CN101734618A - Preparation method of nanostructure - Google Patents
Preparation method of nanostructure Download PDFInfo
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- CN101734618A CN101734618A CN200910161447A CN200910161447A CN101734618A CN 101734618 A CN101734618 A CN 101734618A CN 200910161447 A CN200910161447 A CN 200910161447A CN 200910161447 A CN200910161447 A CN 200910161447A CN 101734618 A CN101734618 A CN 101734618A
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Abstract
The invention relates to a preparation method of a nanostructure, comprising the following steps of: providing a carbon nanotube at least of which a part is arranged in a suspending way; introducing reaction materials into the carbon nanotube; initiating the reaction materials to react, and forming the nanostructure on the surface of the carbon nanotube structure.
Description
Technical field
The present invention relates to a kind of preparation method of nanostructured, relate in particular to a kind of method that adopts template to prepare nanostructured.
Background technology
Nano material is in basic research and practical application, as: there is immense value aspects such as catalysis, sensing.Therefore, preparation of nanomaterials becomes the focus of research.At present, preparation of nanomaterials can be divided into spontaneous growth method (spontaneous growth), template synthetic method (template-based synthesis), electrospinning yarn method (electrospinning), offset printing method (lithography) etc.
Prior art provides a kind of electrospinning yarn legal system to be equipped with the method for titanium dioxide nano thread, see also " Fabrication of Titania Nanofibers by Electrospinning " (Dan Li et al, NanoLetters, vol.3, No.4, p555-560 (2003)).This method prepares titanium dioxide nanostructure by the electrospinning yarn then with the ethanolic solution and the mixed slurry that gets of TiO 2 precursor of mineral oil and polyvinylpyrrolidone (PVP).Further, make mineral oil and polyvinylpyrrolidone evaporation, can obtain pure titanium dioxide nanostructure by heating.This titanium dioxide nanostructure comprises a plurality of titanium dioxide nano threads, and forms a self supporting structure.Though can preparing the bigger nano wire of length and it can be prepared into one, electrospinning yarn method has the nanostructured of self supporting structure, but, electrospinning yarn method needs special electrospinning yarn equipment usually, needs a high voltage, and needs earlier spinning material to be mixed with a slurry.So, adopt electrospinning yarn legal system to be equipped with the nano material complex process, cost is higher.
CNT (Carbon Nanotube, CNT) be a kind of novel nano structure, obtain in prepared in laboratory first in 1991 by Japanology personnel Iijima, see also " Helical Microtubules ofGraphitic Carbon " (S.Iijima, Nature, vol.354, p56 (1991)).Because CNT has the stability of one dimension pattern and chemistry, hot aspect, become the desirable template of template nano materials.
Prior art provides a kind of method that adopts CNT as the template growth beta-silicon nitride nanowire, sees also Chinese publication application CN 1803586A number what sunshine equals on December 19th, 2005 application.This method may further comprise the steps: silica flour is mixed by certain weight ratio with nano-silica powder; Pair of lamina corundum boat is provided, and the mixture of this silica flour and nano-silica powder is placed the lower floor of this bilayer corundum boat; The certain quantity of carbon nanometer pipe powder is placed the upper strata of this bilayer corundum boat; Place a high temperature furnace that contains nitrogen to reduce and nitridation reaction in this bilayer corundum boat, at carbon nano tube surface grown silicon nitride nano wire.In this course of reaction, at first be solid-state Si and SiO
2Reaction generates SiO gas, SiO gas of Sheng Chenging and nitrogen reaction then, and at carbon nano tube surface generation beta-silicon nitride nanowire.Be equipped with nano material with electrospinning yarn legal system and compare, template technology is simple, and easy operating is with low cost.
Yet above-mentioned employing CNT has following deficiency as the method for template growth nano material: the first, and be powder body material as the CNT of template, its limited length is so the silicon nitride nano line length of preparation is less; The second, adopt carbon nanotube dust as the wayward product pattern of template; The 3rd, the carbon nanotube dust skewness, and reunite easily, influence the size and the uniformity of product; The 4th, the beta-silicon nitride nanowire of this method preparation can't form a self supporting structure (so-called self supporting structure is meant that this structure can need not a substrate and keep a given shape, as wire or membranaceous), has limited its use.
People such as Fan Shoushan proposed a kind of method for preparing the CNT rope in 2002, saw also the day for announcing and be China's bulletin patent CN100411979C number on August 20th, 2008; Proposed a kind of method for preparing carbon nano-tube filament in 2005, seeing also open day was Chinese publication application CN1982209A number on June 20th, 2007; Proposed a kind of method for preparing carbon nano-tube thin-film structure in 2007, seeing also open day was Chinese publication application CN101239712A number on August 13rd, 2008; Proposed a kind of preparation method of carbon nano-tube film in 2007, seeing also open day is Chinese publication application CN101314464A number on December 3rd, 2008; Proposed a kind of preparation method of carbon nano-tube film in 2007, seeing also open day is Chinese publication application CN101284662A number on April 13rd, 2007.This CNT rope, carbon nano-tube filament or carbon nano-tube film are the macroscopic carbon nanotube structure with a self-supporting characteristic.
Summary of the invention
In view of this, the necessary carbon nano tube structure that provides a kind of employing to have the self-supporting characteristic prepares the method for nanostructured as template.
A kind of preparation method of nanostructured, it may further comprise the steps: a carbon nano tube structure to the unsettled setting of small part is provided; Introduce reaction raw materials to this carbon nano tube structure; And the initiation reaction raw material reacts, and forms nanostructured on this carbon nano tube structure surface.
A kind of preparation method of metal oxide nanostructure, it may further comprise the steps: the carbon nano tube structure that a unsettled setting is provided; Carbon nano tube structure surface deposition one thickness in this unsettled setting is the metal level of 50 nanometers～100 nanometers; And this metal level of oxidation, obtain metal oxide nanostructure.
Compared to prior art, because this carbon nano tube structure has the self-supporting characteristic, can be to the unsettled setting of small part, have the self-supporting characteristic and to the nanostructured of the unsettled setting of small part so adopt this carbon nano tube structure can directly prepare as template, and technology is simple, and is with low cost.
Description of drawings
Fig. 1 is a nanostructured preparation method's of the present invention flow chart.
Fig. 2 among the present invention as the stereoscan photograph of the CNT membrane of template.
Fig. 3 is the structural representation of the CNT fragment in the CNT membrane among Fig. 2.
Fig. 4 among the present invention as the stereoscan photograph of the non-carbon nano tube line that reverses of template.
Fig. 5 among the present invention as the stereoscan photograph of the carbon nano tube line that reverses of template.
Fig. 6 among the present invention as the stereoscan photograph of the CNT laminate of template, wherein CNT is arranged of preferred orient along same direction.
Fig. 7 among the present invention as the stereoscan photograph of the CNT laminate of template, wherein CNT is arranged of preferred orient along different directions.
Fig. 8 among the present invention as the stereoscan photograph of the CNT waddingization film of template.
Fig. 9 is nanostructured preparation technology's flow chart of first embodiment of the invention.
Figure 10 is the stereoscan photograph of the carbon nano tube structure that deposits titanium layer of first embodiment of the invention preparation.
Figure 11 is the stereoscan photograph of the titanium dioxide nano thread that aligns of first embodiment of the invention preparation.
Figure 12 is the transmission electron microscope photo of the titanium dioxide nano thread that aligns of first embodiment of the invention preparation.
The titanium dioxide nano thread that aligns that Figure 13 prepares for first embodiment of the invention is removed the stereoscan photograph after the CNT template.
Figure 14 is nanostructured preparation technology's flow chart of second embodiment of the invention.
Figure 15 is the stereoscan photograph of the titanium dioxide nano thread arranged in a crossed manner of second embodiment of the invention preparation.
Figure 16 is nanostructured preparation technology's flow chart of third embodiment of the invention.
Figure 17 is nanostructured preparation technology's flow chart of fourth embodiment of the invention.
The specific embodiment
Below with reference to the drawings, the present invention is described in further detail.
See also Fig. 1, the invention provides a kind of preparation method of nanostructured, it may further comprise the steps:
This carbon nano tube structure is a self supporting structure.So-called " self supporting structure " i.e. this carbon nano tube structure need not by a support body supports, also can keep self specific shape.Described carbon nano tube structure comprises at least one carbon nano-tube film, at least one liner structure of carbon nano tube or its combination.When described carbon nano tube structure comprised a plurality of carbon nano-tube film, this carbon nano-tube film can coplane setting or stacked setting.When described carbon nano tube structure only comprised a liner structure of carbon nano tube, this liner structure of carbon nano tube can fold or be wound in a stratiform carbon nano tube structure.When described carbon nano tube structure comprised a plurality of liner structure of carbon nano tube, these a plurality of liner structure of carbon nano tube can be arranged in parallel, arranged in a crossed manner or be woven into a stratiform carbon nano tube structure.When described carbon nano tube structure comprises carbon nano-tube film and liner structure of carbon nano tube, liner structure of carbon nano tube can be arranged at least one surface of carbon nano-tube film.Because the CNT in this carbon nano tube structure has good flexible, makes this carbon nano tube structure have good flexible, can bending fold become arbitrary shape and do not break.
Described carbon nano-tube film comprises a plurality of equally distributed CNTs.Described CNT in order or disorder distribution and combine closely by Van der Waals force.The arrangement of described unordered finger CNT is random, refers to that in order the orientation of most at least CNTs has certain rule.When carbon nano-tube film comprised the CNT of lack of alignment, CNT twined mutually; When carbon nano-tube film comprised orderly carbon nanotubes arranged, CNT was arranged of preferred orient along a direction or a plurality of direction.Described carbon nano-tube film can be CNT membrane, CNT laminate, CNT waddingization film.
CNT in this carbon nano tube structure comprises one or more in SWCN, double-walled carbon nano-tube and the multi-walled carbon nano-tubes.The diameter of described SWCN is 0.5 nanometer～50 nanometers, and the diameter of double-walled carbon nano-tube is 1.0 nanometers～50 nanometers, and the diameter of multi-walled carbon nano-tubes is 1.5 nanometers～50 nanometers.The length of described CNT is greater than 50 microns.Preferably, the length of this CNT is preferably 200 microns～900 microns.
Described CNT membrane is for directly pulling a kind of carbon nano-tube film with self-supporting of acquisition from carbon nano pipe array.Each CNT membrane comprises a plurality ofly to be arranged and is parallel to CNT membrane surface carbon nanotubes arranged along same direction substantially.Described CNT joins end to end by Van der Waals force.See also Fig. 2 and Fig. 3, particularly, each CNT membrane comprise a plurality of continuously and the CNT fragment 143 that aligns.This a plurality of CNT fragment 143 joins end to end by Van der Waals force.Each CNT fragment 143 comprises a plurality of CNTs that are parallel to each other 145, and this a plurality of CNT that is parallel to each other 145 is combined closely by Van der Waals force.This CNT fragment 143 has width, thickness, uniformity and shape arbitrarily.The thickness of described CNT membrane is 0.5 nanometer～100 micron, and width is relevant with the size of the carbon nano pipe array that pulls this CNT membrane, and length is not limit.
Described CNT membrane and preparation method thereof specifically saw also people such as Fan Shoushan in application on February 9th, 2007, in disclosed CN101239712A number Chinese publication application on August 13 " CNT membrane structure and preparation method thereof " in 2008.For saving space, only be incorporated in this, but all technology of above-mentioned application disclose the part that also should be considered as the exposure of the present patent application technology.
When described carbon nano tube structure comprises the multilayer carbon nanotube membrane of stacked setting, form an intersecting angle α between the CNT that is arranged of preferred orient in the adjacent two layers CNT membrane, and α spends (0 °≤α≤90 °) more than or equal to 0 degree smaller or equal to 90.Have certain interval between described a plurality of CNT membrane or between the adjacent CNT among CNT membrane, thereby form a plurality of micropores in carbon nano tube structure, the aperture of micropore is approximately less than 10 microns.
The carbon nano tube structure of the embodiment of the invention can comprise a plurality of CNT membranes along the stacked setting of equidirectional, thereby the CNT in the carbon nano tube structure all is arranged of preferred orient along same direction.
Described carbon nano tube line comprises a plurality of along carbon nano tube line axial orientation carbon nanotubes arranged.Described carbon nano tube line can be non-carbon nano tube line that reverses or the carbon nano tube line that reverses.This non-carbon nano tube line that reverses obtains for the CNT membrane is handled by organic solvent.See also Fig. 4, this non-carbon nano tube line that reverses comprises a plurality of along carbon nano tube line length direction carbon nanotubes arranged.This carbon nano tube line that reverses reverses acquisition for adopting a mechanical force in opposite direction with described CNT membrane two ends.See also Fig. 5, this carbon nano tube line that reverses comprises a plurality of around carbon nano tube line axial screw carbon nanotubes arranged.This non-carbon nano tube line that reverses and the CNT line length of reversing are not limit, and diameter is 0.5 nanometer～100 micron.
Described carbon nano tube line and preparation method thereof specifically sees also people such as Fan Shoushan in application on September 16th, 2002, CN100411979C number China's bulletin patent " a kind of CNT rope and manufacture method thereof " in bulletin on August 20th, 2008, and on December 16th, 2005 application, in disclosed CN1982209A number Chinese publication application " carbon nano-tube filament and preparation method thereof " on June 20 in 2007.For saving space, only be incorporated in this, but all technology of above-mentioned application disclose the part that also should be considered as the exposure of the present patent application technology.
Further, can adopt a volatile organic solvent to handle the carbon nano tube line that this reverses.Under the capillary effect that when volatile organic solvent volatilizees, produces, adjacent CNT is combined closely by Van der Waals force in the carbon nano tube line that reverses after the processing, the diameter and the specific area of the carbon nano tube line that reverses are reduced, and density and intensity increase.
Because this carbon nano tube line obtains for adopting organic solvent or mechanical force to handle above-mentioned CNT membrane, this CNT membrane is a self supporting structure, so this carbon nano tube line is a self supporting structure.In addition, have the gap between the adjacent carbons nanotube in this carbon nano tube line, so this carbon nano tube line has a large amount of micropores, and the aperture of micropore is approximately less than 10 microns.
Described CNT laminate comprises equally distributed CNT, and CNT is arranged of preferred orient along same direction or different directions.CNT in the described CNT laminate mutually part overlaps, and attracts each other by Van der Waals force, combines closely, and makes this carbon nano tube structure have good flexible, can bending fold becomes arbitrary shape and does not break.And owing to attract each other by Van der Waals force between the CNT in the CNT laminate, combine closely, making the CNT laminate is the structure of a self-supporting.Described CNT laminate can obtain by rolling a carbon nano pipe array.CNT in the described CNT laminate forms an angle β with the surface of the growth substrate that forms carbon nano pipe array, wherein, β is more than or equal to 0 degree and smaller or equal to 15 degree (0≤β≤15 °), this angle β is with to be applied to the pressure that carbon nano-pipe array lists relevant, pressure is big more, this angle is more little, and preferably, the CNT in this CNT laminate is parallel to this growth substrate and arranges.This CNT laminate is to obtain by rolling a carbon nano pipe array, and according to the mode difference that rolls, the CNT in this CNT laminate has different spread patterns.Particularly, see also Fig. 6, when when same direction rolls, CNT is arranged of preferred orient along a fixed-direction; See also Fig. 7, when when different directions rolls, CNT is arranged of preferred orient along different directions; When rolling along the direction perpendicular to the growth substrate surface of carbon nano pipe array, carbon nano-tube film is being parallel to the direction isotropism on growth substrate surface.The length of CNT is greater than 50 microns in this CNT laminate.
Described CNT laminate and preparation method thereof specifically saw also people such as Fan Shoushan in application on June 1st, 2007, in disclosed CN101314464A number Chinese publication application on December 3 " preparation method of carbon nano-tube film " in 2008.For saving space, only be incorporated in this, but all technology of above-mentioned application disclose the part that also should be considered as the exposure of the present patent application technology.
The area and the thickness of this CNT laminate are not limit, and can select according to actual needs.The area of this CNT laminate and the size of carbon nano pipe array are basic identical.The height of this CNT laminate thickness and carbon nano pipe array and the pressure that rolls are relevant, can be 1 micron～1 millimeter.The height that is appreciated that carbon nano pipe array is big more and applied pressure is more little, and then the thickness of Zhi Bei CNT laminate is big more; Otherwise the height of carbon nano pipe array is more little and applied pressure is big more, and then the thickness of Zhi Bei CNT laminate is more little.Have certain interval between the adjacent CNT among the described CNT laminate, thereby form a plurality of micropores in the CNT laminate, the aperture of micropore is approximately less than 10 microns.
Described carbon nano tube structure can comprise at least one CNT waddingization film, and this CNT waddingization film comprises mutual winding and equally distributed CNT.The length of CNT is greater than 10 microns, and preferably, the length of CNT is more than or equal to 200 microns and smaller or equal to 900 microns.Attract each other, twine by Van der Waals force between the described CNT, form network-like structure.CNT in the described CNT waddingization film is evenly to distribute, and random arrangement makes this CNT waddingization film isotropism.CNT in the described CNT waddingization film forms a large amount of microcellular structures, and micropore size is approximately less than 10 microns.The length and the width of described CNT waddingization film are not limit.See also Fig. 8, because in CNT waddingization film, CNT twines mutually, so this CNT waddingization film has good flexible, and is a self supporting structure, can bending fold becomes arbitrary shape and does not break.The area and the thickness of described CNT waddingization film are not all limit, and thickness is 1 micron～1 millimeter, are preferably 100 microns.
Described CNT waddingization film and preparation method thereof specifically saw also people such as Fan Shoushan in application on April 13rd, 2007, in disclosed CN101284662A number Chinese publication application on October 15 " preparation method of carbon nano-tube film " in 2008.For saving space, only be incorporated in this, but all technology of above-mentioned application disclose the part that also should be considered as the exposure of the present patent application technology.
Be appreciated that in the present embodiment and further this carbon nano tube structure can also be arranged on the supporter.Described supporter comprises substrate or framework.Be appreciated that, the present invention can be arranged at this carbon nano tube structure this supporting body surface, and pass through this supporter to the unsettled setting of small part, also can all supported body of whole carbon nano tube structure be supported whole this supporting body surface that is arranged at of this carbon nano tube structure.
Step 2 is introduced reaction raw materials in this carbon nano tube structure.
The material of described reaction raw materials is relevant with the material of the nanostructured of required formation.Described reaction raw materials can be solid-state, liquid state or gaseous state.The described method of introducing two kinds of reaction raw materials in carbon nano tube structure specifically comprises following three kinds of situations.
First kind: at first, forming a layer thickness on this carbon nano tube structure surface is the first reaction raw materials layer of 50 nanometers～200 nanometers.
The material of the described first reaction raw materials layer is relevant with the material of the nanostructured that will prepare, and can be in metal, the nonmetal and semiconductor one or more.For example, when the material of nanostructured is a metallic compound, during as metal oxide or metal silicide, the first reaction raw materials layer is a metal level, as titanium layer, aluminium lamination or nickel dam etc.; When the material of nanostructured is a nonmetallic compound, during as silicon nitride or carborundum, the first reaction raw materials layer is a silicon layer.
The described method that forms one first reaction raw materials layer on the carbon nano tube structure surface is not limit, and can comprise in physical vaporous deposition, chemical vapour deposition technique, infusion process, spraying process and the silk screen print method etc. one or more.Be appreciated that material difference, can select the carbon nano tube surface of diverse ways in carbon nano tube structure to form the first reaction raw materials layer according to the first reaction raw materials layer.For example, can be by physical vaporous deposition with metal sputtering to carbon nano tube surface; Can form nonmetal in carbon nano tube surface by chemical vapour deposition technique; The organic ink that contains metal can be formed at the surface of CNT by spraying process or silk screen print method.
Secondly, introduce gaseous state or liquid second reaction raw materials to this carbon nano tube structure.
Described gaseous state second reaction raw materials can be in oxygen, nitrogen, silicon source gas and the carbon-source gas one or more.Described method to carbon nano tube structure introducing gaseous state second reaction raw materials can comprise directly gaseous state second reaction raw materials being passed into the reative cell that is provided with carbon nano tube structure or carbon nano tube structure being arranged at one and contain in the atmosphere of gaseous state second reaction raw materials, thereby gaseous state second reaction raw materials is distributed in around the carbon nano tube structure and the first reaction raw materials layer.
Described liquid second reaction raw materials can be in methyl alcohol, ethanol, acetone and the liquid resin etc. one or more.Described method from liquid second reaction raw materials to carbon nano tube structure that introduce can comprise and directly liquid second reaction raw materials dripped to the carbon nano tube structure surface or carbon nano tube structure is infiltrated in liquid second reaction raw materials, thereby liquid second reaction raw materials is distributed in around the carbon nano tube structure and the first reaction raw materials layer.
Second kind: at first, form one first reaction raw materials layer on this carbon nano tube structure surface; Secondly, on this first reaction raw materials layer, form one second reaction raw materials layer.The gross thickness of the described first reaction raw materials layer and the second reaction raw materials layer is 50 nanometers～200 nanometers.As, the first reaction raw materials layer is a metal level, the second reaction raw materials layer is a silicon layer; The first reaction raw materials layer and the second reaction raw materials layer are metal level, as: the first reaction raw materials layer and the second reaction raw materials layer are aluminium lamination and titanium layer, aluminium lamination and nickel dam etc. respectively.
The third: introduce two kinds of vapor reaction raw materials or two kinds of liquid reaction raw materials or a kind of vapor reaction raw material and a kind of liquid reaction raw material to this carbon nano tube structure simultaneously.Can prepare nanostructured by the control reaction time under this situation.
Being appreciated that when the thickness of the reaction raw materials layer that is deposited on described carbon nano tube structure surface is big, is 50 nanometers～200 nanometers as thickness, can form a plurality of continuous nano wires after the reaction raw materials reaction, and these a plurality of nano wires are formed a nanostructured.When the thickness of the reaction raw materials layer on described carbon nano tube structure surface hour, as less than 50 nanometers, reaction raw materials reaction back forms particle at interval easily.
Be appreciated that the requirement difference of different reaction raw materials to thickness.In the embodiment of the invention, by magnetron sputtering method at carbon nano tube structure surface deposition one titanium layer.Then, this carbon nano tube structure that deposits titanium layer is placed atmospheric environment, make the titanium particle on carbon nano tube structure surface contact with oxygen in the atmosphere.When the thickness of titanium layer is 50 nanometers～100 nanometers, can form a plurality of continuous titanium dioxide nano threads behind titanium layer and the oxygen reaction.When the thickness of titanium layer during, form titania nanoparticles at interval behind titanium layer and the oxygen reaction easily less than 50 nanometers.
Be appreciated that the present invention can also only introduce a kind of reaction raw materials in this carbon nano tube structure, by the decomposition reaction growth of nanostructures.
Step 3, the initiation reaction raw material reacts, growth of nanostructures.
The method that described initiation reaction raw material reacts comprises one or more in the methods such as heating, laser scanning, electric spark.Be appreciated that difference, can select diverse ways to come the initiation reaction raw material to react according to reaction raw materials.As making silicon source gas and carbon source solid/liquid/gas reactions prepare the nanometer silicon carbide structure by heating; Can make metal and oxygen reaction prepare metal oxide nanostructure by laser scanning.
In the embodiment of the invention, adopt laser scanning initiation reaction raw material to react.Adopt laser scanning initiation reaction raw material to react and comprise two kinds of situations: first kind of surface for the whole carbon nano tube structure of employing laser scanning reacted the reaction raw materials on carbon nano tube structure surface; Second kind for adopting the part surface of laser scanning carbon nano tube structure, and the reaction raw materials that makes the carbon nano tube structure surface is begun to carry out the self-diffusion reaction along the CNT orientation by the position of laser scanning.
When adopting second method, whole carbon nano tube structure can be arranged on the substrate, the substrate by selecting different thermal conductivity factors is with the speed of control growth of nanostructures.The thermal conductivity factor of described substrate is big more, and heat is just fast more to the substrate conduction, and just slow more along the conduction of CNT direction, the speed of growth of nanostructured is just slow more.Otherwise then the speed of growth is fast more.Because the thermal conductivity factor of air is very little, so when carbon nano tube structure was provided with by a framework is unsettled, nanostructured had optimum growth speed.In addition, the part surface that can also realize carbon nano tube structure by the position of selecting laser scanning growth of nanostructures selectively.
Described reaction raw materials reacts growth of nanostructures under reaction condition.This nanostructured is grown along the length of carbon nanotube direction in the carbon nano tube structure, and is coated on carbon nano tube surface.Because the CNT in the carbon nano tube structure template that is adopted among the present invention is combined closely by Van der Waals force and is formed a carbon nano tube structure with self-supporting characteristic, so the nanostructured that this reaction is grown also forms a nanostructured with self-supporting characteristic.
Be appreciated that, when adopting the CNT membrane as template, owing to comprise a plurality of join end to end and in the CNT membrane substantially along same direction carbon nanotubes arranged, so, the nanostructured of preparation comprises a plurality of nano wires that are arranged in parallel along CNT, and the length of this nano wire is identical with the length of CNT membrane.Because the length of CNT membrane is not limit, and can reach more than several meters, so the length of nano wire can reach more than several meters in the nanostructured of preparation.By the laying direction of control CNT membrane, also can control the orientation of nano wire in the nanostructured.When adopting the CNT laminate as template, owing to comprise a plurality of CNTs that are arranged of preferred orient along same direction or different directions in the CNT laminate, so the nanostructured of preparation comprises a plurality of nano wires that are arranged of preferred orient along same direction or different directions.When adopting CNT waddingization film as template, owing to comprise the CNT of a plurality of mutual windings in the CNT waddingization film, so the nanostructured of preparation comprises the nano wire of a plurality of mutual windings.
Further, the embodiment of the invention can comprise that also one separates the nanostructured that obtains with this carbon nano tube structure, obtains the step of pure nanostructured.The method of separating is relevant with the material of the nanostructured of acquisition.The embodiment of the invention can be removed carbon nano tube structure by the method for high-temperature oxydation.Particularly, product is placed high temperature furnace, under 500 ℃～1000 ℃ conditions, kept 1 hour～4 hours, obtain pure nanostructured to remove carbon nano tube structure.Be appreciated that high-temperature oxydation removes the method for carbon nano tube structure and only limit to prepare resistant to elevated temperatures nanostructured, as: metal oxide, non-metal nitride etc.
Below, the embodiment of the invention prepares the specific embodiment of nanostructured as template for adopting carbon nano tube structure:
See also Fig. 9, first embodiment of the invention provides a kind of preparation method of titanium dioxide nanostructure 104, specifically may further comprise the steps:
In the present embodiment, two stacked being layed in of CNT membrane are obtained a carbon nano tube structure 100 on the becket, and the CNT orientation is identical in two CNT membranes.
Step 2 is introduced titanium reaction raw materials 102 and oxygen to this carbon nano tube structure 100.
In the present embodiment, by the titanium layer of magnetron sputtering method in carbon nano tube structure 100 surface deposition one decks 100 nanometer thickness.See also Figure 10, the titanium uniform particles is distributed in the carbon nano tube surface in the CNT membrane.Then, this carbon nano tube structure 100 that deposits titanium layer is placed atmospheric environment, make the titanium particle on carbon nano tube structure 100 surfaces contact with oxygen in the atmosphere.
Step 3 causes titanium reaction raw materials 102 and reacts with oxygen, growth titanium dioxide nanostructure 104.
In the present embodiment, adopt laser scanning to cause the self-diffusion reaction.Wherein, the speed of laser scanning is 10 cels～200 cels, and the power of laser scanning is 0.5 watt～10 watts, and the speed of this self-diffusion reaction is greater than 10 cels.Described titanium reaction raw materials 102 reacts growth titanium dioxide nano thread 106 with oxygen under reaction condition.Because present embodiment adopts the CNT membrane as template, comprise a plurality of join end to end and in this CNT membrane along same direction carbon nanotubes arranged, this titanium dioxide nano thread 106 is along the end to end carbon nano tube growth in the CNT membrane, and be coated on carbon nano tube surface, so, obtain a plurality of titanium dioxide nano threads that are arranged in parallel 106 in whole carbon nano tube structure 100 superficial growths.The length of this titanium dioxide nano thread 106 equals the length of CNT membrane.These a plurality of titanium dioxide nano threads that are arranged in parallel 106 form the titanium dioxide nanostructure 104 of two dimension.
See also Figure 11, this titanium dioxide nano thread end to end carbon nano tube growth in this carbon nano tube structure form a plurality of titanium dioxide nano threads that be arranged in parallel, and titanium dioxide nano thread is coated on carbon nano tube surface.Please in the lump referring to Figure 12, the microscopic appearance of titanium dioxide nano thread is a plurality of continuous similar axiolitic granules, and evenly disperses or be coated on carbon nano tube surface.
Further, in the present embodiment, the heat treatment under atmospheric environment of above-mentioned titanium dioxide nanostructure 104 is obtained a pure titanium dioxide nanostructure to remove carbon nano tube structure.Described heat treatment temperature is 900 ℃, and described heat treated programming rate is 10K/ minute.See also Figure 13, described pure titanium dioxide nano thread is one to have the film of self-supporting characteristic.The thickness of this titanium dioxide film is less than 100 nanometers.Titanium dioxide nano thread length in this titanium dioxide film is greater than 900 microns, and diameter is less than 100 nanometers.
Because present embodiment adopts the CNT membrane to prepare titanium dioxide nano thread 106 as template, this CNT membrane comprises a plurality of end to end CNTs, and end to end CNT has bigger length (can reach more than several meters), so, can obtain the two-dimentional titanium dioxide nanostructure of forming by the bigger titanium dioxide nano thread 106 of length 104 in the growth that reaches several meters bigger scope inner control titanium dioxide nano thread 106.The titanium dioxide nano thread that length is bigger helps its application in macroscopical device.
Embodiment 2
See also Figure 14, second embodiment of the invention provides a kind of preparation method of titanium dioxide nanostructure 204.The preparation method of titanium dioxide nanostructure is basic identical in the preparation method of described titanium dioxide nanostructure 204 and the first embodiment of the invention, its difference is: in the present embodiment, stacked and square crossing is laid as template growth titanium dioxide nanostructure 204 with two CNT membranes.
Present embodiment specifically may further comprise the steps:
In the present embodiment, stacked and square crossing is layed in and obtains a carbon nano tube structure 200 on the becket with two CNT membranes.CNT orientation in described two CNT membranes is vertical.
Step 2 is introduced titanium reaction raw materials 202 and oxygen to this two dimension carbon nano tube structure 200.
In the present embodiment, by magnetron sputtering method in the carbon nano tube structure 200 two-sided titanium layers of one deck 100 nanometer thickness that respectively deposit as titanium reaction raw materials 202.Then, this carbon nano tube structure 200 that deposits titanium layer is placed atmospheric environment, make the titanium particle on carbon nano tube structure 200 surfaces contact with oxygen in the atmosphere.
Step 3 causes titanium reaction raw materials 202 and reacts with oxygen, growth titanium dioxide nanostructure 204.
In the present embodiment, adopt laser scanning to cause the self-diffusion reaction.Described titanium reaction raw materials 202 reacts growth titanium dioxide nano thread 206 with oxygen under reaction condition.Because present embodiment adopts the CNT membrane as template, each CNT membrane comprises a plurality of end to end CNTs, and the orientation of CNT is vertical in two CNT membranes, this titanium dioxide nano thread 206 is along the end to end carbon nano tube growth in the CNT membrane, and is coated on carbon nano tube surface.So, form a plurality of titanium dioxide nano threads 206 on these carbon nano tube structure 200 surfaces.These a plurality of titanium dioxide nano threads 206 form two-dimentional titanium dioxide nanostructure 204.Titanium dioxide nano thread 206 parts in this two dimension titanium dioxide nanostructure 204 are arranged in parallel along first direction, and part is arranged in parallel along second direction, and this first direction is vertical mutually with second direction.
In the present embodiment, obtain two-layer titanium dioxide nano thread arranged in a crossed manner 206 in CNT membrane surface preparation.See also Figure 15, this titanium dioxide nano thread is coated on carbon nano tube surface.Because titanium dioxide nano thread distributes or is coated on carbon nano tube surface, so, the macro morphology of titanium dioxide and the consistent appearance of carbon nano tube structure.Therefore, by the laying angle of control CNT membrane, can prepare the titanium dioxide nano thread 206 of different intersecting angles.
Further, in the present embodiment, the heat treatment under atmospheric environment of above-mentioned titanium dioxide nanostructure 204 is obtained a pure titanium dioxide nanostructure to remove carbon nano tube structure.Described heat treatment temperature is 600 ℃, and described heat treated programming rate is 10K/ minute.
Embodiment 3
See also Figure 16, third embodiment of the invention provides a kind of preparation method of nano structure of zinc oxide 304.The preparation method of titanium dioxide nanostructure is basic identical in the preparation method of described nano structure of zinc oxide 304 and the first embodiment of the invention, its difference is: in the present embodiment, adopt at least one carbon nano tube line as template, by metallic zinc and oxygen reaction growth of zinc oxide nano structure 304.
Present embodiment specifically may further comprise the steps:
Described one dimension carbon nano tube structure 300 is a linear structure of being made up of a plurality of CNTs, and this linear structure is the liner structure of carbon nano tube of fascicular texture or the liner structure of carbon nano tube of twisted wire structure.This liner structure of carbon nano tube comprises a plurality of carbon nano tube lines, and the diameter of described carbon nano tube line is less than 100 nanometers.When one dimension carbon nano tube structure 300 was the liner structure of carbon nano tube of fascicular texture, the spacing between described each carbon nano tube line was greater than 5 nanometers, so that grow nanowire.In the present embodiment, this carbon nano tube structure 300 is single carbon nano tube line, and this CNT linear diameter is 50 nanometers.
Step 2 is introduced zinc reaction raw materials 302 and oxygen to this one dimension carbon nano tube structure 300.
In the present embodiment, by magnetron sputtering method at a plurality of zinc particles of carbon nano tube structure 300 surface depositions as zinc reaction raw materials 302.This zinc particle diameter is 10 nanometers～50 nanometers.Then, this carbon nano tube structure 300 that deposits the zinc particle is placed atmospheric environment, make the zinc particle on carbon nano tube structure 300 surfaces contact with oxygen in the atmosphere.
Step 3 causes zinc reaction raw materials 302 and reacts growth of zinc oxide nano structure 304 with oxygen.
In the present embodiment, adopt laser scanning to cause the self-diffusion reaction.Described one dimension carbon nano tube structure 300 is a linear structure of being made up of a plurality of CNTs.Described zinc reaction raw materials 302 reacts under reaction condition with oxygen, and forms an one dimension nano structure of zinc oxide 304 along the growth of one dimension carbon nano tube structure 300 length directions.
Embodiment 4
See also Figure 17, fourth embodiment of the invention provides a kind of preparation method of nano structure of zinc oxide 404.The preparation method of titanium dioxide nanostructure is basic identical in the preparation method of described nano structure of zinc oxide 404 and the first embodiment of the invention, its difference is: in the present embodiment, carbon nano-tube film is prepared into a three-dimensional structure as template, by metallic zinc and oxygen reaction growth of zinc oxide nano structure 404.
Present embodiment specifically may further comprise the steps:
Described three dimensional carbon nanotubes structure 400 can obtain by the CNT membrane among first embodiment, CNT laminate or CNT waddingization film are folded or curl.In the present embodiment, the CNT membrane is arranged on the aluminium chassis 40, framework 40 makes the CNT membrane be rolled into a cylinder as template by curling.A plurality of CNTs in the described CNT membrane join end to end and are parallel to the cylinder axially-aligned.
Step 2 is introduced zinc reaction raw materials 402 and oxygen to this three dimensional carbon nanotubes structure 400.
In the present embodiment, by magnetron sputtering method at carbon nano tube structure 400 surface depositions one zinc layer as zinc reaction raw materials 402.This zinc coating thickness is 80 nanometers.Then, this carbon nano tube structure 400 that deposits the zinc layer is placed atmospheric environment, make the zinc particle on carbon nano tube structure 400 surfaces contact with oxygen in the atmosphere.
Step 3 causes zinc reaction raw materials 402 and reacts growth of zinc oxide nano structure 404 with oxygen.
In the present embodiment, adopt laser scanning to cause the self-diffusion reaction.Described zinc reaction raw materials 402 reacts growth of zinc oxide nano line 406 with oxygen under reaction condition.Owing to comprise a plurality of end to end CNTs in the described three dimensional carbon nanotubes structure 400, this nano wire 406 is along end to end carbon nano tube growth, and be coated on carbon nano tube surface, so, a plurality of zinc oxide nanowires that are arranged in parallel 406 obtained in carbon nano tube structure 400 superficial growths.Described a plurality of zinc oxide nanowire 406 is parallel to the cylinder axially-aligned, and forms a three-dimensional nano structure of zinc oxide 404.
In addition, those skilled in the art also can do other variation in spirit of the present invention, and certainly, the variation that these are done according to spirit of the present invention all should be included within the present invention's scope required for protection.
Claims (25)
1. the preparation method of a nanostructured, it may further comprise the steps:
One carbon nano tube structure to the unsettled setting of small part is provided;
Introduce reaction raw materials to this carbon nano tube structure; And
The initiation reaction raw material reacts, and forms nanostructured on this carbon nano tube structure surface.
2. the preparation method of nanostructured as claimed in claim 1 is characterized in that, described carbon nano tube structure comprises a plurality of even carbon nanotube distribution composition layer structures.
3. the preparation method of nanostructured as claimed in claim 1 is characterized in that, described carbon nano tube structure comprises at least one carbon nano-tube film, at least one liner structure of carbon nano tube or its any combination.
4. the preparation method of nanostructured as claimed in claim 3 is characterized in that, described carbon nano-tube film comprises that a plurality of CNTs are parallel to each other substantially and are parallel to the carbon nano-tube film surface.
5. the preparation method of nanostructured as claimed in claim 4 is characterized in that, described carbon nano-tube film comprises that a plurality of CNTs join end to end by Van der Waals force and are arranged of preferred orient along same direction substantially.
6. the preparation method of nanostructured as claimed in claim 3 is characterized in that, described carbon nano-tube film comprises that a plurality of CNTs twine mutually.
7. the preparation method of nanostructured as claimed in claim 3, it is characterized in that, described liner structure of carbon nano tube comprises at least one carbon nano tube line, and described carbon nano tube line comprises that a plurality of CNTs are arranged in parallel or shape arrangement in the shape of a spiral along this carbon nano tube line length direction.
8. the preparation method of nanostructured as claimed in claim 7 is characterized in that, described liner structure of carbon nano tube comprises that a plurality of carbon nano tube lines are formed fascicular texture substantially mutually side by side or a plurality of carbon nano tube line twines composition twisted wire structure mutually.
9. the preparation method of nanostructured as claimed in claim 3 is characterized in that, described carbon nano tube structure comprises that a plurality of liner structure of carbon nano tube are arranged in parallel, arranged in a crossed manner or mutual braiding setting mutually.
10. the preparation method of nanostructured as claimed in claim 1 is characterized in that, the preparation method of described carbon nano tube structure to the unsettled setting of small part may further comprise the steps: a supporter is provided; This carbon nano tube structure is arranged at this supporting body surface, and passes through this supporter to the unsettled setting of small part.
11. the preparation method of nanostructured as claimed in claim 1 is characterized in that, described method to this carbon nano tube structure introducing reaction raw materials may further comprise the steps: form one first reaction raw materials layer on this carbon nano tube structure surface; Form one second reaction raw materials layer on this first reaction raw materials layer, the gross thickness of the described first reaction raw materials layer and the second reaction raw materials layer is 50 nanometers～200 nanometers.
12. the preparation method of nanostructured as claimed in claim 11 is characterized in that, the described first reaction raw materials layer is a metal level, and the second reaction raw materials layer is silicon layer or metal level.
13. the preparation method of nanostructured as claimed in claim 1, it is characterized in that described method to this carbon nano tube structure introducing reaction raw materials may further comprise the steps: forming a layer thickness on this carbon nano tube structure surface is the first reaction raw materials layer of 50 nanometers～200 nanometers; Introduce gaseous state or the second liquid reaction raw materials to this carbon nano tube structure.
14. the preparation method of nanostructured as claimed in claim 13 is characterized in that, the described first reaction raw materials layer is metal level or silicon layer, and second reaction raw materials of described gaseous state is one or more in oxygen, nitrogen, silicon source gas and the carbon-source gas.
15. the preparation method of nanostructured as claimed in claim 13 is characterized in that, second reaction raw materials of described liquid state is one or more in methyl alcohol, ethanol, acetone and the liquid resin etc.
16. the preparation method of nanostructured as claimed in claim 1, it is characterized in that described method to this carbon nano tube structure introducing reaction raw materials is to introduce two kinds of vapor reaction raw materials, two kinds of liquid reaction raw materials or a kind of vapor reaction raw material and a kind of liquid reaction raw material to this carbon nano tube structure.
17. the preparation method of nanostructured as claimed in claim 1 is characterized in that, described initiation reaction raw material reacts the method that forms nanostructured and comprises in heating, electric spark and the laser scanning one or more.
18. the preparation method of nanostructured as claimed in claim 17, it is characterized in that, described employing laser scanning initiation reaction raw material reacts the method that forms nanostructured and comprises: the whole surface of adopting the laser scanning carbon nano tube structure, the reaction raw materials on carbon nano tube structure surface is reacted, or the part surface of employing laser scanning carbon nano tube structure, make the reaction raw materials on carbon nano tube structure surface carry out the self-diffusion reaction.
19. the preparation method of nanostructured as claimed in claim 1 is characterized in that, described carbon nano tube structure comprises a plurality of CNTs, and described nanostructured is formed at the carbon nano tube surface in the described carbon nano tube structure.
20. the preparation method of nanostructured as claimed in claim 1, it is characterized in that, described initiation reaction raw material reacts and further comprises that one removes the step of this carbon nano tube structure by high-temperature oxydation after the step that forms nanostructured, is formed up to the nanostructured of the unsettled setting of small part.
21. the preparation method of nanostructured as claimed in claim 20 is characterized in that, the temperature of described high-temperature oxydation is 500 ℃～1000 ℃, and the time of described high-temperature oxydation was less than 4 hours.
22. the preparation method of a nanostructured, it may further comprise the steps: at least one carbon nano-tube film is provided, and described carbon nano-tube film comprises that a plurality of CNTs are parallel to each other substantially and are parallel to the carbon nano-tube film surface;
Introduce reaction raw materials to this at least one carbon nano-tube film; And
The initiation reaction raw material reacts, and forms nanostructured on this carbon nano-tube film surface.
23. the preparation method of nanostructured as claimed in claim 22 is characterized in that, describedly comprises further that before this at least one carbon nano-tube film is introduced reaction raw materials one is arranged at step on the supporter with this carbon nano-tube film.
24. the preparation method of a nanostructured, it may further comprise the steps:
The carbon nano tube structure of one unsettled setting is provided;
Carbon nano tube structure surface deposition one thickness in this unsettled setting is the metal level of 50 nanometers～100 nanometers; And
This metal level of oxidation obtains metal oxide nanostructure.
25. the preparation method of nanostructured as claimed in claim 24 is characterized in that, described carbon nano tube structure comprises a plurality of CNTs, and described metal level is formed at the surface of each CNT in the described carbon nano tube structure.
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