CN103879993B - The preparation method of graphene nanobelt - Google Patents
The preparation method of graphene nanobelt Download PDFInfo
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- CN103879993B CN103879993B CN201210558229.8A CN201210558229A CN103879993B CN 103879993 B CN103879993 B CN 103879993B CN 201210558229 A CN201210558229 A CN 201210558229A CN 103879993 B CN103879993 B CN 103879993B
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Abstract
A kind of preparation method of graphene nanobelt, 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 the raw material of this carbon nanometer wall powder as graphene nanobelt, utilizing colds and heat succeed each other makes intercalation carbon nanometer wall peel off obtain the higher graphene nanobelt of dimensional homogeneity by the huge temperature difference instantaneously, this method can at utmost keep graphene nanobelt structural integrity, and oxy radical can not be introduced at the graphene nanobelt finally obtained in preparation process, prepare the good graphene nanobelt of quality.
Description
Technical field
The present invention relates to the synthesis 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-dimensional graphene plane, the zonal structure formed through certain shearing.Graphene nanobelt not only has the performance of Graphene, also possesses the performance that some are special, and such as its length-to-diameter ratio is larger, can up to thousands of times, can copper conductor be replaced at integrated circuit connection, improve integrated level further, 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 usually, first carbon nanotube is immersed in sulfuric acid by this method, heats after adding strong oxidizer, utilizes strong oxidizer make carbon nanotube open loop and obtain graphene nanobelt under high temperature action.Usually the conductivity introducing oxygen-containing functional group and graphene nanobelt of the graphene nanobelt that this side prepares, and the homogeneity of size is difficult to control, and makes the poor of the graphene nanobelt quality finally obtained, is difficult to practical requirement.
Summary of the invention
Based on this, be necessary the preparation method that a kind of graphene nanobelt is provided, with the good graphene nanobelt of preparation quality.
A preparation method for graphene nanobelt, comprises the steps:
Dilute acid soln is used to etch metal substrate;
Under the atmosphere of anaerobic and the first 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, through photochemical catalysis chemical vapour deposition reaction 30 minutes ~ 300 minutes, at described metal substrate surface Formed nanometer wall;
After having reacted, under the atmosphere of described 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 to be positioned on collector and to be pressed into carbon nanometer wall flaps layer and obtain working electrode;
Jointly will be soaked in electrolytic solution electrode, reference electrode and described working electrode, react after 1 hour ~ 20 hours under the current density, room temperature of 5mA/cm2 ~ 100mA/cm2, reacted electrolytic solution is carried out filter, wash filter residue and drying obtains intercalation carbon nanometer wall;
Described intercalation carbon nanometer wall is soaked in the one in liquid nitrogen, liquid argon and liquid hydrogen and cools 0.5 minute ~ 30 minutes; And
Cooled intercalation carbon nanometer wall is processed 30 minutes ~ 300 minutes in the second shielding gas atmosphere, in 800 DEG C ~ 1000 DEG C, after cooling, obtains graphene nanobelt.
Wherein in an embodiment, described use dilute acid soln is specially the step that metal substrate etches: described metal substrate is put into concentration be 0.01mol/L ~ 1mol/L dilute acid soln etching 0.5 minute ~ 10 minutes.
Wherein in an embodiment, described use dilute acid soln carries out etch step to metal substrate and is specially: described metal substrate is put into concentration be 0.1mol/L ~ 0.5mol/L dilute acid soln etching 1 minute ~ 3 minutes.
Wherein in an embodiment, the wavelength of described UV-light is 200 ~ 400nm.
Wherein in an embodiment, a kind of flow in described methane, ethane, propane, acetylene and ethanol is 10sccm ~ 1000sccm.
Wherein in an embodiment, the volume ratio that is a kind of and described first shielding gas in described methane, ethane, propane, acetylene and ethanol is 2 ~ 10:1.
Wherein in an embodiment, described substrate is the one in iron foil, nickel foil and cobalt paper tinsel.
Wherein in an embodiment, described electrolytic solution is selected from least one in formic acid, acetic acid, propionic acid, nitric acid, Nitromethane 99Min..
Wherein in an embodiment, the described washing filter residue also dry step obtaining intercalation carbon nanometer wall is specially: with filter residue described in deionized water wash, and in 60 DEG C ~ 80 DEG C vacuum-dryings 12 hours ~ 24 hours.
Wherein in an embodiment, described first shielding gas and the second shielding gas are the one in helium, nitrogen and argon gas.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, using the raw material of this carbon nanometer wall powder as graphene nanobelt, utilizing colds and heat succeed each other makes intercalation carbon nanometer wall peel off obtain the higher graphene nanobelt of dimensional homogeneity by the huge temperature difference instantaneously, this method can at utmost keep graphene nanobelt structural integrity, and oxy radical can not be introduced at the graphene nanobelt finally obtained 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 carbon nanometer wall prepared by embodiment 1;
Fig. 3 is the SEM figure of graphene nanobelt prepared by embodiment 1.
Embodiment
For enabling above-mentioned purpose of the present invention, feature and advantage become apparent more, are described in detail the specific embodiment of the present invention below in conjunction with accompanying drawing.Set forth a lot of detail in the following description so that fully understand the present invention.But the present invention can be much different from alternate manner described here to implement, those skilled in the art can when without prejudice to doing similar improvement when intension of the present invention, therefore the present invention is by 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 etch metal substrate.
Metal substrate is preferably the one in iron foil, nickel foil and cobalt paper tinsel.
Use dilute acid soln the step that metal substrate etches is specially: metal substrate is put into concentration be 0.01mol/L ~ 1mol/L dilute acid soln etching 0.5 minute ~ 10 minutes.
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 etched, makes metal substrate surface produce defect, effectively can 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, good etching effect can be reached, be conducive to the growth efficiency improving carbon nanometer wall.
Step S120: under the atmosphere of anaerobic and the first shielding gas, metal substrate is heated to 600 DEG C ~ 900 DEG C.
First the metal substrate through over etching is cleaned up with deionized water, ethanol and acetone and drying successively, for subsequent use.
The metal substrate through over etching after cleaning-drying is put into reaction chamber.The air got rid of in reaction chamber also passes into the first shielding gas, makes reaction chamber be in anaerobic state completely, and avoid the participation of oxygen and affect the growth of carbon nanometer wall, the growth for carbon nanometer wall provides a stable environment.
Metal substrate is heated to 600 DEG C ~ 900 DEG C, and insulation is to reacting end.
First shielding gas is preferably at least one in helium, nitrogen, argon gas.
Step S130: under the irradiation of UV-light, passes into the one in methane, ethane, propane, acetylene and ethanol to metal substrate surface, through photochemical catalysis chemical vapour deposition reaction 30 minutes ~ 300 minutes, at metal substrate surface Formed nanometer wall.
Ultraviolet source equipment and metal substrate are just right.Open ultraviolet source equipment, make UV-irradiation on the surface of metal substrate.
UV-light is as photocatalyst.The wavelength of UV-light is preferably 200 ~ 400nm.
Under the irradiation of UV-light, in reaction chamber, pass into carbon source, metal substrate is in the atmosphere of 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 in methane, ethane, propane, acetylene and ethanol through photochemical catalysis chemical vapour deposition reaction 30 minutes ~ 300 minutes, Formed nanometer wall on the metallic substrate.
Step S140: after having reacted, is cooled to room temperature by the metal substrate with carbon nanometer wall, is then scraped from the surface of metal substrate by carbon nanometer wall, obtain carbon nanometer wall powder under the atmosphere of the first shielding gas.
React after 30 minutes ~ 300 minutes; stop passing into carbon source, close heating installation and close ultraviolet source equipment, stop passing into the first shielding gas after question response room and the metal substrate with carbon nanometer wall are cooled to room temperature; the carbon nanometer wall of metal substrate surface is scraped, obtains carbon nanometer wall powder.
Question response room and stop again after being cooled to room temperature with the metal substrate of carbon nanometer wall passing into the first shielding gas, prevents the carbon nanometer wall generated at high temperature to be oxidized, ensures the quality obtaining carbon nanometer wall powder further.
Step S150: carbon nanometer wall powder to be positioned on collector and to be pressed into carbon nanometer wall flaps layer and obtain working electrode.
Carbon nanometer wall powder and binding agent are positioned on collector, then with mould compacting, make collector to be formed carbon nanometer wall flaps layer, obtain the working electrode of three-electrode system.Collector preferably adopts stainless steel collector.
Carbon nanometer wall flaps layer is of a size of 75*40*7mm
3.
Step S160: jointly will be soaked in electrolytic solution, at 5mA/cm electrode, reference electrode and working electrode
2~ 100mA/cm
2current density, reaction after 1 hour ~ 20 hours under room temperature, reacted electrolytic solution carried out filter, wash filter residue and drying obtains intercalation carbon nanometer wall.
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, be inserted between carbon nanowall layer under the driving of potential difference, obtains intercalation carbon nanometer wall.
React after 1 hour ~ 20 hours, reacted electrolytic solution is filtered, the filter residue deionized water wash then will obtained, then by the vacuum-drying 12 hours ~ 24 hours at 60 DEG C ~ 80 DEG C of the filter residue after washing, obtain drying, pure intercalation carbon nanometer wall.
Step S170: intercalation carbon nanometer wall is soaked in the one in liquid nitrogen, liquid argon and liquid hydrogen and cools 0.5 minute ~ 30 minutes.
Enter in small vessels by intercalation carbon nanometer wall, the one immersion this small vessels being placed in liquid nitrogen, liquid argon and liquid hydrogen makes intercalation carbon nanometer wall fully cool for 0.5 minute ~ 30 minutes.
At ambient pressure, the temperature of liquid nitrogen is-196 DEG C, and the temperature of liquid argon is-185.7 DEG C, and the temperature of liquid hydrogen is-252.7 DEG C, and intercalation carbon nanometer wall can be made to cool rapidly.
Step S180: cooled intercalation carbon nanometer wall is processed 30 minutes ~ 300 minutes in the second shielding gas atmosphere, in 800 DEG C ~ 1000 DEG C, obtains graphene nanobelt after cooling.
Cooled intercalation carbon nanometer wall is put into the muffle furnace being filled with the second shielding gas fast, in 800 DEG C ~ 1000 DEG C process 30 minutes ~ 300 minutes, makes intercalation carbon nanometer wall be subject to the huge temperature difference instantaneously and peel off, be cooled to room temperature, obtain graphene nanobelt.
Second shielding gas is preferably the one in helium, nitrogen, argon gas.Heat-treat in the second shielding gas atmosphere, avoid intercalation carbon nanometer wall and graphene nanobelt to be at high temperature oxidized, be conducive to the graphene nanobelt preparing 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 peel off obtain the higher graphene nanobelt of dimensional homogeneity by the huge temperature difference instantaneously.
Utilize UV-light as photocatalyst, carbon source avoids through the method for photochemical catalysis chemical vapour deposition reaction Formed nanometer wall in the metal substrate through over etching that traditional in preparation method, plasma body, can generating structure is comparatively complete, dimensional homogeneity is higher carbon nanometer wall to the destruction of carbon nanometer wall in plasma atmosphere.
The graphene nanobelt that the method adopts the carbon nanometer wall powder prepared voluntarily to prepare as raw material, the preparation of carbon nanometer wall powder is a kind of as carbon source in methane, ethane, propane, acetylene and ethanol, this several carbon source is comparatively cheap, relative to the raw material adopting commercially available carbon nanotube as graphene nanobelt, its advantage of lower cost, and photochemical catalysis effectively can reduce temperature of reaction, reduce energy consumption, reduce production cost.
Adopt cold and hot intercalation carbon nanometer wall of alternately peeling off instantaneously to obtain graphene nanobelt, stripping process, without the need to using chemical reagent, achieves green non-pollution and peels off, and after having peeled off, naturally cool to room temperature, without the need to being separated again.
The equipment that the preparation method of this graphene nanobelt is used is all common chemical industry equipment, lower to the requirement of equipment, and technique is simple, and condition is easily controlled, and is applicable to scale operation.
It is below specific embodiment.
Embodiment 1
1. nickel foil is put into the dilute hydrochloric acid solution etching 0.5 minute that concentration is 1mol/L, good rear the deionized water of etching, ethanol, acetone carry out cleaning also drying;
2. get rid of the air in reaction chamber and pass into nitrogen, nickel foil after cleaning-drying is put into the reaction chamber being connected with nitrogen, and nickel foil is heated to 900 DEG C and is incubated, then ultraviolet source equipment is opened, make UV-irradiation on nickel foil surface, the wavelength of UV-light 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, stop after question response room is cooled to room temperature passing into nitrogen, nickel foil Surface Creation carbon nanometer wall, scrapes it from nickel foil surface, just obtains carbon nanometer wall powder;
4. the preparation of intercalation carbon nanometer wall: adopt stainless steel substrates as collector, put on collector by the above-mentioned carbon nanometer wall powder prepared, being pressed into specification is on a current collector 75*40*7mm
3the carbon nanometer wall flaps layer of (about 2g) as working electrode, using stereotype as to electrode, Hg/Hg
2sO
4as reference electrode, three electrodes, as electrolytic solution, are put into electrolyzer and are fully immersed in electrolytic solution, at 5mA/cm by formic acid
2current density, carry out reaction 20 hours under room temperature, then reacted electrolytic solution is filtered, the filter residue washed with de-ionized water obtained is placed in vacuum drying oven and can obtains pure, dry intercalation carbon nanometer wall after 24 hours in 60 DEG C of dryings;
5. the intercalation carbon nanometer wall getting 100g dried enters in small vessels, and this small vessels is put in the container that liquid nitrogen is housed soak 5 minutes, make intercalation carbon nanometer wall cool rear taking-up completely;
6. cooled intercalation carbon nanometer wall is put into furnace body temperature to be fast 1100 DEG C, to be filled with in the retort furnace of nitrogen, intercalation carbon nanometer wall is peeled off by the huge temperature difference instantaneously, is finally cooled to greenhouse, obtains graphene nanobelt.
Fig. 2 and Fig. 3 is respectively the carbon nanometer wall of embodiment 1 and the SEM figure of graphene nanobelt.
As can be seen from Figures 2 and 3, carbon nanometer wall is perpendicular to substrate dense growth, and thickness is even, be about 30 ~ 60nm, concentrated by the graphene nanobelt width distribution of carbon nanometer wall prepared by raw material, be 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 can keep the integrity of graphene nano band structure in stripping process to greatest extent, and the quality of the graphene nanobelt prepared 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, good rear the deionized water of etching, ethanol, acetone carry out cleaning also drying;
2. the air in eliminating reaction chamber also passes into argon gas, iron foil after cleaning-drying is put into the reaction chamber being connected with argon gas, and iron foil is heated to 600 DEG C and is incubated, then ultraviolet source equipment is opened, make UV-irradiation on iron foil surface, the wavelength of UV-light 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, stop after question response room is cooled to room temperature passing into argon gas, iron foil Surface Creation carbon nanometer wall, scrapes it from iron foil surface, just obtains carbon nanometer wall powder;
4. the preparation of intercalation carbon nanometer wall: adopt stainless steel substrates as collector, put on collector by the above-mentioned carbon nanometer wall powder prepared, being pressed into specification is on a current collector 75*40*7mm
3the carbon nanometer wall flaps layer of (about 2g) as working electrode, using stereotype as to electrode, Hg/Hg
2sO
4as reference electrode, three electrodes, as electrolytic solution, are put into electrolyzer and are fully immersed in electrolytic solution, at 20mA/cm by acetic acid
2current density, carry out reaction 1 hour under room temperature, then reacted electrolytic solution is filtered, the filter residue washed with de-ionized water obtained is placed in vacuum drying oven and can obtains pure, dry intercalation carbon nanometer wall after 20 hours in 70 DEG C of dryings;
5. the intercalation carbon nanometer wall getting 100g dried enters in small vessels, and this small vessels is put in the container that liquid argon is housed soak 30 minutes, make intercalation carbon nanometer wall cool rear taking-up completely;
6. cooled intercalation carbon nanometer wall is put into furnace body temperature to be fast 1000 DEG C, to be filled with in the retort furnace of argon gas, intercalation carbon nanometer wall is peeled off by the huge temperature difference instantaneously, 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, good rear the deionized water of etching, ethanol, acetone carry out cleaning also drying;
2. the air in eliminating reaction chamber also passes into helium, cobalt paper tinsel after cleaning-drying is put into the reaction chamber being connected with helium, and cobalt paper tinsel is heated to 700 DEG C of insulations, then ultraviolet source equipment is opened, make UV-irradiation on cobalt paper tinsel surface, the wavelength of UV-light 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, stop after question response room is cooled to room temperature passing into helium, cobalt paper tinsel Surface Creation carbon nanometer wall, scrapes it from cobalt paper tinsel surface, just obtains carbon nanometer wall powder;
4. the preparation of intercalation carbon nanometer wall: adopt stainless steel substrates as collector, put on collector by the above-mentioned carbon nanometer wall powder prepared, being pressed into specification is on a current collector 75*40*7mm
3the carbon nanometer wall flaps layer of (about 2g) as working electrode, using stereotype as to electrode, Hg/Hg
2sO
4as reference electrode, three electrodes, as electrolytic solution, are put into electrolyzer and are fully immersed in electrolytic solution, at 50mA/cm by propionic acid
2current density, carry out reaction 2 hours under room temperature, then reacted electrolytic solution is filtered, the filter residue washed with de-ionized water obtained is placed in vacuum drying oven and can obtains pure, dry intercalation carbon nanometer wall after 12 hours in 80 DEG C of dryings;
5. the intercalation carbon nanometer wall getting 100g dried enters in small vessels, and this small vessels is put in the container that liquid hydrogen is housed soak 10 minutes, make intercalation carbon nanometer wall cool rear taking-up completely;
6. the intercalation carbon nanometer wall of cooling is put into furnace body temperature to be fast 900 DEG C, to be filled with in the retort furnace of helium, intercalation carbon nanometer wall is peeled off by the huge temperature difference instantaneously, 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, good rear the deionized water of etching, ethanol, acetone carry out cleaning also drying;
2. the air in eliminating reaction chamber also passes into nitrogen, nickel foil after cleaning-drying is put into the reaction chamber being connected with nitrogen, and nickel foil is heated to 750 DEG C and is incubated, then ultraviolet source equipment is opened, make UV-irradiation on nickel foil surface, the wavelength of UV-light 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, stop after question response room is cooled to room temperature passing into nitrogen, nickel foil Surface Creation carbon nanometer wall, scrapes it from nickel foil surface, just obtains carbon nanometer wall powder;
4. the preparation of intercalation carbon nanometer wall: adopt stainless steel substrates as collector, put on collector by the above-mentioned carbon nanometer wall powder prepared, being pressed into specification is on a current collector 75*40*7mm
3the carbon nanometer wall flaps layer of (about 2g) as working electrode, using stereotype as to electrode, Hg/Hg
2sO
4as reference electrode, massfraction be the nitric acid of 68% as electrolytic solution, three electrodes are put into electrolyzer and are fully immersed in electrolytic solution, at 100mA/cm
2current density, carry out reaction 5 hours under room temperature, then reacted electrolytic solution is filtered, the filter residue washed with de-ionized water obtained is placed in vacuum drying oven and can obtains pure, dry intercalation carbon nanometer wall after 15 hours in 75 DEG C of dryings;
5. the intercalation carbon nanometer wall getting 100g dried enters in small vessels, and this small vessels is put in the container that liquid argon is housed soak 0.5 minute, make intercalation carbon nanometer wall cool rear taking-up completely;
6. the intercalation carbon nanometer wall of cooling is put into furnace body temperature to be fast 800 DEG C, to be filled with in the retort furnace of nitrogen, intercalation carbon nanometer wall is peeled off by the huge temperature difference instantaneously, 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, good rear the deionized water of etching, ethanol, acetone carry out cleaning also drying;
2. the air in eliminating reaction chamber also passes into argon gas, iron foil after cleaning-drying is put into the reaction chamber being connected with argon gas, and iron foil is heated to 800 DEG C and is incubated, then ultraviolet source equipment is opened, make UV-irradiation on iron foil surface, the wavelength of UV-light 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, stop after question response room is cooled to room temperature passing into argon gas, iron foil Surface Creation carbon nanometer wall, scrapes it from iron foil surface, just obtains carbon nanometer wall powder;
4. the preparation of intercalation carbon nanometer wall: adopt stainless steel substrates as collector, put on collector by the above-mentioned carbon nanometer wall powder prepared, being pressed into specification is on a current collector 75*40*7mm
3the carbon nanometer wall flaps layer of (about 2g) as working electrode, using stereotype as to electrode, Hg/Hg
2sO
4as reference electrode, three electrodes, as electrolytic solution, are put into electrolyzer and are fully immersed in electrolytic solution, at 80mA/cm by formic acid
2current density, carry out reaction 10 hours under room temperature, then reacted electrolytic solution is filtered, the filter residue washed with de-ionized water obtained is placed in vacuum drying oven and can obtains pure, dry intercalation carbon nanometer wall after 18 hours in 65 DEG C of dryings;
5. the intercalation carbon nanometer wall getting 100g dried enters in small vessels, and this small vessels is put in the container that liquid nitrogen is housed soak 1 minute, make intercalation carbon nanometer wall cool rear taking-up completely;
6. the intercalation carbon nanometer wall of cooling is put into furnace body temperature to be fast 850 DEG C, to be filled with in the retort furnace of argon gas, intercalation carbon nanometer wall is peeled off by the huge temperature difference instantaneously, 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, good rear the deionized water of etching, ethanol, acetone carry out cleaning also drying;
2. the air in eliminating reaction chamber also passes into helium, cobalt paper tinsel after cleaning-drying is put into the reaction chamber being connected with helium, and cobalt paper tinsel is heated to 850 DEG C and is incubated, then ultraviolet source equipment is opened, make UV-irradiation on cobalt paper tinsel surface, the wavelength of UV-light 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, stop after question response room is cooled to room temperature passing into helium, cobalt paper tinsel Surface Creation carbon nanometer wall, scrapes it from cobalt paper tinsel surface, just obtains carbon nanometer wall powder;
4. the preparation of intercalation carbon nanometer wall: adopt stainless steel substrates as collector, put on collector by the above-mentioned carbon nanometer wall powder prepared, being pressed into specification is on a current collector 75*40*7mm
3the carbon nanometer wall flaps layer of (about 2g) as working electrode, using stereotype as to electrode, Hg/Hg
2sO
4as reference electrode, three electrodes, as electrolytic solution, are put into electrolyzer and are fully immersed in electrolytic solution, at 40mA/cm by Nitromethane 99Min.
2current density, carry out reaction 15 hours under room temperature, then reacted electrolytic solution is filtered, the filter residue washed with de-ionized water obtained is placed in vacuum drying oven and can obtains pure, dry intercalation carbon nanometer wall after 20 hours in 60 DEG C of dryings;
5. the intercalation carbon nanometer wall getting 100g dried enters in small vessels, and this small vessels is put in the container that liquid argon is housed soak 20 minutes, make intercalation carbon nanometer wall cool rear taking-up completely;
6. the intercalation carbon nanometer wall of cooling is put into furnace body temperature to be fast 950 DEG C, to be filled with in the retort furnace of helium, intercalation carbon nanometer wall is peeled off by the huge temperature difference instantaneously, 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, good rear the deionized water of etching, ethanol, acetone carry out cleaning also drying;
2. the air in eliminating reaction chamber also passes into nitrogen, nickel foil after cleaning-drying is put into the reaction chamber being connected with nitrogen, and nickel foil is heated to 900 DEG C and is incubated, then ultraviolet source equipment is opened, make UV-irradiation on nickel foil surface, the wavelength of UV-light 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, stop after question response room is cooled to room temperature passing into nitrogen, nickel foil Surface Creation carbon nanometer wall, scrapes it from nickel foil surface, just obtains carbon nanometer wall powder;
4. the preparation of intercalation carbon nanometer wall: adopt stainless steel substrates as collector, put on collector by the above-mentioned carbon nanometer wall powder prepared, being pressed into specification is on a current collector 75*40*7mm
3the carbon nanometer wall flaps layer of (about 2g) as working electrode, using stereotype as to electrode, Hg/Hg
2sO
4as reference electrode, three electrodes, as electrolytic solution, are put into electrolyzer and are fully immersed in electrolytic solution, at 10mA/cm by the mixed solution of acetic acid and Nitromethane 99Min. 1:1 mixing by volume
2current density, carry out reaction 6 hours under room temperature, then reacted electrolytic solution is filtered, the filter residue washed with de-ionized water obtained is placed in vacuum drying oven and can obtains pure, dry intercalation carbon nanometer wall after 12 hours in 80 DEG C of dryings;
5. the intercalation carbon nanometer wall getting 100g dried enters in small vessels, and this small vessels is put in the container that liquid hydrogen is housed soak 4 minutes, make intercalation carbon nanometer wall cool rear taking-up completely;
6. the intercalation carbon nanometer wall of cooling is put into furnace body temperature to be fast 1050 DEG C, to be filled with in the retort furnace of nitrogen, intercalation carbon nanometer wall is peeled off by the huge temperature difference instantaneously, 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, good rear the deionized water of etching, ethanol, acetone carry out cleaning also drying;
2. the air in eliminating reaction chamber also passes into argon gas, iron foil after cleaning-drying is put into the reaction chamber being connected with argon gas, and iron foil is heated to 650 DEG C and is incubated, then ultraviolet source equipment is opened, make UV-irradiation on iron foil surface, the wavelength of UV-light 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, stop after question response room is cooled to room temperature passing into argon gas, iron foil Surface Creation carbon nanometer wall, scrapes it from iron foil surface, just obtains carbon nanometer wall powder;
4. the preparation of intercalation carbon nanometer wall: adopt stainless steel substrates as collector, put on collector by the above-mentioned carbon nanometer wall powder prepared, being pressed into specification is on a current collector 75*40*7mm
3the carbon nanometer wall flaps layer of (about 2g) as working electrode, using stereotype as to electrode, Hg/Hg
2sO
4as reference electrode, formic acid and massfraction be 68% nitric acid by volume 4:1 mixing mixed solution as electrolytic solution, three electrodes are put into electrolyzer and are fully immersed in electrolytic solution, at 30mA/cm
2current density, carry out reaction 8 hours under room temperature, then reacted electrolytic solution is filtered, the filter residue washed with de-ionized water obtained is placed in vacuum drying oven and can obtains pure, dry intercalation carbon nanometer wall after 15 hours in 70 DEG C of dryings;
5. the intercalation carbon nanometer wall getting 100g dried enters in small vessels, and this small vessels is put in the container that liquid argon is housed soak 15 minutes, make intercalation carbon nanometer wall cool rear taking-up completely;
6. the intercalation carbon nanometer wall of cooling is put into furnace body temperature to be fast 1000 DEG C, to be filled with in the retort furnace of argon gas, intercalation carbon nanometer wall is peeled off by the huge temperature difference instantaneously, 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, good rear the deionized water of etching, ethanol, acetone carry out cleaning also drying;
2. the air in eliminating reaction chamber also passes into argon gas, cobalt paper tinsel after cleaning-drying is put into the reaction chamber being connected with helium, and cobalt paper tinsel is heated to 700 DEG C and is incubated, then ultraviolet source equipment is opened, make UV-irradiation on cobalt paper tinsel surface, the wavelength of UV-light 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, stop after question response room is cooled to room temperature passing into helium, cobalt paper tinsel Surface Creation carbon nanometer wall, scrapes it from cobalt paper tinsel surface, just obtains carbon nanometer wall powder.
4. the preparation of intercalation carbon nanometer wall: adopt stainless steel substrates as collector, put on collector by the above-mentioned carbon nanometer wall powder prepared, being pressed into specification is on a current collector 75*40*7mm
3the carbon nanometer wall flaps layer of (about 2g) as working electrode, using stereotype as to electrode, Hg/Hg
2sO
4as reference electrode, propionic acid and massfraction be 68% nitric acid by volume 1:2 mixing mixed solution as electrolytic solution, three electrodes are put into electrolyzer and are fully immersed in electrolytic solution, at 5mA/cm
2current density, carry out reaction 15 hours under room temperature, then reacted electrolytic solution is filtered, the filter residue washed with de-ionized water obtained is placed in vacuum drying oven and can obtains pure, dry intercalation carbon nanometer wall after 20 hours in 80 DEG C of dryings;
5. the intercalation carbon nanometer wall getting 100g dried enters in small vessels, and this small vessels is put in the container that liquid nitrogen is housed soak 30 minutes, make intercalation carbon nanometer wall cool rear taking-up completely;
6. the intercalation carbon nanometer wall of cooling is put into furnace body temperature to be fast 1100 DEG C, to be filled with in the retort furnace of helium, intercalation carbon nanometer wall is peeled off by the huge temperature difference instantaneously, 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, good rear the deionized water of etching, ethanol, acetone carry out cleaning also drying;
2. the air in eliminating reaction chamber also passes into nitrogen, nickel foil after cleaning-drying is put into the reaction chamber being connected with nitrogen, and nickel foil is heated to 800 DEG C and is incubated, then ultraviolet source equipment is opened, make UV-irradiation on nickel foil surface, the wavelength of UV-light 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, stop after question response room is cooled to room temperature passing into nitrogen, nickel foil Surface Creation carbon nanometer wall, scrapes it from nickel foil surface, just obtains carbon nanometer wall powder;
4. the preparation of intercalation carbon nanometer wall: adopt stainless steel substrates as collector, put on collector by the above-mentioned carbon nanometer wall powder prepared, being pressed into specification is on a current collector 75*40*7mm
3the carbon nanometer wall flaps layer of (about 2g) as working electrode, using stereotype as to electrode, Hg/Hg
2sO
4as reference electrode, three electrodes, as electrolytic solution, are put into electrolyzer and are fully immersed in electrolytic solution, at 100mA/cm by acetic acid
2current density, carry out reaction 2 hours under room temperature, then reacted electrolytic solution is filtered, the filter residue washed with de-ionized water obtained is placed in vacuum drying oven and can obtains pure, dry intercalation carbon nanometer wall after 18 hours in 60 DEG C of dryings;
5. the intercalation carbon nanometer wall getting 100g dried enters in small vessels, and this small vessels is put in the container that liquid argon is housed soak 2 minutes, make intercalation carbon nanometer wall cool rear taking-up completely;
6. the intercalation carbon nanometer wall of cooling is put into furnace body temperature to be fast 900 DEG C, to be filled with in the retort furnace of nitrogen, intercalation carbon nanometer wall is peeled off by the huge temperature difference instantaneously, 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, good rear the deionized water of etching, ethanol, acetone carry out cleaning also drying;
2. the air in eliminating reaction chamber also passes into argon gas, cobalt paper tinsel after cleaning-drying is put into the reaction chamber being connected with argon gas, and cobalt paper tinsel is heated to 900 DEG C and is incubated, then ultraviolet source equipment is opened, make UV-irradiation on cobalt paper tinsel surface, the wavelength of UV-light 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, stop after question response room is cooled to room temperature passing into argon gas, cobalt paper tinsel Surface Creation carbon nanometer wall, scrapes it from cobalt paper tinsel surface, just obtains carbon nanometer wall powder;
4. the preparation of intercalation carbon nanometer wall: adopt stainless steel substrates as collector, put on collector by the above-mentioned carbon nanometer wall powder prepared, being pressed into specification is on a current collector 75*40*7mm
3the carbon nanometer wall flaps layer of (about 2g) as working electrode, using stereotype as to electrode, Hg/Hg
2sO
4as reference electrode, three electrodes, as electrolytic solution, are put into electrolyzer and are fully immersed in electrolytic solution, at 50mA/cm by Nitromethane 99Min.
2current density, carry out reaction 1 hour under room temperature, then reacted electrolytic solution is filtered, the filter residue washed with de-ionized water obtained is placed in vacuum drying oven and can obtains pure, dry intercalation carbon nanometer wall after 20 hours in 80 DEG C of dryings;
5. the intercalation carbon nanometer wall getting 100g dried enters in small vessels, and this small vessels is put in the container that liquid hydrogen is housed soak 0.5 minute, make intercalation carbon nanometer wall cool rear taking-up completely;
6. the intercalation carbon nanometer wall of cooling is put into furnace body temperature to be fast 800 DEG C, to be filled with in the retort furnace of argon gas, intercalation carbon nanometer wall is peeled off by the huge temperature difference instantaneously, 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 only have expressed several embodiment of the present invention, and it describes comparatively concrete and detailed, but therefore can not 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 (8)
1. a preparation method for graphene nanobelt, is characterized in that, comprises the steps:
Use dilute acid soln to etch metal substrate, described metal substrate is the one in iron foil, nickel foil and cobalt paper tinsel;
Under the atmosphere of anaerobic and the first 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, through photochemical catalysis chemical vapour deposition reaction 30 minutes ~ 300 minutes, at described metal substrate surface Formed nanometer wall;
After having reacted, under the atmosphere of described 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 to be positioned on collector and to be pressed into carbon nanometer wall flaps layer and obtain working electrode;
Jointly will be soaked in electrolytic solution, at 5mA/cm electrode, reference electrode and described working electrode
2~ 100mA/cm
2current density, reaction after 1 hour ~ 20 hours under room temperature, carried out by reacted electrolytic solution filtering, wash filter residue and drying obtains intercalation carbon nanometer wall, described electrolytic solution is selected from least one in formic acid, acetic acid, propionic acid, nitric acid, Nitromethane 99Min.;
Described intercalation carbon nanometer wall is soaked in the one in liquid nitrogen, liquid argon and liquid hydrogen and cools 0.5 minute ~ 30 minutes; And
Cooled intercalation carbon nanometer wall is processed 30 minutes ~ 300 minutes in the second shielding gas atmosphere, in 800 DEG C ~ 1000 DEG C, after cooling, obtains graphene nanobelt.
2. the preparation method of graphene nanobelt according to claim 1, it is characterized in that, described use dilute acid soln is specially the step that metal substrate etches: described metal substrate is put into concentration be 0.01mol/L ~ 1mol/L dilute acid soln etching 0.5 minute ~ 10 minutes.
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 concentration be 0.1mol/L ~ 0.5mol/L dilute acid soln etching 1 minute ~ 3 minutes.
4. the preparation method of graphene nanobelt according to claim 1, is characterized in that, the wavelength of described UV-light 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 that is a kind of and described 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, it is characterized in that, the described washing filter residue also dry step obtaining intercalation carbon nanometer wall is specially: with filter residue described in deionized water wash, and in 60 DEG C ~ 80 DEG C vacuum-dryings 12 hours ~ 24 hours.
8. the preparation method of graphene nanobelt according to claim 1, is characterized in that, described first shielding gas and the second shielding gas are the one in helium, nitrogen and argon gas.
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