CN103935980A - Preparation method of graphene nanoribbon - Google Patents
Preparation method of graphene nanoribbon Download PDFInfo
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- CN103935980A CN103935980A CN201310019349.5A CN201310019349A CN103935980A CN 103935980 A CN103935980 A CN 103935980A CN 201310019349 A CN201310019349 A CN 201310019349A CN 103935980 A CN103935980 A CN 103935980A
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Abstract
The invention relates to a preparation method of a graphene nanoribbon. The preparation method comprises the following steps: subjecting a metal substrate to acid treatment; placing the metal substrate in an oxygen-free environment, heating the metal substrate to 600-900 DEG C, introducing a protective gas under a condition of UV irradiation to carry out chemical vapor deposition reaction with agas carbonaceous material, and obtaining a carbon nano-wall attached to the surface of the metal substrate after the chemical vapor deposition reaction stops; separating the metal substrate from the carbon nano-wall to obtain carbon nano-wall powder; mixing the carbon nano-wall powder with metal chloride according to a mass ratio of 1:0.8-1:1.2, allowing them to react at 460-550 DEG C, so as to obtain the carbon nano-wall containing metal chloride intercalation; and adding the carbon nano-wall containing metal chloride intercalation into acetone according to a mass volume ratio of 1 g:100-1000 ml, performing centrifugal separation in a parallel magnetic field, and finally obtaining the graphene nanoribbon after a separation and purification process. The size of the graphene nanoribbon produced by the above preparation method can be adjustable.
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), carbon nanotube, the carbon nanofiber etc. of one dimension, the Graphene of two dimension, three-dimensional graphite, diamond etc., carbon nanometer wall (carbon nanowall, 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 shape 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 for the preparation of graphene nanobelt etc.
Graphene nanobelt not only has the performance of Graphene, also possesses some special performances, and for example its length-to-diameter ratio is larger, can be up to thousands of times, can replace copper conductor at integrated circuit connection, further improve integrated level, also can carry out modification to its structure and be prepared into switch device.But due to size control difficulty in graphene nanobelt preparation process, yield poorly, further apply thereby limited it.
Summary of the invention
Based on this, be necessary to provide a kind of preparation method of size adjustable graphene nanobelt.
A preparation method for graphene nanobelt, comprises the steps:
Metal substrate is carried out to acid treatment;
To be placed in oxygen-free environment 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 being attached to the lip-deep carbon nanometer of described metal substrate wall;
Separate described metal substrate and described carbon nanometer wall, obtain carbon nanometer wall powder;
The ratio that is 1:0.8 ~ 1:1.2 with metal chloride according to mass ratio by described carbon nanometer wall powder is mixed, and reaction at 460 ~ 550 DEG C, obtains the carbon nanometer wall of containing metal muriate intercalation;
The ratio that is 1g:100 ~ 1000mL according to mass volume ratio is added to the carbon nanometer wall of described metal chloride intercalation in acetone, and centrifugal peeling off in the parallel magnetic field of 0.01 ~ 1T, obtains described graphene nanobelt after separating-purifying.
Therein in an embodiment, describedly metal substrate carried out to acid-treated step comprise:
Pending metal substrate is put into the acid solution etching 0.5 ~ 10 minute that concentration is 0.01 ~ 1mol/L, then clean with deionized water, ethanol and acetone successively, obtain described metal substrate after acid treatment.
In an embodiment, described metal substrate is iron foil, nickel foil or cobalt paper tinsel therein; Described acid is hydrochloric acid, sulfuric acid or nitric acid.
Therein in an embodiment, the process of described stopped reaction comprises and stops successively passing into described gas carbonaceous material, stops described metal substrate heating, stops described metal substrate to carry out UV-irradiation and after metal substrate is cooled to room temperature, stop passing into the step of protective gas.
In an embodiment, the flow velocity of described gas carbonaceous material is 10 ~ 1000sccm therein, and the volume ratio of described protective gas and gas carbonaceous material is 1:2 ~ 1:10, and the time that passes into described carbonaceous material is 30 ~ 300 minutes.
In an embodiment, described protective gas is helium, nitrogen or argon gas therein.
In an embodiment, described gas carbonaceous material is methane, ethane, propane, acetylene or ethanol therein.
In an embodiment, the step of described separating-purifying is therein: the material after centrifugal peeling off is filtered, and the solids washed with de-ionized water obtaining, until use Ag
+till solution after detection is cleaned produces without precipitation.
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 therein.
In an embodiment, the rotating speed in described centrifugal stripping process is 1000 ~ 10000 revs/min therein, and the described centrifugal time of peeling off is 10 ~ 100 minutes.
The preparation method of above-mentioned graphene nanobelt first adopts acid etch to process and photochemical catalysis two-step chemical gas-phase deposition prepares the more complete carbon nanometer of structure wall; Then prepare the intermediate product of metal chloride intercalation carbon nanometer wall taking carbon nanometer wall and metal chloride as raw material; After the effect and centrifugal treating of parallel magnetic field, can be easy to metal chloride intercalation carbon nanometer wall to peel off into graphene nanobelt again.Due to preparing in the process of carbon nanometer wall, can prepare by the flow velocity of regulation and control gas carbonaceous material and the time that passes into gas carbonaceous material the carbon nanometer wall of different size, then taking size adjustable carbon nanometer wall as raw material, thereby can prepare size adjustable graphene nanobelt.
Brief description of the drawings
Fig. 1 is the preparation method's of the graphene nanobelt of an embodiment schema;
Fig. 2 is the SEM figure that implements the 1 carbon nanometer wall preparing;
Fig. 3 is the SEM figure that implements 1 graphene nanobelt preparing.
Embodiment
Below in conjunction with drawings and the specific embodiments, the preparation method of 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; to be placed in oxygen-free environment 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 being attached to the lip-deep carbon nanometer of metal substrate wall.
Step 130, separating metal substrate and carbon nanometer wall, obtain carbon nanometer wall powder.
Step 140, the ratio that is 1:0.8 ~ 1:1.2 with metal chloride according to mass ratio by carbon nanometer wall powder is mixed, and reaction at 460 ~ 550 DEG C, obtains the carbon nanometer wall of containing metal muriate intercalation.
Step 150, the ratio that is 1g:100 ~ 1000mL according to mass volume ratio is added to the carbon nanometer wall of metal chloride intercalation in acetone, and centrifugal peeling off 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 the acid solution etching 0.5 ~ 10 minute that concentration is 0.01 ~ 1mol/L, then clean with deionized water, ethanol and acetone successively, 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, can also adopt additive method to prepare the substrate after acid treatment.
In the present embodiment, metal substrate is iron foil, nickel foil or cobalt paper tinsel.Iron foil, nickel foil or cobalt paper tinsel are carried out after acid treatment, make the surface of iron foil, nickel foil or cobalt paper tinsel produce defect, thereby can effectively 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, is mainly in order to provide a stable environment to the preparation of carbon nanometer wall, avoids the participation of oxygen and affects 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 that passes into gas carbonaceous material is 30 ~ 300 minutes.
Protective gas, except having the effect that oxygen-free environment is provided, in reaction process, can also reduce the probability of collision between gas carbonaceous material, occurs thereby reduce unnecessary reaction, and object reaction is carried out smoothly.
Gas carbonaceous material need to pass into oxygen-free environment with gaseous form, generally can select the carbonaceous material for gaseous state under normal temperature, can certainly select easily gasification and cheap carbonaceous material, as ethanol (pass into before in oxygen-free environment, first make ethanol gasification).There are impact the flow velocity of gas carbonaceous material and the time that passes into gas carbonaceous material on the thickness of carbon nanometer wall, flow velocity by regulation and control gas carbonaceous material and the time that passes into gas carbonaceous material can be prepared the carbon nanometer wall of different size, and the carbon nanometer wall of different size can affect the size of the graphene nanobelt of preparing taking carbon nanometer wall as raw material.
In the present embodiment, the process of stopped reaction comprises and stops successively passing into gas carbonaceous material, stops metal substrate heating, stops metal substrate carrying out UV-irradiation and after metal substrate is cooled to room temperature, stop passing into the step of protective gas.
First, stop passing into gas carbonaceous material, also stopped supply reactant gases, and now do not stop heating and ultraviolet lighting, can make the gas carbonaceous material in reaction system continue reaction, stop thereby controlling sluggish.And after metal substrate is cooled to room temperature, stop again passing into protective gas, be carbon nanometer wall in order to make to obtain under the condition higher than room temperature always in oxygen-free environment, avoid carbon nanometer wall to react at 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 centrifugal time of peeling off is 10 ~ 100 minutes.
The step of separating-purifying is specially: the material after supersound process is filtered, and the solids washed with de-ionized water obtaining, until use Ag
+till solution after detection is cleaned produces without precipitation.
In the present embodiment, Ag
+by AgNO
3solution provides.
The preparation method of above-mentioned graphene nanobelt first adopts acid etch to process and photochemical catalysis two-step chemical gas-phase deposition prepares the more complete carbon nanometer of structure wall; Then prepare the intermediate product of metal chloride intercalation carbon nanometer wall taking carbon nanometer wall and metal chloride as raw material; 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, can be easy to metal chloride intercalation carbon nanometer wall to peel off into graphene nanobelt.Due to preparing in the process of carbon nanometer wall, can prepare by the flow velocity of regulation and control carbonaceous material and the time that passes into carbonaceous material the carbon nanometer wall of different size, then taking size adjustable carbon nanometer wall as raw material, thereby can obtain size adjustable graphene nanobelt.And photochemical catalysis chemical Vapor deposition process can effectively reduce temperature of reaction, reduce energy consumption, thereby reduce production costs, and effectively avoided existing using plasma to prepare carbon nanometer wall and carbon nano wall structure is damaged, make thickness and the pattern of carbon nanometer wall more even, structure is more complete.
Preparation method's technique of above-mentioned graphene nanobelt is simple, and the productive rate easy to operate and graphene nanobelt for preparing is higher.And the material carbon nanometer wall of preparing graphene nanobelt is prepared voluntarily, required equipment is all common chemical industry equipment, thereby economizes in raw materials and research and develop the cost of equipment, and low as the acetone price of solvent, be conducive to reduce production costs, be applicable to scale operation.
It is below specific embodiment part
Embodiment 1
Nickel foil is put into the dilute hydrochloric acid solution etching 0.5 minute that concentration is 1mol/L, 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 get rid of the air in reaction chamber, then the nickel foil after etching processing is heated to 900 DEG C, open again ultraviolet source equipment, make UV-irradiation on the nickel foil surface after etching processing, 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; Question response chamber stops passing into nitrogen after being cooled to room temperature, obtains being attached to the lip-deep carbon nanometer of the nickel foil wall after etching processing, and it is scraped from the nickel foil surface after etching processing, just obtains carbon nanometer wall powder.
Detect the carbon nanometer wall preparing by scanning electronic microscope, as shown in Figure 2, as can be seen from the figure, carbon nanometer wall is perpendicular to the intensive growth of substrate, and even thickness, is about 30 ~ 60nm.
Take respectively 1g carbon nanometer wall and 0.8g iron(ic) chloride, and insert in silica tube, sealed silica envelope, is warming up to after 460 DEG C, reacts 2 hours at 460 DEG C, after reaction finishes, is cooled to room temperature, obtains iron(ic) chloride intercalation carbon nanometer wall.Then use washed with de-ionized water, and at 80 DEG C, be dried to after constant weight in vacuum drying oven, obtain pure iron(ic) chloride intercalation carbon nanometer wall.Iron(ic) chloride intercalation carbon nanometer wall pure 1g is scattered in 100mL acetone, then be placed in supercentrifuge, and add that at top and the two ends, bottom of supercentrifuge magneticstrength is the constant parallel magnetic field of 1T, setting centrifugal speed is 1000 revs/min, start magnetic field and whizzer, centrifugally peel off 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
3till solution after detection is cleaned produces without precipitation.The solid matter cleaning up is put into and in vacuum drying oven, is dried to constant weight at 60 DEG C and obtains graphene nanobelt.
Detect the graphene nanobelt preparing by scanning electronic microscope, as shown in Figure 3, as can be seen from the figure, graphene nanobelt width distribution is concentrated, and is about 20 ~ 40nm, and length is about 2 ~ 20 μ m, and length-to-diameter ratio is about 50 ~ 1000.
Embodiment 2
Iron foil is put into the dilution heat of sulfuric acid etching 4 minutes that concentration is 0.5mol/L, 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 get rid of the air in reaction chamber, then the iron foil after etching processing is heated to 600 DEG C, open again ultraviolet source equipment, make UV-irradiation on the iron foil surface after etching processing, 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; Question response chamber stops passing into argon gas after being cooled to room temperature, obtains being attached to the lip-deep carbon nanometer of the iron foil wall after etching processing, and it is scraped from the iron foil surface after etching processing, just obtains carbon nanometer wall powder.
Take respectively 1g carbon nanometer wall and 0.9g cupric chloride, and insert in silica tube, sealed silica envelope, is warming up to after 500 DEG C, reacts 3 hours at 500 DEG C, after reaction finishes, is cooled to room temperature, obtains cupric chloride intercalation carbon nanometer wall.Then use washed with de-ionized water, and at 90 DEG C, be dried to after constant weight in vacuum drying oven, obtain pure cupric chloride intercalation carbon nanometer wall.Cupric chloride intercalation carbon nanometer wall pure 1g is scattered in 1000mL acetone, then be placed in supercentrifuge, and add that at top and the two ends, bottom of supercentrifuge magneticstrength is the constant parallel magnetic field of 0.5T, setting centrifugal speed is 2000 revs/min, start magnetic field and whizzer, centrifugally peel off 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
3till solution after detection is cleaned produces without precipitation.The solid matter cleaning up is put into and in anaerobic loft drier, is dried to constant weight at 80 DEG C and obtains graphene nanobelt.
Embodiment 3
Cobalt paper tinsel is put into the dilute nitric acid solution etching 10 minutes that concentration is 0.01mol/L, 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 get rid of the air in reaction chamber, then the cobalt paper tinsel after etching processing is heated to 700 DEG C, open again ultraviolet source equipment, make UV-irradiation on the cobalt paper tinsel surface after etching processing, 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; Question response chamber stops passing into helium after being cooled to room temperature, obtains being attached to the lip-deep carbon nanometer of the cobalt paper tinsel wall after etching processing, and it is scraped from the cobalt paper tinsel surface after etching processing, just obtains carbon nanometer wall powder.
Take respectively 1g carbon nanometer wall and 1.2g nickelous chloride, and insert in silica tube, sealed silica envelope, is warming up to after 480 DEG C, reacts 6 hours at 480 DEG C, after reaction finishes, is cooled to room temperature, obtains nickelous chloride intercalation carbon nanometer wall.Then use washed with de-ionized water, and at 100 DEG C, be dried to after constant weight in vacuum drying oven, obtain pure nickelous chloride intercalation carbon nanometer wall.Nickelous chloride intercalation carbon nanometer wall pure 1g is scattered in 500mL acetone, then be placed in supercentrifuge, and add that at top and the two ends, bottom of supercentrifuge magneticstrength is the constant parallel magnetic field of 0.1T, setting centrifugal speed is 5000 revs/min, start magnetic field and whizzer, centrifugally peel off 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
3till solution after detection is cleaned produces without precipitation.The solid matter cleaning up is put into and in vacuum drying oven, is dried to constant weight at 100 DEG C and obtains graphene nanobelt.
Embodiment 4
Nickel foil is put into the dilute hydrochloric acid solution etching 2 minutes that concentration is 0.2mol/L, 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 get rid of the air in reaction chamber, then the nickel foil after etching processing is heated to 750 DEG C, open again ultraviolet source equipment, make UV-irradiation on the nickel foil surface after etching processing, 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; Question response chamber stops passing into nitrogen after being cooled to room temperature, obtains being attached to the lip-deep carbon nanometer of the nickel foil wall after etching processing, and it is scraped from the nickel foil surface after etching processing, just obtains carbon nanometer wall powder.
Take respectively 1g carbon nanometer wall and 1g cobalt chloride, and insert in silica tube, sealed silica envelope, is warming up to after 550 DEG C, reacts 4 hours at 550 DEG C, after reaction finishes, is cooled to room temperature, obtains cobalt chloride intercalation carbon nanometer wall.Then use washed with de-ionized water, and at 90 DEG C, be dried to after constant weight in vacuum drying oven, obtain pure cobalt chloride intercalation carbon nanometer wall.Cobalt chloride intercalation carbon nanometer wall pure 1g is scattered in 200mL acetone, then be placed in supercentrifuge, and add that at top and the two ends, bottom of supercentrifuge magneticstrength is the constant parallel magnetic field of 0.05T, setting centrifugal speed is 8000 revs/min, start magnetic field and whizzer, centrifugally peel off 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
3till solution after detection is cleaned produces without precipitation.The solid matter cleaning up is put into and in vacuum drying oven, is dried to constant weight at 90 DEG C and obtains graphene nanobelt.
Embodiment 5
Iron foil is put into the dilution heat of sulfuric acid etching 5 minutes that concentration is 0.1mol/L, 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 get rid of the air in reaction chamber, then the iron foil after etching processing is heated to 800 DEG C, open again ultraviolet source equipment, make UV-irradiation on the iron foil surface after etching processing, 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; Question response chamber stops passing into argon gas after being cooled to room temperature, obtains being attached to the lip-deep carbon nanometer of the iron foil wall after etching processing, and it is scraped from the iron foil surface after etching processing, just obtains carbon nanometer wall powder.
Take respectively 1g carbon nanometer wall and 1.1g Repone K, and insert in silica tube, sealed silica envelope, is warming up to after 520 DEG C, reacts 5 hours at 520 DEG C, after reaction finishes, is cooled to room temperature, obtains Repone K intercalation carbon nanometer wall.Then use washed with de-ionized water, and at 85 DEG C, be dried to after constant weight in vacuum drying oven, obtain pure Repone K intercalation carbon nanometer wall.Repone K intercalation carbon nanometer wall pure 1g is scattered in 800mL acetone, then be placed in supercentrifuge, and add that at top and the two ends, bottom of supercentrifuge magneticstrength is the constant parallel magnetic field of 0.01T, setting centrifugal speed is 10000 revs/min, start magnetic field and whizzer, centrifugally peel off 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
3till solution after detection is cleaned produces without precipitation.The filter residue cleaning up is put into and in vacuum drying oven, is dried to constant weight at 70 DEG C and obtains graphene nanobelt.
Embodiment 6
Cobalt paper tinsel is put into the dilute nitric acid solution etching 8 minutes that concentration is 0.4mol/L, 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 get rid of the air in reaction chamber, then the cobalt paper tinsel after etching processing is heated to 850 DEG C, open again ultraviolet source equipment, make UV-irradiation on the cobalt paper tinsel surface after etching processing, 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; Question response chamber stops passing into helium after being cooled to room temperature, obtains being attached to the lip-deep carbon nanometer of the cobalt paper tinsel wall after etching processing, and it is scraped from the cobalt paper tinsel surface after etching processing, just obtains carbon nanometer wall powder.
Take respectively 1g carbon nanometer wall and 0.8g sodium-chlor, and insert in silica tube, sealed silica envelope, is warming up to after 530 DEG C, reacts 2 hours at 530 DEG C, after reaction finishes, is cooled to room temperature, obtains sodium-chlor intercalation carbon nanometer wall.Then use washed with de-ionized water, and at 95 DEG C, be dried to after constant weight in vacuum drying oven, obtain pure sodium-chlor intercalation carbon nanometer wall.Sodium-chlor intercalation carbon nanometer wall pure 1g is scattered in 600mL acetone, then be placed in supercentrifuge, and add that at top and the two ends, bottom of supercentrifuge magneticstrength is the constant parallel magnetic field of 0.2T, setting centrifugal speed is 2000 revs/min, start magnetic field and whizzer, centrifugally peel off 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
3till solution after detection is cleaned produces without precipitation.The solid matter cleaning up is put into and in vacuum drying oven, is dried to constant weight at 60 DEG C and obtains graphene nanobelt.
Embodiment 7
Nickel foil is put into the dilute hydrochloric acid solution etching 3 minutes that concentration is 0.25mol/L, 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 get rid of the air in reaction chamber, then the nickel foil after etching processing is heated to 900 DEG C, open again ultraviolet source equipment, make UV-irradiation on the nickel foil surface after etching processing, 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; Question response chamber stops passing into nitrogen after being cooled to room temperature, obtains being attached to the lip-deep carbon nanometer of the nickel foil wall after etching processing, and it is scraped from the nickel foil surface after etching processing, just obtains carbon nanometer wall powder.
Take respectively 1g carbon nanometer wall and 1.1g magnesium chloride, and insert in silica tube, sealed silica envelope, is warming up to after 490 DEG C, reacts 3 hours at 490 DEG C, after reaction finishes, is cooled to room temperature, obtains magnesium chloride intercalation carbon nanometer wall.Then use washed with de-ionized water, and at 90 DEG C, be dried to after constant weight in vacuum drying oven, obtain pure magnesium chloride intercalation carbon nanometer wall.Magnesium chloride intercalation carbon nanometer wall pure 1g is scattered in 400mL acetone, then be placed in supercentrifuge, and add that at top and the two ends, bottom of supercentrifuge magneticstrength is the constant parallel magnetic field of 0.4T, setting centrifugal speed is 2500 revs/min, start magnetic field and whizzer, centrifugally peel off 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
3till solution after detection is cleaned produces without precipitation.The solid matter cleaning up is put into and in vacuum drying oven, is dried to constant weight at 100 DEG C and obtains graphene nanobelt.
Embodiment 8
Iron foil is put into the dilute hydrochloric acid solution etching 4 minutes that concentration is 1mol/L, 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 get rid of the air in reaction chamber, then the iron foil after etching processing is heated to 650 DEG C, open again ultraviolet source equipment, make UV-irradiation on the iron foil surface after etching processing, 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; Question response chamber stops passing into nitrogen after being cooled to room temperature, obtains being attached to the lip-deep carbon nanometer of the iron foil wall after etching processing, and it is scraped from the iron foil surface after etching processing, just obtains carbon nanometer wall powder.
Take respectively 1g carbon nanometer wall and 1g aluminum chloride, and insert in silica tube, sealed silica envelope, is warming up to after 540 DEG C, reacts 6 hours at 540 DEG C, after reaction finishes, is cooled to room temperature, obtains aluminum chloride intercalation carbon nanometer wall.Then use washed with de-ionized water, and at 100 DEG C, be dried to after constant weight in vacuum drying oven, obtain pure aluminum chloride intercalation carbon nanometer wall.Aluminum chloride intercalation carbon nanometer wall pure 1g is scattered in 300mL acetone, then be placed in supercentrifuge, and add that at top and the two ends, bottom of supercentrifuge magneticstrength is the constant parallel magnetic field of 0.8T, setting centrifugal speed is 1000 revs/min, start magnetic field and whizzer, centrifugally peel off 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
3till solution after detection is cleaned produces without precipitation.The solid matter cleaning up is put into and in vacuum drying oven, is dried to constant weight at 80 DEG C and obtains graphene nanobelt.
Embodiment 9
Cobalt paper tinsel is put into the dilution heat of sulfuric acid etching 2 minutes that concentration is 0.3mol/L, 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 get rid of the air in reaction chamber, then the cobalt paper tinsel after etching processing is heated to 700 DEG C, open again ultraviolet source equipment, make UV-irradiation on the cobalt paper tinsel surface after etching processing, 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; Question response chamber stops passing into helium after being cooled to room temperature, obtains being attached to the lip-deep carbon nanometer of the cobalt paper tinsel wall after etching processing, and it is scraped from the cobalt paper tinsel surface after etching processing, just obtains carbon nanometer wall powder.
Take respectively 1g carbon nanometer wall and 0.9g zinc chloride, and insert in silica tube, sealed silica envelope, is warming up to after 520 DEG C, reacts 5 hours at 520 DEG C, after reaction finishes, is cooled to room temperature, obtains zinc chloride intercalation carbon nanometer wall.Then use washed with de-ionized water, and at 80 DEG C, be dried to after constant weight in vacuum drying oven, obtain pure zinc chloride intercalation carbon nanometer wall.Zinc chloride intercalation carbon nanometer wall pure 1g is scattered in 1000mL acetone, then be placed in supercentrifuge, and add that at top and the two ends, bottom of supercentrifuge magneticstrength is the constant parallel magnetic field of 1T, setting centrifugal speed is 3000 revs/min, start magnetic field and whizzer, centrifugally peel off 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
3till solution after detection is cleaned produces without precipitation.The solid matter cleaning up is put into and in vacuum drying oven, is dried to constant weight at 90 DEG C and obtains graphene nanobelt.
Embodiment 10
Nickel foil is put into the dilute nitric acid solution etching 5 minutes that concentration is 0.5mol/L, 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 get rid of the air in reaction chamber, then the nickel foil after etching processing is heated to 800 DEG C, open again ultraviolet source equipment, make UV-irradiation on the nickel foil surface after etching processing, 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; Question response chamber stops passing into nitrogen after being cooled to room temperature, obtains being attached to the lip-deep carbon nanometer of the nickel foil wall after etching processing, and it is scraped from the nickel foil surface after etching processing, just obtains carbon nanometer wall powder.
Take respectively 1g carbon nanometer wall and 1.1g bariumchloride, and insert in silica tube, sealed silica envelope, is warming up to after 550 DEG C, reacts 4 hours at 550 DEG C, after reaction finishes, is cooled to room temperature, obtains bariumchloride intercalation carbon nanometer wall.Then use washed with de-ionized water, and at 90 DEG C, be dried to after constant weight in vacuum drying oven, obtain pure bariumchloride intercalation carbon nanometer wall.Bariumchloride intercalation carbon nanometer wall pure 1g is scattered in 100mL acetone, then be placed in supercentrifuge, and add that at top and the two ends, bottom of supercentrifuge magneticstrength is the constant parallel magnetic field of 0.1T, setting centrifugal speed is 5000 revs/min, start magnetic field and whizzer, centrifugally peel off 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
3till solution after detection is cleaned produces without precipitation.The solid matter cleaning up is put into and in vacuum drying oven, is dried to constant weight at 70 DEG C and obtains graphene nanobelt.
Embodiment 11
Cobalt paper tinsel is put into the dilute hydrochloric acid solution etching 1 minute that concentration is 0.05mol/L, 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 get rid of the air in reaction chamber, then the cobalt paper tinsel after etching processing is heated to 900 DEG C, open again ultraviolet source equipment, make UV-irradiation on the cobalt paper tinsel surface after etching processing, 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; Question response chamber stops passing into argon gas after being cooled to room temperature, obtains being attached to the lip-deep carbon nanometer of the cobalt paper tinsel wall after etching processing, and it is scraped from the cobalt paper tinsel surface after etching processing, just obtains carbon nanometer wall powder.
Take respectively 1g carbon nanometer wall, 0.6g iron(ic) chloride and 0.6g cupric chloride, and insert in silica tube, sealed silica envelope, is warming up to after 460 DEG C, reacts 2 hours at 460 DEG C, after reaction finishes, is cooled to room temperature, obtains iron(ic) chloride and cupric chloride intercalation carbon nanometer wall.Then use washed with de-ionized water, and at 100 DEG C, be dried to after constant weight in vacuum drying oven, obtain pure iron(ic) chloride and cupric chloride intercalation carbon nanometer wall.Iron(ic) chloride pure 1g and cupric chloride intercalation carbon nanometer wall are scattered in 500mL acetone, then be placed in supercentrifuge, and add that at top and the two ends, bottom of supercentrifuge magneticstrength is the constant parallel magnetic field of 0.01T, setting centrifugal speed is 8000 revs/min, start magnetic field and whizzer, centrifugally peel off 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
3till solution after detection is cleaned produces without precipitation.The solid matter cleaning up is put into and in vacuum drying oven, is dried to constant weight at 100 DEG C and obtains graphene nanobelt.
The above embodiment has only expressed several embodiment of the present invention, and it describes comparatively concrete and detailed, but can not therefore be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection domain of patent of the present invention should be as the criterion with claims.
Claims (10)
1. a preparation method for graphene nanobelt, is characterized in that, comprises the steps:
Metal substrate is carried out to acid treatment;
To be placed in oxygen-free environment 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 being attached to the lip-deep carbon nanometer of described metal substrate wall;
Separate described metal substrate and described carbon nanometer wall, obtain carbon nanometer wall powder;
The ratio that is 1:0.8 ~ 1:1.2 with metal chloride according to mass ratio by described carbon nanometer wall powder is mixed, and reaction at 460 ~ 550 DEG C, obtains the carbon nanometer wall of containing metal muriate intercalation;
The ratio that is 1g:100 ~ 1000mL according to mass volume ratio is added to the carbon nanometer wall of described metal chloride intercalation in acetone, and centrifugal peeling off 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 metal substrate is carried out to acid-treated step comprises:
Pending metal substrate is put into the acid solution etching 0.5 ~ 10 minute that concentration is 0.01 ~ 1mol/L, then clean with deionized water, ethanol and acetone successively, obtain described metal substrate after acid treatment.
3. the preparation method of graphene nanobelt as claimed in claim 1 or 2, is characterized in that, described metal substrate is iron foil, nickel foil or cobalt paper tinsel; 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 and stops successively passing into described gas carbonaceous material, stops the heating of described metal substrate, stops described metal substrate to carry out UV-irradiation and after metal substrate is cooled to room temperature, stop passing into the step of protective gas.
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 that passes into described carbonaceous material is 30 ~ 300 minutes.
6. the preparation method of graphene nanobelt as claimed in claim 1, 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, 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, is characterized in that, the step of described separating-purifying is: the material after centrifugal peeling off is filtered, and the solids washed with de-ionized water obtaining, until use Ag
+till solution after detection is cleaned produces without precipitation.
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, is characterized in that, the rotating speed in described centrifugal stripping process is 1000 ~ 10000 revs/min, and the described centrifugal time of peeling off is 10 ~ 100 minutes.
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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 |
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