CN104760943A - Method for synthesis of spiral carbon nanotube by injection chemical vapor deposition - Google Patents
Method for synthesis of spiral carbon nanotube by injection chemical vapor deposition Download PDFInfo
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- CN104760943A CN104760943A CN201510068324.3A CN201510068324A CN104760943A CN 104760943 A CN104760943 A CN 104760943A CN 201510068324 A CN201510068324 A CN 201510068324A CN 104760943 A CN104760943 A CN 104760943A
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Abstract
The invention discloses a method for synthesis of a spiral carbon nanotube by injection chemical vapor deposition, and the method includes the following steps: 1) using gamma-alumina as a carrier to prepare a Fe-Co or Fe-Ni catalyst; 2) the catalyst is put into a tube furnace for activation in a H2-Ar gas mixture; 3) an absolute ethanol and pyridine mixture is injected into the tube furnace by an injector, and by chemical vapor deposition of the mixture under 600-800 DEG C high-temperature conditions in inert atmosphere, a product is obtained. According to the method, by control of charge capacity, ratio, particle size, growth time, deposition temperature and other factors of an iron alloy catalyst, the productive rate, yield, quality, product form and structure of the helical carbon nanotube can be controlled. The synthesized helical carbon nanotube is high in yield, high in purity, large in specific surface area, simple in synthesis method, and easy to repeat.
Description
Technical field
The present invention relates to a kind of spiral carbon nanotubes synthetic method, particularly a kind of method of injected chemical vapour deposition synthesis spiral carbon nanotubes.
Background technology
Since Japanese carbonization scholar Iijima (S. lijima) Late Cambrian carbon nanotube, people have carried out extensive and deep research to the synthesis of carbon nanotube, properity and application etc.Carbon nanotube is a kind of one-dimensional material with special construction, can think seamless, the hollow " microtubule " that are reeled around central shaft by certain spiral angle by single or multiple lift graphite flake visually.The seamless tube structure that the one-dimensional hollow graphite aspect that carbon nanotube has uniqueness because of it is curled into, thus there is a series of outstanding character, if the chemical stability of height and thermostability, high physical strength, special electric property are (according to the difference of caliber and helicity, can be the conductor not worse than copper, also can be semi-conductor), it is the material that a class has applications well prospect.
Spiral carbon nanotubes is due to its special pattern and microstructure, confirmed that there is many peculiar process based prediction model by theoretical and experiment, carbon nanotube is wound spirane structure, it can be made to show peculiar performance in fields such as electricity, mechanics, magnetics.Such as by the torsion resistance of adjusting screw carbon nanotube, it can be made to be presented as semiconductive or metallicity.The preparation method of spiral carbon nanotubes comprises graphite acr method, laser evaporization method and chemical Vapor deposition process.The output preparing spiral carbon nanotubes due to chemical Vapor deposition process is higher, be therefore the most frequently used is at present also the method for most study.Department of chemistry engineering Wei Fei research group of Tsing-Hua University and Shenyang metal advanced Carbon Materials portion cooperate, utilize layered metal hydroxides as catalyzer, by a kind of chemical vapour deposition technique of growth in situ, directly synthesized double-walled/array of multi-walled carbon nanotubes helical assembly structure (
j. Am. Chem. Soc.132 (2010) 14739).But because synthesis condition is harsh and uncertain for growth conditions and growth mechanism, the growth mechanism for spiral has very large dispute always.The problems such as prepare spiral carbon nanotubes at present and still there is synthesis condition complexity, productive rate is low, and purity is not high, therefore the highly purified carbon nanometer spiral of a large amount of preparation is a very large challenge always, brings very large difficulty to its application.
Summary of the invention
The object of this invention is to provide a kind of method of high yield, high purity synthesis spiral carbon nanotubes, to solve the problems such as applied research that prior art brings in spiral carbon nanotubes low-yield and product development.
The present invention is achieved through the following technical solutions:
A method for injected chemical vapour deposition synthesis spiral carbon nanotubes, its special character is: comprise the following steps:
(1) take gama-alumina as carrier, preparation Fe-Co or Fe-Ni catalyzer; (2) catalyzer is placed in tube furnace, at H
2activate under-Ar gas mixture; (3) dehydrated alcohol and pyridine mixtures are injected tube furnace by syringe, mixture chemical vapour deposition under inert atmosphere, 600-800 DEG C hot conditions, obtain product.
The method of a kind of injected chemical vapour deposition synthesis of the present invention spiral carbon nanotubes, in step (1), the content of Fe-Co or Fe-Ni accounts for 1 ~ 20 wt% of catalyzer, and the atomic ratio of Fe/Co or Fe/Ni is 1/10 ~ 10/1, and the particle diameter of catalyzer is 1 ~ 50 nm.
The method of a kind of injected chemical vapour deposition synthesis of the present invention spiral carbon nanotubes, H in step (2)
2h in-Ar gas mixture
2volume fraction 5 ~ 50%, activation temperature is 300 ~ 500 DEG C, and soak time is at 1 ~ 20 hour.
The method of a kind of injected chemical vapour deposition synthesis of the present invention spiral carbon nanotubes, in dehydrated alcohol and pyridine mixtures, the volume of dehydrated alcohol accounts for 5% ~ 50% in step (3), dehydrated alcohol and pyridine mixtures adopt syringe pump input mode to enter tube furnace beds, flow velocity is 1 ml/hour, and chemical vapour deposition is 70 ~ 100 sccm N at flow velocity
2or carry out under Ar atmosphere, depositing temperature is 600 ~ 800 DEG C, and depositing time is 30 ~ 360 min.
Compared with prior art, the present invention has the following advantages:
(1) can by controlling the charge capacity of iron-based alloy catalyzer, proportioning and particle diameter, growth time, depositing temperatures etc. are because usually controlling the productive rate of spiral carbon nanotubes, yield and quality, product form and structure.
(2) the spiral carbon nanotubes productive rate synthesized is high, purity is high, and specific surface area is large.
(3) method of synthesizing spiral carbon nanotubes is simple, is easy to repetition.
Accompanying drawing explanation
Accompanying drawing 1 is the transmission electron microscope picture of the spiral carbon nanotubes that embodiment 1 is synthesized.
Accompanying drawing 2 is transmission electron microscope pictures of the spiral carbon nanotubes of the 2-in-1 one-tenth of embodiment.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail.
Embodiment 1:
1) preparation of catalyzer:
Take 4.04g iron nitrate (Fe (NO
3)
39H
2o), 5.821g Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES (Co (NO
3)
26H
2o) be dissolved in the deionized water of 500ml, under agitation by the γ-Al of 15.66g
2o
3proceed in above-mentioned solution, supersound process 30min, mixes, and constantly stirs and dries, then dry lower 500 DEG C of roasting 5 hour of 3 hour, Ar atmosphere at 110 DEG C, obtained 10% (Fe-Co)/γ-Al under being placed in room temperature
2o
3catalyzer, this catalyzer in theory alloy accounts for the 10wt% of catalyzer, atomic ratio Fe/Co=1/2.
2) activation of catalyzer:
Be laid in silica tube by above-mentioned catalyzer, be put in tube furnace, to bleed 5 min with mechanical pump after being sealed at boiler tube two ends, be filled with Ar, repeatedly pumping inflates three times.In the Ar air-flow of 60 mL/min, be warmed up to 400 DEG C with the temperature rise rate of 2 DEG C/min, then switch to 10%H
2-Ar gas mixture, flow velocity is 60 mL/min, with this understanding thermal treatment 2 hour.
3) injected chemical vapour deposition synthesis spiral carbon nanotubes:
Treat that catalyst activation terminates, continue to pass into Ar(70mL/min), and the temperature of tube furnace is risen to 600 DEG C with 1 DEG C/min, extract 5% dehydrated alcohol and pyridine mixtures with syringe, be placed in syringe pump; Recirculated water in open water device for cooling; Open syringe pump, in boiler tube, inject 5% dehydrated alcohol and pyridine mixtures with the speed of 1ml/hour, react 1 hour under depositing temperature; Close syringe pump, stop heating, continue to pass into Ar with the speed of 100 mL/min until tube furnace temperature naturally cools to room temperature; After reaction terminates, in the middle of taking out, the crystal reaction tube of flat-temperature zone, covers one deck black fluffy solid above, scrapes tube wall sedimentation products, removes the catalyzer of the inside respectively, obtain spiral carbon nanotubes by alkali lye and acid solution.
The spiral carbon nanotubes physical properties that this embodiment obtains is as shown in the table:
| Physical attribute | Measured value |
| Purity | 95% |
| Specific surface area (m 2/g） | 220 |
| Pore volume (cm 3/g） | 0.70 |
| Caliber (nm) | 30~80 |
| Length (mm) | 10~30 |
Embodiment 2:
1) preparation of catalyzer:
Take 4.04g iron nitrate (Fe (NO
3)
39H
2o), 14.55g nickelous nitrate (Ni (NO
3)
26H
2o) be dissolved in the deionized water of 500ml, under agitation by the γ-Al of 66.4g
2o
3proceed in above-mentioned solution, supersound process 30 min, mixes.Constantly stir under being placed in room temperature and dry, then dry lower 500 DEG C of roasting 5 hour of 3 hour, Ar atmosphere at 110 DEG C, obtain 5% (Fe-Ni)/γ-Al
2o
3catalyzer, this catalyzer in theory alloy accounts for the 5wt% of catalyzer, atomic ratio Fe/Ni=1/5.
2) activation of catalyzer:
Be laid in silica tube by above-mentioned catalyzer, be put in tube furnace, to bleed 5 min with mechanical pump after being sealed at boiler tube two ends, be filled with Ar, repeatedly pumping inflates three times.In the Ar air-flow of 60 mL/min, be warmed up to 500 DEG C with the temperature rise rate of 2 DEG C/min, then switch to 10%H
2-Ar gas mixture, flow velocity is 60 mL/min, with this understanding thermal treatment 15 hour.
3) injected chemical vapour deposition synthesis spiral carbon nanotubes:
Treat that catalyst activation terminates, continue to pass into N
2(100mL/min), and the temperature of tube furnace is risen to 750 DEG C with 1 DEG C/min, extract 5% dehydrated alcohol and pyridine mixtures with syringe, be placed in syringe pump; Recirculated water in open water device for cooling; Open syringe pump, in boiler tube, inject 5% dehydrated alcohol and pyridine mixtures with the speed of 1ml/hour, react 6 hours under depositing temperature; Close syringe pump, stop heating, continue to pass into Ar with the speed of 100 mL/min until tube furnace temperature naturally cools to room temperature; After reaction terminates, in the middle of taking out, the crystal reaction tube of flat-temperature zone, covers one deck black fluffy solid above, scrapes tube wall sedimentation products, removes the catalyzer of the inside respectively, obtain spiral carbon nanotubes by alkali lye and acid solution.
The spiral carbon nanotubes physical properties that this embodiment obtains is as shown in the table:
| Physical attribute | Measured value |
| Purity | 95% |
| Specific surface area (m 2/g） | 160 |
| Pore volume (cm 3/g） | 0.40 |
| Caliber (nm) | 20~80 |
| Length (mm) | 10~100 |
Claims (5)
1. a method for injected chemical vapour deposition synthesis spiral carbon nanotubes, is characterized in that: comprise the following steps:
(1) take gama-alumina as carrier, preparation Fe-Co or Fe-Ni catalyzer; (2) catalyzer is placed in tube furnace, at H
2activate under-Ar gas mixture; (3) dehydrated alcohol and pyridine mixtures are injected tube furnace by syringe, mixture chemical vapour deposition under inert atmosphere, 600-800 DEG C hot conditions, obtain product.
2. the method for a kind of injected chemical vapour deposition synthesis spiral carbon nanotubes according to claim 1, it is characterized in that: the content of Fe-Co or Fe-Ni accounts for 1 ~ 20 wt% of catalyzer, the atomic ratio of Fe/Co or Fe/Ni is 1/10 ~ 10/1, and the particle diameter of catalyzer is 1 ~ 50 nm.
3. the method for a kind of injected chemical vapour deposition synthesis spiral carbon nanotubes according to claim 1 and 2, is characterized in that: H
2h in-Ar gas mixture
2volume fraction 5 ~ 50%, activation temperature is 300 ~ 500 DEG C, and soak time is at 1 ~ 20 hour.
4. the method for a kind of injected chemical vapour deposition synthesis spiral carbon nanotubes according to claim 1 and 2, it is characterized in that: in dehydrated alcohol and pyridine mixtures, the volume of dehydrated alcohol accounts for 5% ~ 50%, dehydrated alcohol and pyridine mixtures adopt syringe pump input mode to enter tube furnace beds, and flow velocity is 1 ml/hour.
5. the method for a kind of injected chemical vapour deposition synthesis spiral carbon nanotubes according to claim 1 and 2, is characterized in that: chemical vapour deposition is 70 ~ 100 sccm N at flow velocity
2or carry out under Ar atmosphere, depositing temperature is 600 ~ 800 DEG C, and depositing time is 30 ~ 360 min.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106829926A (en) * | 2017-03-02 | 2017-06-13 | 西南交通大学 | A kind of high-purity spiral carbon nanotubes and preparation method thereof |
| CN110252304A (en) * | 2018-03-12 | 2019-09-20 | 中国石油化工股份有限公司 | Fe-series catalyst and its preparation method and application and carbon nanotube and preparation method thereof |
| CN115340084A (en) * | 2022-08-11 | 2022-11-15 | 中国计量大学 | Method for preparing carbon nano tube by hydrogen-free chemical vapor deposition |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20020009875A (en) * | 2000-07-27 | 2002-02-02 | 최규술 | Apparatus of vapor phase synthesis for synthesizing carbon nanotubes or carbon nanofibers and synthesizing method of using the same |
| CN1648038A (en) * | 2004-12-13 | 2005-08-03 | 关君正 | Method for preparing spiral carbon nano pipe |
| CN1903793A (en) * | 2005-07-26 | 2007-01-31 | 中国科学院物理研究所 | Carbon silicon composite material, its preparation method and use |
| CN101037197A (en) * | 2007-02-14 | 2007-09-19 | 天津大学 | Method for preparing carbon nano tube including Ethylenediamine double-injection |
| CN101244815A (en) * | 2008-03-17 | 2008-08-20 | 南京大学 | Method and device for producing carbon nano-tube or nitrogen doping carbon nano-tube with liquid phase forerunner article |
| US20090134363A1 (en) * | 2005-12-23 | 2009-05-28 | Arkema France | Method for synthesis of carbon nanotubes |
| CN102745665A (en) * | 2012-01-06 | 2012-10-24 | 中国科学院成都有机化学有限公司 | Method for preparing helical structure carbon nanotubes |
| CN103618072A (en) * | 2013-12-03 | 2014-03-05 | 山东玉皇化工有限公司 | Preparation method for silicon-carbon composite nano tube array |
| CN103723703A (en) * | 2014-01-06 | 2014-04-16 | 四川理工学院 | Method for preparing helical carbon nanotube at low temperature |
| CN104294434A (en) * | 2014-07-31 | 2015-01-21 | 复旦大学 | Spring-shaped carbon nano tube fiber and preparing method and purpose thereof |
-
2015
- 2015-02-10 CN CN201510068324.3A patent/CN104760943B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20020009875A (en) * | 2000-07-27 | 2002-02-02 | 최규술 | Apparatus of vapor phase synthesis for synthesizing carbon nanotubes or carbon nanofibers and synthesizing method of using the same |
| CN1648038A (en) * | 2004-12-13 | 2005-08-03 | 关君正 | Method for preparing spiral carbon nano pipe |
| CN1903793A (en) * | 2005-07-26 | 2007-01-31 | 中国科学院物理研究所 | Carbon silicon composite material, its preparation method and use |
| US20090134363A1 (en) * | 2005-12-23 | 2009-05-28 | Arkema France | Method for synthesis of carbon nanotubes |
| CN101037197A (en) * | 2007-02-14 | 2007-09-19 | 天津大学 | Method for preparing carbon nano tube including Ethylenediamine double-injection |
| CN101244815A (en) * | 2008-03-17 | 2008-08-20 | 南京大学 | Method and device for producing carbon nano-tube or nitrogen doping carbon nano-tube with liquid phase forerunner article |
| CN102745665A (en) * | 2012-01-06 | 2012-10-24 | 中国科学院成都有机化学有限公司 | Method for preparing helical structure carbon nanotubes |
| CN103618072A (en) * | 2013-12-03 | 2014-03-05 | 山东玉皇化工有限公司 | Preparation method for silicon-carbon composite nano tube array |
| CN103723703A (en) * | 2014-01-06 | 2014-04-16 | 四川理工学院 | Method for preparing helical carbon nanotube at low temperature |
| CN104294434A (en) * | 2014-07-31 | 2015-01-21 | 复旦大学 | Spring-shaped carbon nano tube fiber and preparing method and purpose thereof |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106829926A (en) * | 2017-03-02 | 2017-06-13 | 西南交通大学 | A kind of high-purity spiral carbon nanotubes and preparation method thereof |
| CN106829926B (en) * | 2017-03-02 | 2019-03-05 | 西南交通大学 | A kind of high-purity spiral carbon nanotubes and preparation method thereof |
| CN110252304A (en) * | 2018-03-12 | 2019-09-20 | 中国石油化工股份有限公司 | Fe-series catalyst and its preparation method and application and carbon nanotube and preparation method thereof |
| CN110252304B (en) * | 2018-03-12 | 2021-12-17 | 中国石油化工股份有限公司 | Iron-based catalyst, preparation method and application thereof, carbon nano tube and preparation method thereof |
| CN115340084A (en) * | 2022-08-11 | 2022-11-15 | 中国计量大学 | Method for preparing carbon nano tube by hydrogen-free chemical vapor deposition |
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| CN104760943B (en) | 2017-05-03 |
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