CN108726506A - Quickly prepare the method and system of ultra-long horizontal carbon nanotube - Google Patents

Quickly prepare the method and system of ultra-long horizontal carbon nanotube Download PDF

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CN108726506A
CN108726506A CN201710254260.5A CN201710254260A CN108726506A CN 108726506 A CN108726506 A CN 108726506A CN 201710254260 A CN201710254260 A CN 201710254260A CN 108726506 A CN108726506 A CN 108726506A
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carbon
catalyst layer
material film
reative cell
carbon nanotube
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李清文
康黎星
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Suzhou Institute of Nano Tech and Nano Bionics of CAS
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Suzhou Institute of Nano Tech and Nano Bionics of CAS
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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
    • C01B2202/00—Structure or properties of carbon nanotubes
    • C01B2202/02—Single-walled nanotubes
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2202/00—Structure or properties of carbon nanotubes
    • C01B2202/20—Nanotubes characterized by their properties
    • C01B2202/30—Purity
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2202/00—Structure or properties of carbon nanotubes
    • C01B2202/20—Nanotubes characterized by their properties
    • C01B2202/34—Length
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/10—Particle morphology extending in one dimension, e.g. needle-like
    • C01P2004/13—Nanotubes
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/54—Particles characterised by their aspect ratio, i.e. the ratio of sizes in the longest to the shortest dimension
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer

Abstract

The invention discloses a kind of method and system quickly preparing ultra-long horizontal carbon nanotube.The method includes：An at least catalyst layer is fixed in reative cell, and catalyst layer is made to be connect with heating element heat conduction, carbon-source gas and carrier gas are passed through into reative cell, grows with heating element heats catalyst layer and to form ultra-long horizontal carbon nanotube.The system comprises：Reative cell, the reative cell has an at least air inlet and an at least gas outlet, and an at least catalyst layer is further fixedly arranged in reative cell, and the catalyst layer can be contacted with the reaction gas for flowing to gas outlet from air inlet；Heating element is fixedly installed in reative cell and is connect with catalyst layer heat conduction.The present invention uses carbon material film energization rapid thermal response, and heating rate is fast, and energy consumption cost is low, and catalyst activity is high, and the speed of growth of ultra-long horizontal carbon nanotube is fast, prepared by the magnanimity for being conducive to ultra-long horizontal carbon nanotube.

Description

Quickly prepare the method and system of ultra-long horizontal carbon nanotube
Technical field
The present invention relates to a kind of methods quickly preparing ultra-long horizontal carbon nanotube, more particularly to a kind of quickly to prepare overlength The method and system of horizontal carbon nanotube, belong to technical field of nano material.
Background technology
Carbon nanotube has the performances such as excellent electricity, optics and mechanics, is always the heat studied in nano science field Point has broad application prospects in numerous areas such as nanometer electronic device, energy conversion, bio-sensing and composite materials.Overlength Horizontal carbon nanotube refer to the one kind grown in smooth substrate surface be parallel to substrate surface, length up to millimeter, even centimetre with On special appearance carbon nanotube.Such carbon nanotube follows free growing mechanism, between Guan Yuguan distance compared with Greatly, mutual interference can be broken away from, is easy to reach the above length of millimeter, and there is very low defect concentration, it is easier to Embody the theoretical excellent properties of carbon nanotube.It is and existing in addition, ultra-long horizontal carbon nanotube can be grown directly upon silicon chip surface Semiconductor technology is mutually compatible with, and without transfer, is directly used in electronic device preparation, has wide application in nanometer electronic device field Foreground, it is considered to be the material of main part in rear mole of epoch nanometer electronic device.
To realize the application of ultra-long horizontal carbon nanotube, it is necessary to realize the batch system of ultra-long horizontal carbon nanotube first It is standby, especially to realize that length reaches the batch preparation of the overlength carbon nano pipe of meter level even kilometer grade or more.It prepares at present super The method of long horizontal carbon nanotube is mainly chemical vapour deposition technique (CVD).It is generally believed that ultra-long horizontal carbon nano tube growth Air-flow orientation is followed in the process, and catalyst is detached from substrate, floats in the gas phase, due to avoiding the phase interaction of catalyst and substrate With carbon nanotube can grow very long, but growth rate is very slow, and usual method only has 10 μm/s, this has seriously affected overlength water The preparation efficiency of flat carbon nanotube.(Wen Q, Zhang R F, et al.Chem.Mater., 2010,22 (4) such as Wen: 12194-1296.) by the way that a small amount of water is added in reaction gas flow, the growth speed of ultra-long horizontal carbon nanotube has been greatly facilitated Degree, reaches 80~90 μm/s, this is to have reported optimum growth speed at present.Zhang et al. (Zhang R F, Zhang Y Y, Zhang Q,et al.ACS Nano,2013,7:6156-6161.) service life of catalyst is extended by mobile flat-temperature zone method, It is successfully prepared the carbon nanotube up to half meter, this is current carbon nanotube longest in the world, but growth rate is at the soonest only Reach 83 μm/s.In addition, growth temperature in the prior art is usually more than 900 DEG C, mainly use diamond heating, heating rate small In 5 DEG C/s, time-consuming, and catalyst is caused to assemble severity in temperature-rise period, is easy inactivation, is reduced so as to cause catalytic efficiency. Furthermore existing main grower is hot-wall CVD system, and equipment is huge, and height is required to furnace insulation, and technique is unstable, weight Renaturation is poor, and then influences batch and prepare.
Therefore, how to improve the growth rate of ultra-long horizontal carbon nanotube is to further increase the pass of length of carbon nanotube Key and its basis that from now on prepared by magnanimity.
Invention content
Quickly preparing the method and system of ultra-long horizontal carbon nanotube the main purpose of the present invention is to provide a kind of, with gram Take deficiency in the prior art.
For realization aforementioned invention purpose, the technical solution adopted by the present invention includes：
An embodiment of the present invention provides a kind of methods quickly preparing ultra-long horizontal carbon nanotube comprising：
An at least catalyst layer is fixed in reative cell, and the catalyst layer is made to be connect with heating element heat conduction；
Carbon-source gas and carrier gas are passed through into the reative cell；
It grows with catalyst layer described in heating element heats and to form ultra-long horizontal carbon nanotube.
Among some exemplary embodiments, the heating element uses carbon material film.
Among some exemplary embodiments, the method includes：
Catalyst layer is placed in reative cell, and catalyst layer is made to be connect with carbon material film heat conduction；
Carbon-source gas and carrier gas are passed through into the reative cell；
Make the carbon material film heating catalyst layer by way of being passed through electric current into the carbon material film and grows shape At ultra-long horizontal carbon nanotube.
An embodiment of the present invention provides a kind of methods quickly preparing ultra-long horizontal carbon nanotube comprising：
The solution for including catalyst precursor is uniformly coated in substrate surface；
There is the substrate of the catalyst precursor to be fixed in reative cell area load, and make the substrate with as adding The carbon material film heat conduction of thermal element connects；
It is passed through protective gas into the reative cell, to which indoor air discharge will be reacted；
It is passed through reducing gas, carbon-source gas and carrier gas into the reative cell, and electric current is passed through into the carbon material film And the carbon material film is made to heat the substrate, so that the catalyst precursor is decomposed and is restored, in the substrate table Face forms evenly dispersed a plurality of catalyst granules, and growth forms ultra-long horizontal carbon nanotube simultaneously.
Among some exemplary embodiments, the method includes：Only with the carbon material film to the catalyst granules It is heated.
The embodiment of the present invention additionally provides a kind of system quickly preparing ultra-long horizontal carbon nanotube comprising：
Reative cell, the reative cell have an at least air inlet and an at least gas outlet, and also solid in the reative cell Surely it is provided with an at least catalyst layer, the catalyst layer can be contacted with the reaction gas for flowing to gas outlet from air inlet；
Heating element is fixedly installed in the reative cell and is connect with the catalyst layer heat conduction.
Preferably, the heating element uses carbon material film.
Compared with prior art, advantages of the present invention includes：
1) method provided by the invention for quickly preparing ultra-long horizontal carbon nanotube uses carbon film energization rapid thermal response, can It is brought rapidly up, hence it is evident that catalyst caused aggregation and inactivation, catalyst activity in long-time heats up is inhibited to significantly improve.Due to Reducing gas and carbon-source gas are passed through reative cell at the very start, during carbon material film electrical heating, the formation of catalyst and carbon The growth of nanotube is almost completed at the same time, without taking several minutes of catalyst for arriving dozens of minutes as other methods need to undergo Nucleation time, therefore the fast-growth of ultra-long horizontal carbon nanotube may be implemented in this method, is more than existing text up to 960 μm/s Report at least one order of magnitude of peak is offered, thus realizes the quick preparation of ultra-long horizontal carbon nanotube；
2) system provided by the invention for quickly preparing ultra-long horizontal carbon nanotube uses electric heater unit, compared to tradition Tube furnace, equipment is simple, and heating rate is fast, and energy consumption cost is low, and is cold wall CVD, and technology stability is good.Carbon material film Heating temperature and the temperature difference in remaining region in reative cell are more than 800 DEG C, are more advantageous to carbon nano-tube catalyst in the big temperature difference Under the influence of, it is detached from substrate surface, keeps activity for a long time, realizes prepared by the magnanimity of quick ultra-long horizontal carbon nanotube；
3) method of the invention is not limited to the quick preparation of ultra-long horizontal carbon nanotube, the carbon nanotube of other patterns, The vertical array of such as carbon nanotube, agglomerate carbon nanotube can also realize quick preparation.
4) ultra-long horizontal length of carbon nanotube prepared by method using the present invention is up to 4mm, in nanometer electronic device, the energy The fields such as conversion, biosensor, composite material are with a wide range of applications.
Description of the drawings
Fig. 1 is that the system and method flow for quickly preparing ultra-long horizontal carbon nanotube in one embodiment of the present invention is shown It is intended to；
Fig. 2 a- Fig. 2 b are the scanning electron microscope (SEM) photographs of 1 obtained ultra-long horizontal carbon nanotube of the embodiment of the present invention；
Fig. 3 is the transmission electron microscope figure of 1 obtained ultra-long horizontal carbon nanotube of the embodiment of the present invention；
Fig. 4 is the scanning electron microscope (SEM) photograph of 2 obtained overlength carbon nano pipe horizontal array of the embodiment of the present invention；
Fig. 5 is the scanning electron microscope (SEM) photograph of 3 the obtained vertical array of ultra-long horizontal carbon nanotube of the embodiment of the present invention；
Fig. 6 is the scanning electron microscope (SEM) photograph for obtaining horizontal carbon nanotube in comparative example 1 of the present invention using common tube furnace.
Specific implementation mode
In view of deficiency in the prior art, inventor is able to propose the present invention's through studying for a long period of time and largely putting into practice Technical solution.The technical solution, its implementation process and principle etc. will be further explained as follows.
The one side of the embodiment of the present invention provides a kind of method quickly preparing ultra-long horizontal carbon nanotube, packet It includes：
An at least catalyst layer is fixed in reative cell, and the catalyst layer is made to be connect with heating element heat conduction；
Carbon-source gas and carrier gas are passed through into the reative cell；
It grows with catalyst layer described in heating element heats and to form ultra-long horizontal carbon nanotube.
Among some exemplary embodiments, the heating element uses carbon material film.
Preferably, the material of the carbon material film includes any one in carbon nanotube, carbon fiber and graphene or two Kind or more combination, but not limited to this.
Further, the thickness of the carbon material film is 1~100 μm, and especially preferably 5~10 μm, conductivity is more than 104S/m, intensity are more than 100MPa.
Among some exemplary embodiments, the method includes：
Catalyst layer is placed in reative cell, and catalyst layer is made to be connect with carbon material film heat conduction；
Carbon-source gas and carrier gas are passed through into the reative cell；
Make the carbon material film heating catalyst layer by way of being passed through electric current into the carbon material film and grows shape At ultra-long horizontal carbon nanotube.
Preferably, the intensity for being passed through the DC current of the carbon material film is 0.1~5A, especially preferably 0.1~0.5A； The time of energization is 1~1000s, especially preferably 1~5s.
Among some exemplary embodiments, the method specifically includes：
An at least catalyst layer is fixed in reative cell, and the catalyst layer is made to connect with the carbon material film heat conduction It connects；
It is passed through protective gas into the reative cell, to which indoor air discharge will be reacted；
Carbon-source gas and carrier gas are passed through into the reative cell；
With the carbon material film heats the catalyst layer and grows and to form ultra-long horizontal carbon nanotube.
Preferably, the catalyst layer is placed on the carbon material film, and the carbon material film is also fixedly installed on described In reative cell.
Preferably, the method includes：Only the catalyst layer is heated with the heating element.
Preferably, in the growth course of ultra-long horizontal carbon nanotube, the temperature of the catalyst layer than in reative cell its High 800 DEG C of the temperature in remaining region or more.
Preferably, the catalyst layer is supported on substrate surface, and the catalyst layer is through substrate and heating element Heat conduction connects.
Further, area load has the substrate of the catalyst layer to be directly located on the carbon material film.
Further, the catalyst layer includes a plurality of catalyst granules for being evenly distributed on substrate surface.
Preferably, the size of the catalyst granules is 0.5~5nm, and surface density is 10~1000/μm2.Wherein, it urges The size of catalyst particles is more than that 5nm then cannot get single-walled carbon nanotube, and the surface density of catalyst granules can also influence carbon nanometer The density of pipe.
Preferably, the material of the catalyst granules includes metal nanoparticle and/or inorganic nanoparticles.
Further, the metal nanoparticle includes any one in Fe, Co, Ni, Cu, Au, Mo, W, Ru, Rh and Pd Kind or two or more combinations, preferably Fe nano particles, but not limited to this.
Further, the inorganic nanoparticles include SiO2、TiO2With any one or the two or more groups in ZnO It closes, but not limited to this.
Preferably, the substrate surface is horizontal plane.
Preferably, the protective gas includes inert gas.Further, the inert gas includes Ar etc..
Preferably, the carrier gas includes inert gas, and further, the inert gas includes Ar or Ar and H2。
Preferably, the carbon source to form the carbon-source gas includes liquid carbon source and/or gaseous carbon source.
Further, the liquid carbon source can be any one in the carbon compounds such as ethyl alcohol, acetone, benzene and toluene Or two or more combinations, preferably ethyl alcohol, but not limited to this.
Further, the gaseous carbon source can be in the hydrocarbons such as methane, ethylene and acetylene any one or Two or more combinations, preferably acetylene, but not limited to this.
Preferably, the material of the substrate includes SiO2/ Si, ST cuts quartz, R cuts quartz, the faces a alpha-aluminium oxide, the faces r α oxidation Any one in aluminium and magnesia or two or more combinations, preferably SiO2/ Si substrates, but not limited to this.
The embodiment of the present invention another aspect provides it is a kind of quickly prepare ultra-long horizontal carbon nanotube method, packet It includes：
The solution for including catalyst precursor is uniformly coated in substrate surface；
There is the substrate of the catalyst precursor to be fixed in reative cell area load, and make the substrate with as adding The carbon material film heat conduction of thermal element connects；
It is passed through protective gas into the reative cell, to which indoor air discharge will be reacted；
It is passed through reducing gas, carbon-source gas and carrier gas into the reative cell, and electric current is passed through into the carbon material film And the carbon material film is made to heat the substrate, so that the catalyst precursor is decomposed and is restored, in the substrate table Face forms evenly dispersed a plurality of catalyst granules, and growth forms ultra-long horizontal carbon nanotube simultaneously.
Since reducing gas and carbon-source gas are passed through reative cell at the very start, during carbon material film electrical heating, catalysis The formation of agent and the growth of carbon nanotube are almost completed at the same time, and fast-growth may be implemented in this way.
Among some exemplary embodiments, the method includes：Only with the carbon material film to the catalyst layer into Row heating.
Preferably, in the growth course of ultra-long horizontal carbon nanotube, the temperature of the catalyst layer than in reative cell its High 800 DEG C of the temperature in remaining region or more.
Further, the substrate is directly located on the carbon material film.
Preferably, the substrate surface is horizontal plane.
Preferably, the material of the carbon material film includes any one in carbon nanotube, carbon fiber and graphene or two Kind or more combination, but not limited to this.
Preferably, the thickness of the carbon material film is 1~100 μm, and especially preferably 5~10 μm, conductivity is more than 104S/ M, intensity are more than 100MPa.
Preferably, the size of the catalyst granules is 0.5~5nm, and surface density is 10~1000/μm2.Wherein, it urges The size of catalyst particles is more than that 5nm then cannot get single-walled carbon nanotube, and the surface density of catalyst granules can also influence carbon nanometer The density of pipe.
Preferably, the material of the catalyst granules includes metal nanoparticle and/or inorganic nanoparticles.
Preferably, the metal nanoparticle includes any one in Fe, Co, Ni, Cu, Au, Mo, W, Ru, Rh and Pd Or two or more combinations, preferably Fe nano particles, but not limited to this.
Preferably, the inorganic nanoparticles include SiO2、TiO2With any one or the two or more combinations in ZnO, But not limited to this.
Among some exemplary embodiments, the fluid comprising catalyst precursor includes Fe (OH)3/ EtOH is molten Liquid.
Further, the Fe (OH)3A concentration of 0.01~5mmol/L of/EtOH solution, especially preferably 0.05~ 0.5mmol/L。
Among some exemplary embodiments, the method includes：With spin-coating method by described comprising catalyst precursor Solution is coated in the substrate.It, can be effectively by the catalyst pellets in the fluid comprising catalyst precursor using spin-coating method Son is uniformly dispersed in substrate surface, using the catalyst and spin coating machine speed of various concentration, can control urging for substrate surface Catalyst particles density.
Preferably, the spin-coating method includes：Clean substrate is placed on sol evenning machine, it later will be described comprising before catalyst The fluid for driving body is applied to substrate surface in the form of being added dropwise.
Preferably, the protective gas includes inert gas.Further, the inert gas includes Ar etc..
Preferably, the carrier gas includes inert gas, and further, the inert gas includes Ar or Ar and H2。
Preferably, the carbon source to form the carbon-source gas includes liquid carbon source and/or gaseous carbon source.
Further, the liquid carbon source can be any one in the carbon compounds such as ethyl alcohol, acetone, benzene and toluene Or two or more combinations, preferably ethyl alcohol, but not limited to this.
Further, the gaseous carbon source can be in the hydrocarbons such as methane, ethylene and acetylene any one or Two or more combinations, preferably acetylene, but not limited to this.
Preferably, the material of the substrate includes SiO2/ Si, ST cuts quartz, R cuts quartz, the faces a alpha-aluminium oxide, the faces r α oxidation Any one in aluminium and magnesia or two or more combinations, preferably SiO2/ Si substrates, but not limited to this.
Among some exemplary embodiments, the method includes：50~500sccm institutes are first passed through into the reative cell 1~20min of reducing gas is stated, is passed through carbon-source gas and carrier gas described in 50~500sccm later.
Preferably, the method includes：The carbon-source gas is passed through in the reative cell in such a way that carrier gas is bubbled.
Among some exemplary embodiments, the method includes：50~500sccm protections are passed through into the reative cell 1~10min of gas, to which indoor air discharge will be reacted.
Among some exemplary embodiments, the method further includes：It is described after reaction, stop be powered and be passed through Carbon-source gas keeps reducing gas and carrier gas to continue to be passed through, and the temperature of the reative cell is down to room temperature, obtains ultra-long horizontal carbon Nanotube.
Wherein, among one more specific embodiment, the side for quickly preparing ultra-long horizontal carbon nanotube of the invention Method may include：
1) by clean SiO2/ Si substrates are placed on sol evenning machine, and fixation is sucked with mechanical pump, take 1~20 μ L preferably 1 The Fe (OH) of μ L3/ EtOH solution, drips to substrate surface, and spin coating machine speed is arranged, in first 10 seconds preaceleration to about 500rpm, It is raised speed again to 2000rpm, spin coating 1min.
2) electric heater unit connects：It is shown in Figure 1, carbon material film (abbreviation carbon film) is fixed on quartz ampoule with copper electrode It is interior, it connects lead, outside fairlead, is connected on DC power supply.The good catalyst substrate of above-mentioned load is face-up placed on carbon On material membrane, the upper gas circuit of pipe both ends connection.
3) ultra-long horizontal carbon nano tube growth：After above-mentioned electric heater unit connects gas circuit, it is first passed through 50~500sccm 1~the 10min of Ar air-dischargings (preferably 5min) of (preferably 300sccm), then passes to 50~500sccm's (preferably 100sccm) H21~20min (preferably 5min) is used as also Primordial Qi.Then Ar/EtOH (the Ar/ of 50~500sccm (preferably 50sccm) are passed through EtOH refers to being passed through ethanol liquid in the form of Ar is bubbled) prepare to start to grow carbon nanotube, carbon film both ends load 0.1A~5A (preferably 0.3A) electric current, conduction time are 1~1000s, close power supply and stopping later and are passed through carbon source, keep hydrogen and argon gas after It is continuous to be passed through, it is down to room temperature naturally.
The embodiment of the present invention additionally provides a kind of system quickly preparing ultra-long horizontal carbon nanotube comprising：
Reative cell, the reative cell have an at least air inlet and an at least gas outlet, and also solid in the reative cell Surely it is provided with an at least catalyst layer, the catalyst layer can be contacted with the reaction gas for flowing to gas outlet from air inlet；
Heating element is fixedly installed in the reative cell and is connect with the catalyst layer heat conduction.
Preferably, the heating element uses carbon material film.
Further, the material of the carbon material film include in carbon nanotube, carbon fiber and graphene any one or Two or more combinations, but not limited to this.
Preferably, the thickness of the carbon material film is 1~100 μm, and especially preferably 5~10 μm, conductivity is more than 104S/ M, intensity are more than 100MPa.
Preferably, the catalyst layer is placed on the carbon material film.
Further, the catalyst layer is supported on substrate surface, and the catalyst layer is through substrate and heating unit Part heat conduction connects.
Further, area load has the substrate of the catalyst layer to be directly located on the carbon material film.
Preferably, the substrate surface is horizontal plane.
Preferably, the catalyst layer includes a plurality of catalyst granules for being evenly distributed on substrate surface.
Preferably, the size of the catalyst granules is 0.5~5nm, and surface density is 10~1000/μm2.Wherein, it urges The size of catalyst particles is more than that 5nm then cannot get single-walled carbon nanotube, and the surface density of catalyst granules can also influence carbon nanometer The density of pipe.
Preferably, the material of the catalyst granules includes metal nanoparticle and/or inorganic nanoparticles.
Preferably, the metal nanoparticle includes any one in Fe, Co, Ni, Cu, Au, Mo, W, Ru, Rh and Pd Or two or more combinations, preferably Fe nano particles, but not limited to this.
Preferably, the inorganic nanoparticles include SiO2、TiO2With any one or the two or more combinations in ZnO, But not limited to this.
Preferably, the carbon material film is also electrically connected with more than two spaced electrodes, the electrode and power supply electricity Connection.
Further, the material of the electrode includes copper etc..
Preferably, the material of the substrate includes SiO2/ Si, ST cuts quartz, R cuts quartz, the faces a alpha-aluminium oxide, the faces r α oxidation Any one in aluminium and magnesia or two or more combinations, preferably SiO2/ Si substrates, but not limited to this.
The embodiment of the present invention another aspect provides the ultra-long horizontal carbon nanotube prepared by preceding method, it is described super The length of long horizontal carbon nanotube has hollow tubular structure up to 4mm or more, the ultra-long horizontal carbon nanotube.
Preferably, the ultra-long horizontal carbon nanotube includes single-walled carbon nanotube, wherein the single wall carbon described in gross product The content of nanotube is more than 80wt%.
The other side of the embodiment of the present invention additionally provides aforementioned ultra-long horizontal carbon nanotube in nanometer electronic device, the energy It converts, the purposes of biosensor or field of compound material.
Correspondingly, the embodiment of the present invention additionally provides a kind of device, it includes ultra-long horizontal carbon nanotubes above-mentioned.
Wherein, described device is including that can be nanometer electronic device, photoelectric device, sensor etc..
It can be brought rapidly up using the method for quickly preparing ultra-long horizontal carbon nanotube of the present invention, catalyst activity is high, surpasses The speed of growth of long horizontal carbon nanotube is fast, is more than that existing literature reports at least one order of magnitude of peak up to 960 μm/s, It is prepared by the quick magnanimity that ultra-long horizontal carbon nanotube can be achieved.
In addition, by technical scheme of the present invention, the ultra-long horizontal length of carbon nanotube that is obtained is receiving electricity up to 4mm The fields such as sub- device, energy conversion, biosensor, composite material are with a wide range of applications.
Below by way of several embodiments and the technical solution that present invention be described in more detail in conjunction with attached drawing.However, selected Embodiment be merely to illustrate the present invention, and do not limit the scope of the invention.
Embodiment 1
The present embodiment is in SiO2The method that ultra-long horizontal carbon nanotube is quickly prepared in/Si substrates includes the following steps：
1) by clean SiO2/ Si substrates are placed on sol evenning machine, and fixation is sucked with mechanical pump, take the Fe (OH) of 1 μ L3/ EtOH solution, drips to substrate surface, and spin coating machine speed is arranged, in first 10 seconds preaceleration to about 500rpm, then raise speed to 2000rpm, spin coating 1min.
2) electric heater unit connects：It is shown in Figure 1, it is 10 μm thickness, conductivity is 2 × 104S/m, intensity are The carbon film of 200Mpa is fixed on copper electrode in quartz ampoule, connects lead, outside fairlead, is connected on DC power supply.Add above-mentioned The catalyst substrate carried is face-up placed on carbon film, the upper gas circuit of pipe both ends connection.
3) ultra-long horizontal carbon nano tube growth：After above-mentioned electric heater unit connects gas circuit, it is first passed through the Ar rows of 300sccm Air 5min then passes to the H of 100sccm25min is used as also Primordial Qi.Then the Ar/EtOH preparations for being passed through 50sccm start to give birth to Long carbon nanotube, carbon film both ends load 0.3A electric currents, and conduction time 5s closes power supply later and stopping is passed through carbon source, keeps Hydrogen and argon gas continue to be passed through, and are down to room temperature naturally, obtain ultra-long horizontal carbon nanotube.
Further, inventor also produces the more batches of ultra-long horizontal carbon nanotubes prepared with technique described in embodiment 1 Object is characterized, specific as follows：
Refering to Fig. 2 a and Fig. 2 b, the scanning electricity of ultra-long horizontal carbon nanotube is obtained when conduction time is 5s by the present embodiment Mirror (SEM) picture, it can be seen that longest carbon nanotube has 4.8mm, infers that the speed of growth reaches 960 μm/s, than being existing report The optimum growth speed in road improves an order of magnitude.As shown in figure 3, obtaining overlength when conduction time is 5s by the present embodiment Transmission electron microscope (TEM) picture of horizontal carbon nanotube, it can clearly be seen that during the ultra-long horizontal carbon nanotube has Hollow tube-like structure, and the content of single-walled carbon nanotube is more than 80wt% in product.
Embodiment 2
It includes following step that the present embodiment cuts the method that overlength carbon nano pipe horizontal array is quickly prepared in quartz substrate in ST Suddenly：
1) catalyst load connects same embodiment 1 with electric heater unit.
2) growth of overlength carbon nano pipe horizontal array：After above-mentioned electric heater unit connects gas circuit, it is first passed through 300sccm Ar air-discharging 5min, then pass to the H of 300sccm25min is used as also Primordial Qi.Then the Ar/EtOH for being passed through 100sccm is accurate Standby to start to grow carbon nanotube, carbon film both ends load 0.2A electric currents, and conduction time 30s closes power supply later and stopping is passed through Carbon source keeps hydrogen and argon gas to continue to be passed through, is down to room temperature naturally, obtains overlength carbon nano pipe horizontal array as shown in Figure 4, institute It is arranged in parallel to state carbon nanotube, density is more than 1 piece/μm.
Embodiment 3
The present embodiment is in SiO2The method that the vertical array of carbon nanotube is quickly prepared in/Si substrates includes the following steps：
1) catalyst preparation uses electron beam evaporation technique by required Fe and Al2O3Target according to 0.02nm/s rate Deposit to SiO2In/Si substrates, Fe thickness is 0.8nm, Al respectively2O3Thickness is 20nm, monolith design Fe/ respectively Al2O3/SiO2/Si。
2) electric heater unit connection is the same as embodiment 1.
3) the vertical array fast-growth of carbon nanotube：After above-mentioned electric heater unit connects gas circuit, first it is passed through 100sccm's Ar air-discharging 5min, then pass to the H of 100sccm25min is used as also Primordial Qi.Then it is passed through the C of 100sccm2H4Preparation starts Carbon nanotube is grown, carbon film both ends load 0.15A electric currents, and conduction time 60s closes power supply later and stopping is passed through carbon source, It keeps hydrogen and argon gas to continue to be passed through, is down to room temperature naturally, obtains the vertical array of carbon nanotube of fast-growth as shown in Figure 5, Height is more than 100 μm.
Comparative example 1
Common tube furnace growth carbon nanotube horizontal array comparison：
1) catalyst load is the same as embodiment 1.
2) by the above-mentioned SiO for being loaded with catalyst2/ Si substrates are put into 1inch tube furnaces (TF 55035C-1Lindberg/ Blue M) in, it is warming up to 950 DEG C in 35min, is first passed through the Ar air-discharging 5min of 300sccm, then passes to 100sccm's H25min is used as also Primordial Qi.Then it is passed through after the Ar/EtOH growth carbon nanotubes 5min of 50sccm, closes tube furnace, stop It is passed through carbon source, keeps hydrogen and argon gas to continue to be passed through, is down to room temperature naturally, obtains horizontal carbon nanotube.As a result such as Fig. 6, carbon pipe Of length no more than 1mm is grown compared to carbon film electrical heating, and growth time is long, and growth efficiency is low.
Pass through embodiment 1-3, it is found that ultra-long horizontal carbon nanometer may be implemented by the above-mentioned technical proposal of the present invention The quick preparation of pipe, the speed of growth of ultra-long horizontal carbon nanotube is fast, and up to 960 μm/s, and heating rate is fast, energy consumption cost Low, technology stability is good, prepared by the magnanimity for being conducive to ultra-long horizontal carbon nanotube.
In addition, mode of the inventor referring also to embodiment 1- embodiments 3, with the other raw materials listed in this specification It is tested with condition etc., and the ultra-long horizontal carbon nanotube with excellent properties has equally been made.And it, can by test To find, by the ultra-long horizontal carbon nanotube that the above-mentioned technical proposal of the present invention obtains, electrical properties and optical property are excellent, It is with a wide range of applications in fields such as nanometer electronic device, energy conversion, biosensor, composite materials.
It should be appreciated that above-described is only some embodiments of the present invention, it is noted that for the common of this field For technical staff, under the premise of not departing from the concept of the present invention, other modification and improvement can also be made, these are all It belongs to the scope of protection of the present invention.

Claims (10)

1. a kind of method quickly preparing ultra-long horizontal carbon nanotube, it is characterised in that including：
An at least catalyst layer is fixed in reative cell, and the catalyst layer is made to be connect with heating element heat conduction；
Carbon-source gas and carrier gas are passed through into the reative cell；
It grows with catalyst layer described in heating element heats and to form ultra-long horizontal carbon nanotube.
2. according to the method described in claim 1, it is characterized in that：The heating element uses carbon material film；Preferably, described The material of carbon material film includes any one or two or more combinations in carbon nanotube, carbon fiber and graphene；Preferably, The thickness of the carbon material film is 1~100 μm, and especially preferably 5~10 μm, conductivity is more than 104S/m, intensity are more than 100MPa。
3. according to the method described in claim 2, it is characterized by comprising：
Catalyst layer is placed in reative cell, and catalyst layer is made to be connect with carbon material film heat conduction；
Carbon-source gas and carrier gas are passed through into the reative cell；
Make the carbon material film heating catalyst layer by way of being passed through electric current into the carbon material film and grow to be formed it is super Long horizontal carbon nanotube；Preferably, the intensity for being passed through the DC current of the carbon material film is 0.1~5A；
Preferably, the method specifically includes：
An at least catalyst layer is fixed in reative cell, and the catalyst layer is made to be connect with the carbon material film heat conduction；
It is passed through protective gas into the reative cell, to which indoor air discharge will be reacted；
Carbon-source gas and carrier gas are passed through into the reative cell；
With the carbon material film heats the catalyst layer and grows and to form ultra-long horizontal carbon nanotube；
Preferably, the protective gas includes inert gas；Preferably, the inert gas includes Ar；Preferably, the carrier gas Including inert gas；Preferably, the inert gas includes Ar or Ar and H2。
4. according to the method described in claim 3, it is characterized in that：The catalyst layer is placed on the carbon material film, institute Carbon material film is stated also to be fixedly installed in the reative cell；And/or the method includes：Only with the heating element to described Catalyst layer is heated；Preferably, in the growth course of ultra-long horizontal carbon nanotube, the temperature of the catalyst layer is than anti- Answer high 800 DEG C of the temperature or more in remaining indoor region；Preferably, the catalyst layer is supported on substrate surface, and described Catalyst layer is connect through substrate with heating element heat conduction；Especially preferred, area load has the substrate of the catalyst layer straight It connects and is placed on the carbon material film；
And/or the catalyst layer includes a plurality of catalyst granules for being evenly distributed on substrate surface；Preferably, described to urge The size of catalyst particles is 0.5~5nm, and surface density is 10~1000/μm2；Preferably, the material packet of the catalyst granules Include metal nanoparticle and/or inorganic nanoparticles；Preferably, the metal nanoparticle include Fe, Co, Ni, Cu, Au, Mo, W, any one in Ru, Rh and Pd or two or more combinations；Preferably, the inorganic nanoparticles include SiO2、TiO2With Any one in ZnO or two or more combinations；Preferably, the substrate surface is horizontal plane；Preferably, the substrate Material includes SiO2/ Si, ST cuts quartz, R cuts quartz, in the faces a alpha-aluminium oxide, the faces r alpha-aluminium oxide and magnesia any one or Two or more combinations；
And/or the carbon source to form the carbon-source gas includes liquid carbon source and/or gaseous carbon source；Preferably, the liquid Carbon source includes any one or two or more combinations in ethyl alcohol, acetone, benzene and toluene；Preferably, the gaseous carbon source packet Include any one in methane, ethylene and acetylene or two or more combinations.
5. a kind of method quickly preparing ultra-long horizontal carbon nanotube, it is characterised in that including：
The solution for including catalyst precursor is uniformly coated in substrate surface；
There is the substrate of the catalyst precursor to be fixed in reative cell area load, and make the substrate with as heating unit The carbon material film heat conduction of part connects；
It is passed through protective gas into the reative cell, to which indoor air discharge will be reacted；
It is passed through reducing gas, carbon-source gas and carrier gas into the reative cell, and is passed through electric current into the carbon material film and makes The carbon material film heats the substrate, and the catalyst precursor is made to be decomposed and restore, in the substrate surface shape At evenly dispersed a plurality of catalyst granules, and growth forms ultra-long horizontal carbon nanotube simultaneously.
6. according to the method described in claim 5, it is characterized by comprising：Only with the carbon material film to the catalyst granules It is heated；Preferably, in the growth course of ultra-long horizontal carbon nanotube, the catalyst layer of the catalyst granules formation 800 DEG C higher than the temperature in remaining region in reative cell of temperature or more；And/or the substrate is directly located the carbon material film On；Preferably, the substrate surface is horizontal plane；Preferably, the material of the substrate includes SiO2/ Si, ST cuts quartz, R is cut Any one in quartz, the faces a alpha-aluminium oxide, the faces r alpha-aluminium oxide and magnesia or two or more combinations；
And/or the material of the carbon material film include in carbon nanotube, carbon fiber and graphene any one or it is two or more Combination；Preferably, the thickness of the carbon material film is 1~100 μm, and especially preferably 5~10 μm, conductivity is more than 104S/ M, intensity are more than 100MPa；
And/or the size of the catalyst granules is 0.5~5nm, surface density is 10~1000/μm2；Preferably, described to urge The material of catalyst particles includes metal nanoparticle and/or inorganic nanoparticles；Preferably, the metal nanoparticle includes Any one in Fe, Co, Ni, Cu, Au, Mo, W, Ru, Rh and Pd or two or more combinations；Preferably, the inorganic nano Particle includes any one or two or more combinations in SiO2, TiO2 and ZnO；Preferably, described includes complex catalyst precursor The solution of body includes the Fe (OH) of a concentration of 0.01~0.5mmol/L3/ EtOH solution.
7. according to the method described in claim 5, it is characterized in that：The protective gas includes inert gas；Preferably, described Inert gas includes Ar；And/or the carrier gas includes inert gas；Preferably, the inert gas includes Ar or Ar and H2； And/or the carbon source to form the carbon-source gas includes liquid carbon source and/or gaseous carbon source；Preferably, the liquid carbon source Including any one or the two or more combinations in ethyl alcohol, acetone, benzene and toluene；Preferably, the gaseous carbon source includes first Any one in alkane, ethylene and acetylene or two or more combinations.
8. a kind of system quickly preparing ultra-long horizontal carbon nanotube, it is characterised in that including：
Reative cell, the reative cell has an at least air inlet and an at least gas outlet, and also fixation is set in the reative cell It is equipped with an at least catalyst layer, the catalyst layer can be contacted with the reaction gas for flowing to gas outlet from air inlet；
Heating element is fixedly installed in the reative cell and is connect with the catalyst layer heat conduction.
9. system according to claim 8, it is characterised in that：The heating element uses carbon material film；Preferably, described The material of carbon material film includes any one or two or more combinations in carbon nanotube, carbon fiber and graphene；Preferably, The thickness of the carbon material film is 1~100 μm, and especially preferably 5~10 μm, conductivity is more than 104S/m, intensity are more than 100MPa。
10. system according to claim 8, it is characterised in that：The catalyst layer is placed on the carbon material film；It is excellent Choosing, the catalyst layer is supported on substrate surface, and the catalyst layer is connect through substrate with heating element heat conduction；It is excellent Choosing, area load has the substrate of the catalyst layer to be directly located on the carbon material film；Preferably, the catalyst layer A plurality of catalyst granules including being evenly distributed on substrate surface；Preferably, the size of the catalyst granules be 0.5~ 5nm, surface density are 10~1000/μm2；Preferably, the material of the catalyst granules includes metal nanoparticle and/or nothing Machine nano particle；Preferably, the metal nanoparticle includes any one in Fe, Co, Ni, Cu, Au, Mo, W, Ru, Rh and Pd Kind or two or more combinations；Preferably, the inorganic nanoparticles include SiO2、TiO2With any one or two kinds in ZnO Above combination；Preferably, the substrate surface is horizontal plane；Especially preferred, the material of the substrate includes SiO2/Si、 ST cuts quartz, R cuts quartz, any one or two or more combinations in the faces a alpha-aluminium oxide, the faces r alpha-aluminium oxide and magnesia；
And/or the carbon material film is also electrically connected with more than two spaced electrodes, the electrode is electrically connected to a power source； Preferably, the electrode includes copper electrode.
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Application publication date: 20181102