CN102050440A - Process for making carbon nanotubes - Google Patents
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- CN102050440A CN102050440A CN2010105250486A CN201010525048A CN102050440A CN 102050440 A CN102050440 A CN 102050440A CN 2010105250486 A CN2010105250486 A CN 2010105250486A CN 201010525048 A CN201010525048 A CN 201010525048A CN 102050440 A CN102050440 A CN 102050440A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/158—Carbon nanotubes
- C01B32/16—Preparation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
Abstract
The invention relates to a process for making carbon nano-tube, which comprises the following steps: 1) dissolving a oxidizer in a fiber type compound aqueous solution, adding at least one carbonaceous organic monomer to obtain a mixed solution, stirring the mixed solution for a certain period of time, filtering, washing and drying the deposition to obtain polymer nano-tubes which is the carbonaceous pre-body of carbon nano-tube; 2) carbonizing the polymer nano-tubes in the step 1) to obtain carbon nano-tube. The process of the invention achieves the beneficial effects of low cost, simpleness, practicalness, safety and high efficiency; it will not generate dangerous gas, and can prepare carbon nano-tube in large scale.
Description
Technical field
The present invention relates to chemical field, more particularly, relate to a kind of method for preparing carbon nanotube.
Background technology
Carbon nanotube is the isotropic substance obform body of carbon, has columniform nanostructure.Columniform like this carbon molecule has a lot of significant characteristics, exists many potential utility values aspect practical application, such as nanotechnology, electronic technology, Materials science, and building field.Carbon nanotube shows non-general intensity and unique electrology characteristic, and also is thermal conductor efficiently.Since carbon nanotube (Kratschmer W, Lamb LD, Fostiropoulos K, Huffman RD.Nature 1990; 6291 (347): 354-8) be found since, caused academia and industrial great interest, all have every day hundreds and thousands of papers to be delivered about carbon nanotube.
Yet, the research develop rapidly of carbon nanotube science aspect, the commercial applications aspect but develops quite slowly, and this mainly is because the production cost of carbon nanotube is very high.Thereby, aspect academic research and industrial application, low cost, large-scale preparation method of carbon nano-tube has become an important research project.Especially the high quality carbon nanotube for preparing diameter 50-100nm has become long-term goal (Tang NJ, Zhong W, Au CT, Gedanken YY, Du YW.Adv Funct Mater 2007 that materials chemistry is pursued; 17 (9): 1542-50).
Summary of the invention
The technical problem to be solved in the present invention is that the defective at the expensive and more difficult scale operation carbon nanotube that has the carbon nanotube production technology now provides a kind of brand-new large-scale low-cost to prepare the method for carbon nanotube.
The technical solution adopted for the present invention to solve the technical problems is: a kind of method for preparing carbon nanotube is provided, it is characterized in that, may further comprise the steps:
1) oxygenant is dissolved in the fibrous compound water solution, and add at least a carbon containing organic monomer and obtain mixing solutions, stir described mixing solutions certain hour, filtration washing drying precipitation resultant wherein, obtain polymer nanotube, described polymer nanotube is the carbon matrix precursor that contains of carbon nanotube;
2) the described polymer nanocomposite in the described step 1) of carbonization is in control carbon nanotube.
In the method for preparing carbon nanotube of the present invention, described oxygenant is Indian red, ammonium persulphate, Potassium Persulphate or iron nitrate.
In the method for preparing carbon nanotube of the present invention, described carbon containing organic monomer is pyrroles, aniline or thiophene, and the polymer nanotube that correspondence obtains is polypyrrole nanotube, polyaniline nano pipe or Polythiophene nanotube.
In the method for preparing carbon nanotube of the present invention, described fibrous mixture is a tropeolin-D, methyl red, and the benzene orange, or 5,10,15,20-four (4-sulphenyl) porphyrin.
In the method for preparing carbon nanotube of the present invention, the ratio of the molar mass of described fibrous mixture, oxygenant, carbon containing organic monomer is 1: 9～11: 9～11.
In the method for preparing carbon nanotube of the present invention, when carrying out described step 1), temperature continues to stir in 5-26 hour described mixing solutions in room temperature to 130 ℃ scope.
In the method for preparing carbon nanotube of the present invention, carry out described step 2) time, temperature continues to calcine in 3-5 hour described polymer nanotube in 900-2200 ℃ of scope.
In the method for preparing carbon nanotube of the present invention, described carbonization is the described polymer nanotube of calcining in having the quartz tube furnace of nitrogen environment or in vacuum high temperature furnace.
A kind of method for preparing carbon nanotube also is provided, may further comprise the steps:
1) Indian red is dissolved in the aqueous solution that contains tropeolin-D, and the adding pyrroles obtains mixing solutions, the ratio of wherein said tropeolin-D, Indian red, pyrroles's molar mass is 1: 9～11: 9～11, controlled temperature is in room temperature to the 130 ℃ scope, stirred described mixing solutions in lasting 5-26 hour, and filtration washing drying precipitation resultant wherein, obtaining the polypyrrole nanotube, described polypyrrole nanotube is the carbon matrix precursor that contains of carbon nanotube;
2) controlled temperature passed through the described polypyrrole nanotube in the described step 1) of calcining carbonization, and obtained carbon nanotube in 900-2200 ℃ of scope in lasting 3-5 hour in the quartz tube furnace of nitrogen environment.
Implement the method for preparing carbon nanotube of the present invention, have following beneficial effect: low-cost, simple and practical, safe and efficient, can not produce hazardous gas, but and mass preparation carbon nanotube.
Description of drawings
In the accompanying drawing:
Fig. 1 is the main schema that the present invention makes carbon nanotube;
Fig. 2 A and Fig. 2 B are respectively the polypyrrole nanotube of the embodiment of the invention 1 preparation and polypyrrole particulate transmission electron microscope (Transmission Electron Microscope, TEM) imaging as a comparison;
Fig. 3 is the polypyrrole nanotube and thermogravimetric analysis (Thermogravimetric Analysis, TGA) graphic representation of polypyrrole particle as a comparison in nitrogen environment of the embodiment of the invention 1 preparation;
Fig. 4 is the transmission electron microscope imaging of the carbon nanotube of the embodiment of the invention 1 preparation;
Fig. 5 A and Fig. 5 B are respectively transmission electron microscope imaging and the partial high resolution transmission electron microscopy of this carbon nanotube (High ResolutionTransmission Electron Microscopy, the HRTEM) imagings of the carbon nanotube of the embodiment of the invention 1 preparation;
Fig. 6 is X-ray diffraction (X-ray Diffraction, XRD) collection of illustrative plates of the carbon nanotube of the embodiment of the invention 1 preparation;
Fig. 7 is the carbon nanotube of the embodiment of the invention 1 preparation and the transmission electron microscope imaging of iron;
Fig. 8 A and Fig. 8 B are respectively the polypyrrole nanotube of the embodiment of the invention 1 preparation and the Raman spectrogram of carbon nanotube.
Embodiment
The present invention will be further described in detail below in conjunction with embodiment and accompanying drawing.
See also Fig. 1, make the main schema of carbon nanotube for the present invention.As shown in Figure 1, this method comprises two steps:
1) oxygenant is dissolved in (this fibrous material is the complex body material with filamentary structure in the aqueous solution of fibrousness mixture, can be used as the soft template in the chemical reaction), and add at least a carbon containing organic monomer and obtain mixing solutions, controlled temperature is in room temperature to 130 ℃ scope, stirred this mixing solutions in lasting 5-26 hour, and filtration washing drying precipitation resultant wherein obtains polymer nanotube;
2) controlled temperature is in 900-2200 ℃ of scope, and the polymer nanocomposite that generated in the described step 1) of calcining in the quartz tube furnace of nitrogen environment or in the vacuum high temperature furnace in lasting 3-5 hour is in control carbon nanotube.
Can in the aqueous solution of fibrousness mixture, add oxygenant and carbon containing organic monomer and generate polymer nanotube, promptly generate the carbon matrix precursor that contains of carbon nanotube.Wherein, the ratio of the molar mass of fibrous mixture, oxygenant, three kinds of materials of carbon containing organic monomer is 1: 9～11: 9～11.Typical oxidizing agents is an iron trichloride, also can use other oxygenants, can obtain gratifying result equally, for example, and ammonium persulphate, Potassium Persulphate, and iron nitrate.In step 1), the aqueous solution can include only oxygenant and tropeolin-D (negatively charged ion azoic dyestuff).Other materials also can be used for replacing tropeolin-D, for example, and methyl red, benzene orange and 5,10,15,20-four (4-sulphenyl) porphyrin.Typical carbon containing organic monomer is the pyrroles, but also can use other any carbon containing organic monomers, such as, aniline or thiophene.Be understandable that the polymer nanotube that any carbon containing organic monomer generates can be used for realizing the present invention.For example, the polypyrrole nanotube, polyaniline nano pipe and Polythiophene nanotube are typical polymer nanotubes.In step 2) in, polymer nanotube reacts under suitable condition, normally in nitrogen environment, and temperature is carried out calcining in 3-5 hour in 900-2200 ℃ of scope, or under vacuum condition, and temperature carries out baking in 3-5 hour in 900-2200 ℃ of scope.These conditions can be revised by the people of correlative technology field, and obtain the accordingly result under different condition.
According to aforesaid method, in the embodiment of the invention 1, take following method to prepare carbon nanotube.
Embodiment 1
The first step is dissolved in the iron trichloride of 1.5mmol in the deionized water solution that 30mL concentration is the tropeolin-D of 5mmol/l (0.15mmol).Pyrrole monomer with 1.5mmol (105ml) adds in this mixing solutions then, and stirs this mixing solutions 24 hours in room temperature environment.Repeatedly wash the polypyrrole throw out of generation with deionized water/ethanol, become colourless neutral solution, at last with washed polypyrrole throw out in 60 ℃ of vacuum environments dry 24 hours until filtrate.Can obtain the polypyrrole nanotube by above step, this polypyrrole nanotube is a kind of black powder.As a comparison,, but remove use tropeolin-D, synthesized the polypyrrole particle similarly according to above-mentioned steps.
Second step, the further carbonization of polypyrrole nanotube that the first step is obtained, thus obtain carbon nanotube.This carbonization process carries out in having the quartz tube furnace of nitrogen environment.At first polypyrrole nanotube sample is heated to 900 ℃ gradually, the speed of intensification is 3 ℃ of per minutes, then this sample is cooled to room temperature 900 ℃ of maintenances after 5 hours again.So far successfully synthesized carbon nanotube.
By transmission electron microscope, high resolution transmission electron microscopy, Raman spectrum and X-ray diffraction, observational study is by the structure of the carbon nanotube of above-mentioned steps preparation.Analytical results all shows, has successfully made carbon nanotube.
Utilize the SDT2960 thermogravimetric analyzer, studying at flow velocity is 20ml min
-1The purity nitrogen air-flow in the thermostability of polypyrrole.The speed that heats up is 3 ℃ of per minutes.By acceleration voltage is the transmission electron microscope (JEM-2000CX) of 100kV and the high resolution transmission electron microscopy (JEOL-2010) that acceleration voltage is 200kV, and the form of prepared carbon nanotube sample is observed.Several solvents that contain this carbon nanotube are dropped on the copper wire gauze of carbon film coating and evaporate.In room temperature environment, utilize Cu K α radiation, by reflective-mode, on PHILIPS PW 3710 diffractometers, obtain X ray diffracting spectrum.In room temperature environment, (France, JobinYvon) the acquisition scope is 0-3500cm on the Raman spectrometer at labRAM HR 800 as excitation light source to utilize the laser of 532nm
-1Raman spectrum.Above-mentioned measuring result will be elaborated hereinafter in conjunction with the accompanying drawings.
Seeing also Fig. 2 A and Fig. 2 B, is respectively the polypyrrole nanotube of the embodiment of the invention 1 preparation and polypyrrole particulate transmission electron microscope imaging as a comparison.Shown in Fig. 2 A, the polypyrrole nanotube is a hollow structure, the about 70nm of its external diameter, and so the about 50nm of internal diameter is the about 20nm of its wall thickness.Shown in Fig. 2 B, the polypyrrole particle then is solid particulate matter.
See also Fig. 3, be the polypyrrole nanotube (a) of the embodiment of the invention 1 preparation and the thermogravimetric analysis graphic representation of polypyrrole particle (b) in nitrogen environment as a comparison.As shown in Figure 3, in heat-processed, polypyrrole nanotube (a) and polypyrrole particle (b) all have weight loss.Both gravimetric analysis curve display both in heat-processed, divide two stage bodies lost weight.Fs is below 100 ℃, and weight loss is about 5%, and the reason of generation can be summed up as the evaporation of residual moisture content.Subordinate phase is from about 260 ℃, and the reason that weight loss produces can be summed up as the degraded of polypyrrole and the decomposition of impurity.Two curves relatively, under the high temperature, the polypyrrole nanotube has kept former 47% the weight of appointing, and the polypyrrole particle has only kept former 40% the weight of appointing, thereby can reach a conclusion: the weight loss of polypyrrole nanotube is lacked than polypyrrole particulate weight loss.
Because under quite high temperature, the performance of carbon nanotube is also very stable, therefore heating is after 5 hours in 900 ℃ quartz tube furnace, and the polypyrrole nanotube can successfully be converted into carbon nanotube.By the energy-dispersive spectroscopy analyser, analyze the prepared polypyrrole nanotube and the chemical ingredients of carbon nanotube respectively.List in table 1 with analyzing the data that obtained.
The chemical ingredients of table 1 polypyrrole nanotube and carbon nanotube
As can be seen from Table 1, the degree of calcining back carbon obviously increases.This is because in the process of calcining polypyrrole nanotube, carburizing reagent has taken place, and such as dehydrogenation and denitrogenation, has generated the more compact polycondensation graphite material of structure.
Structure for the prepared carbon nanotube of observational study has adopted transmission electron microscope.See also Fig. 4, be the transmission electron microscope imaging of the carbon nanotube of the embodiment of the invention 1 preparation.As shown in Figure 4, after 900 ℃ the pyrolysis, formed tubular structure.The about 15nm of the wall thickness of carbon nanotube, more thinner compared to the wall thickness 20nm of polypyrrole nanotube.Wall thickness reduces, the weight loss in carbonization process and form more compact structure.
Seeing also Fig. 5 A and Fig. 5 B, is respectively the transmission electron microscope imaging and the partial high resolution transmission electron microscopy imaging of this carbon nanotube of the carbon nanotube of the embodiment of the invention 1 preparation.Shown in Fig. 5 A and Fig. 5 B, the carbon nanotube of the embodiment of the invention 1 preparation and some the orderly graphite linings on this carbon nanotube wall as can be seen.The reaction that takes place when 900 ℃ of temperature is mainly carburizing reagent, and the greying reaction occurs in higher temperature, during such as 2200 ℃.
See also Fig. 6, be the X ray diffracting spectrum of the carbon nanotube of the embodiment of the invention 1 preparation.As shown in Figure 6, the wide-angle x-ray diffraction of carbon nanotube comprises 25.68 ° of two broad peak signals and 44.75 °, corresponds respectively to the stack of (002) and graphite-structure reflection (101).The maximum value at X-ray diffraction peak is 2 θ=25.68 °, is equivalent to approximately
Spacing d.Except strong (002) peak, change the X-ray diffraction pattern and also shown 44.75 ° diffraction peak, this may be the diffraction peak (101) of graphite plane.Confirm thus, successfully prepared carbon nanotube.
See also Fig. 7, be the carbon nanotube of the embodiment of the invention 1 preparation and the transmission electron microscope imaging of iron.As shown in Figure 7, after the polypyrrole nanotube formed, some remaining molysite were (as FeCl
2) stay in the polypyrrole nanotube, this is because used the oxygenant of iron trichloride as the oxidizable pyrrole polyreaction.In addition, the chemical oxidising polymerisation reaction causes having mixed picture FeCl
4 -The iron-based material that negative ion is such can be coordinated the skeleton of polymkeric substance.When being heated to 900 ℃ in nitrogen environment, the iron-based material breaks away from the polypyrrole nanotube, and is converted into iron.Be considered to break away from the iron bunch (arrow indication) of polypyrrole nanotube among Fig. 6 than dark-part.
Also can utilize Raman spectrum, the structure of the carbon nanotube that observational study is prepared.Seeing also Fig. 8 A and Fig. 8 B, is respectively the polypyrrole nanotube of the embodiment of the invention 1 preparation and the Raman spectrogram of carbon nanotube.Shown in Fig. 8 B, the Raman spectrum of the carbon fiber in the Raman spectrum of carbon nanotube and the bibliographical information is consistent, has showed the characteristic that intensity is big.The wave band of the relative narrower consistent with graphite species (G-wave band) is 1583cm
-1, the wave band consistent with sp3 carbon species (D-wave band) is 1341cm
-11583cm
-1And 1341cm
-1Wave band can think the wave band that the carbon owing to the carbon of graphite-like and disordered structure produces respectively.With respect to the G-wave band, the D-wave band is intensity increases trend.This result of study further shows, has successfully prepared carbon nanotube.
Write down other embodiment of the present invention below.
Embodiment 2
The first step is dissolved in the ammonium persulphate of 1.5mmol in the deionized water solution that 30mL concentration is the methyl red of 5mmol/l (0.15mmol).Pyrrole monomer with 1.35mmol (105ml) adds in this mixing solutions then, and stirs this mixing solutions 24 hours in 60 ℃.Repeatedly wash the polypyrrole throw out of generation with deionized water/ethanol, become colourless neutral solution, at last with washed polypyrrole throw out in 60 ℃ of vacuum environments dry 24 hours until filtrate.Can obtain the polypyrrole nanotube by above step, this polypyrrole nanotube is a kind of black powder.As a comparison,, but remove the use methyl red, synthesized the polypyrrole particle similarly according to above-mentioned steps.
Second step, the further carbonization of polypyrrole nanotube that the first step is obtained, thus obtain carbon nanotube.Carry out in the quartz tube furnace of this carbonization process in nitrogen environment.At first polypyrrole nanotube sample is heated to 1500 ℃ gradually, the speed of intensification is 3 ℃ of per minutes, then this sample is being cooled to room temperature 1500 ℃ of maintenances after 5 hours.So far successfully synthesized carbon nanotube.
Embodiment 3
The first step is dissolved in the Potassium Persulphate of 1.65mmol in the deionized water solution (0.15mmol) of benzene orange that 30mL concentration is 5mmol/l.Aniline monomer with 1.35mmol (105ml) adds in this mixing solutions then, and stirs this mixing solutions 24 hours in 100 ℃.Repeatedly wash the polyaniline throw out of generation with deionized water/ethanol, become colourless neutral solution, at last with washed polyaniline throw out in 60 ℃ of vacuum environments dry 24 hours until filtrate.Can obtain the polyaniline nano pipe by above step, this polyaniline nano pipe is a kind of black powder.As a comparison,, use the benzene orange, synthesized the polyaniline particle similarly but remove according to above-mentioned steps.
Second step, the further carbonization of polyaniline nano pipe that the first step is obtained, thus obtain carbon nanotube.Carry out in the quartz tube furnace of this carbonization process in nitrogen environment.At first polyaniline nano pipe sample is heated to 1800 ℃ gradually, the speed of intensification is 3 ℃ of per minutes, then this sample is being cooled to room temperature 1800 ℃ of maintenances after 5 hours.So far successfully synthesized carbon nanotube.
Embodiment 4
The first step, it is 15,10,15 of 5mmol/ that the iron nitrate of 1.35mmol is dissolved in 30mL concentration, in the deionized water solution (0.15mmol) of 20-four (4-sulphenyl) porphyrin.Thiophene monomer with 1.65mmol (105ml) adds in this mixing solutions then, and stirs this mixing solutions 24 hours in 130 ℃.Repeatedly wash the Polythiophene throw out of generation with deionized water/ethanol, become colourless neutral solution, at last with washed Polythiophene throw out in 60 ℃ of vacuum environments dry 24 hours until filtrate.Can obtain the Polythiophene nanotube by above step, this Polythiophene nanotube is a kind of black powder.As a comparison, according to above-mentioned steps, use 5,10,15 but remove, 20-four (4-sulphenyl) porphyrin has synthesized the Polythiophene particle similarly.
Second step, the further carbonization of Polythiophene nanotube that the first step is obtained, thus obtain carbon nanotube.Carry out in the quartz tube furnace of this carbonization process in nitrogen environment.At first Polythiophene nanotube sample is heated to 2200 ℃ gradually, the speed of intensification is 3 ℃ of per minutes, then this sample is being cooled to room temperature 2200 ℃ of maintenances after 5 hours.So far successfully synthesized carbon nanotube.
The result that other embodiment of the present invention obtained and the preferred embodiments of the present invention, promptly the result that obtained of embodiment 1 is similar, just gives unnecessary details no longer one by one.
In a word, the invention provides a kind of simple, feasible, practical method, efficient, scale operation carbon nanotube.
The preferred embodiments of the present invention and accompanying drawing are introduced in detail, the invention is not restricted to above-mentioned introduction.Above-mentioned introduction just is used to illustrate the present invention, and unrestricted claim of the present invention.Every equivalent structure transformation that utilizes specification sheets of the present invention and accompanying drawing content to be done, or directly or indirectly be used in other relevant technical fields, all in like manner be included in the scope of patent protection of the present invention.
Claims (9)
1. a method for preparing carbon nanotube is characterized in that, may further comprise the steps:
1) oxygenant is dissolved in the fibrous compound water solution, and add at least a carbon containing organic monomer and obtain mixing solutions, stir described mixing solutions certain hour, filtration washing drying precipitation resultant wherein, obtain polymer nanotube, described polymer nanotube is the carbon matrix precursor that contains of carbon nanotube;
2) the described polymer nanocomposite in the described step 1) of carbonization is in control carbon nanotube.
2. the method for preparing carbon nanotube according to claim 1 is characterized in that, described oxygenant is Indian red, ammonium persulphate, Potassium Persulphate or iron nitrate.
3. the method for preparing carbon nanotube according to claim 1 is characterized in that, described carbon containing organic monomer is pyrroles, aniline or thiophene, and the polymer nanotube that correspondence obtains is polypyrrole nanotube, polyaniline nano pipe or Polythiophene nanotube.
4. the method for preparing carbon nanotube according to claim 1 is characterized in that, described fibrous mixture is a tropeolin-D, methyl red, and the benzene orange, or 5,10,15,20-four (4-sulphenyl) porphyrin.
5. according to any described method for preparing carbon nanotube in the claim 1 to 4, it is characterized in that the ratio of the molar mass of described fibrous mixture, oxygenant, carbon containing organic monomer is 1: 9～11: 9～11.
6. the method for preparing carbon nanotube according to claim 1 is characterized in that, when carrying out described step 1), temperature continues to stir in 5-26 hour described mixing solutions in room temperature to 130 ℃ scope.
7. the method for preparing carbon nanotube according to claim 1 is characterized in that, carries out described step 2) time, temperature continues to calcine in 3-5 hour described polymer nanotube in 900-2200 ℃ of scope.
8. the method for preparing carbon nanotube according to claim 7 is characterized in that, described carbonization is the described polymer nanotube of calcining in having the quartz tube furnace of nitrogen environment or in vacuum high temperature furnace.
9. a method for preparing carbon nanotube is characterized in that, may further comprise the steps:
1) Indian red is dissolved in the aqueous solution that contains tropeolin-D, and the adding pyrroles obtains mixing solutions, the ratio of wherein said tropeolin-D, Indian red, pyrroles's molar mass is 1: 9～11: 9～11, controlled temperature is in room temperature to the 130 ℃ scope, stirred described mixing solutions in lasting 5-26 hour, and filtration washing drying precipitation resultant wherein, obtaining the polypyrrole nanotube, described polypyrrole nanotube is the carbon matrix precursor that contains of carbon nanotube;
2) controlled temperature passed through the described polypyrrole nanotube in the described step 1) of calcining carbonization, and obtained carbon nanotube in 900-2200 ℃ of scope in lasting 3-5 hour in the quartz tube furnace of nitrogen environment.
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| US12/608,016 US20110104040A1 (en) | 2009-10-29 | 2009-10-29 | Simple, effective and scalable process for making carbon nanotubes |
| US12/608,016 | 2009-10-29 |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105355934A (en) * | 2015-10-31 | 2016-02-24 | 哈尔滨工业大学 | Preparation method of nitrogen-doped carbon nanotubes |
| CN107324311A (en) * | 2017-06-29 | 2017-11-07 | 陕西科技大学 | A kind of synthetic method of CNT |
| CN109748259A (en) * | 2017-11-06 | 2019-05-14 | 石河子大学 | A kind of preparation method and application of poly- polyphenol nanotube |
| CN110120504A (en) * | 2019-04-24 | 2019-08-13 | 南开大学 | A kind of phosphorus/tin/carbon compound cathode materials preparation method of richness phosphorus |
| CN115057430A (en) * | 2022-05-18 | 2022-09-16 | 河南师范大学 | Preparation method and application of iron-doped porous carbon nanotube electrode material |
| CN115207378A (en) * | 2022-07-25 | 2022-10-18 | 陕西科技大学 | Polypyrrole nanotube electrocatalyst and preparation method and application thereof |
| CN115354181A (en) * | 2022-07-26 | 2022-11-18 | 昆明理工大学 | Preparation method of carbon nano tube reinforced copper-based composite material |
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| CN103224831B (en) * | 2013-04-12 | 2015-11-18 | 青岛科技大学 | A kind of electrorheological fluid and preparation method thereof |
| CN111137872A (en) * | 2019-12-24 | 2020-05-12 | 大连理工大学 | Large-scale production method of nitrogen-rich doped amorphous carbon/graphitic carbon nanocomposite powder |
| CN113860283B (en) * | 2021-09-29 | 2023-10-24 | 济南大学 | Preparation method and application of metal monoatomic and nitrogen double-doped carbon micro-tube |
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|---|---|---|---|---|
| WO2008048227A2 (en) * | 2005-08-11 | 2008-04-24 | Kansas State University Research Foundation | Synthetic carbon nanotubes |
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2009
- 2009-10-29 US US12/608,016 patent/US20110104040A1/en not_active Abandoned
-
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- 2010-10-29 CN CN2010105250486A patent/CN102050440A/en active Pending
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| 《Macromolecular Rapid Communications》 20051231 Xiaoming Yang et al. Facial fabrication of functional polypyrrole nanotubes via a reactive self-degraded template 1736-1740 1-8 第26卷, * |
| 《Polymer Degradation and Stability》 20061209 Jerzy J. Langer et al. Highly carbonized polyaniline micro- and nanotubes 330-334 1-8 第92卷, * |
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| CN105355934A (en) * | 2015-10-31 | 2016-02-24 | 哈尔滨工业大学 | Preparation method of nitrogen-doped carbon nanotubes |
| CN107324311A (en) * | 2017-06-29 | 2017-11-07 | 陕西科技大学 | A kind of synthetic method of CNT |
| CN109748259A (en) * | 2017-11-06 | 2019-05-14 | 石河子大学 | A kind of preparation method and application of poly- polyphenol nanotube |
| CN110120504A (en) * | 2019-04-24 | 2019-08-13 | 南开大学 | A kind of phosphorus/tin/carbon compound cathode materials preparation method of richness phosphorus |
| CN115057430A (en) * | 2022-05-18 | 2022-09-16 | 河南师范大学 | Preparation method and application of iron-doped porous carbon nanotube electrode material |
| CN115057430B (en) * | 2022-05-18 | 2024-02-20 | 河南师范大学 | Preparation method and application of iron-doped porous carbon nanotube electrode material |
| CN115207378A (en) * | 2022-07-25 | 2022-10-18 | 陕西科技大学 | Polypyrrole nanotube electrocatalyst and preparation method and application thereof |
| CN115207378B (en) * | 2022-07-25 | 2023-09-05 | 陕西科技大学 | Polypyrrole nanotube electrocatalyst and preparation method and application thereof |
| CN115354181A (en) * | 2022-07-26 | 2022-11-18 | 昆明理工大学 | Preparation method of carbon nano tube reinforced copper-based composite material |
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| Publication number | Publication date |
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| US20110104040A1 (en) | 2011-05-05 |
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