CN100443404C - Method for preparing carbon nano tube including Ethylenediamine double-injection - Google Patents
Method for preparing carbon nano tube including Ethylenediamine double-injection Download PDFInfo
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- CN100443404C CN100443404C CNB2007100568113A CN200710056811A CN100443404C CN 100443404 C CN100443404 C CN 100443404C CN B2007100568113 A CNB2007100568113 A CN B2007100568113A CN 200710056811 A CN200710056811 A CN 200710056811A CN 100443404 C CN100443404 C CN 100443404C
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Abstract
The present invention discloses a method of preparing carbon nanotube by ethylene diamine double injection, which belongs to the carbon nanotube preparation technology. The method comprises the steps of: injecting ferrocene liquid hydrocarbon solution into a quartz tube reactor by an injector 1 driven by a microinjection pump, using ferrocene methanol solution and ethylene diamine as raw material, or ferrocene ethanol solution and ethylene diamine as raw material, or ferrocene toluene solution and ethylene diamine as raw material, or ferrocene dimethylbenzene solution and ethylene diamine as raw material, and using argon gas as carrier gas; and injecting ethylene diamine into a quartz tube reactor by an injector 2 driven by a microinjection pump; and obtaining the carbon nanotube by reacting for 40 min at 600~950 DEG C. The present invention has the advantages of that the insolubility and the chemical reaction between the different precursors can be avoided by using double injection to replace single injection; the structure of the carbon nanotube can be controlled by controlling the injection. The carbon nanotube of the present invention is adapted to functional material and composite material.
Description
Technical field
The present invention relates to a kind of Ethylenediamine double-injection that comprises and prepare the method for carbon nanotube, belong to carbon nanotube preparation technology.
Background technology
Carbon nanotube has excellent electricity, mechanical property because of its unique microstructure.Since it is found, just be one of the focus in nano materials research field always, wherein how the carbon nanotube of controlledly synthesis with ad hoc structure and performance is one of challenging work of tool.Infer and experiment showed, that it is the effective means that realizes its controlledly synthesis that carbon nanotube is carried out that nitrogen mixes according to theory.
The nitrogen doping preparation of carbon current nanotube mainly is to use nitrogenous presoma to realize, to comprise ammonia and other carbon nitrogen organic compound.The nitrogen of carbon nanotube mixes and prepares the main single presoma that adopts, mainly to change the adjusting preparation in the nitrogen doping process that temperature of reaction or carrier gas realize carbon nanotube, in " Journal of Physics ChemistryB " 2005 " CVD Growth of N-Doped Carbon Nanotubes on Silicon Substrates and ItsMechanism ", reported that ferrocene acetonitrile solution (0.02g/ml) prepares nitrogen-doped carbon nanometer pipe for presoma as people such as He, amount by feeding hydrogen in the control reaction process is not then pointed out about the variation of nitrogen-doped carbon nanometer pipe microstructure to realize the adjusting of nitrogen-doped carbon nanometer pipe surface nitrogen content.Carbon nitrogen organic compound quadrol is one of raw material of preparation nitrogen-doped carbon nanometer pipe, in " Physica E " 2005 " Synthesis, characterization and low field emissionof CNx nanotubes ", reported with the quadrol to be that presoma is depositing FeCl as people such as Ding
3H
2The method for preparing nitrogen-doped carbon nanometer pipe on the silicon substrate of O.But be confined to the doping preparation of carbon nanotube, the research of the regulating and controlling in the non-impurity-doped process.
It is carbon nitrogen source that the present invention adopts quadrol, compound four kinds of different carbon sources, comprise methyl alcohol, ethanol, toluene and dimethylbenzene, with the ferrocene is catalyst precursor, with kind that change to supply with carbon source be regulating measure prepared nitrogen-doped carbon nanometer pipe with different microstructures with and the self-assembly array and the film that form.
Summary of the invention
The object of the present invention is to provide a kind of Ethylenediamine double-injection that comprises to prepare the method for carbon nanotube.This procedure is simple, and condition is easy to control, for certain condition has been created in the industrialization promotion of this method.
The present invention is realized by the following technical programs: the device of employing comprises: tube type resistance furnace 3, quartz tube reactor 5 is set in tube type resistance furnace, end at quartz tube reactor is provided with the syringe 1 and 2 that two covers are driven by micro-injection pump, quartz plate 4 is set in quartz tube reactor, at quartz tube reactor copper pipe gas exporter 7 is set, temperature controller 6 is set outside Reaktionsofen.Realization comprises that the double injection of quadrol prepares the method for carbon nanotube, and one of method is characterized in that comprising following process: with ferrocene methanol saturated solution and quadrol is raw material, and the 1000ml/min argon gas is carrier gas.The syringe 1 that utilizes micro-injection pump to drive, the rate of injection of ferrocene methanol saturated solution with 10ml/h is injected in the quartz tube reactor: under 800～900 ℃, the syringe 2 that utilizes micro-injection pump to drive simultaneously, quadrol is injected in the quartz tube reactor with 2.5～7.5ml/h, reaction 40min obtains the ring carbon nanotube.
Two of method is characterized in that comprising following process:
Ferrocene ethanolic soln and 7 diamines with 0.025g/ml are raw material, and the 1000ml/min argon gas is carrier gas.The syringe 1 that utilizes micro-injection pump to drive is injected into the ferrocene ethanolic soln in the quartz tube reactor with the 10ml/h rate of injection: under 600～950 ℃ of conditions, the syringe 2 that utilizes micro-injection pump to drive simultaneously, quadrol is injected into quartz tube reactor reaction 40min with 2.5～7.5ml/h, obtains the ring carbon nanotube.
Three of method is characterized in that comprising following process:
Ferrocene toluene solution and quadrol with 0.025g/ml are raw material, and the 1000ml/min argon gas is carrier gas.The syringe 1 that utilizes micro-injection pump to drive is injected into the rate of injection of ferrocene toluene solution with 7.5ml/h in the quartz tube reactor: under 800～900 ℃ of conditions, the syringe 2 that utilizes micro-injection pump to drive is injected into quadrol in the quartz tube reactor with 2.5～5ml/h, reaction 40min obtains the ring carbon nanotube.
Four of method is characterized in that comprising following process:
Ferrocene xylene solution and quadrol with 0.025g/ml are raw material, and the 1000ml/min argon gas is carrier gas.The syringe 1 that utilizes micro-injection pump to drive is injected into the rate of injection of ferrocene xylene solution with 7.5ml/h in the quartz tube reactor: under 800～900 ℃ of conditions, utilize micro-injection pump+syringe 2 that quadrol is injected in the quartz tube reactor with 2.5～5ml/h, reaction 40min obtains spirrillum ring carbon nanotube.
Method of the present invention adopts and comprises that the two carbon source double injections of quadrol prepare carbon nanotube, overcome single injection and prepared the reaction possible between the different presomas that may occur in the carbon nanotube process and the difference of solubleness each other, thereby can be convenient to use the injection of the presoma of different presomas and different amounts, realize controlled, and then the synthetic nitrogen-doped carbon nanometer pipe of control with ad hoc structure and performance.Adopt this method can avoid contact or use toxic compounds, improved the security of nitrogen-doped carbon nanometer pipe preparation.Ring carbon nanotube with this method preparation can be applied to composite material reinforcement body, and the spirrillum ring carbon nanotube of preparation can increase the bonding force that strengthens between body and the matrix.
Description of drawings
The apparatus structure synoptic diagram that Fig. 1 adopts for the present invention.
Among the figure: 1 syringe 1,2 that drives for micro-injection pump is a tube type resistance furnace for the syringe 2,3 that micro-injection pump drives, and 4 is quartz plate, and 5 is quartz tube reactor, and 6 is temperature controller, and 7 is copper pipe gas extracting device.
Fig. 2 is the carbon nanotube images of transmissive electron microscope with example 2 preparations of the present invention.
Fig. 3 is the carbon nanotube images of transmissive electron microscope with example 5 preparations of the present invention.
Fig. 4 is the carbon nanotube images of transmissive electron microscope with example 9 preparations of the present invention.
Fig. 5 is the carbon nanotube images of transmissive electron microscope with example 14 preparations of the present invention.
Embodiment
Example 1
With ferrocene methanol saturated solution and quadrol is raw material, and the 1000ml/min argon gas is carrier gas.The syringe 1 that utilizes micro-injection pump to drive, the rate of injection of ferrocene methanol saturated solution with 10ml/h is incorporated in the quartz tube reactor that is equipped with quartz plate, the syringe 2 that utilizes micro-injection pump to drive simultaneously, quadrol is injected in the quartz tube reactor with 2.5ml/h, at 900 ℃ of reaction 40min, make the ring carbon nanotube.
Example 2
Experiment condition and process change temperature of reaction into 850 ℃ with example 1, make the ring carbon nanotube.
Example 3
Experiment condition and process change temperature of reaction into 800 ℃ with example 1, make the ring carbon nanotube.
Example 4
Experiment condition and process be with example 1, and the rate of injection of ferrocene methanol solution and quadrol is changed with 10ml/h and 7.5ml/h, makes the ring carbon nanotube.
Example 5
Ferrocene ethanolic soln and quadrol with 0.025g/ml are raw material, and the 1000ml/min argon gas is carrier gas.The syringe 1 that utilizes micro-injection pump to drive is injected into the ferrocene ethanolic soln in the quartz tube reactor that is equipped with quartz plate with the 10ml/h rate of injection, the syringe 2 that utilizes micro-injection pump to drive simultaneously, quadrol is injected into quartz tube reactor with 2.5～7.5ml/h, at 950 ℃ of reaction 40min, make the ring carbon nanotube.
Example 6
Experiment condition and process change temperature of reaction into 850 ℃ with example 5, make the ring carbon nanotube.
Example 7
Experiment condition and process change temperature of reaction into 600 ℃ with example 5, make the ring carbon nanotube.
Example 8
Experiment condition and process be with example 5, and the rate of injection of ferrocene methanol solution and quadrol is changed with 10ml/h and 7.5ml/h, makes the ring carbon nanotube.
Example 9
Ferrocene toluene solution and quadrol with 0.025g/ml are raw material, and the 1000ml/min argon gas is carrier gas.The syringe 1 that utilizes micro-injection pump to drive is injected into the rate of injection of ferrocene toluene solution with 7.5ml/h in the quartz tube reactor, the syringe 2 that utilizes micro-injection pump to drive is injected into quadrol in the quartz tube reactor with 2.5ml/h, at 900 ℃ of reaction 40min, make the ring carbon nanotube.
Example 10
Experiment condition and process change temperature of reaction into 850 ℃ with example 9, make the ring carbon nanotube.
Example 11
Experiment condition and process change temperature of reaction into 800 ℃ with example 9, make the ring carbon nanotube.
Example 12
Experiment condition and process be with example 9, and the rate of injection of ferrocene methanol solution and quadrol is changed with 7.5ml/h and 5ml/h, makes the ring carbon nanotube.
Example 13
Ferrocene xylene solution and quadrol with 0.025g/ml are raw material, and the 1000ml/min argon gas is carrier gas.The syringe 1 that utilizes micro-injection pump to drive is injected into the rate of injection of ferrocene xylene solution with 7.5ml/h in the quartz tube reactor, utilize micro-injection pump+syringe 2 that quadrol is injected in the quartz tube reactor with 5ml/h simultaneously, at 900 ℃ of reaction 40min, make spirrillum ring carbon nanotube.
Reaction 40min makes spirrillum ring carbon nanotube.
Example 14
Experiment condition and process change temperature of reaction into 850 ℃ with example 13, make spirrillum ring carbon nanotube.
Example 15
Experiment condition and process change temperature of reaction into 800 ℃ with example 13, make spirrillum ring carbon nanotube.
Example 16
Experiment condition and process be with example 13, and the rate of injection of ferrocene xylene solution and quadrol is changed with 7.5ml/h and 5ml/h, makes spirrillum ring carbon nanotube.
Claims (4)
1. one kind comprises that the double injection of quadrol prepares the method for carbon nanotube, the device that this method adopts comprises: tube type resistance furnace (3), quartz tube reactor (5) is set in tube type resistance furnace, first syringe (1) and second syringe (2) that drive by micro-injection pump in an end setting of quartz tube reactor, quartz plate (4) is set in quartz tube reactor, at quartz tube reactor copper pipe gas extracting device (7) is set, temperature controller (6) is set outside tube type resistance furnace, it is characterized in that comprising following process: with ferrocene methanol saturated solution and quadrol is raw material, the 1000ml/min argon gas is carrier gas, first syringe (1) that utilizes micro-injection pump to drive, the rate of injection of ferrocene methanol saturated solution with 10ml/h is injected in the quartz tube reactor, under 800～900 ℃, second syringe (2) that utilizes micro-injection pump to drive simultaneously, the speed of quadrol with 2.5～7.5ml/h is injected in the quartz tube reactor, and reaction 40min obtains the ring carbon nanotube.
2. one kind comprises that the double injection of quadrol prepares the method for carbon nanotube, adopt the described device of claim 1, it is characterized in that comprising following process: ferrocene ethanolic soln and quadrol with 0.025g/ml are raw material, the 1000ml/min argon gas is carrier gas, first syringe (1) that utilizes micro-injection pump to drive is injected into the rate of injection of ferrocene ethanolic soln with 10ml/h in the quartz tube reactor, under 600～950 ℃ of conditions, second syringe (2) that utilizes micro-injection pump to drive simultaneously, the speed of quadrol with 2.5～7.5ml/h is injected in the quartz tube reactor, reaction 40min obtains the ring carbon nanotube.
3. one kind comprises that the double injection of quadrol prepares the method for carbon nanotube, adopt the described device of claim 1, it is characterized in that comprising following process: ferrocene toluene solution and quadrol with 0.025g/ml are raw material, the 1000ml/min argon gas is carrier gas, first syringe (1) that utilizes micro-injection pump to drive is injected into the rate of injection of ferrocene toluene solution with 7.5ml/h in the quartz tube reactor, under 800～900 ℃ of conditions, second syringe (2) that utilizes micro-injection pump to drive is injected into the speed of quadrol with 2.5～5ml/h in the quartz tube reactor, reaction 40min obtains the ring carbon nanotube.
4. one kind comprises that the double injection of quadrol prepares the method for carbon nanotube, adopt the described device of claim 1, it is characterized in that comprising following process: ferrocene xylene solution and quadrol with 0.025g/ml are raw material, the 1000ml/min argon gas is carrier gas, first syringe (1) that utilizes micro-injection pump to drive is injected into the rate of injection of ferrocene xylene solution with 7.5ml/h in the quartz tube reactor, under 800～900 ℃ of conditions, second syringe (2) that utilizes micro-injection pump to drive is injected into the speed of quadrol with 2.5～5ml/h in the quartz tube reactor, reaction 40min obtains spirrillum ring carbon nanotube.
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| US8410676B2 (en) | 2007-09-28 | 2013-04-02 | Beijing Funate Innovation Technology Co., Ltd. | Sheet-shaped heat and light source, method for making the same and method for heating object adopting the same |
| US8450930B2 (en) | 2007-10-10 | 2013-05-28 | Tsinghua University | Sheet-shaped heat and light source |
| CN101868074B (en) * | 2009-04-20 | 2013-07-03 | 清华大学 | Line heat source |
| CN101868068B (en) * | 2009-04-20 | 2013-08-28 | 清华大学 | Plane heat source |
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| CN104528683B (en) * | 2014-12-08 | 2016-05-11 | 中国科学院长春应用化学研究所 | A kind of preparation method of bamboo-like carbon nano tubes |
| CN104760943B (en) * | 2015-02-10 | 2017-05-03 | 山东玉皇新能源科技有限公司 | Method for synthesis of spiral carbon nanotube by injection chemical vapor deposition |
| CN108455569A (en) * | 2018-04-18 | 2018-08-28 | 复旦大学 | A kind of feed liquor system of the continuous extensive preparation facilities of carbon nano-tube fibre |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US8410676B2 (en) | 2007-09-28 | 2013-04-02 | Beijing Funate Innovation Technology Co., Ltd. | Sheet-shaped heat and light source, method for making the same and method for heating object adopting the same |
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| CN101868059A (en) * | 2009-04-20 | 2010-10-20 | 清华大学 | Three-dimensional heat source |
| CN101868074B (en) * | 2009-04-20 | 2013-07-03 | 清华大学 | Line heat source |
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| CN101868059B (en) * | 2009-04-20 | 2013-10-09 | 清华大学 | Three-dimensional heat source |
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