CN101215691A - Method for in situ synthesizing metal nickel nano particle coating carbon nano-tube composite material - Google Patents
Method for in situ synthesizing metal nickel nano particle coating carbon nano-tube composite material Download PDFInfo
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- CN101215691A CN101215691A CNA200810032419XA CN200810032419A CN101215691A CN 101215691 A CN101215691 A CN 101215691A CN A200810032419X A CNA200810032419X A CN A200810032419XA CN 200810032419 A CN200810032419 A CN 200810032419A CN 101215691 A CN101215691 A CN 101215691A
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Abstract
The invention relates to a method for preparing composite materials of metal nickel nanometer particle coating filling carbon nano-tube which is synthesized by an in situ chemical gas phase reduction, and belongs to the technical field of preparing novel composite materials using vapor deposition and chemical methods. The invention is characterized in that porous anodic oxidation aluminum thin template is used, the oxidation aluminum thin template which is equipped with a plurality of channel intracavities whose diameter is 200nm is used, nickel chloride solution is originally filled under the conditions of existing mixed gas of C2H2 and N2, metal nickel nanometer particles and a carbon nano-tube which is grown in an original position are obtained through producing a reduction reaction in high temperature of 600 DEG C, and at last the composite materials of the metal nickel nanometer particle novel structure which is fully coated and filled by the carbon nano-tube are formed. The invention does not need to prepare the carbon nano-tube in advance, and is obtained in a same time and a same position through the forming of the carbon nano-tube and the producing of the metal nickel nanometer particles.
Description
Technical field
The present invention relates to coat the method for the matrix material of filling carbon nano-pipe, belong to vapour deposition and chemical process and prepare the advanced composite material technical field with the synthetic metal nickel nano particle of in-situ chemical vapor deposition reduction method.
Background technology
Metal nanoparticle is filled in the carbon nanotube, this matrix material has not only changed the character of carbon nanotube, also changed the character of metal nano material itself, studies show that, this matrix material has special chemistry and physical property, as better conductivity, optical property and mechanical property etc., have wide and the potential application prospect is arranged.
Ajavan and Iijima have reported in 1993 and have utilized capillary action to make metal filled method (Ajavan to carbon nanotube, P.M.Iijima, S.Nature, 1993,361:333), the method of this afterwards capillary action principle is widely used on the metal nano particle composite material that the preparation carbon nanotube coats (1. Kumar, T.P.Ramesh, R.Lin, Y.Y.Fey, G.T.K.Electrochem.Commun.2004,6:520; 2. Zhao, L.Gao, L.Carbon, 2004,42:3269; 3. Tyagi, P.K.Singh M.K.Misra A, Palnitkar U, Misra D.S.Titus E, Ali, N, Cabral G, Gracio J, Roy, M, Kulshreshtha, S.K.Thin Solid Films, 2004,469:127).This method need obtain carbon nanotube usually in advance, then carbon nanotube is immersed in aqueous solution molten state or that comprise metal precursor, utilize capillary action that metal precursor is sucked in the tube chamber of carbon nanotube, and then carry out suitable subsequent disposal and make presoma change target product into.Because the very little opening just of diameter very little (less than hundreds of nanometers) of carbon nanotube, and length can reach several easily even tens microns, the metal nanoparticle that is filled in carbon nanotube inside is very inhomogeneous, charging efficiency is not high yet, a large amount of metal precursor can stick on the outer tube wall of carbon nanotube inevitably, it is not high that thereby the carbon nanotube that causes obtaining is coated with the composite structure purity of metal nanoparticle, and productive rate is very low.
Summary of the invention
The objective of the invention is to adopt chemical Vapor deposition process and chemical reduction reaction, the formation of carbon nanotube and the interior at one time original position of generation of metal nanoparticle are obtained simultaneously, obtain the matrix material of metal nanoparticle coating and filling carbon nano-pipe thus; Another purpose of the present invention just provides the processing method of this matrix material of preparation.
The synthetic metal nickel nano particle of a kind of original position of the present invention coats the method for the matrix material of filling carbon nano-pipe, it is characterized in that having following technological process and step:
A. the filling of aluminum oxide film template: the CiCl that the porous anodic alumina film template is placed on 0.1M
2In the aqueous solution, dipping time is 5 hours, is put in drying in the baking oven then, and drying temperature is 70 ℃, and be 5 hours time of drying; Obtain being filled with the aluminum oxide film template of metallic nickel chloride soln thus; The mean pore size of described porous anodic alumina film template is 20nm;
B. the thermal treatment of aluminum oxide film template: the above-mentioned alumina formwork that is filled with nickelous chloride is positioned in the tube furnace, feeds C
2H
2And N
2Gas mixture, C in the gas mixture
2H
2And N
2Volume ratio be: C
2H
2: N
2=1: 9; Feeding the flow that mixes gas is 200cm
3/ second; Simultaneously, be heated to 600 ℃, and continue heating 5 hours in this temperature with 3～10 ℃/minute temperature rise rates; Continue to feed gas mixture and be cooled to room temperature, promptly naturally cool to 20 ℃ of room temperatures until tube furnace; Be the NaOH solution removal aluminum oxide film template of 5N then with concentration, the dissolving time length is 5 hours; Collect insoluble substance then, after washing and drying, promptly get the matrix material of the particle-filled enveloped carbon nanometer tube of metal nickel nano.
The invention provides a kind of novel coating fill method, this method does not need to use the carbon nanotube that obtains in advance, but utilizes the formation of carbon nanotube and the interior at one time original position of preparation of metal nanoparticle to obtain simultaneously.The present invention adopts chemical Vapor deposition process, makes carbon source C
2H
2Evenly by in the alumina formwork duct of having contained nickelous chloride, on the one hand, nickelous chloride is by C for gas
2H
2Reduction generates metal nanoparticle, on the other hand, and C
2H
2The catalytic decomposition of oxidated aluminum alloy pattern plate internal surface is deposited on and forms carbon nanotube on the internal surface.Because carbon nanotube is to be close to the growth of alumina formwork internal surface, in the aluminum oxide inner chamber, reduce the carbon nanotube that the nickel metal nanoparticle that obtains all coated growth in situ and coat from forming on the mechanism all like this, finally formed the novel structure that carbon nanotube is coated with the nickel metal nanoparticle fully.This method has overcome the low charging efficiency that utilizes capillary action preparation, the drawback of low product structural purity, can high efficiencyly obtain structural purity to reach～100% carbon nanotube is coated with metal nano particle composite material fully.
Description of drawings
Fig. 1 is coated with field emission scanning electron microscope (FESEM) photo of nickel metal nanoparticle for the carbon nanotube that uses the in-situ chemical vapor deposition reduction method to obtain.
Fig. 2 is coated with transmission electron microscope (TEM) photo of nickel metal nanoparticle for the carbon nanotube that uses the in-situ chemical vapor deposition reduction method to obtain.
Embodiment
After now specific embodiments of the invention being described in.
Embodiment one: get the NiCl of a porous anodic alumina film (aperture is about 200nm) at 0.1M
2Placed in the aqueous solution 5 hours, then 70 ℃ of dryings 5 hours in baking oven then place tube furnace to heat aluminum oxide film, and feeding 200cm
3The 10%C of/second
2H
2And 90%N
2The mixed gas of forming, be heated to 600 ℃ with 3～10 ℃ of/minute temperature rise rates, continue 5 hours, continue logical gas mixture and naturally cool to room temperature until tube furnace, remove aluminum oxide film in 5 hours with the NaOH aqueous solution soaking of 5.0M then, collect remaining insolubles, use a large amount of deionized water wash, desciccate, the powder that finally obtains are exactly the matrix material that the 200nm carbon nanotube is coated with the Ni metal nanoparticle of 6-10nm.
Fig. 1 is coated with field emission scanning electron microscope (FESEM) photo of Ni metal nanoparticle for the carbon nanotube that obtains of this enforcement preparation, diameter is about the carbon nano pipe array of 200nm as we can see from the figure, can see many small Ni metal nanoparticles in carbon nanotube layer dimly.The component formation of Ni can be confirmed by X-ray diffraction (XRD).
The carbon nanotube that obtains that Fig. 2 prepares for this enforcement is coated with transmission electron microscope (TEM) photo of Ni metal nanoparticle, shows that further the Ni nanoparticle of seeing among Fig. 1 has been filled in the carbon nanotube.Can find from figure: particle diameter is that the Ni nanoparticle of 6-10nm is evenly dispersed in the carbon nanotubes lumen, rather than loads on the outer wall of nanotube, and the structural purity of this carbon nanotube clad structure can be up to～100%.
Claims (1)
1. an original position is synthesized the method that the metal nickel nano particle coats the matrix material of filling carbon nano-pipe, it is characterized in that having following technological process and step:
A. the filling of aluminum oxide film template: the CiCl that the porous anodic alumina film template is placed on 0.1M
2In the aqueous solution, dipping time is 5 hours, is put in drying in the baking oven then, and drying temperature is 70 ℃, and be 5 hours time of drying; Obtain being filled with the aluminum oxide film template of metallic nickel chloride soln thus; The mean pore size of described porous anodic alumina film template is 20nm;
B. the thermal treatment of aluminum oxide film template: the above-mentioned alumina formwork that is filled with nickelous chloride is positioned in the tube furnace, feeds C
2H
2And N
2Gas mixture, C in the gas mixture
2H
2And N
2Volume ratio be: C
2H
2: N
2=1: 9; Feeding the flow that mixes gas is 200cm
3/ second; Simultaneously, be heated to 600 ℃, and continue heating 5 hours in this temperature with 3～10 ℃/minute temperature rise rates; Continue to feed gas mixture and be cooled to room temperature, promptly naturally cool to 20 ℃ of room temperatures until tube furnace; Be the NaOH solution removal aluminum oxide film template of 5N then with concentration, the dissolving time length is 5 hours; Collect insoluble substance then, after washing and drying, promptly get the matrix material of the particle-filled enveloped carbon nanometer tube of metal nickel nano.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA200810032419XA CN101215691A (en) | 2008-01-08 | 2008-01-08 | Method for in situ synthesizing metal nickel nano particle coating carbon nano-tube composite material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA200810032419XA CN101215691A (en) | 2008-01-08 | 2008-01-08 | Method for in situ synthesizing metal nickel nano particle coating carbon nano-tube composite material |
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|---|---|
| CN101215691A true CN101215691A (en) | 2008-07-09 |
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|---|---|---|---|
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102247858A (en) * | 2011-05-24 | 2011-11-23 | 上海应用技术学院 | Aluminium oxide-nickel-rare earth catalytic composite membrane as well as preparation method and application thereof |
| CN103038005A (en) * | 2010-07-30 | 2013-04-10 | 贝克休斯公司 | Nanomatrix metal composite |
| CN103056389A (en) * | 2013-01-28 | 2013-04-24 | 中国科学院合肥物质科学研究院 | Method for preparing germanium nanotubes |
| CN108217628A (en) * | 2018-02-10 | 2018-06-29 | 中国科学院合肥物质科学研究院 | Three-dimensional netted carbon nanotube and its preparation method and application |
-
2008
- 2008-01-08 CN CNA200810032419XA patent/CN101215691A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103038005A (en) * | 2010-07-30 | 2013-04-10 | 贝克休斯公司 | Nanomatrix metal composite |
| CN103038005B (en) * | 2010-07-30 | 2015-09-30 | 贝克休斯公司 | Nanomatrix metal composite |
| CN102247858A (en) * | 2011-05-24 | 2011-11-23 | 上海应用技术学院 | Aluminium oxide-nickel-rare earth catalytic composite membrane as well as preparation method and application thereof |
| CN102247858B (en) * | 2011-05-24 | 2013-06-19 | 上海应用技术学院 | Aluminium oxide-nickel-rare earth catalytic composite membrane as well as preparation method and application thereof |
| CN103056389A (en) * | 2013-01-28 | 2013-04-24 | 中国科学院合肥物质科学研究院 | Method for preparing germanium nanotubes |
| CN103056389B (en) * | 2013-01-28 | 2015-01-21 | 中国科学院合肥物质科学研究院 | Method for preparing germanium nanotubes |
| CN108217628A (en) * | 2018-02-10 | 2018-06-29 | 中国科学院合肥物质科学研究院 | Three-dimensional netted carbon nanotube and its preparation method and application |
| CN108217628B (en) * | 2018-02-10 | 2021-12-07 | 中国科学院合肥物质科学研究院 | Three-dimensional net-shaped carbon nano tube and preparation method and application thereof |
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