CN101164874B - Method for purifying multi-wall carbon nano pipe - Google Patents
Method for purifying multi-wall carbon nano pipe Download PDFInfo
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- CN101164874B CN101164874B CN2007101336325A CN200710133632A CN101164874B CN 101164874 B CN101164874 B CN 101164874B CN 2007101336325 A CN2007101336325 A CN 2007101336325A CN 200710133632 A CN200710133632 A CN 200710133632A CN 101164874 B CN101164874 B CN 101164874B
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Abstract
This invention discloses a method purifying multiple-wall carbon nanometer tubes. It is characterized by first, removing silicon dioxide carrier by using fluorhydric acid; then removing carbon-contaminated impurities by using high temperature oxidation; and finally removing transition metal catalyst particles by using strong acid to obtain high purity carbon nanometer tubes. The advantages of this invention are: simple operation, high efficiency for purification, less damage to carbon nanometer tube products during treatment.
Description
Technical field
The present invention relates to a kind of method of purifying carbon nano-tube, relate in particular to the method for the thick purifying products of carbon nanotube that contains the transition-metal catalyst particle that coated by carbon-coating and silica supports.
Background technology
Since Japanese scientist Iijiam in 1991 finds carbon nanotube (CNTs), owing to it has the very big concern that peculiar physics, chemical property and good application prospects have caused the various countries scientific and technical personnel.The scientists prediction, carbon nanotube will become the most promising monodimension nanometer material of 21 century.Carbon nanotube is the cylindrical structural of the sexangle lattice that forms based on carbon atom, and what have single layer structure is called Single Walled Carbon Nanotube (SWNT), and what have multilayered structure is called multi-walled carbon nano-tubes (MWNTS).For extremely, the preparation technology of carbon nanotube has obtained broad research up till now.Now existing multiple preparation method: arc discharge method, laser ablation, electrolysis, cryogenic solid cracking, hydrocarbon oxidation catalyst decomposition or chemical gas sedimentation etc.Wherein, chemical Vapor deposition process is present a kind of comparatively widely method for preparing carbon nanotube.Generally select for use Fe, Co, Ni and alloy thereof to make catalyzer, clay, silicon-dioxide, diatomite, aluminum oxide and magnesium oxide etc. are made carrier, acetylene, propylene and methane etc. are made carbon source, hydrogen, nitrogen, helium, argon gas or ammonia are made carrier gas, in 530-1130 ℃ of scope, the free carbon ion that the hydrocarbon polymer cracking produces can generate single wall or multi-walled carbon nano-tubes under catalyst action.
Adopt in the product of catalytic pyrolysis method preparation except that containing carbon nanotube, also contain the carbon nano-particle of Fullerenes, graphite particulate, decolorizing carbon and other form and react used impurity such as catalysed particulate, the existence of these impurities influences the performance and the application of carbon nanotube, therefore will carry out purification process to carbon nanotube.At present, proposed the purification process of multiple carbon nanotube, these methods can be divided into physics method and chemical method.Physical purification is to utilize differences of physical properties such as the size of carbon nanotube and impurity, shape, reaches the purification purpose by means of mechanical means such as ultra-sonic dispersion, millipore filtration, centrifugation, spatial exclusion chromatography are separated from each other it.Chemical purification is according to the difference between the chemical property of the carbon of carbon nanotube and other form, and the character of catalyst particle self, react with it with chemical reagent such as gas, acid, salt, generate the material of volatile or solubility, reach and separate the effect of purifying.Wherein mainly contain methods such as vapour phase oxidation process, liquid phase oxidation, electrochemical oxidation process, intercalation oxidation style.The each have their own relative merits of these methods, but up to the present, the transition-metal catalyst particle and the silica supports that are coated by carbon-coating in the carbon nanotube sample that makes with chemical deposition also do not have a kind of very effective purification process, and it is removed totally fully.
Silicon-dioxide is the catalyst support material that is in daily use, and has the purity height, and pore distribution is even, specific surface is big, and characteristics such as strong adsorptivity are when preparing carbon nanotube with chemical deposition, be commonly used for the carrier of catalyzer, but when purified product, have the difficult shortcoming of removing.The document of the relevant purification of Multi-wall Carbon Nanotubes of having published does not all relate to the method for removing impurity with high temperature oxidation and acid treatment combination, not about obtain the purity data of high pure nano-carbon tube by processing yet.
Summary of the invention
The present invention is for avoiding above-mentioned existing in prior technology weak point, a kind of purification process of effective multi-walled carbon nano-tubes is provided, at remaining in transition-metal catalyst particle and the silica supports that is coated by carbon-coating in the thick product of carbon nanotube, utilize high temperature oxidation and the strong acid treatment purifying carbon nano-tube that combines, thereby obtain high pure nano-carbon tube.
The technical scheme that technical solution problem of the present invention is adopted is:
The present invention is directed to and remain in transition-metal catalyst particle and the silica supports that is coated by carbon-coating in the thick product of carbon nanotube, at first utilize the silica supports in the hydrofluoric acid removal sample, utilize the method for high temperature oxidation to remove carbonaceous material in the sample then, utilize strong acid to remove the transition-metal catalyst particle again, obtain high pure nano-carbon tube.
The characteristics of the inventive method also are to carry out as follows:
The carbon nanotube crude samples that 1, will contain transition-metal catalyst particle and silica support, dissolving in weight percent concentration is in 10～48% hydrofluoric acid solutions, fully stirs, normal temperature reacts 12～24 hours down until the silica support of removing fully in the sample;
2, will heat under oxidizing gas through the sample that step 1 is removed silica support, temperature is 300～500 ℃, reacts 1～4 hour, re-uses strong acid and is dipped to colourlessly, removes the metal oxide that produces in oxidising process; Repeat this step two to three times;
3, the sample after step 2 is handled is washed till neutrality with deionized water, 50～300 ℃ of oven dry down, obtains purified carbon nanotube sample.
The characteristics of the inventive method also are:
Described strong acid is hydrochloric acid, nitric acid or sulfuric acid;
Described oxidizing gas is an air or oxygen;
Described transition-metal catalyst is one or more among Fe, Co, Ni or the Mo.
Compared with the prior art, beneficial effect of the present invention is embodied in:
1, the present invention utilizes the method for oxidation and strong acid treatment, can effectively remove the transition metal (Fe, Co, Ni, Mo) catalyzer and the silica support that mix in product, the transition-metal catalyst that is coated by carbon-coating particularly is for purifying carbon nano-tube provides a kind of new way.
2, the inventive method is easy and simple to handle, the purification efficiency height, and treating processes is less to the carbon nanotube damage.
Description of drawings
Fig. 1 is the TEM photo of the multi-walled carbon nano-tubes before and after the purifying, before a is purifying among the figure, after b is purifying.
Fig. 2 is the TGA graphic representation of the multi-walled carbon nano-tubes sample before and after the purifying, and a is a crude samples among the figure, and b is a sample behind the purifying.
Fig. 3 is the EDS figure of the multi-walled carbon nano-tubes sample before and after the purifying, and a is a crude samples among the figure, and b is a sample behind the purifying.
Below pass through embodiment, and in conjunction with the accompanying drawings the present invention is further described.
Embodiment
Embodiment 1:
The carbon nanotube crude samples adopts by loading type catalyst Fe/SiO
2The multi-walled carbon nano-tubes that catalytic pyrolysis acetylene makes, operating process is as follows:
The first step: it is dissolved in weight percent concentration is in 10% the hydrofluoric acid solution, fully stirs, and silica support is removed in normal temperature reaction 24 hours down;
Second step: will remove sample heated oxide reaction under air atmosphere of silica support, temperature is set at 300 ℃, reacts 4 hours; Again with weight percent concentration be 98% nitric acid dousing to colourless, remove the metal oxide that in oxidising process, produces.
The 3rd step: repeat above-mentioned second step, i.e. reheat 4 hours in oxidizing gas is that 98% nitric acid dousing is extremely colourless with weight percent concentration again.Can remove coated metal particulate graphite particulate and decolorizing carbon etc. fully through twice oxidising process, make metal oxide can be fully and acid react.
The 4th step: step 3 gained sample is washed till neutrality with deionized water, under 100 ℃, dries 4 hours, obtains purified carbon nanotube sample.
The EDAX results of Fig. 3 shows in the crude samples before the purifying also contain a large amount of iron, silicon, oxygen, and the sample behind the purifying only to contain micro-iron except carbon nanotube except carbon component.
From the electromicroscopic photograph of Fig. 1 (a), can see the metallics that is covered by carbon nanotube inside and carbon-coating inside.This sample is carried out purification process; Fig. 1 (b) is for handling the electromicroscopic photograph of back sample, and as can be seen from the figure foreign matter content is less.
Sample before and after the purification process is carried out thermogravimetric analysis, and the result as shown in Figure 2.Contain 50% impurity in the sample before handling, the content of handling rear impurity only is 3%.
Embodiment 2:
Different is with embodiment 1, in the present embodiment, in step 2, the strong acid that uses is that weight percentage is 37% hydrochloric acid, oxidizing temperature is 500 ℃, and the time is 1 hour, and used carbon nanometer tube material, operation steps and other requirement are all identical with embodiment 1.Through behind the purifying, analyze the content 3.2% of impurity.
Embodiment 3:
Different is with embodiment 1, and in the present embodiment, in step 1, the operating weight percentage composition is 48% hydrofluoric acid, normal temperature reaction 1 hour down; In step 2, the strong acid of use is that weight percentage is 70% sulfuric acid, and oxidizing temperature is 500 ℃, and the time is 1 hour, and used carbon nanometer tube material, operation steps and other requirement are all identical with embodiment 1.Through behind the purifying, analyze the content 2.3% of impurity.
Embodiment 4:
The carbon nanotube crude samples is to make multi-walled carbon nano-tubes by loaded catalyst Ni/SiO2 catalytic pyrolysis ethene.Purification process is with embodiment 1, and through behind the purifying, the thermogravimetric analysis result proves that the non-carbon impurity in the sample reduces to 5% after the processing by 30% before handling.
Embodiment 5:
The carbon nanotube crude samples is to make multi-walled carbon nano-tubes by loaded catalyst Co/SiO2 catalytic pyrolysis ethene.Purification process is with embodiment 1, and through behind the purifying, the thermogravimetric analysis result proves that the impurity in the sample reduces to 6% after the processing by 40% before handling.
Claims (4)
1. the purification process of multi-walled carbon nano-tubes, it is characterized in that the transition-metal catalyst particle and the silica supports that are coated by carbon-coating in the thick product of carbon nanotube at remaining in, at first utilize the silica supports in the hydrofluoric acid removal sample, utilize the method for high temperature oxidation to remove carbonaceous material in the sample then, utilize strong acid to remove the transition-metal catalyst particle again, obtain high pure nano-carbon tube; Described purification process is to carry out as follows:
A, will contain the carbon nanotube crude samples of transition-metal catalyst particle and silica supports, dissolving in weight percent concentration is in 10～48% hydrofluoric acid solutions, fully stir, normal temperature reacts 12～24 hours down until the silica supports of removing fully in the sample;
B, will heat under oxidizing gas through the sample that step a removes silica supports, temperature is 300～500C, reacts 1～4 hour, re-uses strong acid and is dipped to colourlessly, removes the metal oxide that produces in oxidising process; Repeat this step two to three times;
C, the sample after step b handles are washed till neutrality with deionized water, 50～300 ℃ of oven dry down, obtain purified carbon nanotube sample.
2. the purification process of multi-walled carbon nano-tubes according to claim 1 is characterized in that described strong acid is hydrochloric acid, nitric acid or sulfuric acid.
3. the purification process of multi-walled carbon nano-tubes according to claim 1 is characterized in that described oxidizing gas is an air or oxygen.
4. the purification process of multi-walled carbon nano-tubes according to claim 1 is characterized in that described transition-metal catalyst is one or more among Fe, Co, Ni or the Mo.
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| CN101618868B (en) * | 2008-07-03 | 2013-03-13 | 中国科学院成都有机化学有限公司 | Method for removing amorphous carbon in carbon nanotubes |
| KR101147259B1 (en) * | 2008-09-30 | 2012-05-21 | 한화케미칼 주식회사 | Continuous method and apparatus of purifying Carbon Nanotube |
| CN101746746A (en) * | 2008-12-19 | 2010-06-23 | 索尼株式会社 | Method for preparing and purifying carbon nano tubes, carbon nano tubes and carbon nano tube elements |
| WO2013161317A1 (en) * | 2012-04-27 | 2013-10-31 | 昭和電工株式会社 | Method for purifying multilayered carbon nanotubes |
| CN102745675A (en) * | 2012-06-27 | 2012-10-24 | 合肥工业大学 | Preparation method of spinel-type magnetic MFe2O4/graphene composite material |
| CN106032271A (en) * | 2015-03-11 | 2016-10-19 | 国家电网公司 | Preparation method of carbon nanotube powder with low resistivity |
| CN107473204B (en) * | 2017-09-12 | 2023-06-20 | 焦作集越纳米材料技术有限公司 | Device and method for purifying carbon nano tube powder |
| CN109092245B (en) * | 2018-08-24 | 2020-12-22 | 华南理工大学 | Diatomite-loaded carbon nanotube adsorbent and preparation method thereof |
| CN109650379B (en) * | 2019-02-19 | 2020-08-18 | 厦门大学 | Single-walled carbon nanotube gradient oxidation purification method |
| CN112299394A (en) * | 2019-07-31 | 2021-02-02 | 东华理工大学 | High-performance carbon nano tube and preparation method thereof |
| CN110422838A (en) * | 2019-09-11 | 2019-11-08 | 广州方中化工有限公司 | A kind of preparation of carbon nanotube and separation method |
| CN112875680B (en) * | 2021-01-21 | 2022-10-14 | 电子科技大学 | Preparation method of flaky Fe-based alloy catalytic growth carbon nanotube array |
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| CN1424250A (en) * | 2002-12-24 | 2003-06-18 | 西安交通大学 | Process for growing and purifying carbon nano tube by thermolysis with resistor furnace with single temperature zone |
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| CN1424250A (en) * | 2002-12-24 | 2003-06-18 | 西安交通大学 | Process for growing and purifying carbon nano tube by thermolysis with resistor furnace with single temperature zone |
Non-Patent Citations (3)
| Title |
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| JP特开2007-197314A 2007.08.09 |
| 宋旭春等.MoS2/C复合纳米管的合成.高等学校化学学报26 4.2005,26(4),617-619. |
| 宋旭春等.MoS2/C复合纳米管的合成.高等学校化学学报26 4.2005,26(4),617-619. * |
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