CN103058164A - Preparation method of single-walled carbon nanotube - Google Patents
Preparation method of single-walled carbon nanotube Download PDFInfo
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- CN103058164A CN103058164A CN2011103197130A CN201110319713A CN103058164A CN 103058164 A CN103058164 A CN 103058164A CN 2011103197130 A CN2011103197130 A CN 2011103197130A CN 201110319713 A CN201110319713 A CN 201110319713A CN 103058164 A CN103058164 A CN 103058164A
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- walled carbon
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Abstract
The invention provides a preparation method of a single-walled carbon nanotube. The method comprises steps of: obtaining a cobalt-copper binary catalytic system; placing the cobalt-copper binary catalytic system in a vacuum tube furnace; introducing a carbon source gas; and growing the single-walled carbon nanotube under conditions of a certain temperature and reaction time. The method can synthesize single-walled carbon system with different diameter distribution, so as to meet the needs of different fields. In addition, the raw materials used in the method are easily available in industrial raw material market, and the whole process is simple, rapid, stable, reliable and well reproducible; therefore, the method is suitable for mass production to synthesize single-walled carbon nanotubes with different diameters and high purity.
Description
Technical field
The present invention relates to a kind of preparation method of Single Walled Carbon Nanotube, relate in particular to a kind of preparation method that can in preparation process, regulate diameter of single-wall carbon nano tube.
Background technology
Carbon nanotube can be divided into Single Walled Carbon Nanotube (SWNT), double-walled carbon nano-tube (DWNT) and multi-walled carbon nano-tubes (MWNT) according to the number of plies of the carbon atom that forms tube wall.Wherein, Single Walled Carbon Nanotube can be regarded as by the mono-layer graphite layer around central shaft by the curling seamless open tube that forms of certain helix angle.Because its unique structure and premium properties, have potential and using value widely in different field such as matrix material, new forms of energy battery electrode material, opto-electronic device, heat transfer element and biology, chemical sensors.
The preparation method that SWCNT is comparatively ripe at present mainly comprises: laser evaporation method, arc catalyzing method and chemical Vapor deposition process (CVD).Although front two kinds of methods can be prepared high quality SWCNT, these two kinds of methods also are unwell to the amplification mass, therefore have the shortcoming that is difficult to produce a large amount of Single Walled Carbon Nanotube, have seriously limited their Industry Promotion and development.And for the CVD method, because its technique is relatively simple, cost is low, is easy to amplify large-scale production, therefore more and more comes into one's own in Single Walled Carbon Nanotube industrialization production process and promotes.When adopting CVD method single-wall carbon nanotube synthesizing, catalyzer commonly used has: iron, cobalt, nickel, yttrium etc., support of the catalyst commonly used has SiO
2, Al
2O
3, MgO etc.Wherein, low owing to cost as the MgO of support of the catalyst, and in the aftertreatment purge process, remove easily effective support of the catalyst when becoming synthetic SWCNT.
As everyone knows, the optics of SWCNT, electrical properties depend on that their diameter and chirality distribute.According to diameter and chirality distribute different, SWCNT shows as metallicity and semiconductive.Therefore, in the preparation process of SWCNT, can realize by the diameter Distribution of regulating SWCNT regulation and control to the SWCNT performance.
In recent years, many investigators were devoted to the diameter controllable growth of Single Walled Carbon Nanotube.Zhang Yafei etc. have mentioned a kind of controlled growth method of diameter of Single Walled Carbon Nanotube in Chinese patent 201010234322.4 " preparation method of diameter-controllable single-walled carbon nanotube "; but mainly be for arc catalyzing method; this kind method cost is high, is not easy to large-scale production.The people such as Li Nan are at document " Diameter Tuning of Single-Walled Carbon Nanotubes with Reaction Temperature Using a Co Monometallic Catalyst " (J.Phys.
Chem.C 2009 113:10070-10078) control the diameter of the Single Walled Carbon Nanotube that CVD (Chemical Vapor Deposition) method obtains in by the conditioned reaction temperature, more special support of the catalyst-ordered mesoporous material MCM-41 but this method adopts, its material cost is more expensive, and is difficult to remove in the aftertreatment purge process.
In view of this, be necessary that preparation in the prior art is regulated the existing defective of its diameter during Single Walled Carbon Nanotube to be improved, to address the above problem.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of Single Walled Carbon Nanotube, the method can be regulated the diameter of the Single Walled Carbon Nanotube of preparation effectively, has realized the controllability of diameter of single-wall carbon nano tube, to satisfy the needs of different field.
For achieving the above object, the preparation method of a kind of Single Walled Carbon Nanotube of the present invention, the method comprises the steps: to obtain cobalt-copper binary catalyst system, cobalt-copper binary catalyst system is placed vacuum tube furnace, pass into carbon-source gas, under certain temperature of reaction and reaction times condition, grow Single Walled Carbon Nanotube.
As a further improvement on the present invention, described cobalt-obtaining of copper binary catalyst system comprises the steps:
A., the salt compounds that contains cobalt metal element that mixes with the arbitrary proportion mixture solution with the salt compounds composition of copper-containing metal element is provided;
B. in described mixture solution, add support of the catalyst magnesium-containing compound and specific solvent, fully stir;
C. the solution oven dry that step b is obtained, grind into powder is to obtain cobalt-copper binary catalyst system.
As a further improvement on the present invention, described magnesium-containing compound is selected from magnesium oxide or magnesium hydroxide or magnesiumcarbonate or magnesium basic carbonate or their combination; Described solvent is selected from water or ethanol.
As a further improvement on the present invention, the method also comprises: prepare after the Single Walled Carbon Nanotube powder, it is carried out the purification process of pickling.
As a further improvement on the present invention, described carbon-source gas is methane.
As a further improvement on the present invention, the carrier gas of described carbon-source gas is argon gas.
As a further improvement on the present invention, the gas flow scope of described argon gas is: 0 ~ 3000ml/h.
As a further improvement on the present invention, the gas flow scope of described carbon-source gas is: 0 ~ 1000ml/h.
As a further improvement on the present invention, described range of reaction temperature is 600 ℃ ~ 1000 ℃.
As a further improvement on the present invention, described reaction time range is 10min ~ 120min.
Compared with prior art, the invention has the beneficial effects as follows:
1. adopt cobalt, copper binary catalyst system, by the atom mass rate of cobalt, copper in the change system, can synthesize the Single Walled Carbon Nanotube that different diameter distributes, thereby realize the diameter controllable adjustment of Single Walled Carbon Nanotube;
2. the magnesium oxide as carrier adopts the acid of common concentration just can get rid of in the aftertreatment purge process, and does not destroy the original structure of Single Walled Carbon Nanotube, easily obtains high-purity Single Walled Carbon Nanotube.In addition, not only employed other various raw materials very easily acquisition in the industrial raw materials selling market in present method, and easy quick, reliable and stable, the good reproducibility of whole technological process, therefore this method is suitable for large-scale batch production, synthesizes the Single Walled Carbon Nanotube of high purity, different diameter.
Description of drawings
Fig. 1 is preparation method's schema of the embodiment of the invention;
Fig. 2 is transmission electron microscope (TEM) photo of the prepared Single Walled Carbon Nanotube of the embodiment of the invention one;
Fig. 3 is the Raman spectrogram of the prepared Single Walled Carbon Nanotube of the embodiment of the invention one;
Fig. 4 is the Raman spectrogram of the prepared Single Walled Carbon Nanotube of the embodiment of the invention two;
Fig. 5 is the Raman spectrogram of the prepared Single Walled Carbon Nanotube of the embodiment of the invention three.
Embodiment
Below in conjunction with embodiment the present invention is described in detail; but these embodiments do not limit the present invention, and equivalent transformation or equivalent substitution on the reaction conditions that those of ordinary skills do according to these embodiments, reactant or the raw material consumption all are included in protection scope of the present invention.
As shown in Figure 1, in the present embodiment, cobalt-copper binary catalyst system obtains by the following method:
A., the salt compounds that contains cobalt metal element that mixes with the arbitrary proportion mixture solution with the salt compounds composition of copper-containing metal element is provided, the salt compounds that wherein contains cobalt metal element is selected from Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES or cobaltous acetate, and the salt compounds of copper-containing metal element is selected from cupric nitrate or venus crystals etc.;
B. add magnesium-containing compound and specific solvent in described mixture solution, solvent is selected from water or ethanol etc., fully stirs;
C. the solution oven dry that step b is obtained, and grind into powder are to obtain cobalt-copper binary catalyst system.
Cobalt take magnesium-containing compound as carrier-copper binary catalyst system is placed vacuum tube furnace, and passing into gas flow is the methane carbon-source gas of 0 ~ 1000ml/h, and wherein, the methane carbon-source gas is take argon gas as carrier gas, and the gas flow of argon gas is 0 ~ 3000ml/h.
Under the reaction times condition of 600 ℃ ~ 1000 ℃ temperature of reaction and 10min ~ 120min, grow the Single Walled Carbon Nanotube of black by chemical Vapor deposition process (CVD).
What play katalysis in cobalt-copper binary catalyst system is the oxide compound of cobalt copper, and the oxide compound of cobalt copper is adsorbed on the support of the catalyst.In the present embodiment, support of the catalyst is magnesium-containing compound, is selected from magnesium oxide, perhaps can obtain magnesian material by thermal degradation, such as magnesium hydroxide, magnesiumcarbonate, magnesium basic carbonate etc.Support of the catalyst can also be the combination of above-mentioned substance.
The Single Walled Carbon Nanotube of preparing often contains catalyzer and support of the catalyst, therefore, needs with acid it to be cleaned to reach the purpose of purifying after reaction finishes.The acid of common concentration can be satisfied the requirement of pickling, such as the hydrochloric acid of 1mol/L, nitric acid etc.Simultaneously, the acid treatment process can not destroyed the original structure of Single Walled Carbon Nanotube, easily obtains high-purity Single Walled Carbon Nanotube.
At last, by transmission electron microscope (TEM) and Raman spectrum analysis method the Single Walled Carbon Nanotube for preparing is characterized.
The present invention is described further below in conjunction with several concrete embodiments.
Embodiment one:
Preparation 20ml contains the ethanolic soln of 0.72g Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES and 0.3g cupric nitrate, fully stirring and dissolving adds 20g magnesium oxide and 20ml ethanol afterwards, fully stirs catalyzer is adsorbed on the magnesium oxide, at 80 ℃ of lower oven dry 12h, the last vacuum tube furnace of putting into of pulverizing.Slowly rise to 750 ℃ of temperature of reaction under argon gas atmosphere, argon flow amount is 800ml/h, passes into carbon-source gas methane, and flow is 200ml/h, behind the reaction 1h, turns off methane, and furnace cooling obtains the Single Walled Carbon Nanotube powder of black to room temperature.
Utilize the HCl of 1mol/L that the Single Walled Carbon Nanotube powder that makes is cleaned, remove wherein residual magnesium oxide and metal catalyst.
As shown in Figure 2, transmission electron microscope (TEM) photo of the Single Walled Carbon Nanotube powder that makes for present embodiment can be found out and the structural integrity of Single Walled Carbon Nanotube not contain other impurity particle.
The Raman spectrogram of the Single Walled Carbon Nanotube that makes for present embodiment as shown in Figure 3.Can calculate by RBM peak position in the collection of illustrative plates that the diameter of Single Walled Carbon Nanotube is respectively 1.66nm, 1.43nm, 1.18nm, 1.06nm in the product.
Embodiment two:
Preparation 20ml contains the ethanolic soln of 0.42g Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES and 0.48g cupric nitrate, fully stirring and dissolving adds 20g magnesium oxide and 20ml ethanol afterwards, fully stirs catalyzer is adsorbed on the magnesium oxide, at 80 ℃ of lower oven dry 12h, the last vacuum tube furnace of putting into of pulverizing.Slowly rise to 750 ℃ of temperature of reaction under argon gas atmosphere, argon flow amount is 800ml/h, passes into carbon-source gas methane, and flow is 200ml/h, behind the reaction 1h, turns off methane, and furnace cooling obtains the Single Walled Carbon Nanotube powder of black to room temperature.
Utilize the H of 1mol/L
2NO
3The Single Walled Carbon Nanotube powder that makes is cleaned, remove wherein residual magnesium oxide and metal catalyst.
As shown in Figure 4, be the Raman spectrogram of resulting Single Walled Carbon Nanotube.Can calculate by RBM peak position in the collection of illustrative plates that the diameter of Single Walled Carbon Nanotube is respectively 1.18nm, 1.06nm, 0.94nm, 0.87nm in the product.Compare and to find out with the result of embodiment one, occur minor diameter (＜1nm) Single Walled Carbon Nanotube in the carbon nanotube that is synthesized in the present embodiment.
Embodiment three:
Preparation 20ml contains the ethanolic soln of 0.39g Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES and 0.34g cupric nitrate, fully stirring and dissolving adds 20g magnesium oxide and 20ml ethanol afterwards, fully stirs catalyzer is adsorbed on the magnesium oxide, at 80 ℃ of lower oven dry 12h, the last vacuum tube furnace of putting into of pulverizing.Slowly rise to 750 ℃ of temperature of reaction under argon gas atmosphere, argon flow amount is 800ml/h, passes into carbon-source gas methane, and flow is 200ml/h, behind the reaction 1h, turns off methane, and furnace cooling obtains the Single Walled Carbon Nanotube powder of black to room temperature.
Utilize the HCl of 1mol/L that the Single Walled Carbon Nanotube powder that makes is cleaned, remove wherein residual magnesium oxide and metal catalyst.
As shown in Figure 5, be the Raman spectrogram of resulting Single Walled Carbon Nanotube.The diameter that calculates Single Walled Carbon Nanotube in the product by RBM peak position in the collection of illustrative plates is 1.18nm, 1.06nm, 0.87nm, 0.79nm.Compare and to find out with the result of embodiment two, (＜1nm) the diameter generation considerable change of Single Walled Carbon Nanotube of the minor diameter in the carbon nanotube that is synthesized in the present embodiment.
To those skilled in the art, obviously the invention is not restricted to the details of above-mentioned example embodiment, and in the situation that does not deviate from spirit of the present invention or essential characteristic, can realize the present invention with other specific form.Therefore, no matter from which point, all should regard embodiment as exemplary, and be nonrestrictive, scope of the present invention is limited by claims rather than above-mentioned explanation, therefore is intended to include in the present invention dropping on the implication that is equal to important document of claim and all changes in the scope.Any Reference numeral in the claim should be considered as limit related claim.
In addition, be to be understood that, although this specification sheets is described according to embodiment, but be not that each embodiment only comprises an independently technical scheme, this narrating mode of specification sheets only is for clarity sake, those skilled in the art should make specification sheets as a whole, and the technical scheme among each embodiment also can through appropriate combination, form other embodiments that it will be appreciated by those skilled in the art that.
Claims (10)
1. the preparation method of a Single Walled Carbon Nanotube, it is characterized in that: obtain cobalt-copper binary catalyst system, cobalt-copper binary catalyst system is placed vacuum tube furnace, pass into carbon-source gas, under certain temperature of reaction and reaction times condition, grow Single Walled Carbon Nanotube.
2. the preparation method of Single Walled Carbon Nanotube according to claim 1 is characterized in that, described cobalt-obtaining of copper binary catalyst system comprises the steps:
A., the salt compounds that contains cobalt metal element that mixes with the arbitrary proportion mixture solution with the salt compounds composition of copper-containing metal element is provided;
B. in described mixture solution, add support of the catalyst magnesium-containing compound and specific solvent, fully stir;
C. the solution oven dry that step b is obtained, grind into powder is to obtain cobalt-copper binary catalyst system.
3. the preparation method of Single Walled Carbon Nanotube according to claim 2, it is characterized in that: described magnesium-containing compound is selected from magnesium oxide or magnesium hydroxide or magnesiumcarbonate or magnesium basic carbonate or their combination; Described solvent is selected from water or ethanol.
4. the preparation method of Single Walled Carbon Nanotube according to claim 1, it is characterized in that: the method also comprises: prepare after the Single Walled Carbon Nanotube powder, it is carried out the purification process of pickling.
5. the preparation method of Single Walled Carbon Nanotube according to claim 1, it is characterized in that: described carbon-source gas is methane.
6. the preparation method of Single Walled Carbon Nanotube according to claim 1 or 5, it is characterized in that: the carrier gas of described carbon-source gas is argon gas.
7. the preparation method of Single Walled Carbon Nanotube according to claim 6, it is characterized in that: the gas flow scope of described argon gas is: 0 ~ 3000ml/h.
8. the preparation method of Single Walled Carbon Nanotube according to claim 1, it is characterized in that: the gas flow scope of described carbon-source gas is: 0 ~ 1000ml/h.
9. the preparation method of Single Walled Carbon Nanotube according to claim 1, it is characterized in that: described range of reaction temperature is 600 ℃ ~ 1000 ℃.
10. the preparation method of Single Walled Carbon Nanotube according to claim 1, it is characterized in that: described reaction time range is 10min ~ 120min.
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| CN105016322A (en) * | 2014-04-30 | 2015-11-04 | 上海君江科技有限公司 | Preparation method for carbon nanotube antistatic material easy to disperse |
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| CN1530321A (en) * | 2003-03-14 | 2004-09-22 | 中国科学院成都有机化学研究所 | Catalyst for preparing carbon nanometer pipe with small pipe diameter |
| CN1762589A (en) * | 2005-09-30 | 2006-04-26 | 清华大学 | Method for preparing supported catalyst with single wall or double wall carbon nano tube |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105016322A (en) * | 2014-04-30 | 2015-11-04 | 上海君江科技有限公司 | Preparation method for carbon nanotube antistatic material easy to disperse |
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Application publication date: 20130424 |