CN1837036A - Process for preparing ordered carbon nanotube array - Google Patents
Process for preparing ordered carbon nanotube array Download PDFInfo
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- CN1837036A CN1837036A CN 200610042684 CN200610042684A CN1837036A CN 1837036 A CN1837036 A CN 1837036A CN 200610042684 CN200610042684 CN 200610042684 CN 200610042684 A CN200610042684 A CN 200610042684A CN 1837036 A CN1837036 A CN 1837036A
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Abstract
The invention discloses the Method for preparation of an carray, aiming at the problem in existence of complex technique process, high cost and so on, using a polymer cantains carbon as carbon fountain, anode alumina as cyclostyle, first passing innocuous dipping technics to induct the carbon containing compound in cyclostyle pore passage, and then pyrolysis in inertia ambience condition, prepareing the ordered carbon nanotube inside the cyclostyle pore passage. Because using the technics of carbon containing compound pyrolysis inside the anode alumina cyclostyle pore passage, the top-quality ordered carbon nanotube can be made safely, effectly. The process of this invention neither need advance aggradation catalyzer nor advance polymerization inside cyclostyle pore passage of momomer, furthermore, the carbon containing polymer solution adopting innocuity solvent, the technics couse is easy to control, the repeatability is fine and the request for equipment is low, so the cost is low.
Description
Technical field
The present invention relates to a kind of preparation method's of carbon nanotube, particularly ordered carbon nanotube array preparation method.
Background technology
Carbon nanotube has been applied in the research work of numerous areas such as field-effect transistor, quantum wire, hydrogen storage material, capacitor electrode material, the emission of flat pannel display field.
Document " J.Li, C.Papadopoulos, J.M.Xua, M.Moskovits.Appl Phys Lett, 1999,75:367-369 " discloses a kind of method of utilizing chemical Vapor deposition process to prepare carbon nanotube in the anodic oxidation aluminium formwork duct.At first at anodic oxidation aluminium formwork duct inside deposition Fe, catalyzer such as Co, Ni, the anodic oxidation aluminium formwork that will deposit catalyzer again places among the chemical vapor depsotition equipment, feed hydrocarbon gas such as acetylene then as carbon source, make its high temperature pyrolysis under inert atmosphere, and then at the duct of anodic oxidation aluminium formwork growth inside carbon nanotube.This method needs in advance at template duct inside deposition catalyzer, and after finishing, the deposition process of carbon nanotube needs catalyzer is handled, it is more that whole process of preparation relates to processing parameter, and control is complicated, has shortcomings such as ordered carbon nanotube array preparation cost height, control difficulty.
Document " J.C.Hulteen, H.X.Chen, C.K.Chambliss and C.R.Martin.NanostructuredMaterials, 1997,9:133-136 " discloses a kind of method of utilizing template to prepare ordered carbon nanotube array.This method is utilized acrylonitrile monemer, and pyroprocessing is carried out at first polymerization in the anodic oxidation aluminium formwork duct, cyclisation again, the preparation ordered carbon nanotube.This method is simplified than chemical gaseous phase depositing process, but before pyroprocessing, related polymer monomer polymerization and cyclization process are comparatively complicated.
Document " T.Maiyalagan; B; Viswanathan; Materials Chemistry and Physics; 2005; 93:291-295 " utilizes the dichloromethane solution of anodic oxidation aluminium formwork dipping polyvinylpyrrolidone, handles under 900 ℃ of conditions then, has prepared nitrogenous ordered carbon nanotube.Yet the organic solvent dichloromethane toxicity of using in this method is bigger, flammable, contact the phosgene that can produce severe toxicity with naked light or scorching hot object, and boiling point is low volatile.These are the safety of the healthy and preparation process of serious threat staff all, and increase the operation easier of preparation process.
Summary of the invention
In order to overcome prior art processes process complexity, deficiency that preparation cost is high, the invention provides a kind of preparation method of ordered carbon nanotube array.
The technical solution adopted for the present invention to solve the technical problems is: a kind of preparation method of ordered carbon nanotube array comprises the steps:
1) anodic oxidation aluminium formwork with the two ends perforate places nontoxic carbon containing polymers soln to flood, and is fully soaked into by the carbon containing polymers soln up to anodic oxidation aluminium formwork;
2) use carbon containing polymers soln solvent for use, distilled water successively, will clean up, in baking oven, dry then through the remaining carbon containing polymers soln in anodic oxidation aluminium formwork surface that step 1) is fully soaked into;
3) anodic oxidation aluminium formwork after will drying is placed in the High Temperature Furnaces Heating Apparatus, with vacuum pump High Temperature Furnaces Heating Apparatus is vacuumized subsequently, vacuum tightness reaches-0.09MPa and stable after, feed argon gas again to High Temperature Furnaces Heating Apparatus furnace pressure 0.1MPa, to displace the air in the High Temperature Furnaces Heating Apparatus burner hearth;
4) connect power supply, with the heat-up rate of 2～4 ℃/min the High Temperature Furnaces Heating Apparatus temperature is risen to 500 ℃～1000 ℃, and be incubated 1～5h under this temperature, powered-down cools to room temperature naturally subsequently, and whole process is led to argon shield, and pressure in the burner hearth remains 0.1MPa;
5) fully dissolve anodic oxidation aluminium formwork with concentration greater than 40% hydrofluoric acid aqueous solution after, the ordered carbon nanotube array that obtains is cleaned repeatedly with distilled water, till the pH value that cleans back distilled water is near 7.
The invention has the beneficial effects as follows: be incorporated in the template duct owing to adopt nontoxic impregnation technology will contain carbon polymer, high temperature pyrolysis under inert atmosphere conditions then, prepare ordered carbon nanotube in inside, template duct, thereby can prepare the high quality ordered carbon nanotube array safely, efficiently.Technological process of the present invention does not need deposited catalyst in advance, does not need polymer monomer in the polymerization in advance of inside, template duct yet, and adopts innoxious solvent, and technological process is easy to control, and favorable repeatability is lower to the preparation equipment requirements, thereby preparation cost is low; The present invention can also reach the isoparametric control of diameter, length, density, pattern, wall thickness to the ordered carbon nanotube of preparation by the pore passage structure of adjustment anodic oxidation aluminium formwork and the processing parameter of carbon containing polymers soln steeping process.
Description of drawings
Fig. 1 is preparation method's schema of ordered carbon nanotube array of the present invention.
Fig. 2 is the prepared ordered carbon nanotube array stereoscan photograph of the present invention.
Fig. 3 is the transmission electron microscope photo of the prepared carbon nanotube of the present invention.
Fig. 4 is the tube wall transmission electron microscope photo of the prepared carbon nanotube of the present invention.
Fig. 5 is the energy spectrum analysis figure of the prepared ordered carbon nanotube of the present invention.
Embodiment
Embodiment 1: with reference to Fig. 1, it is 25% phenolic aldehyde ethanolic soln that the anodic oxidation aluminium formwork of two ends perforate is placed concentration, at room temperature fully floods 30min.Use ethanol, distilled water with the remaining phenolic aldehyde ethanolic soln wiped clean in anodic oxidation aluminium formwork surface after the taking-up successively.Then anodic oxidation aluminium formwork is placed on 110 ℃ of oven dry 4h in the baking oven.
Anodic oxidation aluminium formwork after the oven dry is placed on High Temperature Furnaces Heating Apparatus flat-temperature zone part.With vacuum pump High Temperature Furnaces Heating Apparatus burner hearth inside is vacuumized subsequently, vacuum tightness is reached-0.09MPa, applying argon gas is to pressure in the burner hearth 0.1MPa then, and this process repeats 3 times altogether, to displace the air in the High Temperature Furnaces Heating Apparatus burner hearth.
Connect power supply, the High Temperature Furnaces Heating Apparatus temperature is risen to 500 ℃, and at 500 ℃ of insulation 5h down with the heat-up rate of 2 ℃/min, powered-down subsequently, High Temperature Furnaces Heating Apparatus cools to room temperature naturally.Whole process is led to argon shield, and pressure in the burner hearth remains 0.1MPa.From burner hearth, take out anodic oxidation aluminium formwork, can see that the anodic oxidation aluminium formwork color after the pyroprocessing is rendered as black.
With concentration greater than 40% hydrofluoric acid, the anodic oxidation aluminium formwork 18h under the room temperature after the dissolving pyroprocessing.After template is fully dissolved, the ordered carbon nanotube array that in the template duct, prepares, visualize is a black thin film.Clean ordered carbon nanotube array repeatedly with distilled water, till the pH value that cleans back distilled water is near 7.
Embodiment 2: with reference to Fig. 1, it is 30% epoxy acetone soln that the anodic oxidation aluminium formwork of two ends perforate is placed concentration, at room temperature fully floods 30min.Use acetone, distilled water with the remaining epoxy acetone soln wiped clean in anodic oxidation aluminium formwork surface after the taking-up successively.Then anodic oxidation aluminium formwork is placed on 110 ℃ of oven dry 4h in the baking oven.
Anodic oxidation aluminium formwork after the oven dry is placed on High Temperature Furnaces Heating Apparatus flat-temperature zone part.With vacuum pump High Temperature Furnaces Heating Apparatus burner hearth inside is vacuumized subsequently, vacuum tightness is reached-0.09MPa, applying argon gas is to pressure in the burner hearth 0.1MPa then, and this process repeats 3 times altogether, to displace the air in the High Temperature Furnaces Heating Apparatus burner hearth.
Connect power supply, the High Temperature Furnaces Heating Apparatus temperature is risen to 700 ℃, and at 700 ℃ of insulation 4h down with the heat-up rate of 3 ℃/min, powered-down subsequently, High Temperature Furnaces Heating Apparatus cools to room temperature naturally.Whole process is led to argon shield, and pressure in the burner hearth remains 0.1MPa.From burner hearth, take out anodic oxidation aluminium formwork, can see that the anodic oxidation aluminium formwork color after the pyroprocessing is rendered as black.
With concentration greater than 40% hydrofluoric acid, the anodic oxidation aluminium formwork 18h under the room temperature after the dissolving pyroprocessing.After template is fully dissolved, the ordered carbon nanotube array that in the template duct, prepares, visualize is a black thin film.Clean ordered carbon nanotube array repeatedly with distilled water, till the pH value that cleans back distilled water is near 7.
Embodiment 3: with reference to Fig. 1, it is 25% polyoxyethylene glycol ethanolic soln that the anodic oxidation aluminium formwork of two ends perforate is placed concentration, at room temperature fully floods 30min.Use ethanol, distilled water with the remaining polyoxyethylene glycol ethanolic soln wiped clean in anodic oxidation aluminium formwork surface after the taking-up successively.Then anodic oxidation aluminium formwork is placed on 110 ℃ of oven dry 4h in the baking oven.
Anodic oxidation aluminium formwork after the oven dry is placed on High Temperature Furnaces Heating Apparatus flat-temperature zone part.With vacuum pump High Temperature Furnaces Heating Apparatus burner hearth inside is vacuumized subsequently, vacuum tightness is reached-0.09MPa, applying argon gas is to pressure in the burner hearth 0.1MPa then, and this process repeats 3 times altogether, to displace the air in the High Temperature Furnaces Heating Apparatus burner hearth.
Connect power supply, the High Temperature Furnaces Heating Apparatus temperature is risen to 900 ℃, and at 900 ℃ of insulation 3h down with the heat-up rate of 3 ℃/min, powered-down subsequently, High Temperature Furnaces Heating Apparatus cools to room temperature naturally.Whole process is led to argon shield, and pressure in the burner hearth remains 0.1MPa.From burner hearth, take out anodic oxidation aluminium formwork, can see that the anodic oxidation aluminium formwork color after the pyroprocessing is rendered as black.
With concentration greater than 40% hydrofluoric acid, the anodic oxidation aluminium formwork 18h under the room temperature after the dissolving pyroprocessing.After template is fully dissolved, the ordered carbon nanotube array that in the template duct, prepares, visualize is a black thin film.Clean ordered carbon nanotube array repeatedly with distilled water, till the pH value that cleans back distilled water is near 7.
Embodiment 4: with reference to Fig. 1, it is 20% polyvinyl butyral acetal ethanolic soln that the anodic oxidation aluminium formwork of two ends perforate is placed concentration, at room temperature fully floods 30min.Use ethanol, distilled water with the remaining polyvinyl butyral acetal ethanolic soln wiped clean in anodic oxidation aluminium formwork surface after the taking-up successively.Then anodic oxidation aluminium formwork is placed on 110 ℃ of oven dry 4h in the baking oven.
Anodic oxidation aluminium formwork after the oven dry is placed on High Temperature Furnaces Heating Apparatus flat-temperature zone part.With vacuum pump High Temperature Furnaces Heating Apparatus burner hearth inside is vacuumized subsequently, vacuum tightness is reached-0.09MPa, applying argon gas is to pressure in the burner hearth 0.1MPa then, and this process repeats 3 times altogether, to displace the air in the High Temperature Furnaces Heating Apparatus burner hearth.
Connect power supply, the High Temperature Furnaces Heating Apparatus temperature is risen to 1000 ℃, and at 1000 ℃ of insulation 1h down with the heat-up rate of 4 ℃/min, powered-down subsequently, High Temperature Furnaces Heating Apparatus cools to room temperature naturally.Whole process is led to argon shield, and pressure in the burner hearth remains 0.1MPa.From burner hearth, take out anodic oxidation aluminium formwork, can see that the anodic oxidation aluminium formwork color after the pyroprocessing is rendered as black.
With concentration greater than 40% hydrofluoric acid, the anodic oxidation aluminium formwork 18h under the room temperature after the dissolving pyroprocessing.After template is fully dissolved, the ordered carbon nanotube array that in the template duct, prepares, visualize is a black thin film.Clean ordered carbon nanotube array repeatedly with distilled water, till the pH value that cleans back distilled water is near 7.
Above embodiment shows, the preparation method of ordered carbon nanotube array of the present invention is a carbon source to contain carbon polymer, anodised aluminium is a template, at first will contain carbon polymer by nontoxic impregnation technology is incorporated in the template duct, high temperature pyrolysis under inert atmosphere conditions is prepared ordered carbon nanotube in inside, template duct then.
The preparation method's of ordered carbon nanotube array of the present invention carbon source is to contain carbon polymer, comprises that not cited in the above-described embodiments all contain carbon polymer.
From the stereoscan photograph of Fig. 2 prepared ordered carbon nanotube diameter 50～70nm of the present invention as can be seen, open-ended, smooth surface, parallel each other ordered arrangement is the ordered carbon nanotube array structure.
Can see the tubular structure of the carbon nanotube that the present invention is prepared from the transmission electron microscope photo of Fig. 3.
Can see the structural pipe wall of the carbon nanotube that the present invention is prepared from the transmission electron microscope photo of Fig. 4.
The EDAX results of Fig. 5 shows: the prepared ordered carbon nanotube carbon content of the present invention is very high, does not almost have other impurity to occur.
Claims (1)
1, a kind of preparation method of ordered carbon nanotube array comprises the steps:
1) anodic oxidation aluminium formwork with the two ends perforate places nontoxic carbon containing polymers soln to flood, and is fully soaked into by the carbon containing polymers soln up to anodic oxidation aluminium formwork;
2) use carbon containing polymers soln solvent for use, distilled water successively, will clean up, in baking oven, dry then through the remaining carbon containing polymers soln in anodic oxidation aluminium formwork surface that step 1) is fully soaked into;
3) anodic oxidation aluminium formwork after will drying is placed in the High Temperature Furnaces Heating Apparatus, with vacuum pump High Temperature Furnaces Heating Apparatus is vacuumized subsequently, vacuum tightness reaches-0.09MPa and stable after, feed argon gas again to High Temperature Furnaces Heating Apparatus furnace pressure 0.1MPa, to displace the air in the High Temperature Furnaces Heating Apparatus burner hearth;
4) connect power supply, with the heat-up rate of 2～4 ℃/min the High Temperature Furnaces Heating Apparatus temperature is risen to 500 ℃～1000 ℃, and be incubated 1～5h under this temperature, powered-down cools to room temperature naturally subsequently, and whole process is led to argon shield, and pressure in the burner hearth remains 0.1MPa;
5) fully dissolve anodic oxidation aluminium formwork with concentration greater than 40% hydrofluoric acid aqueous solution after, the ordered carbon nanotube array that obtains is cleaned repeatedly with distilled water, till the pH value that cleans back distilled water is near 7.
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Cited By (12)
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| CN100473422C (en) * | 2006-12-31 | 2009-04-01 | 厦门大学 | Preparation method of nanometer ordered structure biomaterial membranous layer based on super hydro philic/hydro phobic characteristic template |
| CN101214947B (en) * | 2008-01-18 | 2010-06-09 | 中国科学技术大学 | Method for preparing carbon nano-tube by catalyzing and carbonizing polymer and /or asphalt |
| CN102263244A (en) * | 2011-06-29 | 2011-11-30 | 福州大学 | Method for preparing carbon confined-clad stannum (Sn)/magnesium oxide (MgO) nanowire array for lithium ion battery |
| CN102502578A (en) * | 2011-10-26 | 2012-06-20 | 上海交通大学 | Chemical vapor synthesis method for growing carbon nanotubes in mode of being attached to wall of pore channel of template |
| CN107253713A (en) * | 2017-07-05 | 2017-10-17 | 中国石油大学(北京) | A kind of length, caliber and the controllable CNT of wall thickness and preparation method thereof |
| CN110734053A (en) * | 2019-10-14 | 2020-01-31 | 深圳烯湾科技有限公司 | Method for producing carbon nanotube and carbon nanotube fiber |
| CN110980692A (en) * | 2019-11-26 | 2020-04-10 | 中国科学院合肥物质科学研究院 | Conical carbon nanotube array and preparation method thereof |
| CN112169845A (en) * | 2020-11-08 | 2021-01-05 | 赵伟 | Preparation method of composite carbon catalytic material |
| CN112169824A (en) * | 2020-11-08 | 2021-01-05 | 赵伟 | Co9S8Preparation method of/N-CCA composite electrode |
| CN112174112A (en) * | 2020-11-08 | 2021-01-05 | 赵伟 | Preparation method of nano rod-shaped carbon material |
| CN112279645A (en) * | 2020-11-08 | 2021-01-29 | 赵伟 | Preparation method of rod-shaped carbon anode material |
| CN114914458A (en) * | 2022-06-16 | 2022-08-16 | 中国科学技术大学 | Air electrode with highly ordered array structure and preparation method thereof |
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- 2006-04-17 CN CNB2006100426847A patent/CN100500557C/en not_active Expired - Fee Related
Cited By (19)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN100473422C (en) * | 2006-12-31 | 2009-04-01 | 厦门大学 | Preparation method of nanometer ordered structure biomaterial membranous layer based on super hydro philic/hydro phobic characteristic template |
| CN101214947B (en) * | 2008-01-18 | 2010-06-09 | 中国科学技术大学 | Method for preparing carbon nano-tube by catalyzing and carbonizing polymer and /or asphalt |
| CN102263244A (en) * | 2011-06-29 | 2011-11-30 | 福州大学 | Method for preparing carbon confined-clad stannum (Sn)/magnesium oxide (MgO) nanowire array for lithium ion battery |
| CN102263244B (en) * | 2011-06-29 | 2013-10-30 | 福州大学 | Method for preparing carbon confined-clad Sn/MgO nanowire array for lithium ion battery |
| CN102502578A (en) * | 2011-10-26 | 2012-06-20 | 上海交通大学 | Chemical vapor synthesis method for growing carbon nanotubes in mode of being attached to wall of pore channel of template |
| CN102502578B (en) * | 2011-10-26 | 2013-11-13 | 上海交通大学 | Chemical vapor synthesis method for growing carbon nanotubes in mode of being attached to wall of pore channel of template |
| CN107253713A (en) * | 2017-07-05 | 2017-10-17 | 中国石油大学(北京) | A kind of length, caliber and the controllable CNT of wall thickness and preparation method thereof |
| CN110734053A (en) * | 2019-10-14 | 2020-01-31 | 深圳烯湾科技有限公司 | Method for producing carbon nanotube and carbon nanotube fiber |
| CN110980692A (en) * | 2019-11-26 | 2020-04-10 | 中国科学院合肥物质科学研究院 | Conical carbon nanotube array and preparation method thereof |
| CN112169845A (en) * | 2020-11-08 | 2021-01-05 | 赵伟 | Preparation method of composite carbon catalytic material |
| CN112169824A (en) * | 2020-11-08 | 2021-01-05 | 赵伟 | Co9S8Preparation method of/N-CCA composite electrode |
| CN112174112A (en) * | 2020-11-08 | 2021-01-05 | 赵伟 | Preparation method of nano rod-shaped carbon material |
| CN112279645A (en) * | 2020-11-08 | 2021-01-29 | 赵伟 | Preparation method of rod-shaped carbon anode material |
| CN112279645B (en) * | 2020-11-08 | 2023-06-09 | 衢州市衢发瑞新能源材料有限公司 | Preparation method of carbon electrode material |
| CN112169824B (en) * | 2020-11-08 | 2023-06-23 | 杭州长氢新材料有限公司 | Preparation method of composite electrode |
| CN112174112B (en) * | 2020-11-08 | 2023-11-03 | 赵伟 | Preparation method of nano rod-shaped carbon material |
| CN112169845B (en) * | 2020-11-08 | 2023-12-26 | 赵伟 | Preparation method of catalytic material |
| CN114914458A (en) * | 2022-06-16 | 2022-08-16 | 中国科学技术大学 | Air electrode with highly ordered array structure and preparation method thereof |
| CN114914458B (en) * | 2022-06-16 | 2024-01-05 | 中国科学技术大学 | Air electrode with highly ordered array structure and preparation method thereof |
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