CN102989398A - Magnetic inorganic nano particle/large-aperture ordered mesopore oxide nuclear shell microspheres and preparation method thereof - Google Patents
Magnetic inorganic nano particle/large-aperture ordered mesopore oxide nuclear shell microspheres and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of advanced nano composite materials, and in particularly relates to magnetic inorganic nano particle/large-aperture ordered mesopore oxide nuclear shell microspheres and a preparation method thereof. The preparation method comprises the following steps of: firstly, wrapping the surface of magnetic inorganic nano particles with a layer of amorphous silica by using a chemical sol-gel synthesis method, so as to form magnetic inorganic nano particles/silica nuclear shell microspheres of uniform size; secondly, filling organic carbon precursor liquid into gaps of the nuclear shell microspheres by using a nano casting method so as to carry out carbonization; forming mesostructures in three-dimensional ordered macroporous carbon by using the nano casting method once more, and roasting so as to obtain the magnetic inorganic nano particle/large-aperture ordered mesopore oxide nuclear shell microspheres. The magnetic composite microspheres have strong mangnetic responsiveness and high specific surface area, and have wide application prospect in aspects of protein absorption, enzyme fixation, nano-catalyst grain loading and the like; and the preparation method of the magnetic inorganic nano particle/large-aperture ordered mesopore oxide nuclear shell microsphere is simple, materials are easily available, and large scale production is suitable.
Description
Technical field
The invention belongs to advanced nano composite material technical field, be specifically related to a kind of magnetic inorganic nano corpuscle/large aperture ordered meso-porous oxide core shell microballoon and preparation method thereof.
Background technology
In recent years, the nucleocapsid complex microsphere becomes a kind of advanced composite material (ACM) with wide application prospect because it can utilize the advantage of its stratum nucleare and shell simultaneously.In recent years, along with people are solidified in bioanalysis separation, enzyme, needs aspect the medical diagnosis on disease, have magnetic nano-particle as nuclear, order mesoporous oxide is subject to people's extensive concern as the nucleocapsid complex microsphere of shell.Its reason is that this complex microsphere has the magnetic response characteristic, can simplify to make things convenient for compartment analysis, and is very low for the toxicity of organism.
Yet the magnetic inorganic nano corpuscle of all reports/order mesoporous oxide core shell microballoon all is to use little molecular surface active agent (such as softex kw) to make synthetic (Deng, the Y. H. that obtains of template at present; Qi, D. W. Deng, C. H.; Zhang, X. M.; Zhao, D. Y.;
J. Am. Chem. Soc.
2008,
130,28-29. Kim, J.; Kim, H. S.; Lee, N.; Kim, T.; Kim, H.; Yu, T.; Song, I. C.; Moon, W. K.; Hyeon, T.;
Angew. Chem. Int. Ed.
2008 , 47,8438 –, 8441. Zhao, W. R.; Chen, H. R.; Li, Y. S.; Li, L.; Lang, M. D.; Shi, J. L.;
Adv. Funct. Mater.
2008,
18,2780 – 2788.), therefore mesoporous very little (less than the 3.0nm) of this material.Often need larger aperture (more than 5 nm) in many applications, such as the load of fixing, the nanocatalyst particle of protein adsorption, enzyme etc.Therefore synthesize monodispersed magnetic inorganic nano corpuscle/large aperture ordered meso-porous oxide core shell microballoon in the urgent need to the exploitation effective way.
The various magnetic particles of the report before being different from/mesopore oxide composite particles, the magnetic inorganic nano corpuscle that the present invention reports/large aperture ordered meso-porous oxide core shell microballoon have magnetic responsiveness height, microballoon shape homogeneous, mesoporous in order and the aperture be easy to more greatly transmit the characteristic of macromolecular substances.The synthetic method that the present invention reports has solved the contradiction of alkaline environment and the acid catalyst that large molecule Composed of Non-ionic Surfactant needs of the requirement of Stober method.Take full advantage of porous and the ball nature of three-dimensional ordered macroporous material, in macropore, place in advance the inorganic magnetic nano particle, then adopt the solvent evaporates of confinement space to induce self assembly to form magnetic inorganic nano corpuscle/large aperture ordered meso-porous oxide core shell microballoon.Have the characteristic that raw material is easy to get, method novel, synthetic material purity is high, be suitable for large-scale production.Because its high-ratio surface that has, high pore volume, the mesoporous characteristic of uniform and ordered have important application prospect in the adsorbing separation field.
Summary of the invention
The object of the present invention is to provide that a kind of magnetic response is effective, the shape homogeneous, have the magnetic inorganic nano corpuscle in large aperture ordered meso-porous duct/large aperture ordered meso-porous oxide core shell microballoon and preparation method thereof.
Magnetic inorganic nano corpuscle proposed by the invention/large aperture ordered meso-porous oxide core shell microballoon is prepared by following methods:
(1) utilizes the sol-gel chemistry synthetic method, coat the last layer amorphous silica on the magnetic inorganic nano corpuscle surface, the magnetic inorganic nano corpuscle of formation size homogeneous/silica core-shell complex microsphere;
(2) complex microsphere that obtains is dispersed in precipitation arrangement formation photonic crystal in the dispersant, then the method by " nanometer casting (Nanocasting) " is packed into the organic carbon precursor liquid in the space of magnetic inorganic nano corpuscle/silica core-shell microspheres, removes silica shell with alkali or salt etching after the carbonization and keeps magnetic inorganic nano corpuscle in three-dimensional ordered macroporous material with carbon element the inside;
(3) method by again " nanometer casting (Nanocasting) " is filled into the precursor liquid of the precursor liquid of mesoporous inorganic oxide or mesopore metal oxide in the macropore of three-dimensional ordered macroporous carbon and the coated magnetic nano particle, precursor liquid is induced self assembly (Evaporation Induced Self-Assembly by solution evaporation, EISA), in three-dimensional ordered macroporous carbon, form mesoscopic structure;
(4) the three-dimensional ordered macroporous carbon of skeleton and surfactant are removed in roasting, obtain magnetic inorganic nano corpuscle/large aperture ordered meso-porous oxide core shell microballoon.
Synthetic resulting complex microsphere diameter range is 200 nm ~ 2 μ m, and specific surface is 100 m
2/ g ~ 600 m
2/ g, pore volume are 0.1 cm
3/ g ~ 0.8 cm
3/ g, mesoporous aperture size is 2 nm ~ 30 nm.
Among the present invention, the inorganic magnetic nano-particles size of use and has water-wetted surface between 100nm ~ 800nm.This microparticle material is tri-iron tetroxide (Fe
3O
4), γ-di-iron trioxide (γ-Fe
2O
3), NiFe
2O
4, CuFe
2O
4, a kind of in the nano iron particles, nano nickel, nanometer cobalt.
Among the present invention, when the parcel amorphous silica of magnetic inorganic nano corpuscle surface, employed silicon source is one or more in sodium metasilicate, ethyl orthosilicate (TEOS), the methyl silicate (TMOS); The base catalyst of employed catalysis silicon source hydrolysis is one or more in NaOH, potassium hydroxide, the concentrated ammonia liquor.Employed solvent is the mixed solution of alkylol and water, and alkylol wherein is one or more classes of methyl alcohol, ethanol or isopropyl alcohol.The mass ratio of alkyl alcohol and water is 9:1 ~ 1:9.
Among the present invention, be dispersed in to staticly settle in the dispersant at magnetic inorganic nano corpuscle/silica core-shell microspheres and arrange form photonic crystal.Dispersant can be one or more of methyl alcohol, ethanol, isopropyl alcohol, water etc.
Among the present invention, method by " nanometer casting (Nanocasting) " is packed into the organic carbon precursor liquid at the magnetic inorganic nano corpuscle that arranges/silica core-shell microspheres photonic crystal in the space, the organic carbon precursor liquid is the prepolymer of phenol or resorcinol and formaldehyde, and solvent can be one or more of methyl alcohol, ethanol, isopropyl alcohol, oxolane etc.
Among the present invention, keep simultaneously magnetic inorganic nano corpuscle in three-dimensional ordered macroporous material with carbon element the inside with removing silica shell with alkali or salt etching after the organic carbon source carbonization, operable alkali has one or more of NaOH, potassium hydroxide, concentrated ammonia liquor, and salt has one or more of sodium borohydride, potassium borohydride, sodium carbonate etc.
Among the present invention, method by again " nanometer casting (Nanocasting) " is filled into the precursor liquid of mesopore oxide in the macropore of three-dimensional ordered macroporous carbon and the coated magnetic nano particle, precursor liquid is induced self assembly (Evaporation Induced Self-Assembly by solution evaporation, EISA), in three-dimensional ordered macroporous carbon, form mesoscopic structure.The silicon source that the mesoporous inorganic oxide uses is one or more in sodium metasilicate, ethyl orthosilicate (TEOS), the methyl silicate (TMOS), and the source metal of mesopore metal oxide is used is one or more of aluminium isopropoxide, aluminic acid four positive butyl esters, tetra-n-butyl titanate, tetraethyl titanate, isopropyl titanate etc.The mesopore oxide precursor liquid hydrolysis catalyst that uses is acidic catalyst, acetic acid, acetic acid, watery hydrochloric acid, nitric acid etc. one or more; Employed surfactant is nonionic surface active agent and block copolymer, and non-ionic surface active agent is the little molecule C that contains polyethers
nH
2n+1EO
mIn one or more (n=5-12, m=10-20); Block copolymer is EO
nPO
mEO
nThe PEO-b-PS(M that (n=20-132, m=47-70) or laboratory are synthetic
w=10000-40000); Employed solvent is methyl alcohol, ethanol, isopropyl alcohol, oxolane or nitrogen, one or more classes of nitrogen-dimethyl formamide equal solvent.
Among the present invention, the order mesoporous structure of the complex microsphere intermediary hole shell that obtains comprises the meso-hole structure in tubulose duct, spherical duct.On the space group of its pore passage structure be
P6mm,
Fm 
m,
Im m,
Pm 
n,
Pm 
m,
Fd 
m,
P6 3 / mmc,
Ia 
dOne or several mixed structure wherein.
Magnetic composite microsphere of the present invention has stronger magnetic responsiveness and higher specific area, the aspects such as load fixing, the nanocatalyst particle at protein adsorption, enzyme have broad application prospects, the inventive method is simple, and raw material is easy to get, and is suitable for amplifying producing.
Description of drawings
Fig. 1 is the transmission electron microscope photo of magnetic ferroferric oxide/meso-porous silica core-shell microspheres (Fe3O4@SBA-15), and wherein, (1) is the enlarged photograph of single microballoon, and (2) are dispersed in the ethanol with the contrast photo before and after the attraction for microballoon.
The specific embodiment
Embodiment 1:
(1) size is dispersed in 280 mL ethanol at the 0.06g of about 180nm magnetic ferroferric oxide nano-particles, in 70 mL deionized waters and the 5 mL concentrated ammonia liquors (28 wt%), add 4ml tetraethoxysilance (TEOS), stir 6 h under the room temperature, the magnetic composite microsphere of layer of silicon dioxide that obtained surface deposition, product separated with magnet and with the mixed solution washing of second alcohol and water, the washing afterproduct continues to be dispersed in the above-mentioned mixed solvent repetition aforesaid operations four times.
(2) magnetic ferroferric oxide/SiO 2 composite microsphere that obtains is dispersed in the ethanol, precipitation is arranged and is formed photonic crystal, 100
oC baking 24 hours is for subsequent use.The ethanolic solution of resol is added drop-wise to the dried ethanol that repeatedly volatilizees for three times on the photonic crystal, then roasting carbonization under nitrogen.Composite is immersed among the 2M NaOH 70
oC refluxed 6 hours, and the silicon shell etching of magnetic ferroferric oxide/SiO 2 composite microsphere is removed.Be formed on the composite (Fe that three-dimensional ordered macroporous material with carbon element the inside keeps magnetic ferroferric oxide nano-particles
3O
4@3DOMC).
(3) precursor liquid (1.0g P123,0.06g 2M hydrochloric acid, 0.9g water, 8g oxolane, 2.08g ethyl orthosilicate) with SBA-15 is filled into Fe
3O
4Among the@3DOMC, 30
oSolvent evaporates is induced self assembly (EISA) 24 hours under the C, with 10ml 1M hydrochloric acid 100
oC hydrothermal treatment consists 12 hours.At last in air 550
oThe C roasting was removed surfactant and skeleton carbon in 6 hours and is obtained diameter greatly about monodispersed magnetic ferroferric oxide/mesoporous silicon dioxide micro-sphere of 450nm.
Embodiment 2:
(1) with the 0.1 g magnetic NiFe of size at about 300nm
2O
4Nano particle is dispersed in 280 mL ethanol, in 70 mL deionized waters and the 5 mL concentrated ammonia liquors (28 wt%), add 4ml tetraethoxysilance (TEOS), stir 6 h under the room temperature, the magnetic composite microsphere of layer of silicon dioxide that obtained surface deposition, product separated with magnet and with the mixed solution washing of second alcohol and water, the washing afterproduct continues the repetition aforesaid operations three times.
(2) with the magnetic NiFe that obtains
2O
4/ SiO 2 composite microsphere is dispersed in the ethanol, and precipitation is arranged and formed photonic crystal, 100
oC baking 24 hours is for subsequent use.The ethanolic solution of resol is added drop-wise to the dried ethanol that repeatedly volatilizees for three times on the photonic crystal, then roasting carbonization under nitrogen.Composite is immersed among the 2M KOH 70
oC refluxed 6 hours, with magnetic NiFe
2O
4The silicon shell etching of/SiO 2 composite microsphere is removed.Be formed on three-dimensional ordered macroporous material with carbon element the inside and keep magnetic NiFe
2O
4Composite (the NiFe of nano particle
2O
4@3DOMC).
(3) precursor liquid (1.0g F127,0.06g 2M hydrochloric acid, 0.9g water, 10g oxolane, 2.08g ethyl orthosilicate) with SBA-16 is filled into NiFe
2O
4Among the@3DOMC, 30
oSolvent evaporates is induced self assembly (EISA) 24 hours under the C, at last in air 550
oThe C roasting was removed surfactant and skeleton carbon in 6 hours and is obtained diameter greatly about the monodispersed magnetic NiFe of 600nm
2O
4/ mesoporous silicon dioxide micro-sphere.
Embodiment 3:
(1) size is dispersed in 280 mL ethanol in 0.1 g magnetic γ-ferric oxide nanoparticles of about 700 nm, in 70 mL deionized waters and the 5 mL concentrated ammonia liquors (28 wt%), add 4ml tetraethoxysilance (TEOS), stir 6 h under the room temperature, the magnetic composite microsphere of layer of silicon dioxide that obtained surface deposition, product separated with magnet and with the mixed solution washing of second alcohol and water, the washing afterproduct continues the repetition aforesaid operations three times.
(2) the magnetic γ that obtains-di-iron trioxide/SiO 2 composite microsphere is dispersed in water, precipitation is arranged and is formed photonic crystal, 100
oC baking 24 hours is for subsequent use.The ethanolic solution of resol is added drop-wise to the dried ethanol that repeatedly volatilizees for three times on the photonic crystal, then roasting carbonization under nitrogen.Composite is immersed in the 1M sodium borohydride 60
oC refluxed 3 hours, and the silicon shell etching of magnetic γ-di-iron trioxide/SiO 2 composite microsphere is removed.Be formed on composite (γ-Fe that three-dimensional ordered macroporous material with carbon element the inside keeps magnetic γ-ferric oxide nanoparticles
2O
3@3DOMC).
(3) precursor liquid (1.0g P123,1.5ml red fuming nitric acid (RFNA), 16g ethanol, 2.04g aluminium isopropoxide) with mesoporous γ-alundum (Al2O3) is filled into γ-Fe
2O
3Among the@3DOMC, 30
oSolvent evaporates is induced self assembly (EISA) 24 hours under the C, at last in air 550
oC is burnt to be removed surfactant and skeleton carbon in 6 hours and obtains diameter greatly about the monodispersed magnetic γ of 1000nm-Fe
2O
3/ mesoporous γ-alundum (Al2O3) microballoon.
Claims (8)
1. the preparation method of magnetic inorganic nano corpuscle/large aperture ordered meso-porous oxide core shell microballoon is characterized in that concrete steps are as follows:
(1) utilizes the sol-gel chemistry synthetic method, coat the last layer amorphous silica on the magnetic inorganic nano corpuscle surface, the magnetic inorganic nano corpuscle of formation size homogeneous/silica core-shell complex microsphere;
(2) complex microsphere that obtains is dispersed in precipitation arrangement formation photonic crystal in the dispersant, then the method by " nanometer casting " is packed into the organic carbon precursor liquid in the space of magnetic inorganic nano corpuscle/silica core-shell microspheres, removes silica shell with alkali or salt etching after the carbonization and keeps magnetic inorganic nano corpuscle in three-dimensional ordered macroporous material with carbon element the inside;
(3) method by again " nanometer casting " is filled into the precursor liquid of the precursor liquid of mesoporous inorganic oxide or mesopore metal oxide in the macropore of three-dimensional ordered macroporous carbon and the coated magnetic nano particle, precursor liquid is induced self assembly by solution evaporation, forms mesoscopic structure in three-dimensional ordered macroporous carbon;
(4) the three-dimensional ordered macroporous carbon of skeleton and surfactant are removed in roasting, obtain magnetic inorganic nano corpuscle/large aperture ordered meso-porous oxide core shell microballoon.
2. preparation method according to claim 1 is characterized in that described magnetic inorganic nano corpuscle is of a size of 100 nm ~ 800 nm, and this particulate material is tri-iron tetroxide, γ-di-iron trioxide, NiFe
2O
4, CuFe
2O
4, nano iron particles, nano nickel, wherein a kind of of nanometer cobalt.
3. desired preparation method according to claim 1 is characterized in that when the parcel amorphous silica of magnetic inorganic nano corpuscle surface, and employed silicon source is a kind of in sodium metasilicate, ethyl orthosilicate, the methyl silicate, or wherein several; Base catalyst is used in catalysis silicon source hydrolysis, and described base catalyst is a kind of in NaOH, potassium hydroxide, the concentrated ammonia liquor, or wherein several; Employed solvent is the mixed solution of alkylol and water, and alkylol wherein is one or more of methyl alcohol, ethanol or isopropyl alcohol, and the mass ratio of alkyl alcohol and water is 9:1 ~ 1:9.
4. preparation method according to claim 1, it is characterized in that being dispersed at magnetic inorganic nano corpuscle/silica core-shell microspheres and staticly settle in the dispersant when arrange forming photonic crystal, used dispersant is a kind of in methyl alcohol, ethanol, isopropyl alcohol, the water, or wherein several.
5. preparation method according to claim 1, it is characterized in that being packed into organic carbon precursor liquid at the magnetic inorganic nano corpuscle that arranges/silica core-shell microspheres photonic crystal in the space by the method for " nanometer casting ", the organic carbon precursor liquid is the prepolymer of phenol or resorcinol and formaldehyde, and solvent is one or more in methyl alcohol, ethanol, isopropyl alcohol, the oxolane.
6. preparation method according to claim 1, it is characterized in that keeping simultaneously magnetic inorganic nano corpuscle in three-dimensional ordered macroporous material with carbon element the inside with removing silica shell with alkali or salt etching after the organic carbon source carbonization, the alkali that uses is as a kind of in NaOH, potassium hydroxide, the concentrated ammonia liquor, or wherein several, salt is a kind of in sodium borohydride, potassium borohydride, the sodium carbonate, or wherein several.
7. preparation method according to claim 1, it is characterized in that method by again " nanometer casting " is filled into the precursor liquid of the precursor liquid of mesoporous inorganic oxide or mesopore metal oxide in the macropore of three-dimensional ordered macroporous carbon and the coated magnetic nano particle, precursor liquid is induced self assembly by solution evaporation, when in three-dimensional ordered macroporous carbon, forming mesoscopic structure, the silicon source that the mesoporous inorganic oxide uses is sodium metasilicate, ethyl orthosilicate, a kind of in the methyl silicate, or wherein several, what the source metal of mesoporous metal was used is aluminium isopropoxide, aluminic acid four positive butyl esters, tetra-n-butyl titanate, tetraethyl titanate, a kind of in the isopropyl titanate, or wherein multiple; Mesoporous inorganic oxide or the mesopore metal oxide precursor liquid hydrolysis catalyst that uses is acidic catalyst, and this acidic catalyst is a kind of in acetic acid, acetic acid, watery hydrochloric acid, the nitric acid, or wherein several; Employed surfactant is nonionic surface active agent and block copolymer, and non-ionic surface active agent is the little molecule C that contains polyethers
nH
2n+1EO
mIn a kind of, or wherein several, n=5-12, m=10-20; Block copolymer is EO
nPO
mEO
n, n=20-132, m=47-70, or PEO-b-PS, its M
w=10000-40000; Employed solvent is a kind of in methyl alcohol, ethanol, isopropyl alcohol, oxolane or the nitrogen nitrogen-dimethyl formamide, or wherein several.
8. the magnetic inorganic nano corpuscle that is prepared by the described method of one of claim 1-7/large aperture ordered meso-porous oxide core shell microballoon, this microsphere diameter scope are 200 nm ~ 2 μ m, and specific surface is 100 m
2/ g ~ 600 m
2/ g, pore volume are 0.1 cm
3/ g ~ 0.8 cm
3/ g, mesoporous aperture size is 2 nm ~ 30 nm; The order mesoporous structure of microballoon intermediary hole shell comprises the meso-hole structure in tubulose duct, spherical duct; On the space group of its pore passage structure be
P6mm,
Fm 
m,
Im 
m,
Pm n,
Pm 
m,
Fd 
m,
P6 3 / mmc,
Ia 
dOne or several mixed structure wherein.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101205420A (en) * | 2007-12-06 | 2008-06-25 | 复旦大学 | Magnetic inorganic nano-particle/ordered meso-porous silica core-shell microspheres and preparation thereof |
| CN101752047A (en) * | 2008-12-05 | 2010-06-23 | 复旦大学 | Three-dimensional ordered inorganic magnetism macroporous material and preparation method thereof |
| CN102614819A (en) * | 2012-04-17 | 2012-08-01 | 哈尔滨工业大学 | Method for preparing magnetic mesoporous carbon nanometer microspheres with high adsorption property |
-
2012
- 2012-12-02 CN CN2012105038294A patent/CN102989398A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101205420A (en) * | 2007-12-06 | 2008-06-25 | 复旦大学 | Magnetic inorganic nano-particle/ordered meso-porous silica core-shell microspheres and preparation thereof |
| CN101752047A (en) * | 2008-12-05 | 2010-06-23 | 复旦大学 | Three-dimensional ordered inorganic magnetism macroporous material and preparation method thereof |
| CN102614819A (en) * | 2012-04-17 | 2012-08-01 | 哈尔滨工业大学 | Method for preparing magnetic mesoporous carbon nanometer microspheres with high adsorption property |
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