CN1199853C - Metal catalyst for low-temp. thermochemical gas-phase precipitation synthesis of carbon nanotubes and synthetic method of carbon nanotubes using the same - Google Patents
Metal catalyst for low-temp. thermochemical gas-phase precipitation synthesis of carbon nanotubes and synthetic method of carbon nanotubes using the same Download PDFInfo
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- CN1199853C CN1199853C CNB021085447A CN02108544A CN1199853C CN 1199853 C CN1199853 C CN 1199853C CN B021085447 A CNB021085447 A CN B021085447A CN 02108544 A CN02108544 A CN 02108544A CN 1199853 C CN1199853 C CN 1199853C
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Abstract
The present invention relates to a synthesis method for carbon nanotubes, particularly to a loading metal catalyst which is applicable to synthesize carbon nanotubes by low-temperature thermochemical vapor deposition. The present invention discloses a loading metal catalyst which is applicable to synthesize carbon nanotubes by low-temperature (below 600 DEG C) thermochemical vapor deposition, which comprises noble metal particles and metal catalysts, wherein the noble metal particles are used as supporters, and a particle diameter is between 0.01 and 10 micrometres; the metal catalysts are deposited on the noble metal particles; the metal catalysts can be iron, cobalt, nickel or alloy of iron, cobalt and nickel, and the weight ratio of each metal catalyst to each noble metal particle is between 0.1:100 and 10:100. The present invention also discloses a method for synthesizing carbon nanotubes at a low temperature directly on base materials by the metal catalysts as the supporters. In the present invention, the catalyst supporters do not need to be removed after the carbon nanotubes are synthesized.
Description
Technical field
The present invention is the synthetic method of relevant a kind of CNT (carbon nano-tube) (carbon nanotubes), especially relevant a kind of loaded metal catalyst that is applicable to low temperature thermal chemical vapor deposition synthesis of carbon nanotube.
Background technology
CNT (carbon nano-tube) (carbon nanotubes) has very special character, special or the like such as low density, high strength, high tenacity, deflection, high surface area, big, the high thermal conductance degree of surperficial curvature, electroconductibility, so attract many research workers to be absorbed in exploitation its possible application mode, for example matrix material, micromodule, flat-panel screens, cableless communication, fuel cell and lithium ion battery or the like.With Field Emission Display (the carbon nanotube field emission displays of CNT (carbon nano-tube) as electron emission source, be called for short CNT-FED) be one to have the novel planar indicating meter of potentiality, usually relatively large CNT-FED processing procedure is the CNT (carbon nano-tube) blending conductive rubber after grinding with purifying, be implanted in the conducting glass substrate surface through mixing technology cloth such as slurry, wire mark, again through the sintering steps of 350 to 500 degree Celsius to remove the polymer substance in the slurry, to form electroconductibility good electron radiation film.Such CNT-FED processing procedure except need through several steps, technology are comparatively loaded down with trivial details, and CNT (carbon nano-tube) is difficult for being dispersed in this conductive rubber.
The method that can synthesize the CNT (carbon nano-tube) that possesses the field emission electron function at present has arc discharge method (arcdischarge), laser method of evaporation (laser vaporization) and thermal chemical vapor deposition method (thermalchemical vapor deposition, thermal CVD) or the like.The length and the caliber of arc discharge method and the not only uncontrollable CNT (carbon nano-tube) product of laser method of evaporation, and its productive rate is quite low.Considerable non-setting carbon (amorphous carbon) can be produced in addition, processing need be further purified.In addition, the service temperature of these processing procedures all surpasses 1000 degree, directly synthesis of carbon nanotube on glass baseplate Celsius.Therefore, it is generally acknowledged the most potential technology main flow that becomes the temperature production CNT (carbon nano-tube) of thermal chemical vapor deposition method.
Past thermal chemical vapor deposition method synthesis of carbon nanotube technology, mainly be to be carrier, and be deposited on reactive metal catalyst on this carrier with impregnation method (impregnation) preparation with poriness silicon oxide (poroussilica), zeolite (zeolite), aluminum oxide (alumina) or magnesium oxide (magnesium oxide).The major cause of selecting above carrier for use is because this type of carrier is the indifferent oxide of quite stable, is difficult for when heating and the reaction of reactive metal catalyst, makes the reactive metal catalyst lose activity, and can't carry out the building-up reactions of CNT (carbon nano-tube).The reactive metal of selecting for use is mainly iron, cobalt or nickel, and adds in addition conditioned reaction activity such as trace metal such as copper, molybdenum, manganese, zinc or platinum etc.The reaction conditions that uses this reactive metal catalyst that is deposited on carrier to carry out catalysis carbon distribution reaction generation CNT (carbon nano-tube) in reactor comprises: reactor is imported rare gas element (helium, argon, nitrogen), hydrogen, reaches carbon-source gas, temperature of reaction is generally 650 to 1000 ℃, pressure is 1 to 2 normal atmosphere, and the reaction times is 1 to 120 minute.Employed carbon source comprises hydrocarbon polymer or carbon monoxide.Need after reaction finishes carrier to be removed, just can obtain purer CNT (carbon nano-tube), use or other purposes for the CNT-FED processing procedure with acid solution.
Generally speaking, deformation temperature (strain temperature) through the heatproof glass of calcination reaches as high as 650 ℃, about 550 ℃ or lower of relatively poor soda glass deformation temperature, so if will directly CNT (carbon nano-tube) be grown in substrate surface with thermal chemical vapor deposition method, then its temperature of reaction can not surpass the deformation temperature of base material, that is is preferably lower than 600 ℃.Yet process temperatures is too low, and catalyst activity just is not enough to synthesis of carbon nanotube, so need exploitation one highly active special catalyst system capable, to carry out CNT (carbon nano-tube) under 600 ℃ the low temperature synthetic to be lower than.
European patent application EP 1061041 A1 have disclosed a kind of low temperature hot CVD equipment and have utilized the method for equipment synthesis of carbon nanotube, be that the reaction tubes in this equipment is divided into abutting gas importation spatially, is used for first district of thermolysis input gas, with on the space in abutting connection with discharge portion, be used to utilize aforesaid decomposition gas synthesis of carbon nanotube second district, and, the temperature that keeps two districts makes the temperature in second district be lower than the temperature in first district.Formation reaction district in CNT (carbon nano-tube) uses two kinds of different catalyst substrates, wherein a slice is used as accelerator, mainly act as to quicken the acetylene cracking, and composition is Pd, Cr and Pt etc., another sheet then deposits iron, cobalt, nickel or its catalytic alloy film, is the catalyst that mainly generates CNT (carbon nano-tube).The catalyst substrate etching gas corrosion that will have iron, cobalt, nickel or its catalytic alloy film, form nano level catalytic particle, utilize aforesaid device prior to the pyrolytic decomposition carbon source gas in first district, then, under the temperature that is equal to or less than the substrate deformation temperature, use the carbon source gas that is decomposed by accelerator by second district, through thermal chemical vapor deposition reaction, growth of vertical carbon nanotubes arranged on each isolated nano level catalytic metal particles on the substrate.The case technology is except the low-temp reaction section that uses 450 to 650 degree Celsius before this, still must use the high temperature of 700 to 1000 degree Celsius to carry out the thermolysis (first district) of carbon source gas, be not to be pure low temperature process, also therefore preceding case technology must be used special CVD reactor.Must on two base materials, form two kinds of different metal solvent layers in this external technology of case before this, again with these two kinds of base materials to be placed in the thermal cvd reactor device across a segment distance between the relative mode of metal level.Clearly, the processing procedure complexity of case technology, cost height and be not easy to implement before this.
European patent application EP 1061043 A1 have disclosed a kind of method of utilizing metal solvent layer low temperature synthesizing carbon nanotubes.In this synthetic method, on base material, form metal solvent layer, the isolated nano level catalytic metal particles of the etched formation of this metal solvent layer.Then, by under the temperature that is equal to or less than the substrate deformation temperature with the carbon source gas that is decomposed, through thermal chemical vapor deposition, growth of vertical carbon nanotubes arranged on each isolated nano level catalytic metal on the substrate.The carbon source gas that this is decomposed is to use a carbon source gas decomposing metal catalyst layer.Must on two base materials, form two kinds of different metal solvent layers in the case technology before this, again with these two kinds of base materials to be placed in the thermal cvd reactor device across a segment distance between the relative mode of metal level.Clearly, the case technology is for improving the processing procedure patent of EP1061041 A1 before this, main progressive is for to change to the one-part form heating system with the two-part heating system, but there is no tangible progressive for catalyst system capable, still needs to use on two plate bases two kinds of different catalyst system capables.
Summary of the invention
A main purpose of the present invention is to provide a kind of loaded metal catalyst that is useful in low temperature thermal chemical vapor deposition synthesis of carbon nanotube, and it can be easy to be produced.
Another object of the present invention is to provide a kind of loaded metal catalyst that is useful in low temperature thermal chemical vapor deposition synthesis of carbon nanotube, this loaded metal catalyst has catalyst and forms the advantage of adjusting and controlling easily.
Another object of the present invention is to provide a kind of directly method of low-temperature synthesis of carbon nanotube on base material, it does not have the shortcoming of aforementioned prior art.
Another object of the present invention is to provide a kind of directly method of low-temperature synthesis of carbon nanotube on base material, it has catalyst system capable and prepares easy advantage.
For achieving the above object, a kind of loaded metal catalyst of finishing according to the present invention that is applicable to low temperature thermal chemical vapor deposition synthesis of carbon nanotube comprises:
Particle diameter is between 0.01 to 10 micron noble metal; And
Be deposited on the metal solvent on this noble metal, wherein this metal solvent is the group that chosen from Fe, cobalt, nickel and alloy thereof are formed, and this metal solvent to the weight ratio of this noble metal between 0.1: 100 to 10: 100.
Preferable, this noble metal is silver, gold, platinum, palladium and copper or their alloy, is better with silver wherein.
Preferable, loaded metal catalyst of the present invention, it is by mixing by this noble metal is added to give with a saline solution of this metal solvent, the mixture that reheat obtained makes this metal solvent be deposited on this noble metal and prepares.The saline solution of this metal solvent can be nitrate solution and sulfate liquor, and this nitrate solution and sulfate liquor can be water or alcohol solution.
Preferable, loaded metal catalyst of the present invention, it is by being prepared by the deposition-precipitation method that may further comprise the steps:
A) this noble metal is scattered in the solvent;
B) saline solution of this metal solvent is incorporated in the dispersion liquid of this noble metal of step a);
C) add a precipitation agent and in the mixture of step b), also heat the mixture that is obtained; And
D) add a reductive agent in the mixture of step c) with reduce this metal solvent ion and this metal solvent is deposited on this noble metal.
Preferable, the solvent of step a) is water or alcohols.
Preferable, the precipitation agent of step c) is ammoniacal liquor or sodium bicarbonate.
Preferable, the reductive agent of step d) is diamine, formaldehyde, hypophosphite or phenyl aldehyde.
The present invention also provides a kind of method of low temperature thermal chemical vapor deposition synthesis of carbon nanotube, comprises the following step:
A) loaded metal catalyst of the present invention is dispersed on the base material; And
B), make a carbon-source gas be deposited on the CNT (carbon nano-tube) of growing up on this loaded metal catalyst by thermal chemical vapor deposition.
Preferable, the step a) of the method for low temperature thermal chemical vapor deposition synthesis of carbon nanotube of the present invention comprises and this loaded metal catalyst is dispersed in one contains in the glue of polymer and organic solvent, obtain to disperse glue to be coated on this base material institute, the coating that heating is obtained is to remove polymer and organic solvent wherein.Better, the coating that this heating obtained with remove wherein polymer and the temperature of organic solvent between 350～500 ℃.
Preferable, the step a) of the method for low temperature thermal chemical vapor deposition synthesis of carbon nanotube of the present invention comprises this loaded metal catalyst is added in the organic solvent, for some time add through the ultrasound concussion and to give dispersion, the dispersion liquid that is obtained is poured on the quartz boat substrate and forms skim and this thin layer of heat drying thereon.
Preferable, the base material of the step a) of the method for low temperature thermal chemical vapor deposition synthesis of carbon nanotube of the present invention is selected from the group that ITO conductive glass, chilled glass, soda glass, quartz, silicon oxide, silicon wafer, aluminium and sheet metal are formed.
Preferable, the thermal chemical vapor deposition of the step b) of the method for low temperature thermal chemical vapor deposition synthesis of carbon nanotube of the present invention is to carry out between 400 to 600 ℃ temperature of reaction one.
Preferable, the thermal chemical vapor deposition of the step b) of the method for low temperature thermal chemical vapor deposition synthesis of carbon nanotube of the present invention is to carry out one between reaction times of 1 to 120 minute one between 0.5 to 2 atmospheric pressure; And this carbon-source gas comprises hydrocarbon polymer or carbon monoxide.This hydrocarbon polymer is preferable contains 1 to 12 carbon.Better, this carbon-source gas is meant methane, acetylene or carbon monoxide.
Preferable, the thermal chemical vapor deposition of the step b) of the method for low temperature thermal chemical vapor deposition synthesis of carbon nanotube of the present invention is to carry out in the presence of hydrogen; And this carbon-source gas comprises hydrocarbon polymer or carbon monoxide.
Compare with preceding case, major advantage of the present invention has: one, carrier metal solvent of the present invention can be used for CNT (carbon nano-tube) synthetic of low temperature (being lower than 600 ℃) thermal chemical vapor deposition.Two, carrier metal solvent of the present invention can be used for the method for direct low-temperature synthesis of carbon nanotube on base material, need not remove the catalyst carrier.Three, the present invention uses single high reactivity catalyst system capable, but not two kinds of catalyst system capables can reduce cost.Four, the present invention uses one-part form low-temperature heat mode, does not need through leading portion high-temperature zone processing carbon-source gas.Five, use the identical conduction layer to be carrier with existing thick film (thick film) processing procedure, can directly embed the original processing procedure of CNT-FED, have compatible completely.
Embodiment
The detailed description of preferred embodiment
The present invention discloses a kind of loaded metal catalyst that is applicable to low temperature (being lower than 600 ℃) thermal chemical vapor deposition synthesis of carbon nanotube, be different from the mode of the cancellation synthesis of nano metal solvent that aforementioned EP application case disclosed, the present invention prepares catalyst with the method for additive properties.At first select the carrier that can be applied to a downstream product, that is this carrier will not influence derived product and its processing procedure with CNT (carbon nano-tube).With CNT-FED is example, and the silver-colored particle in the elargol promptly can be used as the catalyst carrier because elargol be in the CNT-FED processing procedure the essential conductive surface solid that uses, can directly devote in the CNT-FED processing procedure so this carrier will need not be removed.The reactive metal catalyst is implanted in this type of carrier surface with deposition-precipitation method or impregnation method cloth, again this loaded metal catalyst is disperseed or coat substrate surface, after thermal chemical vapor deposition reaction just can generate CNT (carbon nano-tube), and temperature of reaction is controlled at below 600 ℃ still synthesis of carbon nanotube in a large number.
Catalyst carrier of the present invention is a precious metal particles, and as gold and silver, copper, palladium, platinum etc., its particle size dispersion is between the 0.01-10 micron.The method for preparing active catalyst has two kinds, and first kind is the impregnation method, and second kind then is deposition-precipitation method.These two kinds of methods all need earlier noble metal granule to be scattered in the water.
The impregnation method is shaken for example 10 minutes for some time with the silver-colored particle aqueous solution with ultrasound, add then and contain reactive metal salt solution, the aqueous solution of nickelous nitrate for example, wherein reactive metal comprises transition metal, as iron, cobalt, nickel etc., salt can be nitrate or vitriol.After two solution mix, this mixing solutions heating is concentrated, remove solvent, the reactive metal catalyst just is distributed on the carrier, becomes the loaded metal catalyst.
The deposition sedimentation rule adds an alkaline aqueous solution (for example ammoniacal liquor) with the argentiferous particulate aqueous solution, and to make the pH value of solution value be 8～9 to boil for example 30 minutes for some time again, with the carrier surfaction is alkalescence, the aqueous solution that will contain the reactive metal salt again adds, adding precipitation agent and chemical reducing agent after stirring is again precipitated reactive metal and is reduced, precipitation agent is ammoniacal liquor for example, reductive agent is formaldehyde for example, and the removed by filtration solvent can obtain the loaded metal catalyst then.
A kind of low temperature thermochemistry gas of the present invention deposits the method for synthesis of carbon nanotube, comprises aforesaid loaded metal catalyst is scattered on the base material; And use a carbon-source gas by the CNT (carbon nano-tube) of on this loaded metal catalyst, growing up by thermal chemical vapor deposition.
It is as follows that aforesaid loaded metal catalyst is dispersed in one of mode on the base material.Get a plate substrate, be soaked in the acetone, shake to add in about 10 minutes with the ultrasound oscillator and give cleaning, take out drying for standby then, this step is pre-treatment, can increase the sticking power of catalyst system capable at substrate surface.Aforesaid base material can be Silicon Wafer, silica glass, chilled glass, soda glass, ITO conductive glass, sheet metal or silicon oxide.The loaded metal catalyst and the polymer glue that prepare are mixed, the loaded metal catalyst to the blending ratio (weight) of polymer glue from 1: 10 to 3: 1.One proper polymer glue comprises a celluosic resin (Celluloseresin) 35wt%, dl-1-as solvent is right-alkene terpene alcohol (50wt% of dl-α-terpineol), and as sodium phosphate (sodium phosphate) 10wt% and glass powder (glasspowder) 15wt% of dispersion agent (dispersant).The function of this glass powder is for increasing then property.Mode with wire mark is coated on substrate surface with colloid mixture, through 110 ℃ of oven dry after 30 minutes, again through 350～500 ℃ of sintering 30 minutes under air atmosphere, to remove the polymer glue.Loaded metal catalyst of the present invention is dispersed in another way on the base material to be comprised this loaded metal catalyst is added in an organic solvent, for example shake for some time through ultrasound in the ethanol, for example added in 10 minutes and give dispersion, mixed solution is poured on the quartz boat substrate through 110 ℃ of oven dry 30 minutes.
Place a reactor to carry out thermal chemical vapor deposition the aforementioned base material that is dispersed with this loaded metal catalyst and react the CNT (carbon nano-tube) of on this loaded metal catalyst, to grow up.Reactant gases comprises rare gas element (for example helium, argon, nitrogen), hydrogen and carbon-source gas, employed carbon-source gas comprises hydrocarbon polymer or carbon monoxide, temperature of reaction is a 400-600 degree Celsius, and the reaction times is 1-120 minute, and pressure is the 0.5-2 normal atmosphere.The reaction back generates CNT (carbon nano-tube) on catalyst carrier surface, and its caliber is distributed between the 1-200 nanometer.
Embodiment 1
The silver-colored particle of particle size dispersion between the 1-5 micron of 1 gram added the water of 50ml, then with ultrasound oscillation treatment solution 10 minutes.The aqueous solution 1 gram of the nickelous nitrate of concentration 1% is added in the silver-colored aqueous solution that is obtained, and mix.The mixed solution that is obtained then is heated the solvent that removes wherein, and acquisition contains the work in-process of silver-colored carrier catalyst 1.01 grams of 1% nickel metal.
Embodiment 2:
Getting 1.0 gram particle size dispersion adds the 50ml deionized water and stirring at the silver particle powder between the 0.05-0.1 micron to add concentration after 15 minutes again is 28% ammoniacal liquor 0.05 gram restir 5 minutes, then reflux is 30 minutes, nickel nitrate aqueous solution 0.5 gram that slowly adds concentration 10% again, add concentration again and be 28% ammoniacal liquor 0.08 gram, continue to stir and to boil that to add concentration after 4 hours again be 37% formalin 0.44 gram, seethed with excitement again 30 minutes.Filter after cooling, get filter cake, must contain silver-colored carrier catalyst 1.05 grams of 5% nickel metal through 110 ℃ of dryings 4 hours.
Embodiment 3:
Loaded metal catalyst and polymer glue that embodiment 1 is prepared mix, and the loaded metal catalyst is 1: 1 to the blending ratio (weight) of polymer glue.One proper polymer glue comprises a celluosic resin (Cellulose resin) 35wt%, dl-1-as solvent is right-alkene terpene alcohol (dl-α-terpineol) 50wt%, a sodium phosphate as dispersion agent (dispersant) (sodium phosphate) 10wt% and glass powder (glass powder) 15wt%.The substrate that has been coated with the catalyst glue after 30 minutes, places a thermal chemical vapor deposition reactor through 110 ℃ of oven dry, reactor temperature is increased to 500 ℃ then, and sintering is 30 minutes under air atmosphere, to remove polymer and solvent.Argon gas was imported 10 minutes, and flow is 1500ml/min, drives air out of reactor.Begin to begin to carry out the thermal chemical vapor deposition reaction with continuing 5 minutes in argon gas (500ml/min) and hydrogen (75ml/min) the mixing back feeding system, adding again after acetylene (25ml/min) mixes before the reaction.After reaction is carried out 6 minutes, earlier acetylene and hydrogen are closed, again heating power supply is closed, close argon gas etc. system after being cooled to below 100 ℃, then substrate to be taken out, be coated with the catalyst place on the substrate and can be observed black deposit this moment.This black deposit is a CNT (carbon nano-tube) between caliber 20 to 60 nanometers through electron microscope observation.
Embodiment 4:
Repeat the step of embodiment 3, but it is prepared to make carrier metal solvent replacement embodiment 1 with embodiment 2.Distribute between 20 to 60 nanometers at the CNT (carbon nano-tube) caliber that substrate surface grows up to.
Embodiment 5:
Loaded metal catalyst 0.01 gram that embodiment 2 is made is dispersed on the quartz boat substrate.Then this quartz boat substrate places a thermal chemical vapor deposition reactor to be same as the condition step growth CNT (carbon nano-tube) of embodiment 3.Distribute between 20 to 60 nanometers at the CNT (carbon nano-tube) caliber that substrate surface grows up to.
Claims (18)
1. loaded metal catalyst that is applicable to low temperature thermal chemical vapor deposition synthesis of carbon nanotube, comprise: particle diameter is between 0.01 to 10 micron precious metal silver, gold, platinum, palladium and copper or their alloy particle; And
Be deposited on the metal solvent on this precious metal silver, gold, platinum, palladium and copper or their alloy particle, wherein this metal solvent is the group that chosen from Fe, cobalt, nickel and alloy thereof are formed, and this metal solvent to the weight ratio of this noble metal between 0.1: 100 to 10: 100.
2. loaded metal catalyst as claimed in claim 1, wherein this noble metal is a silver.
3. loaded metal catalyst as claimed in claim 1, it is by mixing by this precious metal silver, gold, platinum, palladium and copper or their alloy particle are added to give with a saline solution of this metal solvent, the mixture that reheat obtained makes this metal solvent be deposited on this noble metal and prepares.
4. loaded metal catalyst as claimed in claim 3, the saline solution of metal solvent wherein are nitrate solution and sulfate liquor.
5. loaded metal catalyst as claimed in claim 4, the saline solution of metal solvent wherein are water or alcohol solution.
6. loaded metal catalyst as claimed in claim 1, it is by being prepared by the deposition-precipitation method that may further comprise the steps:
A) this precious metal silver, gold, platinum, palladium and copper or their alloy particle are dispersed in the solvent;
B) one of this metal solvent saline solution is added in this precious metal silver, gold, platinum, palladium and the copper of step a) or the dispersion liquid of their alloy particle;
C) add a precipitation agent and in the mixture of step b), also heat the mixture that is obtained; And
D) add a reductive agent the mixture of step c) with reduce this metal solvent ion and this metal solvent is deposited on this precious metal silver, gold, platinum, palladium and copper or their alloy particle.
7. loaded metal catalyst as claimed in claim 6, wherein the solvent of step a) is water or alcohols.
8. loaded metal catalyst as claimed in claim 6, wherein the precipitation agent of step c) is ammoniacal liquor or sodium bicarbonate.
9. loaded metal catalyst as claimed in claim 6, wherein the reductive agent of step d) is diamine, formaldehyde, hypophosphite or phenyl aldehyde.
10. the method for a low temperature thermal chemical vapor deposition synthesis of carbon nanotube comprises the following step:
A) the described loaded metal catalyst of claim 1 is dispersed on the base material; And
B), make a carbon-source gas be deposited on the CNT (carbon nano-tube) of growing up on this loaded metal catalyst by thermal chemical vapor deposition; Wherein thermal chemical vapor deposition is to carry out between 400 to 600 ℃ temperature of reaction one.
11. method as claimed in claim 10, wherein step a) comprises and this loaded metal catalyst is dispersed in one contains in the glue of polymer and organic solvent, obtain to disperse glue to be coated on this base material institute, the coating that heating is obtained is to remove polymer and organic solvent wherein.
12. method as claimed in claim 11, the temperature of wherein removing polymer and organic solvent is between 350～500 ℃.
13. method as claimed in claim 10, wherein step a) comprises this loaded metal catalyst is added in the organic solvent, for some time add through the ultrasound concussion and to give dispersion, the dispersion liquid that is obtained is poured on the quartz boat substrate and forms skim and this thin layer of heat drying thereon.
14. method as claimed in claim 10, wherein the base material of step a) is selected from the group that ITO conductive glass, chilled glass, soda glass, quartz, silicon oxide, silicon wafer, aluminium and sheet metal are formed.
15. method as claimed in claim 10, wherein the thermal chemical vapor deposition of step b) is to carry out one between reaction times of 1 to 120 minute one between 0.5 to 2 atmospheric pressure; And this carbon-source gas comprises hydrocarbon polymer or carbon monoxide.
16. method as claimed in claim 15, wherein this hydrocarbon polymer contains 1 to 12 carbon.
17. method as claimed in claim 15, wherein this carbon-source gas is meant methane, acetylene or carbon monoxide.
18. method as claimed in claim 10, wherein the thermal chemical vapor deposition of step b) is to carry out in the presence of hydrogen; And this carbon-source gas comprises hydrocarbon polymer or carbon monoxide.
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| CN101029218A (en) * | 2006-03-01 | 2007-09-05 | 财团法人工业技术研究院 | Heat-transferring solution containing heteroatomic nano-carbon ball |
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| JP4379247B2 (en) * | 2004-04-23 | 2009-12-09 | 住友電気工業株式会社 | Method for producing carbon nanostructure |
| WO2006007760A1 (en) * | 2004-07-19 | 2006-01-26 | Lingyong Kong | Double-walled carbon nanotubes and the preparing method of same |
| KR100626016B1 (en) * | 2004-09-20 | 2006-09-20 | 삼성에스디아이 주식회사 | Method for preparing carbon nanocages |
| CN100425984C (en) * | 2005-11-03 | 2008-10-15 | 武汉化工学院 | Method for producing miniflow control chip |
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| CN107308951B (en) * | 2016-04-27 | 2021-04-23 | 中国科学技术大学 | Preparation method of wide-temperature catalyst for preferentially oxidizing CO in hydrogen-rich atmosphere, product and application thereof |
| CN106115659B (en) * | 2016-06-24 | 2018-08-21 | 广西师范大学 | A kind of method of chemical vapor deposition synthesizing carbon nanotubes flower |
| CN109896518B (en) * | 2019-04-08 | 2022-03-18 | 西京学院 | Preparation method of high-purity carbon nanotubes |
| CN115784207A (en) * | 2021-09-13 | 2023-03-14 | 昆山科技大学 | Three-dimensional bundle-shaped multi-walled carbon nanotube, preparation method thereof and electrode application |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101029218A (en) * | 2006-03-01 | 2007-09-05 | 财团法人工业技术研究院 | Heat-transferring solution containing heteroatomic nano-carbon ball |
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