CN103420354A - Preparation method of carbon nanowalls - Google Patents
Preparation method of carbon nanowalls Download PDFInfo
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- CN103420354A CN103420354A CN2012101597576A CN201210159757A CN103420354A CN 103420354 A CN103420354 A CN 103420354A CN 2012101597576 A CN2012101597576 A CN 2012101597576A CN 201210159757 A CN201210159757 A CN 201210159757A CN 103420354 A CN103420354 A CN 103420354A
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Abstract
The invention discloses a preparation method of carbon nanowalls. The method comprises steps of etching a metal substrate with an acid solution having a concentration of 0.01-1 mol/L; placing the etched metal substrate into a reaction chamber, and eliminating air in the reaction chamber; and heating the metal substrate in the reaction chamber to 700-1100 DEG C, then continuously inletting a gas mixture containing a protective gas and a carbon source gas in a volume ratio of 1:2-10 into the reaction chamber that has eliminated air to perform a reaction, and maintaining for 1-300 min to grow the carbon nanowalls on the surface of the metal substrate. The preparation method adopts an etching and chemical vapor deposition two-step method to prepare the carbon nanowalls. The preparation method has simple preparation technology and easily controllable conditions. The preparation method is capable of shortening the etching time, improving the production efficiency, reducing the production cost, and effectively avoiding usage of plasma in the prior art to prepare the carbon nanowalls. The carbon nanowalls prepared by the method are dense.
Description
Technical field
The invention belongs to the carbon field of nanometer technology, specifically relate to a kind of preparation method of carbon nanometer wall.
Background technology
The kind of carbon material has the soccerballene (C60 etc.) of zero dimension, the carbon nanotube of one dimension, carbon nanofiber etc., 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 just is perpendicular to the substrate material surface growth, thickness is greater than the wall shape structure of Graphene, fully different from the feature of soccerballene, carbon nanotube, Graphene etc., mainly can be applicable to the fields such as solar cell, dye-sensitized cell, an emission.
Before finding early than Graphene, people have just begun one's study the preparation of carbon nanometer wall, but, no matter be early stage preparation method or nearest preparation method, all can relate under plasma atmosphere and be reacted.As domestic, disclose through the carbon nm wall of structure control and the structure control method of carbon nm wall, the characteristics of the method are at least a portion of reaction chamber, to form at least take the plasma atmosphere that carbon-source gas plasma that carbon is Constitution Elements forms, to produce plasma atmosphere by plasma apparatus, and reaction must be to carry out, need to use vacuum apparatus under the vacuum tightness of 100～800m Torr.Prepare carbon nanometer wall under this plasma body atmosphere high to equipment requirements, the technique relative complex, condition is wayward, and production cost is high.And while preparing carbon nanometer wall under using plasma atmosphere, the plasma reaction environment changes always, unstable, causes prepared carbon nanometer wall surface thickness low LCL even.
Summary of the invention
The object of the invention is to overcome the above-mentioned deficiency of prior art, provide a kind of condition easy to control, the preparation method of the carbon nanometer wall that technique is simple, with low cost.
In order to realize the foregoing invention purpose, technical scheme of the present invention is as follows:
A kind of preparation method of carbon nanometer wall, comprise the steps:
The acid solution that is 0.01～1mol/L by concentration by metal substrate is carried out etching;
Described metal substrate after etching is placed in to reaction chamber, and gets rid of the air in reaction chamber;
After the described metal substrate that is placed in reaction chamber is heated to 700～1100 ℃; continue to pass into flow volume than being reacted with the mixed gas of carbon-source gas for the protective gas of 1:2～10 in the described reaction chamber of excluding air; and keep 1～300 minute, at the described carbon nanometer of described metal substrate surface growth wall.
The preparation method of above-mentioned carbon nanometer wall adopts etching and two-step chemical gas-phase deposition to prepare vertical carbon nanometer wall, and its preparation technology is simple, and condition is easily controlled, and has shortened etching time, has improved production efficiency, has reduced production cost.In addition; the preparation method of this carbon nanometer wall is by controlling the flow of protective gas and carbon-source gas; can effectively keep the ambient stable in reaction chamber, make the carbon nanometer wall surface even thickness of growth, thereby effectively avoided existing using plasma to prepare the deficiency of carbon nanometer wall.The carbon nanometer wall prepared by the method is intensive.
The accompanying drawing explanation
Fig. 1 is preparation method's process flow diagram of carbon nanometer wall of the present invention;
Fig. 2 is the electronic scanning video picture figure of the carbon nanometer wall that makes of the embodiment of the present invention 1.
Embodiment
In order to make the technical problem to be solved in the present invention, technical scheme and beneficial effect clearer, below in conjunction with embodiment, the present invention is further elaborated.Should be appreciated that specific embodiment described herein, only in order to explain the present invention, is not intended to limit the present invention.
Example of the present invention provides a kind of condition easy to control, the preparation method of the carbon nanometer wall that technique is simple, cost is low.Preparation method's technical process of this carbon nanometer wall refers to Fig. 1, and the method comprises the steps:
S01: to the metal substrate etching: the acid solution that is 0.01～1mol/L by concentration by metal substrate is carried out etching;
S02: get rid of the air in reaction chamber: the metal substrate after step S01 etching is placed in to reaction chamber, and gets rid of the air in reaction chamber;
S03: reaction growth carbon nanometer wall: after the described metal substrate that will be placed in reaction chamber is heated to 700～1100 ℃; to continuing to pass into the protective gas that volume ratio is 1:2～10 in the described reaction chamber of excluding air, with the mixed gas of carbon-source gas, reacted; and keep 1～300 minute, at the described carbon nanometer of this metal substrate surface growth wall.
Concrete, in above-mentioned steps S01, metal substrate provides the platform of growth on the one hand for the carbon nanometer wall in lower step S03, play on the other hand katalysis, and the carbon-source gas under catalysis in step S03 is at metal substrate surface growth carbon nanometer wall.In a preferred embodiment, metal substrate is one or more the combination in iron foil, nickel foil, cobalt paper tinsel, Copper Foil.This preferred metal substrate excellent catalytic effect, improved carbon nanometer wall growth efficiency.
In this step S01, to metal substrate, etching makes metal liner end eclipse surface produce defect, can effectively improve the surface tissue of metal substrate, makes carbon nanometer wall energy enough in this metal substrate surface growth.In a preferred embodiment, the time of this metal substrate of etching is 30～180 seconds, and the concentration of the acid solution of this metal substrate of etching is 0.1～0.5mol/L.This preferred etching condition, can effectively shorten time of etching, improves the growth efficiency of degree of corrosion and carbon nanometer wall.In addition, owing to adopting acid solution to carry out etching, can also, by this acid solution recycling, reduce production costs.
Certainly, after metal substrate is carried out to etch processes, need to carry out clean to metal substrate, the method for cleaning is to adopt successively deionized water, ethanol, acetone to be cleaned, remove the acid solution on metal substrate surface, the metal substrate surface cleaning after the assurance etching.
Above-mentioned steps S02, reaction chamber can adopt original equipment commonly used to provide.The purpose of getting rid of the air in reaction chamber is the oxygen in order to go out in reaction chamber, avoids the participation of oxygen and affects the growth of carbon nanometer wall.In a preferred embodiment, the mode of getting rid of the air in reaction chamber adopts to passing into protective gas in reaction chamber gets rid of the air in described reaction chamber.Wherein, protective gas is preferably at least one in hydrogen, nitrogen, argon gas.Concrete, continue to pass into the protective gas that flow is 10～200sccm in reaction chamber, and keep 1～60 minute.Like this, fully get rid of the air in reaction chamber, for the growth of carbon nanometer wall provides a stable environment.
Above-mentioned steps S03; metal substrate is heated to 700～1100 ℃; after the mixed gas of carbon-source gas and protective gas passes into; under this temperature and metal substrate catalysis; this carbon-source gas reacts; at metal substrate surface growth carbon nanometer wall, wherein, the flow that passes into carbon-source gas is 10～1000sccm.In a preferred embodiment, the temperature of this reaction is 900～1100 ℃, 60～120 minutes reaction times; Carbon-source gas is at least one in methane, ethane, acetylene, ethanol.This preferred carbon-source gas can make carbon-source gas decompose rapidly and, at metal substrate surface growth carbon nanometer wall, improve the growth efficiency of this carbon nanometer wall at range of reaction temperature.In addition, the contriver finds after deliberation, and along with the rising of this temperature of reaction, the density of the carbon nanometer wall of growing is higher, and increases along with the prolongation in reaction times.
Further, after step S03, also comprise that the effects on surface growth has the cooling step of metal substrate of carbon nanometer wall.Particularly, after question response, stop passing into carbon-source gas and stop the metal substrate heating in reaction chamber, the question response chamber stops passing into this protective gas after being cooled to room temperature.Allow like this carbon nanometer wall of growth fully cooling in the environment of anaerobic, oxidized in cooling to prevent this carbon nanometer wall, low to obtain oxygen level, the carbon nanometer wall that purity is high.
Therefore, the preparation method of above-mentioned carbon nanometer wall adopts etching and two-step chemical gas-phase deposition to prepare vertical carbon nanometer wall, and its preparation technology is simple, and condition is easily controlled, and has shortened etching time, has improved production efficiency, has reduced production cost.In addition; the preparation method of this carbon nanometer wall is by controlling the flow of protective gas and carbon-source gas; can effectively keep the ambient stable in reaction chamber, make the carbon nanometer wall surface even thickness of growth, thereby effectively avoided existing using plasma to prepare the deficiency of carbon nanometer wall.Wherein, first to the metal substrate etching, can effectively improve the surface tissue of metal substrate, and effectively shorten etching time, improve the growth efficiency of degree of corrosion and carbon nanometer wall, make carbon nanometer wall energy enough in this metal substrate Surface Vertical growth.Adopting this metal is substrate, in chemical vapour deposition reaction, has avoided adopting existing plasma gas to prepare carbon nanometer wall, has simplified technology and condition prepared by carbon nanometer wall, has reduced production cost.Make at the carbon nanometer wall of substrate surface growth intensive simultaneously.Through this carbon nanometer wall is carried out to the electronic scanning demonstration, this carbon nanometer wall is grown perpendicular to metal substrate, and presents latticed mutual intersection, as shown in Figure 2.
Below by concrete a plurality of embodiment, its preparation method of carbon nanometer wall is described, with and the aspect such as correlated performance.
A kind of preparation method of carbon nanometer wall, concrete steps are as follows:
S11: iron foil is put into to the dilute hydrochloric acid solution etching 180 seconds that concentration is 0.01mol/L, and etching is well cleaned with deionized water, ethanol, acetone afterwards;
S12: cleaned iron foil is put into to reaction chamber and passed into the nitrogen that flow is 10sccm, keep 60 minutes;
S13: the iron foil that will be placed in reaction chamber is heated to 1100 ℃, and the methane that to pass into flow be 250sccm is reacted, and at iron foil surface growth carbon nanometer wall, wherein, in reaction chamber, the methane passed into and the volume ratio of nitrogen are 5:1, keep 10 minutes;
S14: after having reacted, stop passing into methane and iron foil is heated, reaction chamber stops passing into nitrogen after being cooled to room temperature, obtains carbon nanometer wall.
The carbon nanometer wall that the present embodiment 1 is made carries out electronic scanning, and the electronic scanning video picture figure obtained after electronic scanning as shown in Figure 2.Can obviously find out that from Fig. 2 carbon nanometer wall is basically perpendicular to the growth of iron foil substrate, and present latticed mutual intersection, thickness is about 20～30nm, and length is about 0.2～0.5um.
Embodiment 2
A kind of preparation method of carbon nanometer wall, concrete steps are as follows:
S21: nickel foil is put into to the dilution heat of sulfuric acid etching 120 seconds that concentration is 0.1mol/L, and etching is well cleaned with deionized water, ethanol, acetone afterwards;
S22: cleaned nickel foil is put into to reaction chamber and passed into hydrogen 200sccm, keep 5 minutes;
S23: nickel foil is heated to 700 ℃, passes into acetylene 20sccm, the volume ratio of acetylene and hydrogen is 2:1, keeps 300 minutes;
S24: after having reacted, stop passing into acetylene and nickel foil is heated, reaction chamber stops passing into hydrogen after being cooled to room temperature, obtains carbon nanometer wall.
After carbon nanometer wall prepared by the present embodiment carries out electronic scanning, demonstration carbon nanometer wall profile is as the carbon nanometer wall prepared in embodiment 1, and it is directly grown in the nickel foil substrate, and presents latticed mutual intersection.
Embodiment 3
A kind of preparation method of carbon nanometer wall, concrete steps are as follows:
S31: nickel foil is put into to the dilute nitric acid solution etching 50 seconds that concentration is 0.3mol/L, and etching is well cleaned with deionized water, ethanol, acetone afterwards;
S32: cleaned nickel foil is put into to reaction chamber and passed into argon gas 100sccm, keep 20 minutes;
S33: nickel foil is heated to 1000 ℃, passes into ethane 600sccm, the volume ratio of ethane and argon gas is 10:1, keeps 30 minutes;
S34: after having reacted, stop passing into ethane and nickel foil is heated, reaction chamber stops passing into argon gas after being cooled to room temperature, obtains carbon nanometer wall.
Embodiment 4
A kind of preparation method of carbon nanometer wall, concrete steps are as follows:
S41: the cobalt paper tinsel is put into to the dilute hydrochloric acid solution etching 30 seconds that concentration is 0.5mol/L, and etching is well cleaned with deionized water, ethanol, acetone afterwards;
S42: cleaned cobalt paper tinsel is put into to reaction chamber and passed into volume ratio is 2:8 hydrogen and argon gas 50sccm, keeps 50 minutes;
S43: the cobalt paper tinsel is heated to 900 ℃, passes into ethanol 400sccm, the volume ratio of ethanol and hydrogen is 4:1, keeps 100 minutes;
S44: after having reacted, stop passing into ethanol and the cobalt paper tinsel is heated, reaction chamber stops passing into hydrogen and argon gas after being cooled to room temperature, obtains carbon nanometer wall.
Embodiment 5
A kind of preparation method of carbon nanometer wall, concrete steps are as follows:
S51: the cobalt paper tinsel is put into to the dilute hydrochloric acid solution etching 30 seconds that concentration is 0.5mol/L, and etching is well cleaned with deionized water, ethanol, acetone afterwards;
S52: cleaned cobalt paper tinsel is put into to reaction chamber, adopt vacuum machine to take the air in reaction chamber away;
S53: the cobalt paper tinsel is heated to 900 ℃, passes into ethanol 400sccm, the volume ratio of ethanol and hydrogen is 4:1, keeps 100 minutes;
S54: after having reacted, stop passing into ethanol and the cobalt paper tinsel is heated, reaction chamber stops passing into hydrogen after being cooled to room temperature, obtains carbon nanometer wall.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any modifications of doing within the spirit and principles in the present invention, be equal to and replace and improvement etc., within all should being included in protection scope of the present invention.
Claims (10)
1. the preparation method of a carbon nanometer wall, comprise the steps:
The acid solution that is 0.01～1mol/L by concentration by metal substrate is carried out etching;
Described metal substrate after etching is placed in to reaction chamber, and gets rid of the air in described reaction chamber;
After the described metal substrate that is placed in reaction chamber is heated to 700～1100 ℃; to continuing to pass into the protective gas that volume ratio is 1:2～10 in the described reaction chamber of excluding air, with the mixed gas of carbon-source gas, reacted; and keep 1～300 minute, at the described carbon nanometer of described metal substrate surface growth wall.
2. the preparation method of carbon nanometer wall according to claim 1, it is characterized in that: described metal substrate is heated to 900～1100 ℃, 60～120 minutes reaction times.
3. the preparation method of carbon nanometer wall according to claim 1 and 2, it is characterized in that: described carbon-source gas is at least one in methane, ethane, acetylene, ethanol.
4. the preparation method of carbon nanometer wall according to claim 1, it is characterized in that: described acid strength is 0.1～0.5mol/L.
5. according to the preparation method of the described carbon nanometer of claim 1 or 4 wall, it is characterized in that: the time that described acid solution is carried out etching to described metal substrate is 30～180 seconds.
6. the preparation method of carbon nanometer wall according to claim 1 and 2 is characterized in that: described metal substrate is one or more the combination in iron foil, nickel foil, cobalt paper tinsel, Copper Foil.
7. the preparation method of carbon nanometer wall according to claim 1 and 2, it is characterized in that: the method for getting rid of the air in described reaction chamber is to continue to pass into protective gas to get rid of the air in described reaction chamber in described reaction chamber.
8. the preparation method of carbon nanometer wall according to claim 7, it is characterized in that: described protective gas is at least one in hydrogen, nitrogen, argon gas.
9. the preparation method of carbon nanometer wall according to claim 7, it is characterized in that: in described reaction chamber, the flow of described carbon-source gas is 10～1000sccm.
10. the preparation method of carbon nanometer wall according to claim 7; it is characterized in that: after question response; also comprise cooling step: stop passing into carbon-source gas in described reaction chamber and stop, to described metal substrate heating, stopping passing into protective gas after described reaction chamber is cooled to room temperature.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2019238206A1 (en) | 2018-06-11 | 2019-12-19 | Jozef Stefan Institute | Carbon nanostructured materials and methods for forming carbon nanostructured materials |
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Non-Patent Citations (2)
| Title |
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| SEIJI SHIMABUKURO ET AL.: "Effect of hydrogen dilution in preparation of carbon nanowall by hot-wire CVD", 《THIN SOLID FILMS》 * |
| TAKASHI ITOH ET AL.: "Preparation and electron field emission of carbon nanowall by Cat-CVD", 《THIN SOLID FILMS》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019238206A1 (en) | 2018-06-11 | 2019-12-19 | Jozef Stefan Institute | Carbon nanostructured materials and methods for forming carbon nanostructured materials |
| US11673807B2 (en) | 2018-06-11 | 2023-06-13 | National University Corporation Tokai National Higher Education And Research System | Carbon nanostructured materials and methods for forming carbon nanostructured materials |
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Application publication date: 20131204 |