CN103935980B - The preparation method of graphene nanobelt - Google Patents
The preparation method of graphene nanobelt Download PDFInfo
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- CN103935980B CN103935980B CN201310019349.5A CN201310019349A CN103935980B CN 103935980 B CN103935980 B CN 103935980B CN 201310019349 A CN201310019349 A CN 201310019349A CN 103935980 B CN103935980 B CN 103935980B
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Abstract
The present invention relates to a kind of preparation method of graphene nanobelt, the method comprises the steps: to carry out acid treatment to metal substrate; Metal substrate is placed in oxygen-free environment, is heated to 600 ~ 900 DEG C, then under UV-irradiation condition, pass into protective gas and gas carbonaceous material carries out chemical vapour deposition reaction, after stopped reaction, obtain the carbon nanometer wall be attached on metal substrate surface; Separating metal substrate and carbon nanometer wall, obtain carbon nanometer wall powder; Carbon nanometer wall powder is mixed according to the ratio that mass ratio is 1:0.8 ~ 1:1.2 with metal chloride, and reacts at 460 ~ 550 DEG C, obtain the carbon nanometer wall of containing metal muriate intercalation; Be that the carbon nanometer wall of metal chloride intercalation is added in acetone by the ratio of 1g:100 ~ 1000mL according to mass volume ratio, centrifugal stripping in parallel magnetic field, obtains described graphene nanobelt after separating-purifying.Above-mentioned preparation method can obtain size adjustable graphene nanobelt.
Description
Technical field
The present invention relates to nano-carbon material field, particularly relate to a kind of preparation method of graphene nanobelt.
Background technology
The kind of carbon material has the soccerballene (C of zero dimension
60), the carbon nanotube, carbon nanofiber etc. of one dimension, the Graphene of two dimension, three-dimensional graphite, diamond etc., carbon nanometer wall (carbonnanowall, CNW) be the carbon nano structure with two-dimensional diffusion, its most typical pattern is just perpendicular to substrate material surface growth, and thickness is greater than the wall-like structure of Graphene, completely different from the feature of soccerballene, carbon nanotube, Graphene etc., can be used as the raw material of other carbon material of preparation, as the preparation of graphene nanobelt etc.
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.But due to size control difficulty in graphene nanobelt preparation process, yield poorly, thus limit it and apply further.
Summary of the invention
Based on this, be necessary the preparation method that a kind of size adjustable graphene nanobelt is provided.
A preparation method for graphene nanobelt, comprises the steps:
Acid treatment is carried out to metal substrate;
Oxygen-free environment will be placed in through acid-treated described metal substrate, be heated to 600 ~ 900 DEG C, then under UV-irradiation condition, pass into protective gas and gas carbonaceous material carries out chemical vapour deposition reaction, after stopped reaction, obtain the carbon nanometer wall be attached on described metal substrate surface;
Be separated described metal substrate and described carbon nanometer wall, obtain carbon nanometer wall powder;
Described carbon nanometer wall powder is mixed according to the ratio that mass ratio is 1:0.8 ~ 1:1.2 with metal chloride, and reacts at 460 ~ 550 DEG C, obtain the carbon nanometer wall of containing metal muriate intercalation;
Be that the carbon nanometer wall of described metal chloride intercalation is added in acetone by the ratio of 1g:100 ~ 1000mL according to mass volume ratio, centrifugal stripping in the parallel magnetic field of 0.01 ~ 1T, obtains described graphene nanobelt after separating-purifying.
Wherein in an embodiment, describedly acid-treated step carried out to metal substrate comprise:
Pending metal substrate is put into concentration be 0.01 ~ 1mol/L acid solution etching 0.5 ~ 10 minute, then clean with deionized water, ethanol and acetone successively, namely obtain described metal substrate after acid treatment.
Wherein in an embodiment, described metal substrate is iron foil, nickel foil or cobalt paper tinsel; Described acid is hydrochloric acid, sulfuric acid or nitric acid.
Wherein in an embodiment, the process of described stopped reaction comprises stopping successively and passes into described gas carbonaceous material, stops described metal substrate heating, stops carrying out UV-irradiation to described metal substrate and being cooled to until metal substrate the step stopping passing into protective gas after room temperature.
Wherein in an embodiment, the flow velocity of described gas carbonaceous material is 10 ~ 1000sccm, and the volume ratio of described protective gas and gas carbonaceous material is 1:2 ~ 1:10, and the time passing into described carbonaceous material is 30 ~ 300 minutes.
Wherein in an embodiment, described protective gas is helium, nitrogen or argon gas.
Wherein in an embodiment, described gas carbonaceous material is methane, ethane, propane, acetylene or ethanol.
Wherein in an embodiment, the step of described separating-purifying is: filtered by the material after centrifugal stripping, the solids washed with de-ionized water obtained, until use Ag
+detect the solution after cleaning without till precipitation generation.
Wherein in an embodiment, described metal chloride is at least one in iron(ic) chloride, nickelous chloride, cupric chloride, cobalt chloride, Repone K, magnesium chloride, lead chloride, zinc chloride, calcium chloride and bariumchloride.
Wherein in an embodiment, the rotating speed in described centrifugal stripping process is 1000 ~ 10000 revs/min, and the time of described centrifugal stripping is 10 ~ 100 minutes.
First the preparation method of above-mentioned graphene nanobelt adopts acid etch process and photochemical catalysis two-step chemical gas-phase deposition to prepare structure more complete carbon nanometer wall; Then with carbon nanometer wall and metal chloride for raw material prepares the intermediate product of metal chloride intercalation carbon nanometer wall; Again after the effect and centrifugal treating of parallel magnetic field, metal chloride intercalation carbon nanometer wall can be easy to peel off into graphene nanobelt.Due in the process preparing carbon nanometer wall, the carbon nanometer wall of different size can be prepared by the flow velocity of regulation and control gas carbonaceous material and the time passing into gas carbonaceous material, then with size adjustable carbon nanometer wall for raw material, thus size adjustable graphene nanobelt can be prepared.
Accompanying drawing explanation
Fig. 1 is the schema of the preparation method of the graphene nanobelt of an embodiment;
Fig. 2 is the SEM figure of the carbon nanometer wall that enforcement 1 prepares;
Fig. 3 is the SEM figure of the graphene nanobelt that enforcement 1 prepares.
Embodiment
Below in conjunction with drawings and the specific embodiments, the preparation method to graphene nanobelt is further described.
As shown in Figure 1, the preparation method of the graphene nanobelt of an embodiment, comprises the steps:
Step 110, carries out acid treatment to metal substrate.
Step 120; oxygen-free environment will be placed in through acid-treated metal substrate, be heated to 600 ~ 900 DEG C, then under UV-irradiation condition, pass into protective gas and gas carbonaceous material carries out chemical vapour deposition reaction; after stopped reaction, obtain the carbon nanometer wall be attached on metal substrate surface.
Step 130, separating metal substrate and carbon nanometer wall, obtain carbon nanometer wall powder.
Step 140, mixes carbon nanometer wall powder according to the ratio that mass ratio is 1:0.8 ~ 1:1.2 with metal chloride, and reacts at 460 ~ 550 DEG C, obtains the carbon nanometer wall of containing metal muriate intercalation.
Step 150, be that the carbon nanometer wall of metal chloride intercalation is added in acetone by the ratio of 1g:100 ~ 1000mL according to mass volume ratio, centrifugal stripping in the parallel magnetic field of 0.01 ~ 1T, obtains described graphene nanobelt after separating-purifying.
In the present embodiment, metal substrate after acid treatment is prepared as follows: pending metal substrate is put into concentration be 0.01 ~ 1mol/L acid solution etching 0.5 ~ 10 minute, then clean with deionized water, ethanol and acetone successively, namely obtain the metal substrate after acid treatment.Wherein, acid solution can be dilute hydrochloric acid solution, dilution heat of sulfuric acid or dilute nitric acid solution; The concentration of acid solution is preferably 0.1 ~ 0.5mol/L; The acid-treated time is preferably 1.0 ~ 3.0 minutes.The acid-treated time is short, can improve the production efficiency of carbon nanometer wall.Be appreciated that in other embodiments, additive method can also be adopted to prepare the substrate after acid treatment.
In the present embodiment, metal substrate is iron foil, nickel foil or cobalt paper tinsel.After acid treatment is carried out to iron foil, nickel foil or cobalt paper tinsel, make the surface of iron foil, nickel foil or cobalt paper tinsel produce defect, thus effectively can improve the surface tissue of iron foil, nickel foil or cobalt paper tinsel, make the enough surface growths at iron foil, nickel foil or cobalt paper tinsel of carbon nanometer wall energy.
In the present embodiment, whole reaction process is all carried out under oxygen-free environment, mainly in order to provide a stable environment to the preparation of carbon nanometer wall, avoiding the participation of oxygen and affecting the preparation of carbon nanometer wall.
In the present embodiment, protective gas is at least one in helium, nitrogen and argon gas.Gas carbonaceous material is methane, ethane, propane, acetylene or ethanol; The flow velocity of gas carbonaceous material is 10 ~ 1000sccm, and the volume ratio of protective gas and gas carbonaceous material is 1:2 ~ 1:10, and the time passing into gas carbonaceous material is 30 ~ 300 minutes.
Protective gas except have oxygen-free environment is provided effect except, in reaction process, the probability of collision between gas carbonaceous material can also be reduced, thus reduce unnecessary reaction and occur, object be reacted and carries out smoothly.
Gas carbonaceous material needs to pass in a gaseous form in oxygen-free environment, it is the carbonaceous material of gaseous state under generally can selecting normal temperature, easily gasification can certainly be selected and cheap carbonaceous material, as ethanol (pass into before to oxygen-free environment, first make ethanol gasify).The flow velocity of gas carbonaceous material and the thickness of time on carbon nanometer wall passing into gas carbonaceous material have impact, can be prepared the carbon nanometer wall of different size by the flow velocity of regulation and control gas carbonaceous material and time of passing into gas carbonaceous material, and the carbon nanometer wall of different size can affect the size of the graphene nanobelt prepared for raw material with carbon nanometer wall.
In the present embodiment, the process of stopped reaction comprises and stops passing into gas carbonaceous material successively, stops metal substrate heating, stops carrying out UV-irradiation to metal substrate and be cooled to after room temperature until metal substrate stopping passing into the step of protective gas.
First, stop passing into gas carbonaceous material, also namely stopped supply reactant gases, and now do not have stopping heating and ultraviolet lighting, the gas carbonaceous material in reaction system can be made to continue reaction, thus the stopping of control sluggish.And to be cooled to after room temperature until metal substrate and to stop again passing into protective gas, be to make the carbon nanometer wall obtained be in oxygen-free environment under higher than the condition of room temperature always, avoid carbon nanometer wall to react at a relatively high temperature.
In the present embodiment, metal chloride is at least one in iron(ic) chloride, nickelous chloride, cupric chloride, cobalt chloride, Repone K, magnesium chloride, lead chloride, zinc chloride, calcium chloride and bariumchloride.
In the present embodiment, the time of centrifugal stripping is 10 ~ 100 minutes.
The step of separating-purifying is specially: filtered by the material after supersound process, the solids washed with de-ionized water obtained, until use Ag
+detect the solution after cleaning without till precipitation generation.
In the present embodiment, Ag
+by AgNO
3solution provides.
First the preparation method of above-mentioned graphene nanobelt adopts acid etch process and photochemical catalysis two-step chemical gas-phase deposition to prepare structure more complete carbon nanometer wall; Then with carbon nanometer wall and metal chloride for raw material prepares the intermediate product of metal chloride intercalation carbon nanometer wall; Because metal chloride intercalation carbon nanometer wall can't destroy the structure of former carbon nanometer wall, and acetone has good solvability to metal chloride, therefore, after the effect and centrifugal treating of parallel magnetic field, metal chloride intercalation carbon nanometer wall can be easy to peel off into graphene nanobelt.Due in the process preparing carbon nanometer wall, the carbon nanometer wall of different size can be prepared by the flow velocity of regulation and control carbonaceous material and the time passing into carbonaceous material, then with size adjustable carbon nanometer wall for raw material, thus size adjustable graphene nanobelt can be obtained.And photochemical catalysis chemical Vapor deposition process effectively can reduce temperature of reaction, reduce energy consumption, thus reduce production cost, and effectively prevent existing using plasma and prepare carbon nanometer wall and carbon nano wall structure is damaged, make the thickness of carbon nanometer wall and pattern comparatively even, structure is more complete.
Preparation method's technique of above-mentioned graphene nanobelt is simple, easy to operate and productive rate that the is graphene nanobelt prepared is higher.And the material carbon nanometer wall preparing graphene nanobelt is prepared voluntarily, required equipment is all common chemical industry equipment, thus economizes in raw materials and research and develop the cost of equipment, and low as the acetone price of solvent, be conducive to reducing production cost, be applicable to scale operation.
It is below specific embodiment part
Embodiment 1
Nickel foil is put into concentration be 1mol/L dilute hydrochloric acid solution etching 0.5 minute, then with deionized water, ethanol, acetone, the nickel foil after etching processing is cleaned successively.The cleaned nickel foil after etching processing is put into reaction chamber, and the air got rid of in reaction chamber, then the nickel foil after etching processing is heated to 900 DEG C, open ultraviolet source equipment again, make UV-irradiation at the nickel foil after etching processing on the surface, then pass into the methane of 200sccm and the nitrogen of 100sccm, and keep 100 minutes.After having reacted, first stop passing into methane, then stop the nickel foil heating after etching processing and close ultraviolet source equipment; Stop after question response room is cooled to room temperature passing into nitrogen, obtain the carbon nanometer wall be attached on the nickel foil surface after etching processing, it is scraped from the nickel foil surface after etching processing, just obtain carbon nanometer wall powder.
Detect the carbon nanometer wall prepared by scanning electronic microscope, as shown in Figure 2, as can be seen from the figure, carbon nanometer wall is perpendicular to substrate dense growth, and thickness is even, is about 30 ~ 60nm.
Take 1g carbon nanometer wall and 0.8g iron(ic) chloride respectively, and insert in silica tube, sealed silica envelope, after being warming up to 460 DEG C, react 2 hours at 460 DEG C, be cooled to room temperature after reaction terminates, obtain iron(ic) chloride intercalation carbon nanometer wall.Then use washed with de-ionized water, and be dried to constant weight at 80 DEG C in vacuum drying oven after, obtain pure iron(ic) chloride intercalation carbon nanometer wall.Iron(ic) chloride intercalation carbon nanometer wall pure for 1g is scattered in 100mL acetone, then supercentrifuge is placed in, and add that at the top of supercentrifuge and two ends, bottom magneticstrength is the constant parallel magnetic field of 1T, setting centrifugal speed is 1000 revs/min, start magnetic field and whizzer, centrifugal stripping iron(ic) chloride intercalation carbon nanometer wall 100 minutes.After centrifugal end, the material in centrifuge tube is all shifted out, and filters, obtain solid matter; Use washed with de-ionized water solid matter, until use AgNO
3detect the solution after cleaning without till precipitation generation.The solid matter cleaned up is put into and at 60 DEG C, is dried to constant weight in vacuum drying oven and namely obtains graphene nanobelt.
Detect the graphene nanobelt prepared by scanning electronic microscope, as shown in Figure 3, as can be seen from the figure, graphene nanobelt width distribution is concentrated, and be about 20 ~ 40nm, length is about 2 ~ 20 μm, and length-to-diameter ratio is about 50 ~ 1000.
Embodiment 2
Iron foil is put into concentration be 0.5mol/L dilution heat of sulfuric acid etching 4 minutes, then with deionized water, ethanol, acetone, the iron foil after etching processing is cleaned successively.The cleaned iron foil after etching processing is put into reaction chamber, and the air got rid of in reaction chamber, then the iron foil after etching processing is heated to 600 DEG C, open ultraviolet source equipment again, make UV-irradiation at the iron foil after etching processing on the surface, then pass into the ethane of 100sccm and the argon gas of 20sccm, and keep 200 minutes.After having reacted, first stop passing into ethane, then stop the iron foil heating after etching processing and close ultraviolet source equipment; Stop after question response room is cooled to room temperature passing into argon gas, obtain the carbon nanometer wall be attached on the iron foil surface after etching processing, it is scraped from the iron foil surface after etching processing, just obtain carbon nanometer wall powder.
Take 1g carbon nanometer wall and 0.9g cupric chloride respectively, and insert in silica tube, sealed silica envelope, after being warming up to 500 DEG C, react 3 hours at 500 DEG C, be cooled to room temperature after reaction terminates, obtain cupric chloride intercalation carbon nanometer wall.Then use washed with de-ionized water, and be dried to constant weight at 90 DEG C in vacuum drying oven after, obtain pure cupric chloride intercalation carbon nanometer wall.Cupric chloride intercalation carbon nanometer wall pure for 1g is scattered in 1000mL acetone, then supercentrifuge is placed in, and add that at the top of supercentrifuge and two ends, bottom magneticstrength is the constant parallel magnetic field of 0.5T, setting centrifugal speed is 2000 revs/min, start magnetic field and whizzer, centrifugal stripping cupric chloride intercalation carbon nanometer wall 50 minutes.After centrifugal end, the material in centrifuge tube is all shifted out, and filters, obtain solid matter; Use washed with de-ionized water solid matter, until use AgNO
3detect the solution after cleaning without till precipitation generation.The solid matter cleaned up is put into and at 80 DEG C, is dried to constant weight in anaerobic loft drier and namely obtains graphene nanobelt.
Embodiment 3
Cobalt paper tinsel is put into concentration be 0.01mol/L dilute nitric acid solution etching 10 minutes, then with deionized water, ethanol, acetone, the cobalt paper tinsel after etching processing is cleaned successively.The cleaned cobalt paper tinsel after etching processing is put into reaction chamber, and the air got rid of in reaction chamber, then the cobalt paper tinsel after etching processing is heated to 700 DEG C, open ultraviolet source equipment again, make UV-irradiation at the cobalt paper tinsel after etching processing on the surface, then pass into the acetylene of 10sccm and the helium of 1.25sccm, and keep 300 minutes.After having reacted, first stop passing into acetylene, then stop the cobalt paper tinsel heating after etching processing and close ultraviolet source equipment; Stop after question response room is cooled to room temperature passing into helium, obtain being attached to the carbon nanometer wall on the cobalt paper tinsel surface after etching processing, it is scraped from the cobalt paper tinsel surface after etching processing, just obtain carbon nanometer wall powder.
Take 1g carbon nanometer wall and 1.2g nickelous chloride respectively, and insert in silica tube, sealed silica envelope, after being warming up to 480 DEG C, react 6 hours at 480 DEG C, be cooled to room temperature after reaction terminates, obtain nickelous chloride intercalation carbon nanometer wall.Then use washed with de-ionized water, and be dried to constant weight at 100 DEG C in vacuum drying oven after, obtain pure nickelous chloride intercalation carbon nanometer wall.Nickelous chloride intercalation carbon nanometer wall pure for 1g is scattered in 500mL acetone, then supercentrifuge is placed in, and add that at the top of supercentrifuge and two ends, bottom magneticstrength is the constant parallel magnetic field of 0.1T, setting centrifugal speed is 5000 revs/min, start magnetic field and whizzer, centrifugal stripping nickelous chloride intercalation carbon nanometer wall 30 minutes.After centrifugal end, the material in centrifuge tube is all shifted out, and filters, obtain solid matter; And use washed with de-ionized water solid matter, until use AgNO
3detect the solution after cleaning without till precipitation generation.The solid matter cleaned up is put into and at 100 DEG C, is dried to constant weight in vacuum drying oven and namely obtains graphene nanobelt.
Embodiment 4
Nickel foil is put into concentration be 0.2mol/L dilute hydrochloric acid solution etching 2 minutes, then with deionized water, ethanol, acetone, the nickel foil after etching processing is cleaned successively.The cleaned nickel foil after etching processing is put into reaction chamber, and the air got rid of in reaction chamber, then the nickel foil after etching processing is heated to 750 DEG C, open ultraviolet source equipment again, make UV-irradiation at the nickel foil after etching processing on the surface, then pass into the propane of 1000sccm and the nitrogen of 100sccm, and keep 30 minutes.After having reacted, first stop passing into propane, then stop the nickel foil heating after etching processing and close ultraviolet source equipment; Stop after question response room is cooled to room temperature passing into nitrogen, obtain the carbon nanometer wall be attached on the nickel foil surface after etching processing, it is scraped from the nickel foil surface after etching processing, just obtain carbon nanometer wall powder.
Take 1g carbon nanometer wall and 1g cobalt chloride respectively, and insert in silica tube, sealed silica envelope, after being warming up to 550 DEG C, react 4 hours at 550 DEG C, be cooled to room temperature after reaction terminates, obtain cobalt chloride intercalation carbon nanometer wall.Then use washed with de-ionized water, and be dried to constant weight at 90 DEG C in vacuum drying oven after, obtain pure cobalt chloride intercalation carbon nanometer wall.Cobalt chloride intercalation carbon nanometer wall pure for 1g is scattered in 200mL acetone, then supercentrifuge is placed in, and add that at the top of supercentrifuge and two ends, bottom magneticstrength is the constant parallel magnetic field of 0.05T, setting centrifugal speed is 8000 revs/min, start magnetic field and whizzer, centrifugal stripping cobalt chloride intercalation carbon nanometer wall 10 minutes.After centrifugal end, the material in centrifuge tube is all shifted out, and filters, obtain solid matter; And use washed with de-ionized water solid matter, until use AgNO
3detect the solution after cleaning without till precipitation generation.The solid matter cleaned up is put into and at 90 DEG C, is dried to constant weight in vacuum drying oven and namely obtains graphene nanobelt.
Embodiment 5
Iron foil is put into concentration be 0.1mol/L dilution heat of sulfuric acid etching 5 minutes, then with deionized water, ethanol, acetone, the iron foil after etching processing is cleaned successively.The cleaned iron foil after etching processing is put into reaction chamber, and the air got rid of in reaction chamber, then the iron foil after etching processing is heated to 800 DEG C, open ultraviolet source equipment again, make UV-irradiation at the iron foil after etching processing on the surface, then pass into the ethanol of 500sccm and the argon gas of (500/6) sccm, and keep 50 minutes.After having reacted, first stop passing into ethanol, then stop the iron foil heating after etching processing and close ultraviolet source equipment; Stop after question response room is cooled to room temperature passing into argon gas, obtain the carbon nanometer wall be attached on the iron foil surface after etching processing, it is scraped from the iron foil surface after etching processing, just obtain carbon nanometer wall powder.
Take 1g carbon nanometer wall and 1.1g Repone K respectively, and insert in silica tube, sealed silica envelope, after being warming up to 520 DEG C, react 5 hours at 520 DEG C, be cooled to room temperature after reaction terminates, obtain Repone K intercalation carbon nanometer wall.Then use washed with de-ionized water, and be dried to constant weight at 85 DEG C in vacuum drying oven after, obtain pure Repone K intercalation carbon nanometer wall.Repone K intercalation carbon nanometer wall pure for 1g is scattered in 800mL acetone, then supercentrifuge is placed in, and add that at the top of supercentrifuge and two ends, bottom magneticstrength is the constant parallel magnetic field of 0.01T, setting centrifugal speed is 10000 revs/min, start magnetic field and whizzer, centrifugal stripping Repone K intercalation carbon nanometer wall 20 minutes.After centrifugal end, the material in centrifuge tube is all shifted out, and filters, obtain solid matter; And use washed with de-ionized water solid matter, until use AgNO
3detect the solution after cleaning without till precipitation generation.The filter residue cleaned up is put into and at 70 DEG C, is dried to constant weight in vacuum drying oven and namely obtains graphene nanobelt.
Embodiment 6
Cobalt paper tinsel is put into concentration be 0.4mol/L dilute nitric acid solution etching 8 minutes, then with deionized water, ethanol, acetone, the cobalt paper tinsel after etching processing is cleaned successively.The cleaned cobalt paper tinsel after etching processing is put into reaction chamber, and the air got rid of in reaction chamber, then the cobalt paper tinsel after etching processing is heated to 850 DEG C, open ultraviolet source equipment again, make UV-irradiation at the cobalt paper tinsel after etching processing on the surface, then pass into the methane of 800sccm and the helium of 200sccm, and keep 90 minutes.After having reacted, first stop passing into methane, then stop the cobalt paper tinsel heating after etching processing and close ultraviolet source equipment; Stop after question response room is cooled to room temperature passing into helium, obtain being attached to the carbon nanometer wall on the cobalt paper tinsel surface after etching processing, it is scraped from the cobalt paper tinsel surface after etching processing, just obtain carbon nanometer wall powder.
Take 1g carbon nanometer wall and 0.8g sodium-chlor respectively, and insert in silica tube, sealed silica envelope, after being warming up to 530 DEG C, react 2 hours at 530 DEG C, be cooled to room temperature after reaction terminates, obtain sodium-chlor intercalation carbon nanometer wall.Then use washed with de-ionized water, and be dried to constant weight at 95 DEG C in vacuum drying oven after, obtain pure sodium-chlor intercalation carbon nanometer wall.Sodium-chlor intercalation carbon nanometer wall pure for 1g is scattered in 600mL acetone, then supercentrifuge is placed in, and add that at the top of supercentrifuge and two ends, bottom magneticstrength is the constant parallel magnetic field of 0.2T, setting centrifugal speed is 2000 revs/min, start magnetic field and whizzer, centrifugal stripping sodium-chlor intercalation carbon nanometer wall 40 minutes.After centrifugal end, the material in centrifuge tube is all shifted out, and filters, obtain solid matter; And use washed with de-ionized water solid matter, until use AgNO
3detect the solution after cleaning without till precipitation generation.The solid matter cleaned up is put into and at 60 DEG C, is dried to constant weight in vacuum drying oven and namely obtains graphene nanobelt.
Embodiment 7
Nickel foil is put into concentration be 0.25mol/L dilute hydrochloric acid solution etching 3 minutes, then with deionized water, ethanol, acetone, the nickel foil after etching processing is cleaned successively.The cleaned nickel foil after etching processing is put into reaction chamber, and the air got rid of in reaction chamber, then the nickel foil after etching processing is heated to 900 DEG C, open ultraviolet source equipment again, make UV-irradiation at the nickel foil after etching processing on the surface, then pass into the ethane of 300sccm and the nitrogen of 100sccm, and keep 120 minutes.After having reacted, first stop passing into ethane, then stop the nickel foil heating after etching processing and close ultraviolet source equipment; Stop after question response room is cooled to room temperature passing into nitrogen, obtain the carbon nanometer wall be attached on the nickel foil surface after etching processing, it is scraped from the nickel foil surface after etching processing, just obtain carbon nanometer wall powder.
Take 1g carbon nanometer wall and 1.1g magnesium chloride respectively, and insert in silica tube, sealed silica envelope, after being warming up to 490 DEG C, react 3 hours at 490 DEG C, be cooled to room temperature after reaction terminates, obtain magnesium chloride intercalation carbon nanometer wall.Then use washed with de-ionized water, and be dried to constant weight at 90 DEG C in vacuum drying oven after, obtain pure magnesium chloride intercalation carbon nanometer wall.Magnesium chloride intercalation carbon nanometer wall pure for 1g is scattered in 400mL acetone, then supercentrifuge is placed in, and add that at the top of supercentrifuge and two ends, bottom magneticstrength is the constant parallel magnetic field of 0.4T, setting centrifugal speed is 2500 revs/min, start magnetic field and whizzer, centrifugal stripping magnesium chloride intercalation carbon nanometer wall 60 minutes.After centrifugal end, the material in centrifuge tube is all shifted out, and filters, obtain solid matter; And use washed with de-ionized water solid matter, until use AgNO
3detect the solution after cleaning without till precipitation generation.The solid matter cleaned up is put into and at 100 DEG C, is dried to constant weight in vacuum drying oven and namely obtains graphene nanobelt.
Embodiment 8
Iron foil is put into concentration be 1mol/L dilute hydrochloric acid solution etching 4 minutes, then with deionized water, ethanol, acetone, the iron foil after etching processing is cleaned successively.The cleaned iron foil after etching processing is put into reaction chamber, and the air got rid of in reaction chamber, then the iron foil after etching processing is heated to 650 DEG C, open ultraviolet source equipment again, make UV-irradiation at the iron foil after etching processing on the surface, then pass into the acetylene of 200sccm and the argon gas of 100sccm, and keep 180 minutes.After having reacted, first stop passing into acetylene, then stop the iron foil heating after etching processing and close ultraviolet source equipment; Stop after question response room is cooled to room temperature passing into nitrogen, obtain the carbon nanometer wall be attached on the iron foil surface after etching processing, it is scraped from the iron foil surface after etching processing, just obtain carbon nanometer wall powder.
Take 1g carbon nanometer wall and 1g aluminum chloride respectively, and insert in silica tube, sealed silica envelope, after being warming up to 540 DEG C, react 6 hours at 540 DEG C, be cooled to room temperature after reaction terminates, obtain aluminum chloride intercalation carbon nanometer wall.Then use washed with de-ionized water, and be dried to constant weight at 100 DEG C in vacuum drying oven after, obtain pure aluminum chloride intercalation carbon nanometer wall.Aluminum chloride intercalation carbon nanometer wall pure for 1g is scattered in 300mL acetone, then supercentrifuge is placed in, and add that at the top of supercentrifuge and two ends, bottom magneticstrength is the constant parallel magnetic field of 0.8T, setting centrifugal speed is 1000 revs/min, start magnetic field and whizzer, centrifugal stripping aluminum chloride intercalation carbon nanometer wall 80 minutes.After centrifugal end, the material in centrifuge tube is all shifted out, and filters, obtain solid matter; And use washed with de-ionized water solid matter, until use AgNO
3detect the solution after cleaning without till precipitation generation.The solid matter cleaned up is put into and at 80 DEG C, is dried to constant weight in vacuum drying oven and namely obtains graphene nanobelt.
Embodiment 9
Cobalt paper tinsel is put into concentration be 0.3mol/L dilution heat of sulfuric acid etching 2 minutes, then with deionized water, ethanol, acetone, the cobalt paper tinsel after etching processing is cleaned successively.The cleaned cobalt paper tinsel after etching processing is put into reaction chamber, and the air got rid of in reaction chamber, then the cobalt paper tinsel after etching processing is heated to 700 DEG C, open ultraviolet source equipment again, make UV-irradiation at the cobalt paper tinsel after etching processing on the surface, then pass into the propane of 50sccm and the helium of 10sccm, and keep 240 minutes.After having reacted, first stop passing into propane, then stop the cobalt paper tinsel heating after etching processing and close ultraviolet source equipment; Stop after question response room is cooled to room temperature passing into helium, obtain being attached to the carbon nanometer wall on the cobalt paper tinsel surface after etching processing, it is scraped from the cobalt paper tinsel surface after etching processing, just obtain carbon nanometer wall powder.
Take 1g carbon nanometer wall and 0.9g zinc chloride respectively, and insert in silica tube, sealed silica envelope, after being warming up to 520 DEG C, react 5 hours at 520 DEG C, be cooled to room temperature after reaction terminates, obtain zinc chloride intercalation carbon nanometer wall.Then use washed with de-ionized water, and be dried to constant weight at 80 DEG C in vacuum drying oven after, obtain pure zinc chloride intercalation carbon nanometer wall.Zinc chloride intercalation carbon nanometer wall pure for 1g is scattered in 1000mL acetone, then supercentrifuge is placed in, and add that at the top of supercentrifuge and two ends, bottom magneticstrength is the constant parallel magnetic field of 1T, setting centrifugal speed is 3000 revs/min, start magnetic field and whizzer, centrifugal stripping zinc chloride intercalation carbon nanometer wall 50 minutes.After centrifugal end, the material in centrifuge tube is all shifted out, and filters, obtain solid matter; And use washed with de-ionized water solid matter, until use AgNO
3detect the solution after cleaning without till precipitation generation.The solid matter cleaned up is put into and at 90 DEG C, is dried to constant weight in vacuum drying oven and namely obtains graphene nanobelt.
Embodiment 10
Nickel foil is put into concentration be 0.5mol/L dilute nitric acid solution etching 5 minutes, then with deionized water, ethanol, acetone, the nickel foil after etching processing is cleaned successively.The cleaned nickel foil after etching processing is put into reaction chamber, and the air got rid of in reaction chamber, then the nickel foil after etching processing is heated to 800 DEG C, open ultraviolet source equipment again, make UV-irradiation at the nickel foil after etching processing on the surface, then pass into the ethanol of 20sccm and the nitrogen of 2.5sccm, and keep 300 minutes.After having reacted, first stop passing into ethanol, then stop the nickel foil heating after etching processing and close ultraviolet source equipment; Stop after question response room is cooled to room temperature passing into nitrogen, obtain the carbon nanometer wall be attached on the nickel foil surface after etching processing, it is scraped from the nickel foil surface after etching processing, just obtain carbon nanometer wall powder.
Take 1g carbon nanometer wall and 1.1g bariumchloride respectively, and insert in silica tube, sealed silica envelope, after being warming up to 550 DEG C, react 4 hours at 550 DEG C, be cooled to room temperature after reaction terminates, obtain bariumchloride intercalation carbon nanometer wall.Then use washed with de-ionized water, and be dried to constant weight at 90 DEG C in vacuum drying oven after, obtain pure bariumchloride intercalation carbon nanometer wall.Bariumchloride intercalation carbon nanometer wall pure for 1g is scattered in 100mL acetone, then supercentrifuge is placed in, and add that at the top of supercentrifuge and two ends, bottom magneticstrength is the constant parallel magnetic field of 0.1T, setting centrifugal speed is 5000 revs/min, start magnetic field and whizzer, centrifugal stripping bariumchloride intercalation carbon nanometer wall 10 minutes.After centrifugal end, the material in centrifuge tube is all shifted out, and filters, obtain solid matter; And use washed with de-ionized water solid matter, until use AgNO
3detect the solution after cleaning without till precipitation generation.The solid matter cleaned up is put into and at 70 DEG C, is dried to constant weight in vacuum drying oven and namely obtains graphene nanobelt.
Embodiment 11
Cobalt paper tinsel is put into concentration be 0.05mol/L dilute hydrochloric acid solution etching 1 minute, then with deionized water, ethanol, acetone, the cobalt paper tinsel after etching processing is cleaned successively.The cleaned cobalt paper tinsel after etching processing is put into reaction chamber, and the air got rid of in reaction chamber, then the cobalt paper tinsel after etching processing is heated to 900 DEG C, open ultraviolet source equipment again, make UV-irradiation at the cobalt paper tinsel after etching processing on the surface, then pass into the methane of 100sccm and the argon gas of 10sccm, and keep 30 minutes.After having reacted, first stop passing into methane, then stop the cobalt paper tinsel heating after etching processing and close ultraviolet source equipment; Stop after question response room is cooled to room temperature passing into argon gas, obtain being attached to the carbon nanometer wall on the cobalt paper tinsel surface after etching processing, it is scraped from the cobalt paper tinsel surface after etching processing, just obtain carbon nanometer wall powder.
Take 1g carbon nanometer wall, 0.6g iron(ic) chloride and 0.6g cupric chloride respectively, and insert in silica tube, sealed silica envelope, after being warming up to 460 DEG C, react 2 hours at 460 DEG C, be cooled to room temperature after reaction terminates, obtain iron(ic) chloride and cupric chloride intercalation carbon nanometer wall.Then use washed with de-ionized water, and be dried to constant weight at 100 DEG C in vacuum drying oven after, obtain pure iron(ic) chloride and cupric chloride intercalation carbon nanometer wall.Iron(ic) chloride pure for 1g and cupric chloride intercalation carbon nanometer wall are scattered in 500mL acetone, then supercentrifuge is placed in, and add that at the top of supercentrifuge and two ends, bottom magneticstrength is the constant parallel magnetic field of 0.01T, setting centrifugal speed is 8000 revs/min, start magnetic field and whizzer, centrifugal stripping iron(ic) chloride and cupric chloride intercalation carbon nanometer wall 100 minutes.After centrifugal end, the material in centrifuge tube is all shifted out, and filters, obtain solid matter; And use washed with de-ionized water solid matter, until use AgNO
3detect the solution after cleaning without till precipitation generation.The solid matter cleaned up is put into and at 100 DEG C, is dried to constant weight in vacuum drying oven and namely obtains graphene nanobelt.
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 (10)
1. a preparation method for graphene nanobelt, is characterized in that, comprises the steps:
Carry out acid treatment to metal substrate, described metal substrate is iron foil, nickel foil or cobalt paper tinsel;
Oxygen-free environment will be placed in through acid-treated described metal substrate, be heated to 600 ~ 900 DEG C, then under UV-irradiation condition, protective gas is passed into and gas carbonaceous material carries out chemical vapour deposition reaction, after stopped reaction, obtain the carbon nanometer wall be attached on described metal substrate surface;
Be separated described metal substrate and described carbon nanometer wall, obtain carbon nanometer wall powder;
Described carbon nanometer wall powder is mixed according to the ratio that mass ratio is 1:0.8 ~ 1:1.2 with metal chloride, and reacts at 460 ~ 550 DEG C, obtain the carbon nanometer wall of containing metal muriate intercalation;
Be that the carbon nanometer wall of described metal chloride intercalation is added in acetone by the ratio of 1g:100 ~ 1000mL according to mass volume ratio, centrifugal stripping in the parallel magnetic field of 0.01 ~ 1T, obtains described graphene nanobelt after separating-purifying.
2. the preparation method of graphene nanobelt as claimed in claim 1, is characterized in that, describedly carries out acid-treated step to metal substrate and comprises:
Pending metal substrate is put into concentration be 0.01 ~ 1mol/L acid solution etching 0.5 ~ 10 minute, then clean with deionized water, ethanol and acetone successively, namely obtain described metal substrate after acid treatment.
3. the preparation method of graphene nanobelt as claimed in claim 1 or 2, it is characterized in that, described acid is hydrochloric acid, sulfuric acid or nitric acid.
4. the preparation method of graphene nanobelt as claimed in claim 1; it is characterized in that, the process of described stopped reaction comprises stopping successively and passes into described gas carbonaceous material, stops described metal substrate heating, stops carrying out UV-irradiation to described metal substrate and being cooled to until metal substrate the step stopping passing into protective gas after room temperature.
5. the preparation method of graphene nanobelt as claimed in claim 1; it is characterized in that; the flow velocity of described gas carbonaceous material is 10 ~ 1000sccm, and the volume ratio of described protective gas and gas carbonaceous material is 1:2 ~ 1:10, and the time passing into described carbonaceous material is 30 ~ 300 minutes.
6. the preparation method of graphene nanobelt as claimed in claim 1, it is characterized in that, described protective gas is helium, nitrogen or argon gas.
7. the preparation method of graphene nanobelt as claimed in claim 1, it is characterized in that, described gas carbonaceous material is methane, ethane, propane, acetylene or ethanol.
8. the preparation method of graphene nanobelt as claimed in claim 1, it is characterized in that, the step of described separating-purifying is: filtered by the material after centrifugal stripping, the solids washed with de-ionized water obtained, until use Ag
+detect the solution after cleaning without till precipitation generation.
9. the preparation method of graphene nanobelt as claimed in claim 1, it is characterized in that, described metal chloride is at least one in iron(ic) chloride, nickelous chloride, cupric chloride, cobalt chloride, Repone K, magnesium chloride, lead chloride, zinc chloride, calcium chloride and bariumchloride.
10. the preparation method of graphene nanobelt as claimed in claim 1, it is characterized in that, the rotating speed in described centrifugal stripping process is 1000 ~ 10000 revs/min, and the time of described centrifugal stripping is 10 ~ 100 minutes.
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| JPH04193953A (en) * | 1990-11-27 | 1992-07-14 | Shimadzu Corp | Method and device for forming hard carbon film |
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| WO2012035551A1 (en) * | 2010-09-14 | 2012-03-22 | Council Of Scientific & Industrial Research | Electrochemical process for synthesis of graphene |
| CN102807213A (en) * | 2012-08-30 | 2012-12-05 | 中国科学院苏州纳米技术与纳米仿生研究所 | Method for electrochemically preparing graphene |
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| JPH04193953A (en) * | 1990-11-27 | 1992-07-14 | Shimadzu Corp | Method and device for forming hard carbon film |
| CN1277145A (en) * | 1999-06-11 | 2000-12-20 | 李铁真 | Method for synthetizing vertical arrangement high-purity carbon nanometre tube in large-scale on large size substrate using hot CVD method |
| WO2012035551A1 (en) * | 2010-09-14 | 2012-03-22 | Council Of Scientific & Industrial Research | Electrochemical process for synthesis of graphene |
| CN102807213A (en) * | 2012-08-30 | 2012-12-05 | 中国科学院苏州纳米技术与纳米仿生研究所 | Method for electrochemically preparing graphene |
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