CN102500296B - Preparation method for mesoporous silicon oxide hollow microspheres with magnetic nanoparticles embedded in shell layers - Google Patents
Preparation method for mesoporous silicon oxide hollow microspheres with magnetic nanoparticles embedded in shell layers Download PDFInfo
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Abstract
The invention relates to a preparation method for mesoporous silicon oxide hollow microspheres with magnetic nanoparticles embedded in shell layers. In the invention, the magnetic nanoparticles are prepared by using a coprecipitation method, are subjected to oleic acid surface modification and then are dispersed in normal octane; an oil phase constructed by styrene monomer, cetane, normal octane dispersion of the magnetic nanoparticles, alkoxysilane and a silane coupling agent is mixed with a water phase which dissolves a surfactant; a fine emulsion liquid droplet system is obtained through pre-emulsification and fine emulsification processes; controlling formation of silicon oxide and phase separation of organic and inorganic components in the system to obtain a template with a nested structure during free radial polymerization of the liquid droplets by adding a base catalyst; based on the template, generating a raw material by taking long-chain alkyl silane coupling agent and alkoxysilane as mesoporous silicon oxide; performing one-step ablation to remove an inner core of a polymer and a pore forming agent; or by taking a cationic surfactant as the pore forming agent, removing the pore forming agent and the inner core of the polymer through a solvent dissolving method and obtaining the magnetic/mesoporous silicon oxide hollow composite microspheres. The composite microspheres have large specific surface area and good magnetic operability and can be used for application fields of biomedicine, environment, water treatment and the like.
Description
Invention field
The invention belongs to the preparing technical field of inorganic nano composite material, be specifically related to the preparation method of the mesopore silicon oxide tiny balloon of embedded magnetic nano particle in a kind of shell.
Background technology
Mesoporous material has very important application as a kind of emerging material in fields such as photochemistry, catalysis, Environmental Water processing, bio-separation and medicine carryings, is one of focus of current research.Mesoporous material refers to that the aperture is the porous material of 2.0-50 nm, such as aeroge, column clay, M41S, SBA series material.Because it has larger specific area, the aperture is homogeneous, adjustable very, and has the orderly characteristics of dimension, therefore compares with some traditional material to have unique advantage when using.In recent years, the synthetic of meso pore silicon oxide material makes great progress.The meso-porous hollow silica is with respect to solid mesoporous material, has the controlled cavity of size and the mesopore orbit of inside and outside mutual perforation, so aspect the diffusion of material or the transmission very large advantage is being arranged.Magnetic nanoparticle is such as Fe
3O
4Because at many biomedical sectors, magnetic carrier such as magnetic resonance imaging, drug delivery system, have great application prospect in bio-separation, the mark, so based on the composite of mesopore silicon oxide hollow-core construction and superparamagnetic nano particle, can have the surface characteristic of mesoporous material and the characteristics that can carry out by externally-applied magnetic field displacement and separation and concentration of pore passage structure and magnetic material concurrently, therefore, the research of the composite manufacture of mesoporous material and magnetic nanoparticle has caused widely concern.This composite with hollow-core construction also is different from the spherical nucleocapsid material of magnetic kernel/mesoporous shell, renders a service and have more significant carrier band.
Can be used at present preparing the method for the mesopore silicon oxide tiny balloon that is embedded with a certain proportion of magnetic nanoparticle also seldom, mainly be after adopting the multilayer assembling to form nucleocapsid structure, certain one deck in the etching nucleocapsid structure optionally again, its building-up process is: at first preparation table is worn the polystyrene microsphere of carboxyl, and magnetic nanoparticle, then pass through electrostatic interaction, magnetic nanoparticle is adsorbed on Surfaces of Polystyrene Microparticles, composite construction after this absorption is as seed, the presoma and the long chain alkane pore-foaming agent that add silica carry out copolycondensation, by the thermal ablation method polystyrene kernel are removed at last.This method does not require stricter to the condition control of each step in the preparation, easy to operate and output is limited, and perhaps the content of magnetic nanoparticle in composite is limited, skewness.
In order to address the above problem, we propose the trielement composite material of the silica/magnetic hybrid shell/polymer kernel based on nested nucleocapsid structure, sol-gel process in conjunction with simple possible, select different types of pore-foaming agent, one step of method by thermal ablation or dissolution with solvents is removed pore-foaming agent and polymer kernel, prepare the mesopore silicon oxide tiny balloon of embedded magnetic nano particle in a kind of shell, the method can overcome above-mentioned shortcoming; The well-regulated pore passage structure of material tool and cavity, in the inorganic mesoporous silica material evenly embedding a lot of magnetic nanoparticles, present domestic and international similar report not also.
Summary of the invention
The present invention relates to the preparation method of the mesopore silicon oxide tiny balloon of embedded magnetic nano particle in a kind of shell.The present invention adopts has the magnetic silicon oxide/high molecular composite microsphere of nested nucleocapsid structure (yolk-shell) as template, in conjunction with sol gel reaction, take long chain alkane organo silane coupling agent or cationic surface active agent as pore-foaming agent, controlling mesoporous layer grows at the inorganic shell of template, method by step heat treatment or a dissolution with solvents can be removed pore-foaming agent and polymer kernel simultaneously, the mesopore silica dioxide hollow sphere of a large amount of magnetic-particles that obtained this even embedding.Through the preparation process of this substep, can effectively control structure and the magnetisable material content of microballoon, thus the performance of Effective Regulation tiny balloon.This magnetic mesoporous silica tiny balloon is because the template among employing the present invention, and have comparatively unique microstructure, there is comparatively orderly meso-hole structure on the inside and outside surface that is hollow ball, have a circle to arrange comparatively closely magnetic nanoparticle in the whole mesopore silicon oxide shell, shell is divided into not only connect each other, but also mutual two parts of isolation; This special structure, owing to have very large specific area, inside and outside relatively independent mesopore orbit, and include a large amount of magnetic nanoparticles, and will process in Environmental Water, there is good application prospect medicine, gene carrier band and control release aspect.The method relatively is fit to high-volume test.
Main technical schemes of the present invention: magnetic nanoparticle adopts the coprecipitation preparation, through being dispersed in the normal octane after the oleic acid finishing, obtains blocks of solid after the normal octane volatilization; By the normal octane dispersion liquid of styrene monomer, hexadecane, magnetic nanoparticle, the oil phase that ethyl orthosilicate forms, mix with the water that has dissolved surfactant, obtain miniemulsion drop system through mechanical agitation pre-emulsification and thin emulsification ultrasonic procedure, use radical polymerization initiator under heating condition, to carry out cinnamic radical polymerization, can obtain the coated magnetic-particle of silica as nested nucleocapsid structure (yolk-shell) microballoon of shell polystyrene microsphere as kernel; Behind this complex microsphere process magnetic separating, washing purifying, be dispersed in a certain proportion of water/absolute ethyl alcohol mixed solvent, with alkali as catalyst, add the tetraalkyl orthosilicate of the long carbochain silane coupler that contains certain mol proportion as the presoma of silica, pass through sol gel reaction, the product that obtains after 550 ℃ of lower ablations, just can obtain magnetic/mesoporous SiO 2 tiny balloon; Perhaps, in containing the water of base catalyst/absolute ethyl alcohol mixed solvent, add a certain proportion of cationic surfactant as pore-foaming agent, add again tetraalkyl orthosilicate as the presoma of silica, the product that the process sol gel reaction obtains, in the methanol solution that contains acid, soak, remove pore-foaming agent and template, just can obtain magnetic/mesoporous SiO 2 tiny balloon.By changing the consumption of silicon source presoma, can regulate the thickness of mesopore silicon oxide shell.In addition, by regulating the ratio of silane coupler and tetraalkyl orthosilicate, can regulate mesoporous aperture and pore passage structure.
Concrete steps are as follows:
(1) use coprecipitation to prepare magnetic nanoparticle, with the FeCl of mol ratio 1.5-1.8:1
36H
2O and FeCl
27H
2O is dissolved in the deionized water, adds ammoniacal liquor, logical N
2Gas at 80 ℃ of lower heating 30 min, then adds oleic acid, continues heating stirring reaction 1 h, then stops logical N
2Volatilization ammoniacal liquor, until have a large amount of black precipitate to occur after stopping to stir, then stop reaction, magnetic is washed till neutrality with deionized water with precipitation respectively under separating, and respectively washes 3 times with deionized water and ethanol again, obtain magnetic nanoparticle, be dispersed in an amount of normal octane magnetic nanoparticle is ultrasonic, rotary evaporation evaporate to dryness normal octane is for subsequent use again;
(2) proper amount of surfactant is dissolved in a certain amount of deionized water obtains water, the magnetic nanoparticle that styrene monomer, super-hydrophobic dose, tetraalkyl orthosilicate and step (1) are obtained mixes the ultrasonic uniform oil phase of making, then mixed with water, under the 500W ultrasonic thin emulsification 5-10 minute; Adding is with respect to the initator of styrene monomer quality 1-2%, and stirring at room is led to N
2Then 30 min change reaction system in the heated water bath over to initiated polymerization; After polymerisation 90-100 minute, add alkali, system pH is adjusted between the 8.0-10.0; Reaction was carried out under 50-80 ℃ 2-3 hour again, and the polymerizate that obtains is auxiliary lower in the magnetic separation, used deionized water cyclic washing 3 times, namely obtained the mould material of nested nucleocapsid structure; Whole system is according to weight percent meter, the inorganic magnetic nano particle accounts for 0.05-0.15 %, styrene monomer accounts for 12.5-15.0%, surfactant accounts for 0.19-0.43 %, super-hydrophobic dose accounts for 0.76-0.84 %, and initator accounts for 0.1-0.3 %, and tetraalkyl orthosilicate accounts for 2.1-7.6 %, residue satisfies 100% for deionized water, its gross weight;
(3) mould material that obtains in step (2) reaction is dispersed in the percent by volume of water in the deionized water of 20-40%/absolute ethyl alcohol mixed solvent, adding with respect to the alkali of mixed solvent 3.0-7.0% as the sol gel reaction catalyst, add again with respect to doubly long carbochain silane coupler of the 2.7-3.8 of mould material quality/tetraalkyl orthosilicate mixture, the mol ratio of long carbochain silane coupler and tetraalkyl orthosilicate is 3.5-6.0:1, after mechanical agitation is reacted under the room temperature, product is carried out magnetic separate the cyclic washing several times, under 450-650 ℃, carry out 3-5 hour ablation, obtain the mesoporous SiO 2 tiny balloon of even embedded magnetic nano particle;
Perhaps adopt cationic surfactant chain alkyl ammonium salt as pore-foaming agent, be in the deionized water/absolute ethyl alcohol mixed solvent of 40-60% in the percent by volume of water, adding with respect to the alkali of mixed solvent 3.0-7.0% as the sol gel reaction catalyst, adding with respect to the cationic surfactant chain alkyl ammonium salt of mixed solvent 0.15-0.3% as pore-foaming agent, add again with respect to the presoma of the 2.0-5.0 of mould material quality tetraalkyl orthosilicate doubly as silica, the product that the process sol gel reaction obtains, in the methanol solution that contains acid, soak a period of time, remove pore-foaming agent and template, just can obtain magnetic/mesoporous SiO 2 tiny balloon.
Among the present invention, used magnetic nanoparticle can be Fe
3O
4Particle, γ-Fe
2O
3Particle or containing transition metal element manganese, chromium, cobalt, zinc or/and in the Nano-Ferrite Particle of nickel any.Optimal is the nanometer Fe of superparamagnetism
3O
4Particle, γ-Fe
2O
3Particle is preferably modified through oleic acid molecular.
Among the present invention, in the step (2) used surfactant can be in lauryl sodium sulfate (SDS), neopelex (SDBS) or the softex kw (CTAB) etc. any.
Among the present invention, used super-hydrophobic dose can be in the alcohol etc. of hexadecane long chain alkane or hexadecanol band long-chain any.
Among the present invention, used alkali can be a kind of in ammoniacal liquor, potassium hydroxide, NaOH or the TMAH etc. in the step (2).
Among the present invention, in the step (3) used alkali can be in ammoniacal liquor, potassium hydroxide or the NaOH any.
Among the present invention, used initator can be a kind of in azodiisobutyronitrile or the potassium peroxydisulfate etc.
Among the present invention, used alcohol can be one to several in methyl alcohol, ethanol or the isopropyl alcohol etc.
Among the present invention, used tetraalkyl orthosilicate can be in methyl silicate or the ethyl orthosilicate etc. any.
Among the present invention, used long chain silane coupling agent be in cetyl trimethoxy silane, octadecyl trimethoxy silane or the cetyl triethoxysilane etc. any.
Among the present invention, used chain alkyl ammonium salt is softex kw, in Cetyltrimethylammonium bromide, hexadecyltrimethylammonium chloride or the OTAC etc. any.
The magnetic mesoporous silica tiny balloon of the present invention preparation, its particle diameter can change between 180-500 nm, and the particle diameter of the mould material by controlling nested nucleocapsid structure can be regulated the overall dimensions of tiny balloon; The mesopore silicon oxide wall thickness of tiny balloon can change in 15-60 nm scope in addition, by the consumption of control TEOS with long carbochain silane coupler, can regulate the wall thickness of tiny balloon; By changing the ratio of TEOS and long carbochain silane coupler, structure and the size that can regulate duct in the mesopore silicon oxide; By changing the consumption of magnetic nanoparticle, can regulate the magnetisable material content of tiny balloon.The inventive method is simple, and cost of material is low, be easy to get.The particle diameter narrow distribution of prepared mesopore silicon oxide magnetic hollow complex microsphere, and have high magnetisable material content, and all there is the mesopore silicon oxide structure on the inside and outside surface of tiny balloon, thereby further increasing specific surface area.
Description of drawings
Fig. 1 is the transmission electron microscope photo of tri-iron tetroxide/mesopore silicon oxide compound hollow microballoon, the ethyl orthosilicate that uses and cetyl trimethoxy silane are 410% with respect to the mass fraction of nested structure template, A is low multiplication factor electromicroscopic photograph, and B is the high-amplification-factor electromicroscopic photograph.
Fig. 2 is the magnetic property curve of tri-iron tetroxide/mesopore silicon oxide compound hollow microballoon.
Fig. 3 is the BET curve of tri-iron tetroxide/mesopore silicon oxide compound hollow microballoon.
Fig. 4 is the transmission electron microscope photo of tri-iron tetroxide/mesopore silicon oxide compound hollow microballoon, the ethyl orthosilicate that uses and cetyl trimethoxy silane are 590% with respect to the mass fraction of nested structure template, A is low multiplication factor electromicroscopic photograph, and B is the high-amplification-factor electromicroscopic photograph.
Fig. 5 is the stereoscan photograph of tri-iron tetroxide/mesopore silicon oxide compound hollow microballoon, and the ethyl orthosilicate of use and cetyl trimethoxy silane are 590% with respect to the mass fraction of nested structure template.
The specific embodiment
Further specify the present invention below by embodiment.
Embodiment 1.With 24 g FeCl
36H
2O and 9.82 g FeCl
27H
2O is dissolved in the suitable quantity of water, adds proper ammonia, logical N
2Gas at 80 ℃ of lower heating 30min, then adds 3.86 g oleic acid, continues heating stirring reaction 1h, then stops logical N
2Volatilization ammoniacal liquor, until have a large amount of black precipitate to occur after stopping to stir, then reaction can stop, and magnetic is washed till neutrality with deionized water with precipitation respectively under separating, and respectively washes 3 times with deionized water and ethanol again, the magnetic nanoparticle that obtains, be dispersed in an amount of normal octane magnetic-particle is ultrasonic, rotary evaporation evaporate to dryness normal octane is for subsequent use again; 0.104 g SDS is dissolved in the 40 g deionized waters, the dispersion liquid of 9 g styrene monomers, 0.4 g hexadecane, 1 g TEOS and 55 mg magnetic-particles is mixed the ultrasonic uniform oil phase of making, then with the aqueous solution of surfactant, ultrasonic thin emulsification 10 min under 500 W.Adding is with respect to the AIBN of styrene monomer 1.0 %, and stirring at room is led to N
2Then 30 min change reaction system over to the water-bath of 70 ℃ of temperature ranges, and the beginning initiated polymerization after 90 min are carried out in polymerization, adds the ammoniacal liquor of 0.05 mL, and 6 h are carried out in reaction again under 70 ℃; Product separates auxiliary lower deionized water cyclic washing 2-3 time of using at magnetic.The mould material that obtains after the washing is dispersed in the mixed solvent of deionized water and absolute ethyl alcohol, adds again the cetyl trimethoxy silane of 0.08 g tetraethyl orthosilicate and 0.029 g, carry out the reaction of 18 h mechanical agitation under the room temperature condition.After the reaction end, deionized water was repeatedly fully washed and is removed the various reagent that fully do not react in the system under magnetic separated, and ablated in 550 ℃ of Muffle furnaces, and the kernel of step removal polystyrene is removed pore-foaming agent simultaneously, obtains meso-porous hollow microballoon (Fig. 1); Microballoon overall size 360 nm, mesopore silicon oxide shell average thickness is about 22 nm, its specific saturation magnetization is 9.2 emu/g(Fig. 2).The BET specific area of typical material is 200m
2About/g (Fig. 3).
Embodiment 2.Adopt the same method to prepare the magnetic nanoparticle that coprecipitation is prepared oleic acid modified, and prepare the magnetic-particle that disperses again evaporate to dryness through normal octane.0.12 g SDBS is dissolved in the 40 g deionized waters, the dispersion liquid of 8 g styrene monomers, 0.4 g hexadecane, 2 g methyl silicates and 80 mg magnetic-particles is mixed the ultrasonic uniform oil phase of making, then with the aqueous solution of surfactant, ultrasonic thin emulsification 10 min under 500 W.Adding is with respect to the potassium peroxydisulfate of styrene monomer 1.0 %, and stirring at room is led to N
2Then 30 min change reaction system over to the water-bath of 70 ℃ of temperature ranges, and the beginning initiated polymerization after 90 min are carried out in polymerization, adds the ammoniacal liquor of 0.1 mL, and 6 h are carried out in reaction again under 70 ℃; Product separates auxiliary lower deionized water cyclic washing 2-3 time of using at magnetic.The mould material that obtains after the washing is dispersed in the mixed solvent of deionized water and absolute ethyl alcohol, adds again the cetyl trimethoxy silane of 0.114 g tetraethyl orthosilicate and 0.041 g, carry out the reaction of 18 h mechanical agitation under the room temperature condition.After the reaction end, deionized water was repeatedly fully washed and is removed the various reagent that fully do not react in the system under magnetic separated, and ablated in 550 ℃ of Muffle furnaces, and the kernel of step removal polystyrene is removed pore-foaming agent simultaneously, obtains meso-porous hollow microballoon (Fig. 4,5); Microballoon overall size 340 nm, mesopore silicon oxide shell average thickness is about 41 nm.
Embodiment 3.Adopt the same method to prepare the magnetic nanoparticle that coprecipitation is prepared oleic acid modified, and prepare the magnetic-particle that disperses again evaporate to dryness through normal octane.0.23 g SDS is dissolved in the 40 g deionized waters, the dispersion liquid of 8 g styrene monomers, 0.4 g hexadecanol, 1 g TEOS and 55 mg magnetic-particles is mixed the ultrasonic uniform oil phase of making, then with the aqueous solution of surfactant, ultrasonic thin emulsification 10 min under 500 W.Adding is with respect to the AIBN of styrene monomer 1.0 %, and stirring at room is led to N
2Then 30 min change reaction system over to the water-bath of 70 ℃ of temperature ranges, and the beginning initiated polymerization after 60 min are carried out in polymerization, adds the sodium hydrate aqueous solution of 0.05 mL1%, and 6 h are carried out in reaction again under 70 ℃; Product separates auxiliary lower deionized water cyclic washing 2-3 time of using at magnetic.The mould material that obtains after the washing is dispersed in the mixed solvent of deionized water and absolute ethyl alcohol, adds again the cetyl trimethoxy silane of 0.08 g tetraethyl orthosilicate and 0.029 g, carry out the reaction of 18 h mechanical agitation under the room temperature condition.After reaction finishes, deionized water was repeatedly fully washed and is removed the various reagent that fully react in the system under magnetic separated, in 550 ℃ of Muffle furnaces, ablate, one step was removed the kernel of polystyrene, remove simultaneously pore-foaming agent, obtain the meso-porous hollow microballoon, microballoon overall size 260 nm, average shell thickness 23 nm of mesopore silicon oxide.
Embodiment 4.Adopt the same method to prepare the magnetic nanoparticle that coprecipitation is prepared oleic acid modified, and prepare the magnetic-particle that disperses again evaporate to dryness through normal octane.0.08 g CTAB is dissolved in the 40 g deionized waters, the dispersion liquid of 8 g styrene monomers, 0.4 g hexadecane, 2 g methyl silicates and 20 mg magnetic-particles is mixed the ultrasonic uniform oil phase of making, then with the aqueous solution of surfactant, ultrasonic thin emulsification 10 min under 500 W.Adding is with respect to the potassium peroxydisulfate of styrene monomer 1.0 %, and stirring at room is led to N
2Then 30 min change reaction system over to the water-bath of 70 ℃ of temperature ranges, and the beginning initiated polymerization after 60 min are carried out in polymerization, adds the ammoniacal liquor of 0.1 mL, and 6 h are carried out in reaction again under 70 ℃; Product separates auxiliary lower deionized water cyclic washing 2-3 time of using at magnetic.The mould material that obtains after the washing is dispersed in the mixed solvent of deionized water and absolute ethyl alcohol, adds again the softex kw of the positive quanmethyl silicate of 0.16 g and 0.12 g, carry out the reaction of 6 h mechanical agitation under the room temperature condition.After the reaction end, deionized water was repeatedly fully washed and is removed the various reagent that fully do not react in the system under magnetic separated, product 75 ℃ of return stirring 2 h in hydrochloric acid/ethanol system, and 60 degree vacuum drying, 12 h obtain the meso-porous hollow microballoon; Microballoon overall size 400 nm, mesopore silicon oxide shell average thickness is about 36 nm.
Claims (10)
1. the preparation method of the mesopore silicon oxide tiny balloon of embedded magnetic nano particle in the shell, its feature is as follows in concrete steps:
(1) use coprecipitation to prepare magnetic nanoparticle, with the FeCl of mol ratio 1.5-1.8:1
36H
2O and FeCl
27H
2O is dissolved in the deionized water, adds ammoniacal liquor, logical N
2Gas at 80 ℃ of lower heating 30 min, then adds oleic acid, continues heating stirring reaction 1 h, then stops logical N
2Volatilization ammoniacal liquor, until have a large amount of black precipitate to occur after stopping to stir, then stop reaction, magnetic is washed till neutrality with deionized water with precipitation respectively under separating, and respectively washes 3 times with deionized water and ethanol again, obtain magnetic nanoparticle, be dispersed in an amount of normal octane magnetic nanoparticle is ultrasonic, rotary evaporation evaporate to dryness normal octane is for subsequent use again;
(2) proper amount of surfactant is dissolved in a certain amount of deionized water obtains water, the inorganic magnetic nano particle that styrene monomer, super-hydrophobic dose, tetraalkyl orthosilicate and step (1) are obtained mixes the ultrasonic uniform oil phase of making, then mixed with water, under 500 W ultrasonic thin emulsification 5-10 minute; Adding is with respect to the initator of styrene monomer quality 1-2%, and stirring at room is led to N
2Then 30 min change reaction system in the heated water bath over to initiated polymerization; After polymerization 90-100 minute, add alkali, system pH is adjusted between the 8.0-10.0; Reaction was carried out under 50-80 ℃ 2-3 hour again, and the polymerizate that obtains is auxiliary lower in the magnetic separation, used deionized water cyclic washing 3 times, namely obtained the mould material of nested nucleocapsid structure; Whole system is according to weight percent meter, the inorganic magnetic nano particle accounts for 0.05-0.15 %, styrene monomer accounts for 12.5-15.0%, surfactant accounts for 0.19-0.43 %, super-hydrophobic dose accounts for 0.76-0.84 %, and initator accounts for 0.1-0.3 %, and tetraalkyl orthosilicate accounts for 2.1-7.6 %, residue satisfies 100% for deionized water, its gross weight; Super-hydrophobic dose be in the alcohol of hexadecane long chain alkane or hexadecanol band long-chain any;
(3) mould material that obtains in step (2) reaction is dispersed in the percent by volume of water in the deionized water of 20-40%/absolute ethyl alcohol mixed solvent, adding with respect to the alkali of mixed solvent 3.0-7.0% as the sol gel reaction catalyst, add again with respect to doubly long carbochain silane coupler of the 2.7-3.8 of mould material quality/tetraalkyl orthosilicate mixture, the mol ratio of long carbochain silane coupler and tetraalkyl orthosilicate is at 3.5-6.0:1, after mechanical agitation is reacted under the room temperature, product is carried out magnetic separate the cyclic washing several times, under 450-650 ℃, carry out 3-5 hour ablation, obtain the mesoporous SiO 2 tiny balloon of even embedded magnetic nano particle;
Perhaps adopt cationic surfactant chain alkyl ammonium salt as pore-foaming agent, percent by volume at water is in 40-60% deionized water/absolute ethyl alcohol mixed solvent, adding with respect to the alkali of mixed solvent 3.0-7.0% as the sol gel reaction catalyst, adding with respect to the cationic surfactant chain alkyl ammonium salt of mixed solvent 0.15-0.3% as pore-foaming agent, add again with respect to the presoma of the 2.0-5.0 of template quality tetraalkyl orthosilicate doubly as silica, the product that the process sol gel reaction obtains, in the alcoholic solution that contains acid, reflux a period of time, remove pore-foaming agent and template, obtain magnetic/mesoporous SiO 2 tiny balloon.
2. preparation method according to claim 1 is characterized in that used magnetic nanoparticle is Fe
3O
4Particle, γ-Fe
2O
3Particle or containing transition metal element manganese, chromium, cobalt, zinc or/and in the Nano-Ferrite Particle of nickel any.
3. preparation method according to claim 1, it is characterized in that used surfactant be in lauryl sodium sulfate, neopelex or the softex kw any.
4. preparation method according to claim 1 is characterized in that used alkali in the step (2) is a kind of in ammoniacal liquor, potassium hydroxide, NaOH or the TMAH.
5. preparation method according to claim 1 is characterized in that used alkali in the step (3) is a kind of in ammoniacal liquor, potassium hydroxide or the NaOH.
6. preparation method according to claim 1 is characterized in that used initator is a kind of in azodiisobutyronitrile or the potassium peroxydisulfate.
7. preparation method according to claim 1 is characterized in that used alcohol is one to several in methyl alcohol, ethanol or the isopropyl alcohol.
8. preparation method according to claim 1, it is characterized in that used tetraalkyl orthosilicate be in methyl silicate or the ethyl orthosilicate any.
9. preparation method according to claim 1, it is characterized in that used long chain silane coupling agent be in cetyl trimethoxy silane, octadecyl trimethoxy silane or the cetyl triethoxysilane any.
10. preparation method according to claim 1 is characterized in that used long chain alkyl ammonium salt is softex kw, in Cetyltrimethylammonium bromide, hexadecyltrimethylammonium chloride or the OTAC any.
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| CN101721964A (en) * | 2009-11-12 | 2010-06-09 | 同济大学 | Method for preparing shell-core micrometer/nanometer spheres capable of preventing functional materials |
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