CN101927995A - Method for preparing carbon nano tube with great inside diameter and controllable length - Google Patents
Method for preparing carbon nano tube with great inside diameter and controllable length Download PDFInfo
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- CN101927995A CN101927995A CN 201010175101 CN201010175101A CN101927995A CN 101927995 A CN101927995 A CN 101927995A CN 201010175101 CN201010175101 CN 201010175101 CN 201010175101 A CN201010175101 A CN 201010175101A CN 101927995 A CN101927995 A CN 101927995A
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Abstract
The invention discloses a method for preparing a carbon nano tube with great inside diameter and controllable length. Mixed liquid of dimethyl benzene and ethanol is used as a carbon source, a mixture of dicyclopentadienyl iron and dicyclopentadienyl nickel is used as a catalyst, nitrogen or hydrogen is used as a carrier gas, a mixture of sulfur and thiophane is used as an additive, and the carbon nano tube with great inside diameter and controllable length is prepared in a horizontal electric furnace at 950 to 1,100 DEG C by adopting a floating catalysis method. A proper amount of dicyclopentadienyl nickel is added into the dicyclopentadienyl iron to form iron-nickel alloy nano granules so as to regulate the carbon settling speed of the catalyst, enlarge the inside diameter of the carbon tube and shorten the length of the carbon tube. The method has the advantages of convenient and simple operation, low cost, no pollution and simple equipment, and realizes low-cost batch preparation.
Description
Technical field
The invention belongs to the synthetic field of inorganic materials, relate to catalytic chemical vapor deposition technique and prepare carbon nanotube.
Background technology
Carbon nanotube is a piped nano level graphite crystal, centers on the hollow tubular structure that central shaft curls and forms by certain spiral angle by individual layer or multilayer graphite flake.Fill and the load certain material at carbon nanotube cavity and outside surface, the oxidation-resistance of combined carbon nanotube and thermostability can obtain to have the function nano matrix material of specific end use, as filling iron, can be used for magnetic recording, the load iron oxysome can be used for microwave absorbing.Studies show that the carbon nanotube that obtains suitable hollow structure is the basis of realizing its filling and load.The hollow structure of research control multi-walled carbon nano-tubes influence the important component part that rule also is the fundamental research of carbon nanotube controllable growth.Therefore synthesizing thin wall (large diameter) carbon nanotube realizes that to the hollow structure that makes full use of carbon nanotube the interior nano material of filling has great importance.
The normal foundation waits (" Materials Science and Engineering journal ", 2008,26 (1), 49～52) to adopt the cracking catalyst method, is that carbon source, ferrocene are catalyzer with the dichlorobenzene, produced thin-walled (large diameter) carbon nanotube.Studied the influence of hydrogen flowing quantity, temperature of reaction and catalyst concn to the thin wall carbon nano-tube preparation.
(Chinese patent CN101214949A) such as the Wang Jian of Shanghai Communications University farmings with ferrocene as catalyzer, normal hexane and methyl alcohol as carbon source and solvent; with the rare gas element is shielding gas; carbon source and catalyzer are brought into reaction zone; dilute a part of carbon source with methyl alcohol; obtained the carbon nanotube of various diameters and wall thickness; diameter is 3～46nm, and wall thickness is 2～10.7nm.
But in the existing technology of preparing, prepared carbon nanotube caliber is distributed in below the 50nm, and caliber is inhomogeneous; And length is uncontrollable.And the above carbon nanotube of the carbon nanotube of large diameter, particularly internal diameter 50nm still is difficult to synthetic so far.
Summary of the invention
The objective of the invention is shortcoming and defect, a kind of length controlled is provided, uniform diameter, and the method for preparing the large diameter carbon nanotube of carbon source environmental protection at prior art.
The present invention is with floating catalytic method catalytic pyrolysis carbon source at a certain temperature, it is characterized in that this method is that catalyzer, dimethylbenzene and alcoholic acid mixed solution are that carbon source, nitrogen or hydrogen are carrier gas with the mixture of ferrocene and nickelocene, the mixture that adds sulphur and thiophene is a catalyst aid, adopts the floating catalytic method to prepare carbon nano tube with great inside diameter and controllable length in 950～1100 ℃ of scopes.
The method of synthetic carbon nano tube with great inside diameter and controllable length provided by the present invention is the dimethylbenzene ethanolic soln that is dissolved with ferrocene, nickel, in the constant-flux pump input, is taken in the reactor with carrier gas, 950～1100 ℃ of catalytic decomposition.Wherein the carbon unstripped gas of usefulness is dimethylbenzene and alcoholic acid mixed solution, carrier gas is nitrogen or argon gas, hydrogen, in the preparation process, transition metal ferrocene, nickel are added in dimethylbenzene and the alcohol mixeding liquid, the mixing solutions that contains catalyzer, be input to the reactor front end by constant-flux pump, be brought into the reactor stage casing by carrier gas again, the thermal degradation reduction obtains.Dimethylbenzene is 1: 1～1: 2 with the ethanolic soln ratio, transition metal (iron, nickel) and sulphur ratio are 10: 0.5～10: 2, the thiophene add-on is 0.1%～0.5% of a dimethylbenzene alcohol mixeding liquid volume, concentration is 20～40mg/ml to transition metal (iron, nickel) in the dimethylbenzene alcohol mixeding liquid, nickel):, ferrocene and nickelocene mass ratio are 10: 0.02～10: 0.05.The sample size of catalyzer is 0.1～0.5ml/min, furnace temperature is at 950～1100 ℃, 40～60 minutes reaction times, collect the cotton-shaped product of black at the silica tube afterbody, these black flosss mainly are made up of the large diameter thin wall carbon nano-tube, measure by scanning electronic microscope, transmission electron microscope, thermogravimetric analyzer, caliber is 40～70nm, internal diameter 30～55nm, and being about is 1～10 μ m, oxidizing temperature is 630～650 ℃, and purity reaches 95%.
Method provided by the invention adds an amount of nickelocene in ferrocene, gasification is decomposed the back and formed the iron-nickel alloy nano particle, the alloy composition modulation carbon laydown speed of catalyzer, make that the carbon bore increases, length shortens.Synthetic carbon nanotube external diameter 40～70nm, internal diameter is 30～55nm, long 1～10 μ m.Reached the purpose of the length controlled of large diameter carbon nanotube, become 1～10 μ m, more helped the filling of nanotube inner chamber by 1～20 μ m of the prior art.
Dimethylbenzene goes out carbon through the catalysis thermal degradation, alcohol dilution part carbon source in the carbon source, and the degree of decomposition of inhibition carbon source, and suitable hydrogen stream has suppressed the deposition of carbon, thus the internal diameter of control multi-walled carbon nano-tubes forms.
And the present invention can be by regulating the volume ratio of ethanol and dimethylbenzene, and between 40～70nm, internal diameter has obtained the large diameter carbon nanotube that is more evenly distributed between 30～55nm with the outside diameter control of carbon nanotube.The present invention has simultaneously avoided the use of chlorobenzene and methyl alcohol, has realized the more purpose of environmental protection of production process.
The ratio of regulating catalyst adjuvant sulphur and thiophene reduces the bending of carbon nanotube, and the surface is more smooth.
This preparation method temperature of reaction is lower than 950 ℃ and generates a large amount of amorphous carbons, is higher than 1100 ℃ of calibers productive rate that attenuates and reduces.
In sum, the method for preparing the large diameter carbon nanotube provided by the invention has the more environmental protection of carbon source solvent, and with low cost, equipment is simple, easy suitability for industrialized production, caliber distribution uniform, the advantage of length controlled.
Figure of description:
Fig. 1, Fig. 2 are the transmission of embodiment 1 product, electron scanning micrograph;
Fig. 3, Fig. 4 are the transmission of embodiment 2 products, electron scanning micrograph;
Fig. 5, Fig. 6 are the transmission of embodiment 3 products, electron scanning micrograph;
Fig. 7, Fig. 8 are the transmission of embodiment 4 products, electron scanning micrograph.
Embodiment:
Below embodiments of the invention are elaborated, present embodiment is being to implement under the prerequisite with the technical solution of the present invention, and its concrete operations step is as follows
Embodiment 1
Synthetic is to carry out in horizontal quartz reactor; leading under the situation of nitrogen protection; be warmed up to 950 ℃～1100 ℃; temperature rise rate is 10～20 ℃/min; feed hydrogen 10～100L/h; after about 5 minutes; be dissolved with ferrocene by the constant-flux pump input; sulphur; the xylene solution of thiophene; catalyst solution spirt reactor termination temperature remains on 200～300 ℃, and sample rate is 0.1～0.5ml/min, and ferrocene concentration is 50～80mg/ml; thiophene concentration is 0.2～0.5ml/100ml; ferrocene and sulphur mol ratio are 10: 0.5～10: 2, and nitrogen flow is 50～100L/h, and the reaction times is 60 minutes.Collecting the cotton-shaped product of black in silica tube afterbody and tail gas bottle, is 100～700nm carbon fiber through scanning electronic microscope, determination of transmission electron microscopy, has the amorphous carbon ball simultaneously, and output 4～6g is 15～20 times of catalyzer.See Fig. 1, Fig. 2.
Embodiment 2
Building-up reactions is carried out in horizontal quartz reactor; be warmed up to 950 ℃～1100 ℃ under the situation of feeding nitrogen protection; temperature rise rate is 10～20 ℃/min; feed hydrogen 10～100L/h; after about 5 minutes; be dissolved with ferrocene by the constant-flux pump input; sulphur; the dimethylbenzene ethanolic soln of thiophene; sample rate is 0.1～0.5ml/min; the volume ratio of ethanol and dimethylbenzene is 1: 1～2: 1; ferrocene concentration is 30～40mg/ml, and thiophene concentration is 0.2～0.5ml/100ml, and ferrocene and sulphur ratio are 10: 0.5～10: 2; nitrogen flow is 80～100L/h, and the reaction times is 60 minutes.Collect the cotton-shaped product of black in silica tube afterbody and tail gas bottle, output 3～5g is about 15～20 times of catalyzer.Through scanning electronic microscope, determination of transmission electron microscopy, caliber is 40～70nm multi-walled carbon nano-tubes, and internal diameter is 30～55nm, long 5～20nm.See Fig. 3, Fig. 4.
Embodiment 3
Building-up reactions is carried out in horizontal quartz reactor; be warmed up to 950 ℃～1100 ℃ under the situation of feeding nitrogen protection; temperature rise rate is 10～20 ℃/min; feed hydrogen 10～100L/h; after about 5 minutes; be dissolved with ferrocene by the constant-flux pump feeding; nickelocene; sulphur; the dimethylbenzene ethanolic soln of thiophene; sample rate is 0.1～0.5ml/min; ferrocene concentration is 30～40mg/ml; the mass ratio of ferrocene and nickelocene is 10: 0.02～10: 0.05, and thiophene concentration is 0.2～0.5ml/100ml, and the mol ratio of ferrocene and sulphur is 10: 0.5～10: 2; nitrogen flow is 80～100L/h, and the reaction times is 60 minutes.Collect the cotton-shaped product of black in silica tube afterbody and tail gas bottle, output 3～5g is about 15～20 times of catalyzer.Through scanning electronic microscope, determination of transmission electron microscopy, caliber is 40～70nm multi-walled carbon nano-tubes, and internal diameter is 30～55nm, long 1～10nm.See Fig. 5, Fig. 6.
Embodiment 4
Building-up reactions is carried out in horizontal quartz reactor; be warmed up to 950 ℃～1200 ℃ under the situation of feeding nitrogen protection; temperature rise rate is 10～20 ℃/min; feed hydrogen 20～100L/h; after about 5 minutes; be dissolved with ferrocene by the constant-flux pump input; sulphur; the dimethylbenzene ethanolic soln of thiophene; sample rate is 0.1ml/min; ferrocene concentration is 30～40mg/ml; dimethylbenzene and ethanol volume ratio are 1: 1～1: 2, and thiophene concentration is 0.5ml/100ml, and the mol ratio of ferrocene and sulphur is 10: 0.5～10: 2; nitrogen flow is 100～120L/h, and the reaction times is 60 minutes.Collect the cotton-shaped product of black in silica tube afterbody and tail gas bottle, output 3～5g is about 15～20 times of catalyzer.Be about 60～70% through scanning electronic microscope, determination of transmission electron microscopy ribbon content, use Raman spectrometer to detect, have the RBM characteristic peak of single wall or double-walled carbon nano-tube.See Fig. 7, Fig. 8.
Claims (6)
1. method for preparing carbon nano tube with great inside diameter and controllable length, with the floating catalytic method at a certain temperature the catalytic pyrolysis carbon-source gas carry out the preparation of carbon nanotube, it is characterized in that this method is that catalyzer, dimethylbenzene and alcoholic acid mixed solution are that carbon source, nitrogen or hydrogen are carrier gas with the mixture of ferrocene and nickelocene, the mixture that adds sulphur and thiophene is a catalyst aid, adopts the floating catalytic legal system to be equipped with carbon nano tube with great inside diameter and controllable length.
2. according to the method for claim 1, it is characterized in that the mass ratio of ferrocene and nickelocene is 10: 0.02～0.05 in the described catalyzer, dimethylbenzene and ethanol volume ratio are 1: 1～2.
3. according to the method for claim 1, the mol ratio that it is characterized in that ferrocene and sulphur is 10: 1～0.05, and the thiophene volume is 0.1%～0.5% of dimethylbenzene and an alcohol mixture volume.
4. according to the method for claim 1, it is characterized in that catalyst concn is catalyzer 20～40mg in every milliliter of dimethylbenzene and the alcohol mixeding liquid.
5. according to the method for claim 1, it is characterized in that temperature of reaction is 950～1100 ℃.
6. according to the method for claim 1, it is characterized in that carrier gas flux is dimethylbenzene and alcohol mixeding liquid flow 1000～5000 times.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103170633A (en) * | 2011-12-22 | 2013-06-26 | 中国科学院大连化学物理研究所 | Preparation method of pod-shaped carbon nanotube encapsulation non-noble metal nano-particles |
| CN105347326A (en) * | 2015-11-19 | 2016-02-24 | 南昌大学 | Preparation method of carbon nano-gourd-shaped structure materials |
| CN106744818A (en) * | 2017-03-03 | 2017-05-31 | 东南大学 | A kind of method that microwave prepares CNT |
| CN107188158A (en) * | 2017-06-01 | 2017-09-22 | 沙冰娟 | A kind of preparation method of carbon nano-tube film |
| CN107623110A (en) * | 2016-07-15 | 2018-01-23 | 微宏动力***（湖州）有限公司 | Silicon substrate composite negative pole material, preparation method and lithium rechargeable battery |
| CN107662915A (en) * | 2017-09-12 | 2018-02-06 | 刘云芳 | A kind of three-dimensional vertical configuration CNT and preparation method thereof |
| CN110040720A (en) * | 2019-04-22 | 2019-07-23 | 中国科学院金属研究所 | High-purity, narrow diameter distribution, minor diameter double-walled carbon nano-tube preparation method |
| CN110451486A (en) * | 2019-08-08 | 2019-11-15 | 江西铜业技术研究院有限公司 | A kind of device and method of batch preparation carbon nanotube |
| CN112909257A (en) * | 2021-02-04 | 2021-06-04 | 陕西科技大学 | Carbon nanotube material prepared by FeNi alloy catalytic growth through electromagnetic induction heating method and application thereof |
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| CN1258637A (en) * | 1998-12-25 | 2000-07-05 | 中国科学院金属研究所 | Mass preparation of nanometer carbon fiber by using sulfur growth promoter |
| CN1365946A (en) * | 2002-02-22 | 2002-08-28 | 清华大学 | Process for directly synthesizing ultra-long single-wall continuous nano carbon tube |
| CN1948145A (en) * | 2006-11-09 | 2007-04-18 | 上海交通大学 | Method of continuously synthesizing large diameter single wall carbon nano-tube |
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Patent Citations (3)
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| CN1258637A (en) * | 1998-12-25 | 2000-07-05 | 中国科学院金属研究所 | Mass preparation of nanometer carbon fiber by using sulfur growth promoter |
| CN1365946A (en) * | 2002-02-22 | 2002-08-28 | 清华大学 | Process for directly synthesizing ultra-long single-wall continuous nano carbon tube |
| CN1948145A (en) * | 2006-11-09 | 2007-04-18 | 上海交通大学 | Method of continuously synthesizing large diameter single wall carbon nano-tube |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103170633A (en) * | 2011-12-22 | 2013-06-26 | 中国科学院大连化学物理研究所 | Preparation method of pod-shaped carbon nanotube encapsulation non-noble metal nano-particles |
| CN103170633B (en) * | 2011-12-22 | 2015-01-28 | 中国科学院大连化学物理研究所 | Preparation method of pod-shaped carbon nanotube encapsulation non-noble metal nano-particles |
| CN105347326A (en) * | 2015-11-19 | 2016-02-24 | 南昌大学 | Preparation method of carbon nano-gourd-shaped structure materials |
| CN107623110A (en) * | 2016-07-15 | 2018-01-23 | 微宏动力***（湖州）有限公司 | Silicon substrate composite negative pole material, preparation method and lithium rechargeable battery |
| CN106744818A (en) * | 2017-03-03 | 2017-05-31 | 东南大学 | A kind of method that microwave prepares CNT |
| CN107188158A (en) * | 2017-06-01 | 2017-09-22 | 沙冰娟 | A kind of preparation method of carbon nano-tube film |
| CN107662915A (en) * | 2017-09-12 | 2018-02-06 | 刘云芳 | A kind of three-dimensional vertical configuration CNT and preparation method thereof |
| CN110040720A (en) * | 2019-04-22 | 2019-07-23 | 中国科学院金属研究所 | High-purity, narrow diameter distribution, minor diameter double-walled carbon nano-tube preparation method |
| CN110451486A (en) * | 2019-08-08 | 2019-11-15 | 江西铜业技术研究院有限公司 | A kind of device and method of batch preparation carbon nanotube |
| CN110451486B (en) * | 2019-08-08 | 2022-11-22 | 江西铜业技术研究院有限公司 | Device and method for preparing carbon nanotubes in batches |
| CN112909257A (en) * | 2021-02-04 | 2021-06-04 | 陕西科技大学 | Carbon nanotube material prepared by FeNi alloy catalytic growth through electromagnetic induction heating method and application thereof |
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Application publication date: 20101229 |