CN104030294A - Preparation method of mesoporous silicon-dioxide-coated single-wall carbon nanotubes - Google Patents
Preparation method of mesoporous silicon-dioxide-coated single-wall carbon nanotubes Download PDFInfo
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- CN104030294A CN104030294A CN201410246919.9A CN201410246919A CN104030294A CN 104030294 A CN104030294 A CN 104030294A CN 201410246919 A CN201410246919 A CN 201410246919A CN 104030294 A CN104030294 A CN 104030294A
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Abstract
The invention discloses a preparation method of mesoporous silicon-dioxide-coated single-wall carbon nanotubes. The surfactant molecules are fixed to the surfaces of the single-wall carbon nanotubes by a one-step process, and the coating growth of the mesoporous silicon dioxide shell is induced in a non-covalent bond mode, thereby implementing control on the thickness of the mesoporous silicon dioxide shell and eliminating the occurrence of the self-nucleation phenomenon of silicon oxide. The method can be used for modifying different functional groups on the external surfaces of the mesoporous pore wall and shell, so that the composite material can be easily dispersed in various solvents, thereby enhancing the dispersion stability of the single-wall carbon nanotubes; and meanwhile, the mesoporous pores can be used for loading and transmitting different guest molecules, and thus, the method has wide application prospects.
Description
Technical field
The present invention relates to composite nano materials preparation field, relate in particular to a kind of preparation method of mesoporous silicon oxide coated single-walled carbon nano tube.
Background technology
From 1991, (Nature since doctor Iijima of Japan finds carbon nanotube, 354 volumes, 56 pages, 1991), this nano material with typical one dimension hollow tubular structure is because of its excellent properties representing at aspects such as mechanics, optics, electricity and calorifics, and obtained the extensive concern of scientists.Wherein Single Walled Carbon Nanotube can be considered curling the forming of graphene sheet layer by individual layer, length can reach hundreds of nanometers to several microns, and internal diameter is less than two nanometers, there is larger specific surface area and length-to-diameter ratio, performance is also more outstanding, has therefore obtained more research in fields such as matrix material, electron device, drug conveying, chemical catalysis, biosensors.
But Single Walled Carbon Nanotube is due to the surface energy of surperficial hydrophobicity, conjugated electrons cloud effect and superelevation, easily reunion, difficulty are peeled off each other, are insoluble to each kind solvent, are therefore difficult to, by large-scale controlled manipulation, be subject in actual applications very big restriction.Increase at present the deliquescent method of carbon nanotube and mainly contain two classes, i.e. chemical modification method and physisorphtion (Carbon, 50 volumes, 3 pages, 2012).The former modifies all kinds of chemical groups by the mode of covalent linkage at port and the sidewall of carbon nanotube, effectively to improve the dispersiveness in solution, but chemically modified is damaged the structure that makes carbon nanotube itself, the performances such as its optics, mechanics can be affected.The latter makes carbon nano tube surface adsorb amphipathic tensio-active agent, macromolecular compound, biomacromolecule etc. by Intermolecular Forces, but this physical adsorption way unstable in organic solvent, easily come off, and the thermostability of this class organic macromolecule is also poor.Based on above consideration, at the inorganic parcel shell of carbon nano tube surface growth non covalent bond effect, can solve the problem of dispersion stabilization, protect again the structure of carbon pipe itself, therefore cause gradually in recent years part Study person's interest.
Metaporous silicon dioxide material has huge specific surface area and pore volume, adjustable aperture, good biocompatibility and surface are easy to the advantages such as modification, has obtained research widely at aspects such as guest molecule loading and conveying, chemical catalysis, biomolecular screenings.If on Single Walled Carbon Nanotube surface by the coated uniform mesoporous silicon oxide shell of the mode of action of non covalent bond, both can solve its dispersion stabilization in solution, structure that again can protection itself is not damaged, and brings into play that it is functional.This composite nano-line is in copying the unique one-dimentional structure of Single Walled Carbon Nanotube, and its shell has again vesicular structure, can further increase specific surface area, loads or transmits more guest molecule.Meanwhile, the silicon hydroxyl that be rich on composite nano-line surface is easy to chemically modified, can further carry out modification.
At present actually rare at the report of Single Walled Carbon Nanotube surface growth mesoporous silicon oxide shell, and equal Shortcomings and defect.The people such as Ding (J.Mater.Chem., 19 volumes, 3725 pages, 2009) in aqueous phase solution, synthesize the composite nano-line of mesoporous silicon oxide coated single-walled carbon nano tube, but too complicated in the operation steps of Single Walled Carbon Nanotube surface fixed surface promoting agent in this research, and the composite nano-line pattern Shortcomings finally obtaining, has the mesoporous monox nanometer particle of more spontaneous nucleation to generate; The people such as Paula (Chem.Eur.J., 17 volumes, 3228 pages, 2011) Single Walled Carbon Nanotube that obtains taking acidic treatment is raw material, in the basic solution of water/ethanol, it is carried out to the coated of mesoporous silicon oxide shell, but finally not obtaining evenly coated composite nano-line of shell, part Single Walled Carbon Nanotube surface is naked state, and matrix material is mutually reunited and is intertwined.
Therefore the present invention is devoted to step simple to operation, and at the complete mesoporous silicon oxide shell of Single Walled Carbon Nanotube surface growth homogeneous, shell thickness is adjustable and pattern is controlled.
Summary of the invention
For achieving the above object, the invention provides a kind of preparation method of mesoporous silicon oxide coated single-walled carbon nano tube.Described method is fixed on Single Walled Carbon Nanotube surface by single stage method by surfactant molecule, induce the coated growth of mesoporous silicon oxide shell in the mode of non covalent bond, not only realize the regulation and control to mesoporous silicon oxide shell thickness, and can eliminate the generation of silicon oxide spontaneous nucleation phenomenon; This method can also be modified different functional groups at mesoporous wall and shell outside surface in addition, make matrix material be easy to be scattered in each kind solvent, improve the dispersion stabilization of Single Walled Carbon Nanotube, mesopore orbit can be used to load and transmit different guest molecules simultaneously, has broad application prospects.
Mesoporous silicon oxide coated single-walled carbon nano tube prepared by the present invention, comprises as the Single Walled Carbon Nanotube of kernel and is wrapped in its surperficial meso-porous titanium dioxide silicon layer, this matrix material has nucleocapsid structure; Described diameter of single-wall carbon nano tube is less than 2nm; Described mesoporous silicon oxide shell thickness can reach 3nm～20nm, mesoporous aperture can reach 2nm～10nm, and mesoporous wall and shell outside surface can be modified with one or more in hydroxyl, amino, sulfydryl, methyl acid phosphate base, alkyl chain, epoxy group(ing), carbonyl and phenyl.
The preparation method of above-mentioned mesoporous silicon oxide coated single-walled carbon nano tube, comprises the following steps:
1. Single Walled Carbon Nanotube, tensio-active agent and deionized water are mixed for 1:1～100:5000～20000 in mass ratio, ultrasonic dispersion 5～720 minutes, obtain stable single-walled carbon nanotube dispersion liquid, described tensio-active agent is a kind of or above-mentioned any multiple any proportioning in several in cats product Tetradecyl Trimethyl Ammonium Bromide, cetyl trimethylammonium bromide, Cetyltrimethylammonium bromide, tetradecyl trimethyl ammonium chloride, palmityl trimethyl ammonium chloride and octadecyl trimethyl ammonium chloride.
2. be 8.0～12.0 by the pH regulator of above-mentioned solution, add four alkoxyl silicones and silane coupling agent, fully reaction under 25 DEG C～75 DEG C conditions, described four alkoxyl silicones are a kind of or above-mentioned any multiple any proportioning in several in positive quanmethyl silicate, tetraethyl orthosilicate and positive silicic acid orthocarbonate, and the mass ratio of described four alkoxyl silicones and described Single Walled Carbon Nanotube is 5～80:1; The end group of described silane coupling agent is amino, sulfydryl, methyl acid phosphate base, alkyl chain, epoxy group(ing), carbonyl or phenyl, and the mass ratio of described silane coupling agent and described four alkoxyl silicones is 0～0.2:1.
3., after reaction finishes, separate and obtain black precipitate.Remove template, the product obtaining is mesoporous silicon oxide coated single-walled carbon nano tube, and the method for described removal template is ion exchange method or thermal treatment calcination method.
Preparation method of the present invention has the following advantages:
1. this method has avoided multistep methodology at Single Walled Carbon Nanotube surface fixed surface active agent molecule, both can obtain stable single-walled carbon nanotube dispersion liquid by a step ultrasonic method, simply effective, easy handling.
2. this method has realized the even growth of mesoporous silicon oxide coating layer, and shell thickness is adjustable and pattern is easy to control, and can carry out the modification of difference in functionality group to mesoporous wall and shell outside surface simultaneously.
3. mesoporous silicon oxide coating layer can effectively improve the dispersion stabilization of Single Walled Carbon Nanotube in each kind solvent, lays a good foundation for realizing large-scale manipulation and assembling.
4. in mesoporous silicon oxide coating layer, be rich in a large amount of mesopore orbits, further increased the specific surface area of matrix material, and can load targetedly and transmit different target guest molecules by modifying different functional groups.
5. to be non covalent bond to Single Walled Carbon Nanotube coated for mesoporous silicon oxide, and the structure of destroying carbon nanometer tube not in the process of growth of shell, therefore can not affect the functional of Single Walled Carbon Nanotube itself.
Below with reference to accompanying drawing, the technique effect of design of the present invention, concrete structure and generation is described further, to understand fully object of the present invention, feature and effect.
Brief description of the drawings
Fig. 1 is the diameter Distribution data plot that embodiments of the invention 3 (curve 1), embodiment 4 (curve 2), embodiment 5 (curve 3) prepare gained mesoporous silicon oxide coated single-walled carbon nano tube;
Fig. 2 is the transmission electron microscope photo as a kind of Single Walled Carbon Nanotube of raw material in the present invention;
Fig. 3 is the electron scanning micrograph as a kind of Single Walled Carbon Nanotube of raw material in the present invention;
Fig. 4 is the low power transmission electron microscope photo that embodiments of the invention 5 are prepared gained mesoporous silicon oxide coated single-walled carbon nano tube;
Fig. 5 is the high power transmission electron microscope photo that embodiments of the invention 5 are prepared gained mesoporous silicon oxide coated single-walled carbon nano tube;
Fig. 6 is the electron scanning micrograph that embodiments of the invention 5 are prepared gained mesoporous silicon oxide coated single-walled carbon nano tube;
Fig. 7 is the low power transmission electron microscope photo that embodiments of the invention 6 are prepared gained mesoporous silicon oxide coated single-walled carbon nano tube;
Fig. 8 is the high power transmission electron microscope photo that embodiments of the invention 6 are prepared gained mesoporous silicon oxide coated single-walled carbon nano tube;
Fig. 9 is the electron scanning micrograph that embodiments of the invention 6 are prepared gained mesoporous silicon oxide coated single-walled carbon nano tube;
Figure 10 is that in the present invention, as a kind of Single Walled Carbon Nanotube of raw material, (curve a), embodiment 5 prepares gained mesoporous silicon oxide coated single-walled carbon nano tube (curve b), and embodiment 6 prepares gained mesoporous silicon oxide coated single-walled carbon nano tube (curve Raman spectrogram c).
Embodiment
Embodiment 1
In three-necked flask, add 10mg Single Walled Carbon Nanotube, 10mg cetyl trimethylammonium bromide, 50mL deionized water, ultrasonic dispersion 5min, obtains stable single-walled carbon nanotube dispersion liquid.
The pH value of above-mentioned dispersion liquid is adjusted to 8.0 with the sodium hydroxide solution of 2M, adds 0.15mL tetraethyl orthosilicate, under 25 DEG C of conditions, react 4h, make meso-porous titanium dioxide silicon layer be coated on uniformly the surface of Single Walled Carbon Nanotube.
After reaction finishes, obtain black precipitate by 11000rpm is centrifugal.Calcine 3h to remove template by being deposited in the retort furnace of 300 DEG C, get final product to obtain mesoporous silicon oxide coated single-walled carbon nano tube
Embodiment 2
In three-necked flask, add 10mg Single Walled Carbon Nanotube, 1000mg cetyl trimethylammonium bromide, 200mL deionized water, ultrasonic dispersion 720min, obtains stable single-walled carbon nanotube dispersion liquid.
The pH value of above-mentioned dispersion liquid is adjusted to 12.0 with the sodium hydroxide solution of 2M, adds 0.15mL tetraethyl orthosilicate, under 75 DEG C of conditions, react 8h, make meso-porous titanium dioxide silicon layer be coated on uniformly the surface of Single Walled Carbon Nanotube.
After reaction finishes, obtain black precipitate by 11000rpm is centrifugal.Calcine 3h to remove template by being deposited in the retort furnace of 300 DEG C, get final product to obtain mesoporous silicon oxide coated single-walled carbon nano tube.
Embodiment 3
In three-necked flask, add 10mg Single Walled Carbon Nanotube, 500mg cetyl trimethylammonium bromide, 100mL deionized water, ultrasonic dispersion 4h, obtains stable single-walled carbon nanotube dispersion liquid.
The pH value of above-mentioned dispersion liquid is adjusted to 11.3 with the sodium hydroxide solution of 2M, adds 0.15mL tetraethyl orthosilicate, under 60 DEG C of conditions, react 12h, make meso-porous titanium dioxide silicon layer be coated on uniformly the surface of Single Walled Carbon Nanotube.
After reaction finishes, obtain black precipitate by 11000rpm is centrifugal.Calcine 3h to remove template by being deposited in the retort furnace of 300 DEG C.
As shown in curve in Fig. 11, in the present embodiment, the diameter Distribution of gained mesoporous silicon oxide coated single-walled carbon nano tube is between 7nm～13nm.
Embodiment 4
In three-necked flask, add 10mg Single Walled Carbon Nanotube, 500mg cetyl trimethylammonium bromide, 100mL deionized water, ultrasonic dispersion 4h, obtains stable single-walled carbon nanotube dispersion liquid.
The pH value of above-mentioned dispersion liquid is adjusted to 11.3 with the sodium hydroxide solution of 2M, adds 0.30mL tetraethyl orthosilicate, under 60 DEG C of conditions, react 12h, make meso-porous titanium dioxide silicon layer be coated on uniformly the surface of Single Walled Carbon Nanotube.
After reaction finishes, obtain black precipitate by 11000rpm is centrifugal.Calcine 3h to remove template by being deposited in the retort furnace of 300 DEG C.
As shown in curve in Fig. 12, in the present embodiment, the diameter Distribution of gained mesoporous silicon oxide coated single-walled carbon nano tube is between 10nm～20nm.
Embodiment 5
In three-necked flask, add 10mg Single Walled Carbon Nanotube, 500mg cetyl trimethylammonium bromide, 100mL deionized water, ultrasonic dispersion 4h, obtains stable single-walled carbon nanotube dispersion liquid.
The pH value of above-mentioned dispersion liquid is adjusted to 11.3 with the sodium hydroxide solution of 2M, adds 0.50mL tetraethyl orthosilicate, under 60 DEG C of conditions, react 12h, make meso-porous titanium dioxide silicon layer be coated on uniformly the surface of Single Walled Carbon Nanotube.
After reaction finishes, obtain black precipitate by 11000rpm is centrifugal.Precipitation is scattered in 60mL dehydrated alcohol again, and adds 60mg ammonium nitrate, ultrasonic 2h under normal temperature.This step is in triplicate fully to remove template.
As shown in curve in Fig. 13, in the present embodiment, the diameter Distribution of gained mesoporous silicon oxide coated single-walled carbon nano tube is between 15nm～26nm.
As shown in Figure 2 and Figure 3, be less than 2nm as the diameter of the Single Walled Carbon Nanotube of raw material, and the formation nanometer bundle that is intertwined of reuniting mutually.
As shown in Fig. 4, Fig. 5, Fig. 6, Single Walled Carbon Nanotube surface has successfully been coated mesoporous silicon oxide shell, and the Single Walled Carbon Nanotube of coating layer agglomerated has occurred to peel off, and dispersiveness significantly improves.And in coating layer, have a large amount of orderly mesopore orbits perpendicular to carbon nano tube surface growth, pore size distribution is between 2nm～4nm.
Embodiment 6
In three-necked flask, add 10mg Single Walled Carbon Nanotube, 500mg cetyl trimethylammonium bromide, 100mL deionized water, ultrasonic dispersion 4h, obtains stable single-walled carbon nanotube dispersion liquid.
The pH value of above-mentioned dispersion liquid is adjusted to 11.3 with the sodium hydroxide solution of 2M, add successively 0.45mL tetraethyl orthosilicate and 0.05mL γ-aminopropyl triethoxysilane, under 60 DEG C of conditions, react 12h, make amido modified meso-porous titanium dioxide silicon layer be coated on uniformly the surface of Single Walled Carbon Nanotube.
After reaction finishes, obtain black precipitate by 11000rpm is centrifugal.Precipitation is scattered in 60mL dehydrated alcohol again, and adds 60mg ammonium nitrate, ultrasonic 2h under normal temperature.This step is in triplicate fully to remove template.
As shown in Fig. 7, Fig. 8, Fig. 9, Single Walled Carbon Nanotube surface has successfully been coated mesoporous silicon oxide shell, and the Single Walled Carbon Nanotube of the same agglomerated of coating layer has occurred to peel off, and dispersiveness significantly improves.The mesopore orbit that simultaneously also has a large amount of orderly radial growths in coating layer, pore size distribution is between 2nm～4nm.This illustrates the order that can not destroy mesoporous formation and arrangement thereof that adds of silane coupling agent.
As shown in figure 10, G peak represents the graphite peaks of Single Walled Carbon Nanotube, and D peak represents the defect peak of Single Walled Carbon Nanotube.Can see, before coating mesoporous silicon-dioxide (curve a), rear (curve b and c), all there is not considerable change in the G peak of Single Walled Carbon Nanotube, the position at D peak and intensity, the growth of this explanation mesoporous silicon oxide shell (curve b) and the modification of functional group (curve c) does not destroy the structure of Single Walled Carbon Nanotube, is a kind of coated process of non covalent bond effect.
More than describe preferred embodiment of the present invention in detail.The ordinary skill that should be appreciated that this area just can design according to the present invention be made many modifications and variations without creative work.Therefore, all technician in the art, all should be in by the determined protection domain of claims under this invention's idea on the basis of existing technology by the available technical scheme of logical analysis, reasoning, or a limited experiment.
Claims (5)
1. a preparation method for mesoporous silicon oxide coated single-walled carbon nano tube, is characterized in that, comprises the following steps:
(1) Single Walled Carbon Nanotube, tensio-active agent and deionized water are mixed for 1:1～100:5000～20000 in mass ratio, ultrasonic dispersion 5～720 minutes, obtains solution a;
(2) the pH value of described solution a is adjusted between 8.0～12.0, adds four alkoxyl silicones and silane coupling agent, under 25 DEG C～75 DEG C conditions, react, obtain solution b;
(3) by described solution b centrifugation, obtain black precipitate, described black precipitate is removed to template, the product obtaining is described mesoporous silicon oxide coated single-walled carbon nano tube.
2. preparation method as claimed in claim 1, it is characterized in that, described tensio-active agent is a kind of or above-mentioned any multiple any proportioning in several in cats product Tetradecyl Trimethyl Ammonium Bromide, cetyl trimethylammonium bromide, Cetyltrimethylammonium bromide, tetradecyl trimethyl ammonium chloride, palmityl trimethyl ammonium chloride and octadecyl trimethyl ammonium chloride.
3. preparation method as claimed in claim 1, is characterized in that, described four alkoxyl silicones are a kind of or above-mentioned any multiple any proportioning in several in positive quanmethyl silicate, tetraethyl orthosilicate and positive silicic acid orthocarbonate.
4. preparation method as claimed in claim 1, is characterized in that, the end group of described silane coupling agent is the one in amino, sulfydryl, methyl acid phosphate base, alkyl chain, epoxy group(ing), carbonyl or phenyl.
5. preparation method as claimed in claim 1, is characterized in that, the method for described removal template is ion exchange method or thermal treatment calcination method.
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