CN102020266A - Method for preparing and purifying massive single-wall carbon nanotubes - Google Patents
Method for preparing and purifying massive single-wall carbon nanotubes Download PDFInfo
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- CN102020266A CN102020266A CN 201010613605 CN201010613605A CN102020266A CN 102020266 A CN102020266 A CN 102020266A CN 201010613605 CN201010613605 CN 201010613605 CN 201010613605 A CN201010613605 A CN 201010613605A CN 102020266 A CN102020266 A CN 102020266A
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Abstract
The invention relates to a method for preparing and purifying massive single-wall carbon nanotubes, belonging to the technical field of carbon nanotube preparation. The method provided by the invention mainly comprises the following steps: doping graphitized carbon powder with a nickel catalyst and a yttrium catalyst, wherein the atom molar ratio of carbon to nickel to yttrium is 0.95:0.04:0.01; evenly mixing the mixture, then pressing the mixture into a cylindrical carbon electrode bar, processing the cylindrical carbon electrode bar at high temperature to serve as an anode, adopting a pure carbon electrode bar as a cathode, performing direct current arc discharge under a helium atmosphere to evaporate the anode, and obtaining high-crystallinity single-wall carbon nanotubes containing the nickel catalyst and the yttrium catalyst in a reaction cavity; and then, purifying to remove amorphous carbon, carbon nanoparticles and impurities of the nickel catalyst and yttrium catalyst formed in the preparation process. The purifying method comprises the following two steps: firstly, oxidizing the obtained high-crystallinity single-wall carbon nanotubes for 1 hour in the air at the temperature of 420 DEG C, performing ultrasonic processing for 2 hours by concentrated nitric acid, and filtering the mixture by distilled water until the mixture is neutral; and drying to obtain the purified single-wall carbon nanotube powder.
Description
Technical field
The present invention relates to a kind of a large amount of method for preparing Single Walled Carbon Nanotube and purification thereof, belong to made of carbon nanotubes Technology field.
Background technology
In recent years, carbon nanotube particularly the less carbon nanotube of diameter be subjected to people's attention.They can be used to prepare functional material, for example can be with very occlusion material, field-emitter display annex, electrode materials or the thermally conductive material of the integrated molecular element of high-density, occlusion such as all gases such as hydrogen.This wherein Single Walled Carbon Nanotube because its extensive studies space becomes the focus of research gradually.
The method of manufacture order wall carbon nano tube mainly comprises arc discharge method, CVD (chemical Vapor deposition process) method and laser evaporation method.Is a kind of important method for preparing carbon nanotube with metallic particles as the Preparation of Catalyst carbon nanotube, and catalyzer mainly contains composite catalyzing of iron, nickel-yttrium and iron and heavy metal or the like.But, use the charcoal granule foreign that all comprises in the crude product of any production in these methods in a large number such as amorphous carbon etc.Therefore, the carbon nanotube of these carbon nano-particle impurity must being separated from carbon nanotube and purified.The purification of making the carbon nanotube of Preparation of Catalyst with iron can realize, and the record of existing document; But utilize the Single Walled Carbon Nanotube output of iron catalyst preparation lower.The output of making the Preparation of Catalyst Single Walled Carbon Nanotube with nickel-yttrium is higher, and relevant report has abroad been arranged; But the single wall carbon nano pipe purity of preparation is lower, and does not also have method of purification preferably at present.And the own purity of Single Walled Carbon Nanotube that the method for utilizing us prepares is just very high, and the two step methods of purification of utilizing us to develop can realize a large amount of preparations and the purification of Single Walled Carbon Nanotube.
Summary of the invention
The purpose of this invention is to provide and a kind ofly can prepare the method for Single Walled Carbon Nanotube and purification thereof in a large number.
The invention provides a kind of a large amount of method for preparing Single Walled Carbon Nanotube and purification thereof, it is characterized in that having following process and step:
A. preparation contains the electrode bar of carbon-nickel-yttrium: but greying carbon dust, nickel catalyzator and yttrium catalyzer are pressed atomic molar than 0.95:0.04:0.01 weigh batching, be put in the ball mill ball milling after mixing 8～24 hours, and then mixed powder be pressed into the cylindrical electrode rod that diameter is 6～10mm waiting under the static pressure; Then under 800～1200 ℃ and 1400～2000 ℃ of high temperature respectively the counter electrode rod heat-treat;
B. prepare Single Walled Carbon Nanotube in a large number: with above-mentioned electrode bar after heat treatment as anode, with the pure carbon electrode bar as negative electrode: in He gas atmosphere, air pressure is under 200～760Torr condition, utilize system for manufacturing carbon nm tube, use the direct current arc electric discharge, growth makes the Single Walled Carbon Nanotube that contains nickel and yttrium catalyzer; The electric current that is applied is 50～200A;
C. Single Walled Carbon Nanotube is purified: the above-mentioned Single Walled Carbon Nanotube that contains nickel and yttrium catalyzer for preparing oxide treatment 1 hour under 420 ℃ of temperature condition, treat to put it into again after it is lowered the temperature naturally in the concentrated nitric acid solution and handled 2 hours, to remove carbon nano-particle and nickel and yttrium catalyst impurities; Use the distilled water suction filtration until neutrality solution then; Single Walled Carbon Nanotube after dry back obtains to purify.
Advantage of the present invention and characteristics: the inventive method can prepare the higher Single Walled Carbon Nanotube of purity in a large number, and the preparation carbon nanotube can purify in a large number, purity can reach 90%.Its caliber distribution uniform of the prepared Single Walled Carbon Nanotube of the present invention; The high crystalline Single Walled Carbon Nanotube that the inventive method makes has wide application prospect at numerous areas such as hydrogenation dehydrogenation, hydrogeneration processes, microwave absorbing, fuel cells.The inventive method technology is simple, and is easy to operate.
Description of drawings
Fig. 1 is the stereoscan photograph figure of Single Walled Carbon Nanotube before that purifies in the embodiment of the invention;
Fig. 2 is the stereoscan photograph figure of Single Walled Carbon Nanotube afterwards that purifies in the embodiment of the invention;
Fig. 3 is the transmission electron microscope photo figure of Single Walled Carbon Nanotube afterwards that purifies in the embodiment of the invention;
Fig. 4 be purify in the embodiment of the invention before and the Raman spectrogram of Single Walled Carbon Nanotube afterwards;
Fig. 5 is the composition analysis result's of Single Walled Carbon Nanotube the energy spectrogram (EDS collection of illustrative plates) afterwards of purifying in the embodiment of the invention.
Embodiment
After now specific embodiments of the invention being described in.
Embodiment:But greying carbon dust, nickel powder and yttrium oxide powder are respectively 1,2.1 and 10.1 grams (atomic molar than for 0.95:0.04:0.01) mix the back with ball mill ball milling 24 hours, utilization waits static pressure 120Mpa to be pressed into the cylindrical electrode rod of the about 10mm of diameter, this electrode bar is carried out twice thermal treatment of 1000 and 1800 degree respectively under nitrogen atmosphere, soaking time all is 2 hours.With the electrode bar after the thermal treatment as anode, the pure carbon electrode bar is a negative electrode, interelectrode distance is that 2mm is in He atmosphere, air pressure is in the system for manufacturing carbon nm tube under the 500 Torr conditions, the Single Walled Carbon Nanotube of and yttrium catalyzer nickeliferous with the direct current arc discharge growth, be 30 minutes discharge time, and it is 100A that institute adds electric current.Is 420 degree oxide treatment 1 hour with the Single Walled Carbon Nanotube of preparation in temperature, naturally after the cooling with supersound process in its adding concentrated nitric acid solution 2 hours, to remove carbon nano-particle and nickel and yttrium catalyst impurities; Use the distilled water suction filtration until being neutral solution, dry, grinding obtains Single Walled Carbon Nanotube (SWCNTs) powder after the purification.
To making the instrument detecting of product
The embodiment products therefrom is carried out every instrument detecting, and measured result is referring to the Fig. 1 to Fig. 5 in the accompanying drawing.
Fig. 1 is the stereoscan photograph figure of Single Walled Carbon Nanotube before that purifies in the embodiment of the invention, and impurity is more as can be seen.
Fig. 2 be purify in the embodiment of the invention after the stereoscan photograph figure of Single Walled Carbon Nanotube, most impurity is processed have been fallen.
Fig. 3 is the transmission electron microscope photo figure of Single Walled Carbon Nanotube afterwards that purifies in the embodiment of the invention.
Fig. 4 be purify in the embodiment of the invention before and the Raman test collection of illustrative plates of Single Walled Carbon Nanotube afterwards, the diameter of Single Walled Carbon Nanotube has very high crystallinity less than 2 nanometers.
Fig. 5 is the composition analysis result's of Single Walled Carbon Nanotube the energy spectrogram (EDS collection of illustrative plates) afterwards of purifying in the embodiment of the invention 1, and extremely strong as can be observed from Figure carbon peak illustrates that the purity of carbon pipe is very high.
Claims (1)
1. one kind prepares the method for Single Walled Carbon Nanotube and purification thereof in a large number, it is characterized in that having following process and step:
A. preparation contains the electrode bar of carbon-nickel-yttrium: but greying carbon dust, nickel catalyzator and yttrium catalyzer are pressed atomic molar than 0.95:0.04:0.01 weigh batching, be put in the ball mill ball milling after mixing 8～24 hours, mixed powder is pressed into the cylindrical electrode rod that diameter is 6～10mm waiting under the static pressure then; Then under 800～1200 ℃ and 1400～2000 ℃ of high temperature respectively the counter electrode rod heat-treat;
B. prepare Single Walled Carbon Nanotube in a large number: with above-mentioned electrode bar after heat treatment as anode, with the pure carbon electrode bar as negative electrode: in He gas atmosphere, air pressure is under 200～760Torr condition, utilize system for manufacturing carbon nm tube, use the direct current arc electric discharge, growth makes the Single Walled Carbon Nanotube that contains nickel and yttrium catalyzer; The electric current that is applied is 50～200A;
C. Single Walled Carbon Nanotube is purified: the above-mentioned Single Walled Carbon Nanotube that contains nickel and yttrium for preparing oxide treatment 1 hour under 420 ℃ of temperature condition, treat to put it into again after it is lowered the temperature naturally in the concentrated nitric acid solution and handled 2 hours, to remove carbon nano-particle impurity; Use the distilled water suction filtration until neutrality solution then; Single Walled Carbon Nanotube after obtaining after the drying purifying.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104555981A (en) * | 2014-12-23 | 2015-04-29 | 昆明理工大学 | Method for selectively oxidizing and purifying carbon nano tube by utilizing microwave |
| TWI503272B (en) * | 2012-03-21 | 2015-10-11 | Hon Hai Prec Ind Co Ltd | Preparation of semiconducting single-walled carbon nanotube |
| CN108190860A (en) * | 2018-01-31 | 2018-06-22 | 南京大学 | A kind of method that microwave prepares single-walled carbon nanotube |
| CN108220997A (en) * | 2018-01-31 | 2018-06-29 | 中国科学院福建物质结构研究所 | A kind of carbon containing nickel coat single-walled carbon nanotube composite material and its preparation method and application |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1522955A (en) * | 2003-09-12 | 2004-08-25 | 大连理工大学 | Method for preparing single wall nanometer carbon tube using mesophase asphalt as raw material |
| CN1544319A (en) * | 2003-11-26 | 2004-11-10 | 大连理工大学 | Carbon nanometer tube arc discharge preparation method under vacuum condition |
-
2010
- 2010-12-30 CN CN 201010613605 patent/CN102020266A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1522955A (en) * | 2003-09-12 | 2004-08-25 | 大连理工大学 | Method for preparing single wall nanometer carbon tube using mesophase asphalt as raw material |
| CN1544319A (en) * | 2003-11-26 | 2004-11-10 | 大连理工大学 | Carbon nanometer tube arc discharge preparation method under vacuum condition |
Non-Patent Citations (2)
| Title |
|---|
| 《Chemical Physics Letters》 20000623 Yoshinori Ando,et.al Mass production of single-wall carbon nanotubes by the arc plasma jet method 580-585 1 第323卷, 2 * |
| 《纳米科技》 20050228 赵廷凯等 单壁碳纳米管的提纯 27-30 1 , 第1期 2 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI503272B (en) * | 2012-03-21 | 2015-10-11 | Hon Hai Prec Ind Co Ltd | Preparation of semiconducting single-walled carbon nanotube |
| CN104555981A (en) * | 2014-12-23 | 2015-04-29 | 昆明理工大学 | Method for selectively oxidizing and purifying carbon nano tube by utilizing microwave |
| CN108190860A (en) * | 2018-01-31 | 2018-06-22 | 南京大学 | A kind of method that microwave prepares single-walled carbon nanotube |
| CN108220997A (en) * | 2018-01-31 | 2018-06-29 | 中国科学院福建物质结构研究所 | A kind of carbon containing nickel coat single-walled carbon nanotube composite material and its preparation method and application |
| CN108220997B (en) * | 2018-01-31 | 2019-06-18 | 中国科学院福建物质结构研究所 | A kind of carbon containing nickel coat single-walled carbon nanotube composite material and preparation method and purposes |
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Application publication date: 20110420 |