CN100443403C - Method of continuously synthesizing large diameter single wall carbon nano-tube - Google Patents
Method of continuously synthesizing large diameter single wall carbon nano-tube Download PDFInfo
- Publication number
- CN100443403C CN100443403C CNB200610118118XA CN200610118118A CN100443403C CN 100443403 C CN100443403 C CN 100443403C CN B200610118118X A CNB200610118118X A CN B200610118118XA CN 200610118118 A CN200610118118 A CN 200610118118A CN 100443403 C CN100443403 C CN 100443403C
- Authority
- CN
- China
- Prior art keywords
- ferrocene
- carbon nano
- wall carbon
- tube
- diameter single
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Abstract
The present invention relates to a method for continuously synthesizing large-diameter single-wall carbon nano tube, belonging to the field of nano material preparation technology. Said method is characterized by that it includes the following steps: using transition metal organics ferrocene as catalyst, using thiophene as accelerating agent, using methyl alcohol or ethyl alcohol as carbon source and solent, using inert gas as protection gas and carrier gas, introducing the carbon source and catalyst into high-temperature zone, in the high-temperature zone making the metal iron atoms decomposed out from metal organics ferrocene be agglomerated and formed into nano iron particles, under the catalytic action of high-temperature and transition metal iron particles making the carbon decomposed out from methyl alcohol or ethyl alcohol be formed into large-diameter single-wall carbon nano tube, at the same time continuously supplying alcohol and metal organics ferrocene, collecting formed single-wall carbon nano tubes in collector so as to implement continuous synthesis of large-diameter single-wall carbon nano tube.
Description
Technical field
The present invention relates to a kind of method of nano material preparation technical field, it specifically is a kind of method of continuously synthesizing large diameter single wall carbon nano-tube, promptly be carbon source with alcohol, thiophene phenol is the method for the floating catalytic continuously synthesizing large diameter single wall carbon nano-tube (SWCNTs) of growth control agent.
Background technology
SWCNTs has zig-zag according to the difference of roll angle), armchair shape and other spirane structure.Different spirane structures makes SWCNTs have different performances with diameter, and the discovery of SWCNTs has been opened up a uncharted field that is full of vitality for the research of nanoelectronics, nanochemistry, nanomaterial science.The discovery of SWCNTs in 1997 and application are chosen as one of big science discovery in the current year ten by world authority magazine Science.The application of SWCNTs has been subjected to the restriction of numerous factors: commercially produce in enormous quantities, purity, reunion, controllable size degree etc.At present major diameter SWCNTs synthetic mainly contains three kinds of methods: arc process, laser method and chemical Vapor deposition process.Arc process equipment is simple, but power consumption is bigger, and productive rate is lower.Laser rule apparatus expensive, preparation amount is limited and be difficult to promote.Chemical Vapor deposition process is divided into two kinds according to catalyzer introducing mode: fixed catalytic cracking process and floating catalytic cracking process.The fixed catalytic cracking process is that catalyzer such as iron, cobalt, nickel are dispersed on pottery, silicon, graphite or the glass substrate at first, and by catalytic pyrolysis carbon compound synthetic SWCNTs on substrate, the carbon compound of use is generally hydro carbons or carbon monoxide.This method resultant velocity generates with multi-walled carbon nano-tubes slowly and often, is difficult to a large amount of synthetic.As the improvement of fixed catalytic agent method, the floating catalytic cracking process is that catalyst precursor such as ferrocene, iron carbonyl etc. are evaporated to reactor, directly is decomposed to form SWCNTs in gas phase.This method realizes the serialization mass production easily, but relatively stricter to processing requirement.
Find through literature search prior art, Ecole Centrale Paris, LaboratoireMSS/MAT Quang-Hong Yang[Large-Diameter Single-Walled Carbon NanotubesSynthesized by Chemical Vapor Deposition (chemical Vapor deposition process synthesizing large diameter single wall carbon nano-tube), Adv.Mater. (advanced material) 2003,15 (10), 792. once adopted the method for chemical vapour deposition to prepare synthesizing large diameter SWCNTs, but the method for the catalytic decomposition that they adopt, it is very short that major diameter SWCNTs prepares the time length, can only last several minutes, output is very low, and the collection of product can only be collected at the inwall of quartz glass tube, can't reach the purpose of large scale continuous prod.
Summary of the invention
The object of the invention is at the deficiencies in the prior art, a kind of method of continuously synthesizing large diameter single wall carbon nano-tube is provided, with alcohol is carbon source, thiophene is a growth control agent, adopt the method for floating catalytic, make it at high temperature directly decomposite carbon and catalyst nanoparticles, growth rapidly and efficiently forms high-quality diameter SWCNTs.
The present invention is achieved by the following technical solutions; the present invention uses the transition metal organics ferrocene as catalyzer; methyl alcohol or ethanol are as carbon source and solvent; with the rare gas element is that shielding gas and carrier gas are brought carbon source and catalyzer into high-temperature zone fast; reunion forms nano iron particles to the metallic iron atom that decomposites at high temperature reaction zone metallorganics ferrocene in the high-temperature zone; methyl alcohol or ethanol decomposite carbon under the katalysis of high temperature and transition metal iron particle, form major diameter SWCNTs.While is because ethanol and metallorganics ferrocene can be supplied with continuously, and the SWCNTs of generation collects in collector, thus realization serialization synthesizing large diameter SWCNTs.
Below the inventive method is further described, method steps is as follows:
(1) is reflected in the horizontal quartz tube reactor and carries out, feed rare gas element, be warmed up to temperature of reaction 1000-1100 ℃ with the speed of 20 ℃/min.
(2) feed the alcoholic solution that is dissolved with catalyzer by electronic peristaltic pump, catalyst concn is 0.5g/300ml-6g/300ml, thiophene concentration is 0-9ml/300ml, feeding speed is 0.1-0.8ml/min, regulate carrier gas flux and be adjusted to 80-180l/h, carry catalyzer, growth control agent and carbon source fast and enter reaction zone.
(3) sustainable the carrying out of reaction, reactant is collected by the collector that links to each other with the silica tube outlet.The product of collecting refluxed one hour at 120 ℃ with nitric acid, removed wherein granules of catalyst and a spot of decolorizing carbon.
The present invention adopts alcohol as carbon source, be dissolved in the alcohol as the thiophene of the transition metal ferrocene of catalyzer and growth control agent and feed in the liquid mode, can feed the velocity of evaporation that the position adjustment is dissolved with the alcoholic solution of catalyzer by adjusting catalyzer, to guarantee to supply with evenly, and can regulate flow rate of carrier gas and adjust reactant by high-temperature zone speed, the granules of catalyst of avoiding decompositing is grown up at the high-temperature zone overstand, and the effect that nozzle reaches further homogenizing can be installed at the catalyst outlet place.Pure and mild catalyzer is supplied with simultaneously, decomposites carbon and nano-iron particle in the high-temperature zone, directly forms major diameter SWCNTs.Thereby solved the needed long-time complex process of carried catalyst, also solved the influence that is subjected to fire door temperature, catalyst precursor placement location at fire door place placement catalyst precursor easily simultaneously, be suitable for serialization production.The present invention is simple for process, can be according to the difference of carbon source carbon content, suitable by the concentration of regulating catalyst concn and thiophene growth control agent easily with the ratio of security deposit's metal catalyst and carbon, with control product pattern, can in the scope of broad, produce high-quality product.
The present invention adopts alcohol as carbon source, and raw material is simple and easy to, and is with low cost, environmentally safe; Adopt protection of inert gas, do not have obvious inflammable dangerous raw material; Product is easy to handle, the yield height, and equipment is simple, can continuous operation, be suitable for mass production.Resulting SWCNTs mean diameter is about 5.79nm, and maximum single diameter of single-wall carbon nano tube is 10.5nm, and fasciculation reduces, and SWCNTs is more to be occurred with single form.
Embodiment
Below embodiments of the invention are elaborated: present embodiment has provided detailed embodiment and process being to implement under the prerequisite with the technical solution of the present invention, but protection scope of the present invention is not limited to following embodiment.
Embodiment 1
Synthetic is to carry out in horizontal quartz reactor; under the situation that feeds nitrogen protection; be warmed up to 1000 ℃; temperature rise rate is 20 ℃/min, feeds the ethanolic soln that is dissolved with ferrocene, thiophene by electronic peristaltic pump then, and concentration is 0.5g/300ml; thiophene concentration is 0; feeding speed is 0.8ml/min, and the flow of regulating argon gas is 120l/h, and the reaction times continues 3 hours.Collect membranaceous product in the exit.Products therefrom is carbon nanotube bundles, and the diameter of its single Single Walled Carbon Nanotube is about 2nm.Single Walled Carbon Nanotube is comparatively pure, and there is the absorption of little metal iron particle on the surface.
Embodiment 2
Synthetic is to carry out in horizontal quartz reactor; under the situation that feeds argon shield; be warmed up to 1100 ℃; temperature rise rate is 20 ℃/min, feeds the methanol solution that is dissolved with ferrocene, thiophene by electronic peristaltic pump then, and ferrocene concentration is 4g/300ml; thiophene concentration is 3ml/300ml; feeding speed is 0.5ml/min, and the flow of regulating argon gas is 180l/h, and the reaction times continues 3 hours.Collect membranaceous product in the exit.Primary product in nitric acid 120 ℃ handled one hour, clean oven dry, can obtain purified product.Resulting SWCNTs mean diameter is about 5.79nm, and maximum single SWCNTs diameter is 10.5nm, and fasciculation reduces, and SWCNTs is more to be occurred with single form.Analysis of statistical data shows that the ratio of 4-9.5nm major diameter SWCNTs reaches 78%.
Embodiment 3
Under argon shield; speed with 20 ℃/min is warmed up to 1100 ℃; feed the ethanolic soln that is dissolved with ferrocene, thiophene with electronic peristaltic pump then; ferrocene concentration is 6g/300ml; the concentration of thiophene is 3ml/300ml; feeding speed is 0.1ml/min, and the adjusting argon flow amount is 160l/h, duration of the reaction 2 hours.Collect membranaceous product in the exit, contain the nano particle of iron, single Single Walled Carbon Nanotube, Single Walled Carbon Nanotube tube bank and a small amount of multi-walled carbon nano-tubes in the resultant product.The mean diameter of SWCNTs is about 5nm.
Embodiment 4
Under protection of nitrogen gas; speed with 20 ℃/min is warmed up to 1050 ℃; feed the methanol solution that is dissolved with ferrocene, thiophene with electronic peristaltic pump then; ferrocene concentration is 4g/1000ml; the concentration of thiophene is 9ml/300ml; feeding speed is 0.6ml/min, and the adjusting nitrogen flow is 160l/h, duration of the reaction 3 hours.The product of collecting in the exit is membranaceous, has very strong adsorptivity.Resulting product is single SWCNTs and SWCNTs tube bank.The mean diameter of SWCNTs is about 4.5nm.
Claims (4)
1; a kind of method of continuously synthesizing large diameter single wall carbon nano-tube; it is characterized in that: use the transition metal organics ferrocene as catalyzer; thiophene is a promotor; methyl alcohol or ethanol are as carbon source and solvent; with the rare gas element is that shielding gas and carrier gas are brought carbon source and catalyzer into high-temperature zone; reunion forms nano iron particles to the metallic iron atom that decomposites at high-temperature zone metallorganics ferrocene in the high-temperature zone; methyl alcohol or ethanol decomposite carbon under the katalysis of high temperature and transition metal iron particle; form large diameter single wall carbon nano-tube; supply with pure and mild ferrocene simultaneously continuously; the Single Walled Carbon Nanotube that generates is collected in collector; thereby realize the serialization synthesizing large diameter single wall carbon nano-tube; described high-temperature zone, its temperature are 1000-1100 ℃.
2, the method for continuously synthesizing large diameter single wall carbon nano-tube according to claim 1 is characterized in that, step is as follows:
(1) is reflected in the horizontal quartz tube reactor and carries out, feed argon gas or nitrogen, be warmed up to temperature of reaction 1000-1100 ℃ with the speed of 20 ℃/min;
(2) feed methyl alcohol or the ethanolic soln that is dissolved with ferrocene and thiophene by electronic peristaltic pump, ferrocene concentration is 0.5g/300ml-6g/300ml, thiophene concentration is 0-9ml/300ml, regulates carrier gas flux to 80-180l/h, carries catalyzer, growth control agent and carbon source rapidly and enters reaction zone;
(3) reaction continues to carry out, and reactant is collected by the collector that links to each other with the silica tube outlet, and the product of collecting refluxes with nitric acid, removes wherein granules of catalyst and a spot of decolorizing carbon.
3, the method for continuously synthesizing large diameter single wall carbon nano-tube according to claim 2 is characterized in that, and is described with the nitric acid backflow, is meant: refluxed one hour at 120 ℃ with nitric acid.
4, the method for continuously synthesizing large diameter single wall carbon nano-tube according to claim 2 is characterized in that, feeds methyl alcohol or the ethanolic soln that is dissolved with ferrocene and thiophene by electronic peristaltic pump, and feeding speed is 0.1-0.8ml/min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB200610118118XA CN100443403C (en) | 2006-11-09 | 2006-11-09 | Method of continuously synthesizing large diameter single wall carbon nano-tube |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB200610118118XA CN100443403C (en) | 2006-11-09 | 2006-11-09 | Method of continuously synthesizing large diameter single wall carbon nano-tube |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1948145A CN1948145A (en) | 2007-04-18 |
| CN100443403C true CN100443403C (en) | 2008-12-17 |
Family
ID=38017789
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB200610118118XA Expired - Fee Related CN100443403C (en) | 2006-11-09 | 2006-11-09 | Method of continuously synthesizing large diameter single wall carbon nano-tube |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100443403C (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101927995A (en) * | 2009-04-30 | 2010-12-29 | 中国科学院成都有机化学有限公司 | Method for preparing carbon nano tube with great inside diameter and controllable length |
| CN101891184B (en) * | 2010-07-12 | 2012-07-25 | 同济大学 | Method for continuously synthesizing single-wall carbon nano tube by high temperature chemical vapor deposition method |
| CN102179235A (en) * | 2011-05-06 | 2011-09-14 | 同济大学 | Preparation method of novel magnetically separable absorbent for removing dye |
| CN102582199B (en) * | 2012-02-14 | 2014-09-03 | 北京航空航天大学 | Preparation method of bionic lamellar high-content CNT (carbon nano tube) polymer composite material |
| CN103204492A (en) * | 2013-05-03 | 2013-07-17 | 苏州汉纳材料科技有限公司 | New method for improving yield of single-walled carbon nanotube |
| WO2016044749A1 (en) | 2014-09-19 | 2016-03-24 | Nanosynthesis Plus. Ltd. | Methods and apparatuses for producing dispersed nanostructures |
| CN104627980B (en) * | 2015-02-11 | 2017-04-26 | 北京石油化工学院 | Controllable flame burner and method for synthesizing carbon nano tubes |
| CN109941963A (en) * | 2019-03-27 | 2019-06-28 | 常州大学 | Micro nano structure direct-writing device based on floating catalyst system chemical gas phase reaction |
| CN112898101A (en) * | 2021-02-01 | 2021-06-04 | 常州大学 | Preparation method of carbon nano tube doped octogen composite flexible explosive |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1273286A (en) * | 1999-05-06 | 2000-11-15 | 中国科学院金属研究所 | Process for preparing nm-class carbon fibres as hydrogen storing material |
| CN1365946A (en) * | 2002-02-22 | 2002-08-28 | 清华大学 | Process for directly synthesizing ultra-long single-wall continuous nano carbon tube |
| US20060073275A1 (en) * | 2002-12-27 | 2006-04-06 | Shigeo Maruyama | Process and apparatus for producing single-walled carbon nanotube |
| US20060133982A1 (en) * | 2002-11-14 | 2006-06-22 | Cambridge University Technical Services Limited | Method for producing carbon nanotubes and/or nanofibres |
-
2006
- 2006-11-09 CN CNB200610118118XA patent/CN100443403C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1273286A (en) * | 1999-05-06 | 2000-11-15 | 中国科学院金属研究所 | Process for preparing nm-class carbon fibres as hydrogen storing material |
| CN1365946A (en) * | 2002-02-22 | 2002-08-28 | 清华大学 | Process for directly synthesizing ultra-long single-wall continuous nano carbon tube |
| US20060133982A1 (en) * | 2002-11-14 | 2006-06-22 | Cambridge University Technical Services Limited | Method for producing carbon nanotubes and/or nanofibres |
| US20060073275A1 (en) * | 2002-12-27 | 2006-04-06 | Shigeo Maruyama | Process and apparatus for producing single-walled carbon nanotube |
Non-Patent Citations (2)
| Title |
|---|
| CVD法制备单壁碳纳米管的纯化与表征. 邹红玲，杨延莲，武斌，卿泉，李清文，张锦，刘忠范.物理化学学报，第18卷第5期. 2002 |
| CVD法制备单壁碳纳米管的纯化与表征. 邹红玲，杨延莲，武斌，卿泉，李清文，张锦，刘忠范.物理化学学报，第18卷第5期. 2002 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1948145A (en) | 2007-04-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100443403C (en) | Method of continuously synthesizing large diameter single wall carbon nano-tube | |
| JP3945586B2 (en) | Method for producing carbon nanocage | |
| FI121334B (en) | Method and apparatus for making carbon nanotubes | |
| Li et al. | Co-production of hydrogen and multi-wall carbon nanotubes from ethanol decomposition over Fe/Al2O3 catalysts | |
| Yeheskel et al. | Thermolysis of methane in a solar reactor for mass-production of hydrogen and carbon nano-materials | |
| CN101214949B (en) | Method for controlling growth, diameter and wall thickness of carbon nano-tube by methanol | |
| CN101891184B (en) | Method for continuously synthesizing single-wall carbon nano tube by high temperature chemical vapor deposition method | |
| Athar et al. | Wet synthesis of monodisperse cobalt oxide nanoparticles | |
| CN102730673A (en) | Apparatus and method for continuously preparing thin-layer grapheme or hybrid combining thin-layer grapheme with thin-walled carbon nanotube | |
| Meng et al. | High-purity helical carbon nanotubes by trace-water-assisted chemical vapor deposition: Large-scale synthesis and growth mechanism | |
| JP4443423B2 (en) | Single-walled carbon nanotube manufacturing method and manufacturing apparatus | |
| Lv et al. | Formation of carbon nanofibers/nanotubes by chemical vapor deposition using Al2O3/KOH | |
| TW201544452A (en) | Method and apparatus for producing nanomaterial | |
| CN101734641A (en) | Heater and synthesis method for synthesizing carbon nano tubes by pyrolysis | |
| KR20070110739A (en) | Method of manufacturing catalyst for synthesis of carbon nanotubes and apparatus for manufacturing the same | |
| CN100387516C (en) | Method for direct and continuous preparing supershort carbon nanometer tube | |
| Mansoor et al. | Optimization of ethanol flow rate for improved catalytic activity of Ni particles to synthesize MWCNTs using a CVD reactor | |
| CN1170767C (en) | Continuous synthesis process of single-wall carbon nanotube | |
| CN1259234C (en) | Method for flowing catalyst continuous synthetic single-wall carbon nanometer tube with alcohol as carbon source | |
| Zhou et al. | Flame synthesis of carbon nanotubes with high density on stainless steel mesh | |
| CN100372761C (en) | Method for preparing hollow Nano carbon balls in graphite structure under solid state | |
| KR20080000033A (en) | Method of manufacturing catalyst for synthesis of carbon nanotubes and apparatus for manufacturing the same | |
| Zhang et al. | Effects of the size of nano-copper catalysts and reaction temperature on the morphology of carbon fibers | |
| CN110040720A (en) | High-purity, narrow diameter distribution, minor diameter double-walled carbon nano-tube preparation method | |
| CN101857461B (en) | Preparation method of semiconductor carbon nanotube array |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20081217 Termination date: 20111109 |