CN1463920A - Process for preparing tree-shaped carbon nano tube - Google Patents
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- CN1463920A CN1463920A CN 02122640 CN02122640A CN1463920A CN 1463920 A CN1463920 A CN 1463920A CN 02122640 CN02122640 CN 02122640 CN 02122640 A CN02122640 A CN 02122640A CN 1463920 A CN1463920 A CN 1463920A
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Abstract
The preparation process of dendriform carbon nanotube includes following steps: preparing catalyst through dissolving cobalt salt in alcohol, soaking magnesia as catalyst carrier in the alcohol solution of cobalt salt, ultrasonic dispersion, evaporating, drying and crushing; and preparing dendriform carbon nanotube through set quartz boat holding the catalyst inside quartz tube, leading in hydrogen to eliminate air in the reaction system, heating to 850-1100 deg.c, leading in methane for reaction, cooling in hydrogen atmosphere, acidifying, washing, and vacuum drying. The process is suitable for industrial production, and the prepared dendriform carbon nanotube has special electrical and dynamic properties and is one ideal material for constituting nano devices.
Description
Technical field:
The present invention relates to a kind of preparation of nanomaterials, relate in particular to a kind of preparation method of tree-shaped carbon nanotube.
Background technology:
Carbon nanotube is because its unique electricity and mechanical property, and becomes specific function and the nano-device material that has potentiality.The same with microelectronic device, nano-device also will be with the various heterogeneous construction units of becoming.Theory shows with experimental study: different with helicity according to diameter, carbon nanotube shows a series of electrical properties (Odom, the T.W. from the semi-conductor to the metal; Huang, J.-L.; Kim, P.; Lieber, C.M.J.Phys.Chem.B2000,104,2794.), as seen the carbon nanotube of the linear structure of two different electrical properties is linked together and can produce a heterojunction, this is significant to constructing based on the nano-device of carbon nanotube.At present the method for this carbon nanotube heterojunction of preparation has two kinds: a kind of is to have carbon nanotube of different nature with two to intersect and be placed on the substrate and produce knot; Another kind method is the carbon nanotube that directly preparation has bifurcation structure.Because the former needs complex apparatus and operative technique, cost is higher, therefore explores the carbon nanotube that preparation has bifurcation structure and has prior practical significance for constructing nano-device.Reported at present and prepared various carbon nanotubes with single bifurcation structure, as Y shape, T shape is L shaped etc.These carbon nanotubes have the two dimension knot, but construct nano-device except needs two dimension knot, also need three-dimensional knot.Ming etc. make catalyzer with iron, at 1000 ℃ of thermo-cracking methane, obtain network-like carbon nanotube, and the carbon nanotube of this shape contains two dimension or three-dimensional knot (J-.M.Jing, C-.CChang, Appl.Phys.Lett.2002,80,324).But do not see the relevant report that contains the tree-shaped carbon nanotube of two and three dimensions knot so far as yet.
Summary of the invention:
The present invention relates to a kind of carbon nanotube of novel texture---tree-shaped carbon nanotube and preparation method thereof.Adopt certain catalyzer and processing method, need not any template, direct growth goes out to have the tree-shaped carbon nanotube of two dimension knot or three-dimensional knot.This carbon nanotube with novel structure can be used for the nanometer circuit based on the carbon pipe.
A kind of tree-shaped carbon nanotube provided by the invention is all reached from the branch of the multiple bifurcated of trunk by trunk to be formed, and the pipe diameter is 10～100 nanometers, and length is 1～300 micron.This CNT (carbon nano-tube) has the knot or the three-dimensional knot of two dimension.
The present invention is used to prepare the device employing popular response equipment of tree-shaped carbon nanotube, mainly by reactor, and gas distributing system, temperature controlling system is formed: (1) reactor is made up of silica tube and electric tube furnace; (2) gas distributing system is made up of gas circuit and mass-flow gas meter, can control kind, flow, the ratio of carrier gas; (3) temperature controlling system is made up of programmed temperature control instrument.
The preparation method of a kind of tree-shaped carbon nanotube provided by the invention, carry out according to following sequential steps:
A. Preparation of catalysts:
Cobalt salt is dissolved in the alcohol, support of the catalyst magnesium oxide is immersed in the alcoholic solution of above-mentioned cobalt salt, ultra-sonic dispersion got final product, magnesium oxide powder is uniformly dispersed in alcoholic solution in general 0.5～2 hour.Evaporation (can adopt Rotary Evaporators etc.) removes the blocks of solid thing that desolvates and obtain sky-blue then.To obtain white block solids after this blocks of solid thing drying, drying conditions is preferred: temperature is 100 ℃～200 ℃; Time is 5～20 hours.Grind at last 80～150 purpose powder for use, wherein the content of catalyzer in the weight of simple substance cobalt 1%～6%.
Described cobalt salt is Xiao Suangu, rose vitriol, cobaltous acetate; Described alcohol is ethanol, methyl alcohol etc.
Described cobalt salt with alcohol weight ratio be preferably 1: 50～200, optimum is 1: 100～150; Cobalt element and magnesian weight ratio are preferably 1～6: 100, and optimum is 1～3: 100.
B. the preparation of tree-shaped carbon nanotube
The quartz boat that catalyzer is housed is placed silica tube, feed the air of hydrogen in catching up with clean reactive system.Then be warming up to 850 ℃～1100 ℃.Feed then after methane gas reacts, cut off methane gas and power supply, but continue logical hydrogen, product is cooled off in nitrogen atmosphere.Adopt the ordinary method acidifying at last, washing, vacuum-drying obtains tree-shaped carbon nanotube product.
Further, can adopt following concrete scheme:
The quartz boat that catalyzer is housed is placed the middle part of silica tube, and the volume of catalyzer is 1/5～4/5 of a quartz boat capacity.Feeding flow is the air of hydrogen in catching up with clean reactive system of 20～150 milliliters of per minutes.Then in 5～15 minutes, be warming up to 850 ℃～1100 ℃.Change the flow of hydrogen then, and feed methane gas, the volume ratio of hydrogen/methane is 2～8: 1, be preferably 3～5: and 1, the volume of hydrogen/methane is best than being 4: 1, and total gas couette is 100～600 milliliters of per minutes, is preferably 200～400 milliliters.Keep reaction after 1～20 minute, cut off methane gas and power supply, but continue logical hydrogen, product is cooled off in nitrogen atmosphere.Adopt ordinary method concentrated hydrochloric acid acidifying at last, washing, vacuum-drying obtains tree-shaped carbon nanotube product.
The feature and advantage of a kind of tree-shaped carbon nanotube provided by the invention:
1. tree-shaped carbon nanotube provided by the invention is made up of trunk and many branches, and these branches derive from trunk, repeats to produce bifurcated.
2. tree-shaped carbon nanotube provided by the invention not only contains the knot of two dimension but also contains three-dimensional knot.
3. the pipe diameter Distribution of tree-shaped carbon nanotube provided by the invention is even, generally exists
10～100 nanometers, length are 1～300 micron.
4. the structure of tree-shaped carbon nanotube provided by the invention is novel unique, has special electricity and mechanical property, is a kind of nano-device desirable material of constructing.
5. the inventive method prepares tree-shaped carbon nanotube, processing ease, and technology is simple, and is with low cost, is suitable for suitability for industrialized production.
Description of drawings: Fig. 1 the present invention prepares the device synoptic diagram of tree-shaped carbon nanotube.1---electric tube furnace 2---silica tube 3---the tree-shaped carbon nanotube photo that the tree-shaped high multiple of carbon nanotube photo Fig. 3 scanning electronic microscope that the low multiple of temperature controller 4---quartz boat 5---gas-flow rate controller Fig. 2 scanning electronic microscope photographs photographs
Embodiment:
The present invention is described in detail below in conjunction with drawings and Examples.
Embodiment 1 is dissolved in 0.356 gram cobalt nitrate hexahydrate in the 50ml dehydrated alcohol, adds 5 gram magnesium oxide powders again.Mixture mixed solution in ultrasonic 1 hour.Remove by Rotary Evaporators then and desolvate, and then dry 13 hours catalyzer under 130 ℃ with the acquisition complete drying.This dried solid mixture is ground thinner powder.Obtain containing the cobalt element weight percent like this and be 1.25% catalyzer.(tube furnace is produced by Beijing Electric Stove Factory, and model is SK as map device
2-4-13) shown in, one quartz boat (5 milliliters) that the above-mentioned catalyzer of 2 grams is housed is placed the silica tube middle part, connect gas distributing system, flow with 300 milliliters of per minutes feeds hydrogen, and it is 1000 ℃ that temperature is set, and rapidly temperature is risen to 1000 ℃ (in 12 minutes), flow with 75 milliliters of per minutes feeds methane gas, react after 10 minutes, cut off methane source of the gas and power supply, continue logical hydrogen and make product cooling in hydrogen divides.The thick product of refrigerative is handled to remove magnesium oxide and cobalt metal with 50 milliliters concentrated hydrochloric acid, used distilled water wash until neutrality again, subsequently 70 ℃ of following vacuum-dryings.The pattern of carbon nanotube, length, diameter and purity are used electron scanning micrograph respectively, and (Fig. 2 Fig. 3) records.Can know the product of gained that from Fig. 2 comprise that Y shape, T shape, H shape etc. have the unifurcate carbon nanotube of different shape of two dimension knot, it is tree-shaped to also have a large amount of products to present, these tree-shaped carbon nanotubes not only contain the knot of two dimension but also contain three-dimensional knot.Shown in Figure 3 is typical tree-shaped carbon nanotube, and this tree-shaped carbon nanotube diameter is 38 nanometers.Embodiment 2 is according to the preparation method of embodiment 1, just the quality of cobalt nitrate hexahydrate is changed to 0.712 gram and obtains 2.5% catalyzer, and adopting this catalyzer to make to contain tree-shaped carbon nanotube is 80% product.Embodiment 3 just will mix total gas flow and be adjusted to 300 milliliters of per minutes according to the preparation method of embodiment 2, and the volume ratio of hydrogen and methane is adjusted to 4: 1, and the diameter that makes is that tree-shaped carbon nanotube and its content of 52 nanometers reaches 75%.Embodiment 4 just is changed to 0.251 gram heptahydrate with 0.356 gram cobalt nitrate hexahydrate and obtains 1.25% catalyzer according to the preparation method of embodiment 1, and the diameter that adopts this catalyzer to make is that tree-shaped carbon nanotube and its content of 43 nanometers reaches 70%.Embodiment 5 just is changed to 0.305 gram, four water cobaltous acetates with 0.356 gram cobalt nitrate hexahydrate and obtains 1.25% catalyzer according to the preparation method of embodiment 1, and the diameter that adopts this catalyzer to make is that tree-shaped carbon nanotube and its content of 45 nanometers reaches 70%.Embodiment 6 is according to the preparation method of embodiment 1, and the tree-shaped carbon nanotube and its content that just ethanol are changed to diameter that methyl alcohol makes and are 39 nanometers reach 80%.Embodiment 7 is according to the preparation method of embodiment 4, and the tree-shaped carbon nanotube and its content that just ethanol are changed to diameter that methyl alcohol makes and are 45 nanometers reach 75%.Embodiment 8 is according to the preparation method of embodiment 5, and the tree-shaped carbon nanotube and its content that just ethanol are changed to diameter that methyl alcohol makes and are 45 nanometers reach 70%.
Claims (8)
1. the preparation method of a tree-shaped carbon nanotube, carry out according to following sequential steps:
A. Preparation of catalysts:
Cobalt salt is dissolved in the alcohol, support of the catalyst magnesium oxide is immersed in the alcoholic solution of above-mentioned cobalt salt, ultra-sonic dispersion, evaporation removes the blocks of solid thing that desolvates and obtain sky-blue then, to obtain white block solids after this blocks of solid thing drying, grind into 80～150 purpose powder for use; Wherein the content of catalyzer in the weight of simple substance cobalt 1%～6%;
B. the preparation of tree-shaped carbon nanotube
The quartz boat that catalyzer is housed is placed silica tube, feed the air of hydrogen in catching up with clean reactive system, then be warming up to 850 ℃～1100 ℃.Feed then after methane gas reacts, cut off methane gas and power supply, but continue logical hydrogen, product is cooled off in nitrogen atmosphere, adopt the ordinary method acidifying at last, washing, vacuum-drying obtains tree-shaped carbon nanotube product.
2. according to the preparation method of claim 1, it is characterized in that: described cobalt salt is 1: 50～200 with the weight ratio of alcohol; Cobalt element and magnesian weight ratio are 1～6: 100.
3. according to the preparation method of claim 1, it is characterized in that: described cobalt salt is 1: 100～150 with the weight ratio of alcohol; Cobalt element and magnesian weight ratio are 1～3: 100.
4. the preparation method arbitrary according to claim 1 to 3 is characterized in that: described cobalt salt is Xiao Suangu, rose vitriol, cobaltous acetate; Described alcohol is ethanol, methyl alcohol.
5. the preparation method arbitrary according to claim 1 to 3 is characterized in that: the preparation process of the tree-shaped carbon nanotube of step b is as follows: the quartz boat that catalyzer will be housed places the middle part of silica tube, and the volume of catalyzer is 1/5～4/5 of a quartz boat capacity.Feeding flow is the air of hydrogen in catching up with clean reactive system of 20～150 milliliters of per minutes, change the flow of hydrogen then, and feed methane gas, the volume ratio of hydrogen/methane is 2～8: 1, total gas couette is 100～600 milliliters of per minutes, keep reaction after 1～20 minute, cut off methane gas and power supply, but continue logical hydrogen, product is cooled off in nitrogen atmosphere, adopt ordinary method concentrated hydrochloric acid acidifying at last, washing, vacuum-drying obtains tree-shaped carbon nanotube product.
6. according to the preparation method of claim 5, it is characterized in that: the volume ratio of described hydrogen/methane is 3～5: 1.
7. according to the preparation method of claim 5, it is characterized in that: the volume ratio of described hydrogen/methane is 4: 1.
8. according to the preparation method of claim 5, it is characterized in that: described total gas couette is 200～400 milliliters of per minutes.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1982212B (en) * | 2005-12-16 | 2010-05-19 | 细美事有限公司 | Device and method for synthesizing carbon nanotube |
| CN101311110B (en) * | 2007-05-25 | 2010-08-04 | 北京大学 | Method for directly producing carbon nano tube without metal impurities |
| CN101293629B (en) * | 2007-06-08 | 2010-09-08 | 北京大学 | Process for producing carbon nano-tube or nano-wire bifurcate structure |
| CN101896424B (en) * | 2007-12-12 | 2015-05-13 | 新日铁住金化学株式会社 | Metal encapsulated dendritic carbon nanostructure, carbon nanostructure, process for producing metal encapsulated dendritic carbon nanostructure, process for producing carbon nanostructure, and capacitor |
| CN109384217A (en) * | 2018-11-13 | 2019-02-26 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of branching shape carbon nano-tube material and products thereof and application |
-
2002
- 2002-06-18 CN CNB021226407A patent/CN1171781C/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1982212B (en) * | 2005-12-16 | 2010-05-19 | 细美事有限公司 | Device and method for synthesizing carbon nanotube |
| CN101311110B (en) * | 2007-05-25 | 2010-08-04 | 北京大学 | Method for directly producing carbon nano tube without metal impurities |
| CN101293629B (en) * | 2007-06-08 | 2010-09-08 | 北京大学 | Process for producing carbon nano-tube or nano-wire bifurcate structure |
| CN101896424B (en) * | 2007-12-12 | 2015-05-13 | 新日铁住金化学株式会社 | Metal encapsulated dendritic carbon nanostructure, carbon nanostructure, process for producing metal encapsulated dendritic carbon nanostructure, process for producing carbon nanostructure, and capacitor |
| CN109384217A (en) * | 2018-11-13 | 2019-02-26 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of branching shape carbon nano-tube material and products thereof and application |
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