon nanometer wall moment be subject to the huge temperature difference and peel off, and is finally cooled to greenhouse, 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 ℃ and insulation, then open ultraviolet source equipment, make UV-irradiation on cobalt paper tinsel surface, ultraviolet light wavelength is 200nm, 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 ℃ and can obtains pure, dry intercalation carbon nanometer wall after dry 20 hours by washed with de-ionized water;
5. get the dried intercalation carbon nanometer wall of 100g and enter in small vessels, and this small vessels is put in the container that liquid hydrogen is housed and soaked 0.5 minute, make the cooling rear taking-up completely of intercalation carbon nanometer wall;
6. cooling intercalation carbon nanometer wall to be put into furnace body temperature be fast 800 ℃, be filled with in the retort furnace of argon gas, makes intercalation carbon nanometer wall moment be subject to the huge temperature difference and peel off, and is finally cooled to greenhouse, 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 the first shielding gas, described metal substrate is heated to 600 ℃ ~ 900 ℃;
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 the first 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;
Described intercalation carbon nanometer wall is soaked in the one in liquid nitrogen, liquid argon and liquid hydrogen to cooling 0.5 minute ~ 30 minutes; And
Cooled intercalation carbon nanometer wall in the second shielding gas atmosphere, process 30 minutes ~ 300 minutes in 800 ℃ ~ 1000 ℃, is obtained to graphene nanobelt after cooling.
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 the first 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 substrate is the one in iron foil, nickel foil and cobalt paper tinsel.
8. 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..
9. 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 ℃ ~ 80 ℃ vacuum-dryings 12 hours ~ 24 hours.
10. the preparation method of graphene nanobelt according to claim 1, is characterized in that, described the first shielding gas and the second shielding gas are the one in helium, nitrogen and argon gas.
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