CN1868868A - Method of in-situ filling symbiotic iron nanometer wire on thin wall nanometer pipe - Google Patents
Method of in-situ filling symbiotic iron nanometer wire on thin wall nanometer pipe Download PDFInfo
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Abstract
A process for preparing the in-situ symbiotic thin-wall carbon nano-tubes and iron nanowires filled in said nanotube includes such steps as dissolving ferrocene in Cl contained organic solvent, filling Ar gas in air-tight quartz tube, heating, controlling the temp at the end of capillary tube inserted in said quartz tube to be 250-300 deg.C, filling H2, pumping said solution in reactor, reaction, stopping to fill H2, and cooling.
Description
Technical field
The present invention relates to the method that a kind of original position symbiotic iron nanometer wire is filled in thin wall carbon nano-tube, belong to the synthetic and applied technical field of carbon nanomaterial.
Background technology
Carbon nanotube is by one deck or the several layers of monodimension nanometer material that the graphite synusia curls and forms according to certain helix angle.Carbon nanotube is divided into single wall, double-walled and multi-walled carbon nano-tubes.Carbon nanotube is owing to the performance of its particular structure and excellence has caused the research boom of the whole world to carbon nanotube.The energy gap width of carbon nanotube is different along with the difference of helix angle, and its electroconductibility is between conductor and semi-conductor; For example, the current capacity of carbon nanotube is up to 10
9A/cm
2Magnitude is higher 1000 times than copper; Theoretical Calculation shows that the Young's modulus of carbon nanotube can reach 1TPa, shows and overlength Single Walled Carbon Nanotube rope is carried out macroscopical stretching experiment result, and the tensile strength of Single Walled Carbon Nanotube long filament is up to 2.4GPa, and Young's modulus reaches 77GPa; Molecular dynamics simulation shows, because the bigger average phonon free path of carbon nanotube, carbon nanotube has up to 6600Wm
-1K
-1The axial thermal conductivity coefficient.
How to utilize the aperture structure of carbon pipe uniqueness to attract numerous people's interest.Current, fill magneticmetal especially Fe, Ni at the carbon tube cavity, be a current big research focus.Iron is the excellent magnetism material, and is easily oxidized in air.When filling Fe nanowire (Fe/CNTs) at carbon nanotube cavity and since carbon nanotube preferably thermostability shield, guaranteed iron not oxidized and corrosion under comparatively high temps, and the katalysis of iron can also promote carbon nano tube growth.People such as Mariana (Mariana et al., Physical Review B 73,125,435 2006), interaction mechanism and its influence of pattern of filling out Fe nanowire and carbon nanotube in having analyzed theoretically to magnetic performance.In a word, owing to combine the dielectric properties of carbon nanotube and the magnetic performance of metal (Fe, Ni, Co), make Fe/CNTs extremely wide application prospect (P.C.P.Watts et al. be arranged in fields such as micro-nano electron device, high density recording material, anti-electromagnetic radiation and microwave absorbing, Appl.Phys.A 78, and 79-83 2004).
At present, the technology of filling magneticmetal nano wire mainly contains base and plants template and pressed powder two-region heating method in carbon nanotube.People (Renchao Che et al., Adv.Mater., 16, No.5 401-4052004) such as the Renchao Che of Peking University utilize base to plant template, with Fe
2(SO
4)
35H
2O prepares Al as the presoma of catalyzer iron by sol-gel method
2O
3-SiO
2As carrier, with CH
4As carbon source, fill out the carbon nanotube of Fe nanowire in having made.People such as the JianchunBao of Nanjing University (Jianchun Bao et al., Appl.Phys.Lett., Vol.81, No.24,2002) also utilize the method for electrochemical deposition, utilizing porous alumina is that template is filled the nickel nano wire toward directed multi-wall carbon nano-tube tube cavity.But this method operation is various, and early-stage preparations and subsequent technique are miscellaneous, and process controllability is relatively poor, and the filling ratio of iron is lower in addition and amorphous carbon is more, its Fe nanowire limited length.In addition, on mechanism, template can not realize that metal nanometer line is in the compound continuous filling of the inner original position of carbon pipe.
Current in the world the application of carbon nanotube cavity filler metal nano wire more be pressed powder two-region heating method, promptly utilize the metallorganics pressed powder as presoma, fill out the carbon nanotube of Fe nanowire in two-region heatable catalytic cracking makes.Its technology as shown in Figure 1.People (C.N.R Rao et al. such as C.N.R Rao, J.Chem.Soc.Chem.Commun.15,15251998) carry out pyrogenically prepared Fe/CNTs with the ferrocene powder as presoma, but the carbon nanotube crystallization degree that makes is low, tube wall is very thick, and granules of catalyst is also a lot.People (N.Grobert, Appl.Phys.Lett., Vol.75,3363, No.21,1999) such as N.Grobert used ferrocene and C instead afterwards
60As raw material, the crystallization of carbon nanotube is increased, and in what fill out is single-crystal iron.(Leibniz Institute for Solid State and MaterialsResearch Dresden, Dresden Germany) fills out in carbon nanotube on the magneticmetal nano wire, has done a large amount of and secular system works in another seminar.T.M ü hl (T.M ü hl et al., J.Appl.Phys., Vol.93, No.10, May 2003) use ferrocene as presoma, and the concrete crystalline state of filling out iron in having analyzed.People such as Radinka (Radinka et al., AppliedSurface Science 238 (2004) 355-359) utilize dicyclopentadienylcobalt as presoma, fill out the directed multi-walled carbon nano-tubes (Fe filled MWCNT) of Co nano wire in having made.People such as E.Borowiak-Palen (E.Borowiak-Palen et al., Chemical Physics Letters 421 (2006) 129-133) utilize FeCl
3The way of solution intercalation is inserted iron in the Single Walled Carbon Nanotube.The magnetic performance that the carbon nanotube of magneticmetal is also internally filled out by this study group characterizes.In a word, their result of study shows, Fe, Ni and Co inserted the matrix material that carbon nanotube forms have extraordinary application prospect aspect the magnetics material.But this method of filling out Fe nanowire has a lot of significant disadvantages.To be example at the interior Fe nanowire of filling out, when heating pyrolyze ferrocene powder, the rate of cleavage that can not control ferrocene exactly is the feed speed of raw material just, greatly reduces the controllability of this technology.Because ferrocene is all evaporations soon, and do not have new presoma to replenish up, this carbon nanotube form of internally filling out iron has very big influence.Rough as the carbon nanotube tube wall, the caliber thickness differs, and tube wall is thicker; Impurity is more in the product, has inserted a little Fe toward the contact meeting in the carbon nanotube
3C; Filling ratio is lower, and Fe nanowire length is below micron dimension.
Based on above-mentioned consideration, the present invention proposes a kind of simple process of filling Fe nanowire at carbon nanotube cavity, this technology can effectively improve iron filling ratio and in fill out Fe nanowire length, attenuate carbon nanotube thickness of pipe, and realize carbon nanotube and in fill out Fe nanowire the continuous in-situ symbiosis.
Summary of the invention
The purpose of this invention is to provide the method for filling out the thin wall carbon nano-tube of Fe nanowire in a kind of direct synthesizing, the present invention mainly solves following technical barrier:
1) directly synthetic big hollow, thin wall carbon nano-tube.The degree of hollowness usefulness carbon nanotube internal diameter of common carbon nanotube and the ratio of wall thickness
Value is weighed.Because carbon nanotube continuous growth in the vitellarium will original position be filled Fe nanowire in carbon nanotubes lumen, must directly synthetic high-quality big hollow thin wall carbon nano-tube.This needs the speed of growth of controlling carbon nanotube and the wall thickness of carbon nanotube.
2) continuity of carbon nanotube endosymbiosis Fe nanowire.Usually iron only is particulate state in carbon nanotube, is difficult to connect continuously the nano wire of growing up.Iron is as the catalyzer of carbon nano-tube, and the nano level iron particle surface that is come out by the ferrocene thermo-cracking at first becomes the nucleating center of carbon nano-tube and is wrapped in carbon nanotube cavity.Because carbon nanotube is easy to grow up at iron particle surface forming core, what make one one of iron particle axially fills the Fe nanowire that forms than high length-diameter ratio continuously along carbon nanotube cavity, but not becoming crystalline nucleation to form many cavity carbon nanotubes separately, this is a very challenging difficult problem.
3) filling ratio of Fe nanowire in the raising carbon nanotube is promptly realized most of carbon nanotube cavities filling Fe nanowires.Usually iron has only in few carbon nanotubes lumen to be filled with iron as catalyzer.
4) realization preparation technology's simple controllable.Base kind template and the pressed powder two-region heating method of using because raw material supplying can not accurately be controlled continuously, can not realize the original position symbiosis growth of Fe nanowire in carbon nanotube at present.And operation is miscellaneous in the middle of these two kinds of methods, so also be unfavorable for realizing producing in batches.
5) seek to mate carbon nanotube and in fill out the presoma and the technology of the Fe nanowire speed of growth.Fill out the effect quality of Fe nanowire, key is that can presoma and preparation technology mate the original position symbiosis speed of Fe nanowire at carbon nanotube cavity preferably.The ferrocene powder or the ferrocene/xylene solution of common usefulness, the effect of last carbon nano-tube filled Fe nanowire is also bad.Therefore, must choose suitable presoma and growth technique.
The big hollow thin wall carbon nano-tube of filling out Fe nanowire in the two-region heating floating catalytic cracking preparation is to be based upon the floating catalytic cracking process to be grown up on the technical foundation of synthesizing carbon nanotubes macroscopic body in batches.
A kind of original position symbiotic iron nanometer wire is filled in the method for thin wall carbon nano-tube, and preparation original position symbiotic iron nanometer wire thin wall carbon nano-tube in quartz tube reactor is characterized in that this method may further comprise the steps:
(1) ferrocene is dissolved in the chloro-carbon solvent, the pale brown look clear solution that is mixed with 0.050～0.100g/ml is standby;
(2) substrate of reactor quartz substrate is equipped on the quartz boat, again quartz boat is slowly pushed the silica tube middle part,, utilize the heated air expanding method to guarantee the silica tube resistance to air loss with seal gum sealing silica tube two ends;
(3) feed argon gas in the described airtight good silica tube of step (2), flow is 200～300mL/min; Heated air temperature to 750～900 ℃;
(4) utilize temperature controller to make the kapillary port temperature of inserting in the silica tube remain on 250～300 ℃;
(5) argon flow amount of the described feeding of set-up procedure (3) is to 3000mL/min, and feeds the hydrogen of 200mL/min;
(6) with accurate flow pump step (1) solution that disposes is pumped into reactor, speed is 0.4～0.8mL/min;
(7) after reaction for some time, stop logical hydrogen, reduce argon flow amount, reduce to room temperature, close argon stream until furnace to 200mL/min;
All can obtain original position symbiotic iron nanometer wire thin wall carbon nano-tube at quartz substrate and silica tube middle part.
The present invention is raw materials used to be ferrocene/chloride organic solution.The present invention utilizes accurate flow pump, under 200～300 ℃ preheating temperature, accurately successive sucks the silica tube preheating zone with solution, ((0.3～0.8ml/min), the controllability of technology is very strong for the velocity of evaporation of 0.4～1.2rpm) control solution and speed of feed by setting preheating zone temperature and flow pump rotating speed.Compare with pressed powder two-region heating method with the base kind template that present application is more, the present invention has remarkable advantages.Base kind method and template are carbon nano-tubes on sedimentary nano iron particles in advance, carbon nanotube does not just have catalyzer iron particle " coating " chamber within it source of iron to replenish thereafter and inserts carbon nanotube, wants depositing nano iron particle in advance, also to remove template, complex process afterwards.In addition, with regard to filling mechanism, also continuous supply and the original position composite growth with the present invention's proposition has essential distinction.Pressed powder two-region heating method is the direct exposure of ferrocene powder to be placed on the preheating zone pyrolysis be blown into reaction chamber.Because the powder thermal degradation is too fast, thereby be difficult to accurately control raw material supplying speed, amorphous carbon is a lot of in the product, and the carbon nanotube degree of graphitization is not high.The technology simple controllable.
The present invention has realized the original position symbiosis growth of Fe nanowire and carbon nanotube, and the carbon nanotube of preparation has shape characteristic preferably.Reach 1mm as macroscopic thickness, the micron dimension in document improve a lot (Baoyu Liu et al., Journalof Crystal Growth 277 2005 293-297; T.M ü hl et al., J.Appl.Phys., Vol.93, No.10, May 2003; N.Grobert et al., Appl.Phys.Lett., Vol.75, No.21,1999; B.C.Satishkumar., Chemical Physics Letters 3632002301-306); Tube wall is very thin, has very big degree of hollowness in addition, and the Fe nanowire filling ratio improves a lot, and reaches 80% (T.Ruskov et al., J.Appl.Phys., Vol.96, No.12,2004).Than base kind template (Renchao Che et al., Adv.Mater., 16, No.5 401-4052004) and pressed powder two-region heating method (N.Grobert et al., Appl.Phys.Lett., Vol.75, No.21,1999; Leonhardt et al., J.Appl.Phys.98,074,315 2005), it is much simple that technology of the present invention is wanted, and the controllability of technology is stronger, more helps realizing continuous production in enormous quantities.The present invention make in fill out the Fe nanowire thin wall carbon nano-tube prospect that has a very wide range of applications in fields such as quantum lead, micro-nano electron device, high density magnetic recording material and microwave absorbing.
Description of drawings
Fig. 1: be process schematic representation of the present invention.
Fig. 2: the big hollow thin wall carbon nano-tube film photomacrograph of filling out Fe nanowire on the quartz substrate.
Fig. 3: in fill out the low power transmission electron microscope photo of the big hollow thin wall carbon nano-tube film of Fe nanowire.
Fig. 4: in fill out the high-resolution-ration transmission electric-lens photo of the big hollow thin wall carbon nano-tube film of Fe nanowire.
Embodiment
The big hollow thin wall carbon nano-tube of filling out Fe nanowire in the two-region heating floating catalytic cracking preparation is to be based upon the floating catalytic cracking process to be grown up on the technical foundation of synthesizing carbon nanotubes macroscopic body in batches.Fig. 1: be process schematic representation of the present invention.
(1) be dissolved in (chloride chlorobenzene, dichlorobenzene and Ethylene Dichloride) in the chloro-carbon solvent with ferrocene, the brown yellow solution that is made into 0.050～0.100g/ml is as raw material for standby.
(2) accurate flow pump is pumped into silica tube preheating zone (200～300 ℃) evaporation to presoma, utilize mixed carrier gas (argon flow amount is 2000～5000sccm, hydrogen flowing quantity be 200～600sccm) above-mentioned solution steam is blown in the middle of high temperature (700～1000 ℃) district cracking synthetic product.
(3) utilize accurate flow pump control presoma feed speed to make that the suction speed of solution is 0.4mL/min.
(4) through after the 30min reaction, in silica tube, can collect pulverous product, 30 * 40mm is also arranged on quartz substrate in addition
2Black thin film form.
Fig. 2 be utilize that the present invention makes in 30min in fill out Fe nanowire thin wall carbon nano-tube film photomacrograph, further analyze and find that it has pattern characteristics preferably:
(1) it is fine to fill out the continuity of Fe nanowire in the carbon nanotube, the iron great majority be elongated wire but not particulate state or sphere-packing at the inner chamber of thin-walled carbon pipe.
(2) it is very high to fill out the filling ratio of Fe nanowire (Fe/CNTs) in the carbon nanotube, and most carbon tube cavities have all filled up Fe nanowire.Fig. 3 is the low power transmission electron microscope photo of film, and as we know from the figure, Fe/CNTs has higher charging efficiency; In addition, in to fill out the carbon nanotube tube wall of Fe nanowire very thin, wall thickness is about 4nm, has very big degree of hollowness, the Fe nanowire diameter is about 25nm, intracavity diameter/carbon thickness of pipe＞6, most of Fe nanowire length＞2 μ m, Fe nanowire length-to-diameter ratio＞80; The carbon nanotube degree of graphitization is very high, and it is smooth that pipe shaft is straight, and (30～40nm), Fig. 4 is the high-resolution-ration transmission electric-lens photo of film sample to carbon pipe uniform diameter.
Embodiment 1:
1) takes by weighing 1.0g ferrocene powder, be dissolved in the 20mL dichlorobenzene solution, mix and form pale brown look clear solution;
2) the quartz substrate substrate is equipped on the quartz boat, again quartz boat is slowly pushed the silica tube middle part,, utilize heated air expansible method to guarantee the resistance to air loss of silica tube with seal gum sealing silica tube two ends.
3) lead to argon gas in silica tube, flow is 200mL/min, is heated to temperature required 750 ℃ of test;
4) utilize temperature controller, the kapillary port temperature of inserting in the silica tube is remained between 250 ℃;
5) adjust argon gas to 3000mL/min, and feed the hydrogen of 200mL/min;
6) open accurate flow pump, reaction soln is sucked silica tube with the speed of feed of 0.4mL/min;
7) behind the 30min, stop logical hydrogen, reduce argon flow amount, reduce to room temperature until furnace, closed gas flow to 200mL/min.All can collect reaction product at quartz substrate and silica tube middle part.Find that through scanning electronic microscope and transmission electron microscopy observation product is that (about 20～50nm), 60% carbon nanotube cavity of diameter is filled with Fe nanowire to the non-directional multi-walled carbon nano-tubes.
Embodiment 2:
1) takes by weighing 1.2g ferrocene powder and be dissolved in the 20mL dichlorobenzene solution, mix and form pale brown look clear solution.
2) the quartz substrate substrate is equipped on the quartz boat, again quartz boat is slowly pushed the silica tube middle part,, utilize heated air expansible method to guarantee the resistance to air loss of silica tube with seal gum sealing silica tube two ends.
3) lead to argon gas in silica tube, flow is 300mL/min, is heated to temperature required 900 ℃ of test.
4) utilize temperature controller, the kapillary port temperature of inserting in the silica tube is remained between 300 ℃.
5) adjust argon gas to 3000mL/min, and feed the hydrogen of 200mL/min.
6) open accurate flow pump, reaction soln is sucked silica tube with the speed of feed of 0.6mL/min.
7) behind the 30min, stop logical hydrogen, reduce argon flow amount, reduce to room temperature until furnace, closed gas flow to 200mL/min.All can collect reaction product at quartz substrate and silica tube middle part.Find through scanning electronic microscope and transmission electron microscopy observation, product be the non-directional multi-walled carbon nano-tubes (diameter is about 20～60nm), and pipe shaft is straight, impurity seldom, 80% carbon nanotube cavity is filled with Fe nanowire.
Embodiment 3:
1) takes by weighing 1.8g ferrocene powder and be dissolved in the 20mL dichlorobenzene solution, mix and form pale brown look clear solution.
2) the quartz substrate substrate is equipped on the quartz boat, again quartz boat is slowly pushed the silica tube middle part,, utilize heated air expansible method to guarantee the resistance to air loss of silica tube with seal gum sealing silica tube two ends.
3) lead to argon gas in silica tube, flow is 300mL/min, is heated to temperature required 820 ℃ of test.
4) utilize temperature controller, the kapillary port temperature of inserting in the silica tube is remained between 300 ℃.
5) adjust argon gas to 3000mL/min, and feed the hydrogen of 200mL/min.
6) open accurate flow pump, reaction soln is sucked silica tube with the speed of feed of 0.8mL/min.
7) behind the 30min, stop logical hydrogen, reduce argon flow amount, reduce to room temperature until furnace, closed gas flow to 200mL/min.All can collect reaction product at quartz substrate and silica tube middle part.Find through scanning electronic microscope and transmission electron microscopy observation, product be the non-directional multi-walled carbon nano-tubes (diameter is about 20～60nm), and pipe shaft is straight, impurity seldom, 70% carbon nanotube cavity is filled with Fe nanowire.X-ray diffraction shows that the inside is filled with body-centred cubic single-crystal iron.
Embodiment 4:
1) takes by weighing 1.2g ferrocene powder and be dissolved in the 20mL chlorobenzene solution, mix and form pale brown look clear solution;
2) the quartz substrate substrate is equipped on the quartz boat, again quartz boat is slowly pushed the silica tube middle part,, utilize heated air expansible method to guarantee the resistance to air loss of silica tube with seal gum sealing silica tube two ends.
3) lead to argon gas in silica tube, flow is 300mL/min, is heated to temperature required 860 ℃ of test.
4) utilize temperature controller, the kapillary port temperature of inserting in the silica tube is remained between 300 ℃.
5) adjust argon gas to 3000mL/min, and feed the hydrogen of 200mL/min.
6) open accurate flow pump, reaction soln is sucked silica tube with the speed of feed of 0.6mL/min.
7) behind the 30min, stop logical hydrogen, reduce argon flow amount, reduce to room temperature until furnace, closed gas flow to 200mL/min.All can collect reaction product at quartz substrate and silica tube middle part.Find through scanning electronic microscope and transmission electron microscopy observation, product be the non-directional multi-walled carbon nano-tubes (diameter is about 20～60nm), and pipe shaft is straight, impurity seldom, 90% carbon nanotube cavity is filled with Fe nanowire.Tube wall layer number seldom is about 8 layers, and thickness of pipe is greatly about 5nm.The electronics selected diffraction shows, that fills out in the carbon pipe also includes face-centred cubic monocrystalline iron nanometer thread.
Embodiment 5:
1) takes by weighing 2.0g ferrocene powder and be dissolved in 20mL Ethylene Dichloride solution, mix and form pale brown look clear solution.
2) the quartz substrate substrate is equipped on the quartz boat, again quartz boat is slowly pushed the silica tube middle part,, utilize heated air expansible method to guarantee the resistance to air loss of silica tube with seal gum sealing silica tube two ends.
3) lead to argon gas in silica tube, flow is 300mL/min, is heated to temperature required 860 ℃ of test.
4) utilize temperature controller, the kapillary port temperature of inserting in the silica tube is remained between 300 ℃.
5) adjust argon gas to 3000mL/min, and feed the hydrogen of 200mL/min.
6) open accurate flow pump, reaction soln is sucked silica tube with the speed of feed of 0.6mL/min.
7) behind the 60min, stop logical hydrogen, reduce argon flow amount, reduce to room temperature until furnace, closed gas flow to 200mL/min.Can collect one deck black thin film at quartz substrate, the powder of about 0.5g all can be collected in the silica tube middle part.Find through scanning electronic microscope and transmission electron microscopy observation, product be the non-directional multi-walled carbon nano-tubes (diameter is about 20～60nm), the very high and impurity of the degree of graphitization of pipe shaft seldom, 70% carbon nanotube cavity is filled with Fe nanowire.Electronics selected diffraction and X-ray diffraction result show, that fills out in the carbon nanotube that Fe nanowire has a body-centered cubic structure also has a face-centred cubic structure.In the Fe nanowire length of filling out longer.
Claims (2)
1, a kind of original position symbiotic iron nanometer wire is filled in the method for thin wall carbon nano-tube, and preparation original position symbiotic iron nanometer wire thin wall carbon nano-tube in quartz tube reactor is characterized in that this method may further comprise the steps:
(1) ferrocene is dissolved in the chloro-carbon solvent, the pale brown look clear solution that is mixed with 0.050～0.100g/ml is standby;
(2) substrate of reactor quartz substrate is equipped on the quartz boat, again quartz boat is slowly pushed the silica tube middle part,, utilize the heated air expanding method to guarantee the silica tube resistance to air loss with seal gum sealing silica tube two ends;
(3) feed argon gas in the described airtight good silica tube of step (2), flow is 200～300mL/min; Heated air temperature to 750～900 ℃;
(4) utilize temperature controller to make the kapillary port temperature of inserting in the silica tube remain on 250～300 ℃;
(5) argon flow amount of the described feeding of set-up procedure (3) is to 3000mL/min, and feeds the hydrogen of 200mL/min;
(6) with accurate flow pump step (1) solution that disposes is pumped into reactor, speed is 0.4～0.8mL/min;
(7) after reaction for some time, stop logical hydrogen, reduce argon flow amount, reduce to room temperature, close argon stream until furnace to 200mL/min;
All can obtain original position symbiotic iron nanometer wire thin wall carbon nano-tube at quartz substrate and silica tube middle part.
2, a kind of original position symbiotic iron nanometer wire according to claim 1 is filled in the method for thin wall carbon nano-tube, preparation original position symbiotic iron nanometer wire thin wall carbon nano-tube in quartz tube reactor, it is characterized in that described chloro-carbon solvent is any in chloride chlorobenzene solution, dichlorobenzene solution or the Ethylene Dichloride solution.
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| CN102070134B (en) * | 2010-07-07 | 2012-10-31 | 江西理工大学 | Transparent macro-tube continuum formed by carbon nano-tubes and composite method thereof |
| CN102070134A (en) * | 2010-07-07 | 2011-05-25 | 江西理工大学 | Transparent macro-tube continuum formed by carbon nano-tubes and composite method thereof |
| CN102205957B (en) * | 2011-04-07 | 2012-10-31 | 上海大学 | Method for generating carbon chain in multi-wall carbon nanotube |
| CN102205957A (en) * | 2011-04-07 | 2011-10-05 | 上海大学 | Method for generating carbon chain in multi-wall carbon nanotube |
| CN104190948A (en) * | 2014-08-25 | 2014-12-10 | 西安近代化学研究所 | Method for preparing carbon nanotube - aluminium powder composite material |
| CN104860295A (en) * | 2015-05-11 | 2015-08-26 | 苏州德生材料科技有限公司 | Automatic high-purity carbon nano tube preparation device and method |
| CN109205589A (en) * | 2017-07-07 | 2019-01-15 | 天津大学 | The preparation method of porous rib cage shape carbon material |
| CN109205589B (en) * | 2017-07-07 | 2022-04-01 | 天津大学 | Preparation method of porous rib-shaped carbon material |
| CN114751399A (en) * | 2022-04-29 | 2022-07-15 | 北京航空航天大学 | Carbon nanotube confinement metal nanowire material and preparation method and application thereof |
| CN114751399B (en) * | 2022-04-29 | 2024-04-09 | 北京航空航天大学 | Carbon nanotube domain-limited metal nanowire material, and preparation method and application thereof |
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