CN104909401A - Nanorods or nanowires formed by carbon nanotubes filled with metal sulfide in inner cavities, and preparation method thereof - Google Patents
Nanorods or nanowires formed by carbon nanotubes filled with metal sulfide in inner cavities, and preparation method thereof Download PDFInfo
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Abstract
The invention discloses nanorods or nanowires formed by carbon nanotubes filled with metal sulfide in inner cavities, and a preparation method thereof. A carbon nanotube epoxy porous membrane is used for replacing truncated dispersed carbon nanotubes in carbon nanotube internal filling experiments and studies. In the porous membrane, the outside of the carbon nanotubes is protected by a high-molecular substrate, and the inner walls of the carbon nanotubes are the only places that the carbon nanotubes can contact a precursor. That is to say, it can be ensured that the metal sulfide can be generated only inside the carbon nanotubes. Also, the diffusion capacities of substances on the two sides of a diffusion tank upon the carbon nanotubes are different, and the carbon nanotube array exists in a form of a membrane. Therefore, different concentrations or pressures can be configured on the two sides of the membrane, and the substances on the two sides can enter the inside of the carbon nanotubes under control. Therefore, a reaction product can be just generated inside the carbon nanotubes. With the method, the carbon nanotubes do not need to be truncated with severe conditions, and carbon nanotube property is not influenced. With the method, ultra-long nanowires with a uniform size can be prepared.
Description
Technical field
The present invention relates to the nanometer rod of carbon nanotube cavity filler metal sulfide or nano wire, preparation method to carbon nanotube cavity filler metal sulfide nanometer rod or nano wire.
Background technology
Carbon nanotube is a kind of hollow one-dimensional carbon nano material curled into along special angle by one or more layers Graphene that doctor Iijima found in 1991.Except outside modification and compound, it is another important directions that carbon nanotube is studied that the inside of carbon nanotube is filled.The lar nanometric cavities of carbon nanotube small-sized, what have even can be less than 1nm.Theoretical investigation shows, the chemical reaction in the inner a kind of so narrow space of carbon nanotube will be very different with the reaction under usual terms.This special property of carbon nanotube cavity has evoked the interest of many investigators, and they think that the material in carbon nanotube inside can show the composition and character being different from body.So a lot of investigators attempts various material to be filled into carbon nanotube inside.Due to special construction and the character of carbon nanotube, the metal of filling therein or its compound also can be subject to the impact of its particular electrical minor structure and space confinement condition.Study this phenomenon, just first must find out the effective ways preparing carbon nanotube filled with metal (M@CNT, M represents metallic compound) compound.The method of material filling carbon nano-pipe mainly contains five kinds: growth in situ filling, supercutical fluid filling, evaporation filling, melting filling, wet chemistry are filled.Wherein wet chemistry fill be use at most and the widest method of suitability.Filled by wet chemistry, a lot of metals is successfully introduced carbon nanotube inside, forms nano wire or nanoparticle structure.But this method still has some weak point:
First, due to wet chemistry fill be by by carbon nanotube dispersed in the solution of precursor (or nano particle) needing filler, utilize ultrasonic and stir, make presoma enter carbon nanotube inside.Finally by appropriate means, metal is reduced in carbon nanotube inside again.From then on can find out in process, the inside and outside surface of carbon nanotube can touch precursor, also can adsorb precursor at carbon nanotube outer wall.If do not have the metallic precursor of the specific reduction carbon nanotube inside of method energy, so after reduction, metal nanoparticle just all can exist in the inside of carbon nanotube and outer wall.Such situation studies separately carbon nanotube inner material Quality Research to many needs very large interference;
Secondly, in the process that wet chemistry is filled, in order to make the more high efficiency wetting carbon nanotubes of precursor solution inner, usually need carbon nanotube brachymemma, this also just means and is difficult to obtain longer M@CNT matrix material;
In addition, the brachymemma of carbon nanotube needs to carry out under more violent condition, but these violent conditions can not only make carbon nanotube by brachymemma, and also make the destruction that the outer wall construction of carbon nanotube suffers to a certain degree, character also can change.This is unfavorable for the character studying M@CNT mixture.
For this some weak point, we have proposed and utilize carbon nano tube epoxy resin porous-film to replace the carbon nanotube of brachymemma dispersion to fill experiment and research to carry out carbon nanotube inside.
Summary of the invention
The object of this invention is to provide a kind of nanometer rod or nano wire and preparation method thereof of carbon nanotube cavity filler metal sulfide, solve carbon nanotube brachymemma, be unfavorable for studying the problem such as character of carbon nanotube inner material.
The invention provides a kind of nanometer rod or nano wire of carbon nanotube cavity filler metal sulfide, described nanometer rod is outer or nano wire is outer is wrapped up by carbon nanotube porous-film, and described nanometer rod is bar-shaped metallic sulfide or described nano wire skin is metallic threadlike sulfide.
Further technical scheme, the diameter of described nanometer rod or nano wire is 8nm ~ 15nm.
The present invention also provides a kind of nanometer rod of carbon nanotube cavity filler metal sulfide or the preparation method of nano wire, it is characterized in that, comprising:
(1) choose the carbon nanotube epoxy porous-film of both ends open, described carbon nanotube epoxy porous-film is put into dispersion device and fix;
(2) pass into solution A in one end of described carbon nanotube epoxy porous-film, described solution A is sodium hydrosulfide or sodium sulfide solution, and pass into B solution at the other end of described carbon nanotube epoxy porous-film, described B solution is the salts solution of metal;
(3) stir A, B two kinds of solution, make it react in described carbon nanotube epoxy porous-film inside, generate bar-shaped metallic sulfide or metallic threadlike sulfide.
Further technical scheme, in described step (2), the concentration of described solution A is 0.01mol/L ~ 0.1mol/L, and the concentration of described B solution is 0.01mol/L ~ 0.1mol/L.
Further technical scheme, in described step (2), the solvent of described solution A is water or ethanol, and the solvent of described B solution is water or ethanol.
Further technical scheme, in described step (1), the preparation method of described carbon nanotube epoxy porous-film comprises:
(1) prepare carbon nano pipe array: silicon chip evaporation being had aluminium or aluminum oxide, put into tube furnace, obtain carbon nano pipe array by chemical Vapor deposition process growth;
(2) carbon nano pipe array is embedded: dropped in by epoxy resin on described carbon nano pipe array, it is made to solidify 12 hours at the temperature of 90 DEG C, then hydrofluoric acid dips is put into, be separated silicon chip and obtain sheet carbon nano tube epoxy resin matrix material, again described sheet carbon nano tube epoxy resin matrix material is put into round shape embedding device and instill epoxy resin, 10-20 hour is solidified, obtained carbon nano tube epoxy resin matrix material at the temperature of 70-100 DEG C;
(3) section carbon nano tube epoxy resin matrix material: by described carbon nano tube epoxy resin matrix material microtome, obtained carbon nanotube epoxy porous-film.
Further technical scheme, in described step (1), described chemical Vapor deposition process comprises:
(1) silicon chip containing catalyzer is positioned in the middle part of single-phase stove silica tube, passes into argon gas and get rid of inner air tube, start after 5-10min to heat up, pass into hydrogen from room temperature to 750-780 DEG C simultaneously;
(2) when temperature-stable is at 750-780 DEG C, start to pass into ethene, pass into the argon gas with water vapor in autoclave simultaneously, to make in whole atmosphere water vapour content at 50 ~ 300ppm, and keep 10 ~ 20min, obtained carbon nano pipe array;
(3) after obtained described carbon nano pipe array, stop passing into described ethene and water vapour, and lower the temperature.
Further technical scheme, in described step (2), described epoxy resin is by epoxy monomer SPI-PON 812, NMA, and stir after DDSA mixing, add altax P-30 stirring again to obtain, the mass ratio of described epoxy monomer SPI-PON 812:NMA:DDSA:DMP-30 is 2.5 ~ 3:1.5 ~ 2:0.5 ~ 1:0.05 ~ 0.1.
Further technical scheme, in described step (3), the chip rate of described slicing machine is 50-60 rev/min, and slice thickness is 9-12 micron.
Further technical scheme, in described step (1), described dispersion device comprises the first diffusion cell, second diffusion cell, first silica-gel plate and the second silica-gel plate, described first diffusion cell, second diffusion cell, first silica-gel plate and the second silica-gel plate are respectively equipped with the first through hole, second through hole, third through-hole and fourth hole, described first silica-gel plate and the second silica-gel plate are folded between described first diffusion cell and the second diffusion cell, the carbon nanotube epoxy porous-film of described both ends open is clipped between third through-hole and fourth hole, described first through hole, second through hole, the diameter of third through-hole and fourth hole mates mutually.
Advantage of the present invention is: the present invention fills experiment and research by utilizing carbon nanotube epoxy porous-film to replace the carbon nanotube of brachymemma dispersion to carry out carbon nanotube inside.In such porous-film, because carbon nanotube outer is protected by macromolecule matrix, its inwall becomes the place that whole carbon nanotube uniquely contacts with presoma, that is can ensure that metallic sulfide uniquely generates in carbon nanotube inside.Secondly, because the material of diffusion cell both sides is different to the diffusibility of carbon nanotube, and carbon nano pipe array exists in membrane form, the present invention can arrange different concns or pressure on the both sides of film, what make both sides material equilibrium enters carbon nanotube inside, thus reaction product is generated in carbon nanotube inside just.This method does not need violent condition to carry out shortening carbon nano-tube, so the character of carbon nanotube also can not be affected, simultaneously also can with for template, preparation overlength and the nano wire of size uniformity.This template is than conventional template such as aluminum oxide, and its length and diameter can be effectively controlled simultaneously.Differently from another of alumina formwork be that carbon nanotube of the present invention has higher degree of graphitization and less internal diameter size, the space of this small scale can be more obvious on the impact of inside stuffing.
Accompanying drawing explanation
In order to be illustrated more clearly in the technical scheme of the embodiment of the present invention, below the accompanying drawing used required in describing embodiment is briefly described, apparently, accompanying drawing in the following describes is only some embodiments of the present invention, for those of ordinary skill in the art, under the prerequisite not paying creative work, other accompanying drawing can also be obtained according to these accompanying drawings.Wherein,
Fig. 1 be a kind of carbon nanotube cavity filler metal sulfide of the present invention nanometer rod or nano wire and preparation method thereof in embodiment 1 described copper sulphide nano rod TEM figure;
Fig. 2 be a kind of carbon nanotube cavity filler metal sulfide of the present invention nanometer rod or nano wire and preparation method thereof in example 2 described copper sulphide nano rod TEM figure;
Fig. 3 be a kind of carbon nanotube cavity filler metal sulfide of the present invention nanometer rod or nano wire and preparation method thereof in example 2 described copper sulphide nano rod EDX figure;
Fig. 4 be a kind of carbon nanotube cavity filler metal sulfide of the present invention nanometer rod or nano wire and preparation method thereof in embodiment 3 described silver sulfide nano line TEM figure.
Embodiment
The skin of carbon nano-tube filled nano metal sulfide rod of the present invention or nano wire is wrapped up by carbon nanotube epoxy porous-film, and the diameter of described nanometer rod or nano wire is 8nm ~ 15nm, and its orientation depends on the orientation of carbon nanotube.
The above-mentioned nanometer rod of carbon nanotube cavity filler metal sulfide of the present invention or the preparation method of nano wire, comprise step:
Step one: the carbon nanotube epoxy porous-film choosing both ends open, puts into dispersion device and fixes by described carbon nanotube epoxy porous-film.
In one embodiment, above-mentioned steps one specifically performs and is: the carbon nanotube epoxy porous-film choosing both ends open, and described carbon nanotube epoxy porous-film is put into dispersion device and fix, the preparation method of described carbon nanotube epoxy porous-film comprises:
(1) prepare carbon nano pipe array: silicon chip evaporation being had aluminium or aluminum oxide, put into tube furnace, obtain carbon nano pipe array by chemical Vapor deposition process growth, described chemical Vapor deposition process comprises:
Silicon chip containing catalyzer is positioned in the middle part of single-phase stove silica tube, passes into argon gas and get rid of after inner air tube and start to heat up, pass into hydrogen from room temperature to 750-780 DEG C simultaneously; When temperature-stable is at 750-780 DEG C, start to pass into ethene, pass into the argon gas with water vapor in autoclave simultaneously, to make in whole atmosphere water vapour content at 50 ~ 300ppm, and keep 10 ~ 20min, obtained carbon nano pipe array; After obtained described carbon nano pipe array, stop passing into described ethene and water vapour, and lower the temperature; Herein, pass into argon gas and get rid of after inner air tube and start to heat up, pass into hydrogen from room temperature to 770 DEG C simultaneously; When temperature-stable is at 770 DEG C, start to pass into ethene for best.If control lower than 750 DEG C by the temperature after heating up here, the carbon nano pipe array height grown out is lower, is unfavorable for the section in later stage.And if temperature is controlled higher than 780 DEG C, the carbon nano pipe array " ring " grown out is more, and quality is low, is unfavorable for the filling in later stage.
(2) carbon nano pipe array is embedded: dropped in by epoxy resin on described carbon nano pipe array, it is made to solidify 12 hours at the temperature of 90 DEG C, then hydrofluoric acid dips is put into, be separated silicon chip and obtain sheet carbon nano tube epoxy resin matrix material, again described sheet carbon nano tube epoxy resin matrix material is put into round shape embedding device and instill epoxy resin, 10-20 hour is solidified, obtained carbon nano tube epoxy resin matrix material at the temperature of 70-100 DEG C.In this step: described epoxy resin is by epoxy monomer SPI-PON 812, NMA, and stir after DDSA mixing, add altax P-30 stirring again to obtain, the mass ratio of described epoxy monomer SPI-PON 812:NMA:DDSA:DMP-30 is 2.5 ~ 3:1.5 ~ 2:0.5 ~ 1:0.05 ~ 0.1;
(3) section carbon nano tube epoxy resin matrix material: by described carbon nano tube epoxy resin matrix material microtome, obtained carbon nanotube epoxy porous-film.In this step, the chip rate of described slicing machine is 50-60 rev/min, and slice thickness is 9-12 micron.The chip rate of slicing machine herein determines primarily of the hardness of carbon nanotube epoxy composite material, when this material hardness is larger with 50 revs/min, when composite hardness is less with 60 revs/min, ensures that the porous-film quality cut out is better like this.Slice thickness is also have carbon nanotube epoxy composite material hardness to determine, when this material hardness is larger, cuts into slices thicker, when this material hardness is less, cut into slices thinner.The hardness of carbon nanotube epoxy composite material is by SPI-PON 812, NMA, DDSA, and the proportioning of these three kinds of materials determines, and the proportion relation of these three kinds of materials is by how many comprehensive decisions of the density of carbon nano pipe array, height and its agraphitic carbon content.
In another embodiment, above-mentioned steps one specifically performs: described dispersion device comprises the first diffusion cell, second diffusion cell, first silica-gel plate and the second silica-gel plate, described first diffusion cell, second diffusion cell, first silica-gel plate and the second silica-gel plate are respectively equipped with the first through hole, second through hole, third through-hole and fourth hole, described first silica-gel plate and the second silica-gel plate are folded between described first diffusion cell and the second diffusion cell, the carbon nanotube epoxy porous-film of described both ends open is clipped between third through-hole and fourth hole, described first through hole, second through hole, the diameter of third through-hole and fourth hole mates mutually.
Tell about a kind of dispersion device in detail below: comprise a square shaped diffusion cell and a pair silica-gel plate composition, by a pair silica-gel plate alignment, be placed in the middle of two diffusion cells.Described square diffusion cell is the polytetrafluoroethylcontainer container of a square shaped, the side wall of container of two square diffusion cells is opened the aperture of a 6mm respectively, two described silica-gel plates are also square, its size is just identical with that sidewall of diffusion cell perforate, and two silica-gel plates respectively have an aperture that can coincide with tetrafluoroethylene diffusion cell aperture.By a pair silica-gel plate alignment, put in the middle of two diffusion cells, carbon nanotube epoxy porous-film is clipped in silica-gel plate through above-mentioned four apertures, entangles with bungee the dispersion device that whole device just defines complete set.
Step 2: pass into solution A in one end of described carbon nanotube epoxy porous-film, described solution A is sodium hydrosulfide or sodium sulfide solution, pass into B solution at the other end of described carbon nanotube epoxy porous-film, described B solution is the salts solution of metal.
In one embodiment, above-mentioned steps two specifically performs and is: the concentration of described solution A is 0.01mol/L ~ 0.1mol/L, and the concentration of described B solution is 0.01 mol/L ~ 0.1mol/L.
In another embodiment, above-mentioned steps two specifically performs and is: the solvent of described solution A is water or ethanol, and the solvent of described B solution is water or ethanol.
Step 3: stir A, B two kinds of solution, make it react in described carbon nanotube epoxy porous-film inside, generate bar-shaped metallic sulfide or metallic threadlike sulfide.
For enabling above-mentioned purpose of the present invention, feature and advantage become apparent more, further illustrate technical scheme of the present invention below in conjunction with drawings and Examples.But the invention is not restricted to listed embodiment, also should be included in other any known changes in interest field of the presently claimed invention.
First, alleged herein " embodiment " or " embodiment " refers to special characteristic, structure or the characteristic that can be contained at least one implementation of the present invention.Different local in this manual " in one embodiment " occurred not all refers to same embodiment, neither be independent or optionally mutually exclusive with other embodiments embodiment.
Secondly, the present invention utilizes structural representation etc. to be described in detail, and when describing the embodiment of the present invention in detail, for ease of illustrating, schematic diagram can be disobeyed general ratio and be made partial enlargement, and described schematic diagram is example, and it should not limit the scope of protection of the invention at this.In addition, the three-dimensional space of length, width and the degree of depth should be comprised in actual fabrication.
Embodiment one
In electron beam evaporation equipment Ei-5z, successively with the polished surface of the monocrystalline silicon piece of the speed evaporation 10nm Al of 0.3nm/s and 0.1nm/s and 1nm Fe to 4inch diameter.Had by evaporation the silicon chip of catalyzer to be placed in middle part that internal diameter is the silica tube of 1inch.The argon gas 10min of first logical 300sccm gets rid of the air in silica tube.Argon flow amount be decreased to 100 and start after passing into the hydrogen of 40sccm to heat up, in 13, rising to 770 DEG C from room temperature.Until temperature-stable after, pass into the ethene of 30sccm, keep 10.After completing, stop logical ethene and start cooling.When temperature drops to after below 700 DEG C, stop logical hydrogen.After temperature continues to be reduced to room temperature, carbon nano pipe array prepared by taking-up also stops argon gas.
Carbon nano pipe array is transferred in a culture dish, to prepare and the resin precursor adding promotor pours culture dish into, make it complete wetting and submergence carbon nano pipe array, then make the gas between carbon nanotube all overflow under vacuo, then carbon nano tube/epoxy resin composite material is pulled out from culture dish to be placed in vacuum drying oven and be warming up to 90 DEG C and make it solidification 12 hours.After having solidified, carbon nano pipe array/epoxy resin composite block is put into imbedded mold, add epoxy resin precursor and again vacuumize removing bubble, be then warming up to 90 DEG C of solidifications 12 hours.After completing, it is taken out from imbedded mold and the carbon nano pipe array/epoxy resin porous porous film becoming 9 micron thickness of cutting into slices.Wherein, the epoxy resin ingredient content used for twice must be consistent, and each constituent mass is respectively: SPI-PON 812:2.5g NMA:0.5g DDSA:1.5g DMP-30:0.07g.
First the carbon nano tube/epoxy resin porous-film water oxygen plasma treatment we prepared, the wetting ability making it surface is improved.Process is as follows: aqueous vapor is brought into the inside in plasma cleaning chamber by oxygen by Bubbling method with the flow of 100sccm.The vacuum tightness in plasma cleaning chamber is 500mtorr, and power is 18w, and scavenging period is 10min.Between two silica gel holes film being placed in two diffusion cells, detect whether our film used is have perviousness and do not have large gap with Repone K diffusion experiment and nm gold particles diffusion experiment.After qualified porous-film being detected, the liquid in the diffusion cell of film both sides is changed to ultrapure water, and is placed in vacuum drying oven and vacuumizes 12h, order about gas and discharge from the surface of film and carbon nanotube inside.Dispersion device deionized water is on one side changed the sodium sulfide solution for the 0.1M through exhaust, and the ultrapure water of opposite diffusion cell being changed to concentration is 0.1M copper sulfate solution, carries out the diffusion of 72h.After completing, take out film and use washed with de-ionized water surface repeatedly rear dry.Remove the part not touching liquid level and do not have carbon nanotube.The film of pruning is put into the time that concentrated hydrochloric acid solution clears up 3 days.With filtration unit, carbon nanotube is filtered out, after dispersion, carry out TEM sign.Refer to Fig. 1, Fig. 1 be a kind of carbon nanotube cavity filler metal sulfide of the present invention nanometer rod or nano wire and preparation method thereof in embodiment 1 described copper sulphide nano rod TEM figure.
As shown in Figure 1, we can be clearly seen that cupric sulfide is inner at carbon nanotube, and the length of nanometer rod or nano wire is at about 100nm.Nanometer rod is in strict accordance with the axial direction due orientation of carbon nanotube.In addition the growth of nanochannel to nano metal sulphide of carbon nanotube serves extraordinary constraint and template action, all nanometer rod be grown in same carbon pipe all have identical diameter, the arrangement architecture of this rule likely makes this novel material have special resonance and optical properties, thus obtains application in the optical electric field regulation and control field of nanoscale.Utilize the metallic sulfide cupric sulfide just of filling inside the EDX analytical proof of constituency.In addition we do not see that having copper sulfide particle to be attached to carbon nanotube outer wall is reduced, these results show that our this employing carbon nano pipe array/epoxy resin porous-film is as template, and unique method of carrying out the filling of metal cupric sulfide in carbon nanotube inside is successful.
Embodiment two
Working method is with example 1, and when preparing epoxy resin, each constituent mass is respectively: SPI-PON 812:2.7g NMA:0.7g DDSA:1.7g DMP-30:0.07g.Embedded and to have cut into slices to it afterwards, change the slice thickness of slicing machine into 12 microns, speed reduces to 50 revs/min, to adapt to the epoxy resin hardness of this kind of proportioning.Dispersion device deionized water is on one side changed the Sodium sulfhydrate ethanolic soln for the 0.1M through exhaust, and the ultrapure water of opposite diffusion cell being changed to concentration is 0.1M neutralized verdigris ethanolic soln, carries out the diffusion of 72h.All the other conditions are constant, the carbon nano-tube filled metal copper sulphide nano rod obtained.
Refer to Fig. 2 and Fig. 3, Fig. 2 be a kind of carbon nanotube cavity filler metal sulfide of the present invention nanometer rod or nano wire and preparation method thereof in example 2 described copper sulphide nano rod TEM figure, as can be seen from the figure the weighting material contrast of carbon nanotube inside is apparently higher than its tube wall, and the structure of its multistage has also highlighted the peculiar property of the material prepared by the present invention.Fig. 3 be a kind of carbon nanotube cavity filler metal sulfide of the present invention nanometer rod or nano wire and preparation method thereof in example 2 described copper sulphide nano rod EDX figure, can determine that this weighting material is exactly cupric sulfide from the Elemental redistribution figure.
Embodiment three
The same embodiment of working method, the argon gas 10min of first logical 300sccm gets rid of the air in silica tube.Argon flow amount be decreased to 100sccm and start after passing into the hydrogen of 150sccm to heat up, in 13, rising to 780 DEG C from room temperature.Until temperature-stable after, pass into the ethene of 150sccm, keep 10.After completing, stop logical ethene and start cooling.When temperature drops to after below 700 DEG C, stop logical hydrogen.After temperature continues to be reduced to room temperature, carbon nano pipe array prepared by taking-up also stops argon gas.The method of the carbon nano pipe array embodiment 2 grown is embedded and cuts into slices, then be clipped in the middle of diffusion cell, dispersion device deionized water is on one side changed the Sodium sulfhydrate ethanolic soln for the 0.1M through exhaust, the ultrapure water of opposite diffusion cell being changed to concentration is 0.1M silver nitrate aqueous solution, carries out the diffusion of 72h.All the other conditions are constant, the carbon nano-tube filled metal silver sulfide nano line obtained.
Refer to Fig. 4, the TEM figure of the nanometer rod or nano wire and preparation method thereof of Fig. 4 a kind of carbon nanotube cavity filler metal sulfide of the present invention described silver sulfide nano line in embodiment 3.This interstitital texture length is more than 1 micron, filling the inside that only (can be generally tens nanometers) in shorter size and obtain carbon pipe from traditional wet method fills different, our metallic sulfide structure can grow and reach hundreds of nanometer and even longer carbon pipe inside, this has absolutely proved that our method its charging efficiency for traditional method is higher, and controllability is also stronger.
In sum, the invention discloses a kind of carbon nano-tube filled nano metal sulfide rod and preparation method thereof, replace the carbon nanotube of brachymemma dispersion to carry out carbon nanotube inside by utilizing carbon nanotube epoxy porous-film and fill experiment and research.In such porous-film, because carbon nanotube outer is protected by macromolecule matrix, its inwall becomes the place that whole carbon nanotube uniquely contacts with presoma, that is can ensure that metal uniquely generates in carbon nanotube inside.Secondly, because the material of diffusion cell both sides is different to the diffusibility of carbon nanotube, and carbon nano pipe array exists in membrane form, the present invention can arrange different concns or pressure on the both sides of film, what make both sides material equilibrium enters carbon nanotube inside, thus reaction product is generated in carbon nanotube inside just.This method does not need violent condition to carry out shortening carbon nano-tube, so the character of carbon nanotube also can not be affected, simultaneously also can with for template, preparation overlength and the nano wire of size uniformity.This template is than conventional template such as aluminum oxide, and its length and diameter can be effectively controlled simultaneously.Differently from another of alumina formwork be that carbon nanotube of the present invention has higher degree of graphitization and less internal diameter size, the space of this small scale can be more obvious on the impact of inside stuffing.
It should be noted that, above embodiment is only in order to illustrate technical scheme of the present invention and unrestricted, although with reference to preferred embodiment to invention has been detailed description, those of ordinary skill in the art is to be understood that, can modify to technical scheme of the present invention or equivalent replacement, and not departing from the spirit and scope of technical solution of the present invention, it all should be encompassed in the middle of right of the present invention.
Claims (10)
1. the nanometer rod of a carbon nanotube cavity filler metal sulfide or nano wire, it is characterized in that, described nanometer rod is outer or nano wire is outer is wrapped up by carbon nanotube epoxy porous-film, and described nanometer rod is bar-shaped metallic sulfide or described nano wire skin is metallic threadlike sulfide.
2. the nanometer rod of carbon nanotube cavity filler metal sulfide according to claim 1 or nano wire, is characterized in that: the diameter of described nanometer rod or nano wire is 8nm ~ 15nm.
3. the nanometer rod of carbon nanotube cavity filler metal sulfide or a preparation method for nano wire, is characterized in that, comprising:
(1) choose the carbon nanotube epoxy porous-film of both ends open, described carbon nanotube epoxy porous-film is put into dispersion device and fix;
(2) pass into solution A in one end of described carbon nanotube epoxy porous-film, described solution A is sodium hydrosulfide or sodium sulfide solution, and pass into B solution at the other end of described carbon nanotube epoxy porous-film, described B solution is the salts solution of metal;
(3) stir A, B two kinds of solution, make it react in described carbon nanotube epoxy porous-film inside, generate bar-shaped metallic sulfide or metallic threadlike sulfide.
4. the nanometer rod of carbon nanotube cavity filler metal sulfide according to claim 3 or the preparation method of nano wire, it is characterized in that: in step (2), the concentration of described solution A is 0.01mol/L ~ 0.1mol/L, and the concentration of described B solution is 0.01mol/L ~ 0.1mol/L.
5. the nanometer rod of carbon nanotube cavity filler metal sulfide according to claim 3 or the preparation method of nano wire, it is characterized in that: in step (2), the solvent of described solution A is water or ethanol, and the solvent of described B solution is water or ethanol.
6. the nanometer rod of carbon nanotube cavity filler metal sulfide according to claim 3 or the preparation method of nano wire, is characterized in that, in step (1), the preparation method of described carbon nanotube epoxy porous-film comprises:
(1) prepare carbon nano pipe array: silicon chip evaporation being had aluminium or aluminum oxide, put into tube furnace, obtain carbon nano pipe array by chemical Vapor deposition process growth;
(2) carbon nano pipe array is embedded: dropped in by epoxy resin on described carbon nano pipe array, it is made to solidify 12 hours at the temperature of 90 DEG C, then hydrofluoric acid dips is put into, be separated silicon chip and obtain sheet carbon nano tube epoxy resin matrix material, again described sheet carbon nano tube epoxy resin matrix material is put into round shape embedding device and instill epoxy resin, 10-20 hour is solidified, obtained carbon nano tube epoxy resin matrix material at the temperature of 70-100 DEG C;
(3) section carbon nano tube epoxy resin matrix material: by described carbon nano tube epoxy resin matrix material microtome, obtained carbon nanotube epoxy porous-film.
7. the nanometer rod of carbon nanotube cavity filler metal sulfide according to claim 6 or the preparation method of nano wire, is characterized in that, in step (1), described chemical Vapor deposition process comprises:
(1) silicon chip containing catalyzer is positioned in the middle part of single-phase stove silica tube, passes into argon gas and get rid of inner air tube, start after 5-10min to heat up, pass into hydrogen from room temperature to 750-780 DEG C simultaneously;
(2) when temperature-stable is at 750-780 DEG C, start to pass into ethene, pass into the argon gas with water vapor in autoclave simultaneously, to make in whole atmosphere water vapour content at 50 ~ 300ppm, and keep 10 ~ 20min, obtained carbon nano pipe array;
(3) after obtained described carbon nano pipe array, stop passing into described ethene and water vapour, and lower the temperature.
8. the nanometer rod of carbon nanotube cavity filler metal sulfide according to claim 6 or the preparation method of nano wire, it is characterized in that, in step (2), described epoxy resin is by epoxy monomer SPI-PON 812, NMA, and DDSA mixing after stir, then add altax P-30 stir obtain, the mass ratio of described epoxy monomer SPI-PON 812:NMA:DDSA:DMP-30 is 2.5 ~ 3:1.5 ~ 2:0.5 ~ 1:0.05 ~ 0.1.
9. the nanometer rod of carbon nanotube cavity filler metal sulfide according to claim 6 or the preparation method of nano wire, is characterized in that, in step (3), the chip rate of described slicing machine is 50-60 rev/min, and slice thickness is 9-12 micron.
10. the nanometer rod of carbon nanotube cavity filler metal sulfide according to claim 3 or the preparation method of nano wire, it is characterized in that: in step (1), described dispersion device comprises the first diffusion cell, second diffusion cell, first silica-gel plate and the second silica-gel plate, described first diffusion cell, second diffusion cell, first silica-gel plate and the second silica-gel plate are respectively equipped with the first through hole, second through hole, third through-hole and fourth hole, described first silica-gel plate and the second silica-gel plate are clipped between described first diffusion cell and the second diffusion cell, the carbon nanotube epoxy porous-film of described both ends open is clipped between third through-hole and fourth hole, described first through hole, second through hole, the diameter of third through-hole and fourth hole mates mutually.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107895648A (en) * | 2017-11-15 | 2018-04-10 | 哈尔滨理工大学 | The preparation method of CuS nanoparticles powder and multi-walled carbon nanotube combination electrode |
| CN109337293A (en) * | 2018-10-15 | 2019-02-15 | 河南机电职业学院 | Shape memory nanocomposite of microwave fast reaction and preparation method thereof |
| CN112279293A (en) * | 2020-11-02 | 2021-01-29 | 贵州理工学院 | Preparation method of copper sulfide nano material |
-
2015
- 2015-05-25 CN CN201510267215.4A patent/CN104909401A/en active Pending
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| GAOMIN LIAO ET AL.: "A novel method to encapsulate a Au nanorod array in 15 nm radius multiwalled carbon nanotubes", 《NANOSCALE》 * |
| GUSTAVO E. FERNANDES ET AL.: "Infrared Photoresponses from PbS Filled Multiwall Carbon Nanotubes", 《J.PHYS.CHEM.C》 * |
| ZHIPENG LIU ET AL.: "Efficient encapsulation of conducting polyaniline chains inside carbon nanotubes: a new strategy to prepare endohedral CNT materials", 《JOURNAL OF MATERIALS CHEMISTRY A》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107895648A (en) * | 2017-11-15 | 2018-04-10 | 哈尔滨理工大学 | The preparation method of CuS nanoparticles powder and multi-walled carbon nanotube combination electrode |
| CN109337293A (en) * | 2018-10-15 | 2019-02-15 | 河南机电职业学院 | Shape memory nanocomposite of microwave fast reaction and preparation method thereof |
| CN109337293B (en) * | 2018-10-15 | 2021-02-09 | 河南机电职业学院 | Shape memory nano composite material with microwave rapid reaction and preparation method thereof |
| CN112279293A (en) * | 2020-11-02 | 2021-01-29 | 贵州理工学院 | Preparation method of copper sulfide nano material |
| CN112279293B (en) * | 2020-11-02 | 2023-08-25 | 贵州理工学院 | Preparation method of copper sulfide nano material |
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