CN103714929A - Magnetic mesoporous silica composite microsphere with Yolk-Shell structure and manufacturing method thereof - Google Patents
Magnetic mesoporous silica composite microsphere with Yolk-Shell structure and manufacturing method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of advanced nano materials, and particularly relates to a magnetic mesoporous silica composite microsphere with a Yolk-Shell structure and a manufacturing method of the magnetic mesoporous silica composite microsphere. Firstly, a sol-gel chemical synthesis method is adopted, and a magnetic nanoparticle is coated with a macromolecule layer of amorphous silicon dioxide and a macromolecule layer of polymer resin in sequence; then the self-assembling behavior of organic surface active agents as structural guiding agents and inorganic substances in solutions is utilized, and the magnetic nanoparticle is coated with a layer of silicon dioxide/surface active agent composite materials with an ordered mesostructure; the surface active agents and the macromolecule layers are removed through roasting, and then the materials of the magnetic mesoporous silica composite microsphere with the Yolk-Shell structure are obtained. The composite microsphere is provided with a large adjustable cavity, a high specific surface area and mesoporous shell layers evenly perpendicular to an interface, has magnetic responsiveness strong in stability, and has wide application prospects in nanoreactors, drug sustained release, high-capacity bioseparation and absorption. The method is simple, raw materials are easy to obtain, and amplification production can be achieved.
Description
Technical field
The invention belongs to advanced technical field of nano material, be specifically related to a class and there is magnetic mesoporous silica composite microsphere material of Yolk-Shell structure and preparation method thereof.
Background technology
In recent years, Yolk-Shell structure composite microballoon, owing to having inner large cavity, can provide larger storage volumes, and combine the character of core and shell simultaneously, in medicine transmission, control and discharge, nano-reactor, catalysis, jumbo absorption has many potential application with the aspect such as separated.Have magnetic iron oxide particle as core, Metaporous silicon dioxide material is as shell, and the Yolk-Shell structure composite microballoon of the large adjustable cavity that falls between is subject to people's extensive concern.Its reason is that this complex microsphere has magnetic response characteristic, can simplify and facilitate compartment analysis, large adjustable cavity provides larger storage volumes, greatly improve this microballoon to the load capacity of guest species and reacting environment, outer shell mesoporous, the mesopore orbit with high-ratio surface and homogeneous, the transmission channel of material is provided, be convenient to entering of guest molecule, simultaneously very low for the toxicity of organism, and can be by chemical modification the group in the different functionalization of silica surface grafting, thereby increase its application.
But, up to the present, the magnetic mesoporous silicon oxide microsphere material of synthetic Yolk-Shell structure in existing report, main by selective etch intermediate layer silica, restore di-iron trioxide core and realize, complex steps, etching process is consuming time longer, in etching process, easily destroy outer field pore passage structure, and be difficult to control its cavity size.Or the synthetic minimum ferriferrous oxide nano-particle of employing oil phase is nuclear material.Synthesized obtains composite material and has magnetic response weak effect, and composite material pattern is inhomogeneous, and cavity size is difficult to control, and iron oxide is exposed in air, dispersed bad, the destructurized deficiency that waits of mesopore orbit.（Huixia?Wu,?Gang?Liu,?Shengjian?Zhang,?Jianlin?Shi,?Lingxia?Zhang,?Yu?Chen,?Feng?Chen,?Hangrong?Chen,?J.?Mater.?Chem.
2011,?21,?3037.?Wenru?Zhao,?Hangrong?Chen,?Yongsheng?Li,?Liang?Li,?Meidong?Lang,?and?Jianlin?Shi,?Adv.?Funct.?Mater.
2008,?18,?2780.?Yu?Chen,?Hangrong?Chen,?Limin?Guo,?Qianjun?He,?Feng?Chen,?Jian?Zhou,?Jingwei?Feng,?Jianlin?Shi,?ACS?Nano
2010,?4?,?529.?Wenru?Zhao,?Jinlou?Gu,?Lingxia?Zhang,?Hangrong?Chen,?and?Jianlin?Shi,?J.?Am.?Chem.?Soc.
2005,?127,?8916.?Xiaoliang?Fang,?Zhaohui?Liu,?Ming-Feng?Hsieh,?Mei?Chen,?Pengxin?Liu,?Cheng?Chen,?Nanfeng?Zheng,?ACS?Nano
2012,?6,?4434.?L.?Zhang,?S.?Z.?Qiao,?Y.?G.?Jin,?Z.?G.?Chen,?H.?C.?Gu,?G.?Q.?Lu,?Adv.?Mater.
2008,?20,?805.?Y.?F.?Zhu,?E.?Kockrick,?T.?Ikoma,?N.?Hanagata,?S.?Kaskel,?Chem.?Mater.
2009,?21,?2547.。
Summary of the invention
The object of the present invention is to provide a kind of magnetic response effective, shape homogeneous, good dispersion, has adjustable large cavity, and a kind of magnetic mesoporous silica complex microsphere with Yolk-Shell structure of ordered mesoporous pore canals and preparation method thereof.
A class proposed by the invention has the magnetic mesoporous silica composite microsphere material of Yolk-Shell structure, by following methods, is prepared:
(1) take magnetic inorganic nanoparticle as core, utilize sol-gel chemistry principle, first adopt the presoma hydrolysis of silicon source at the coated last layer amorphous silica in magnetic particle surface;
(2) at silica surface, utilize sol-gel chemistry principle, the macromolecule layer of coated one deck polymer resin, as cavity template, obtains having the magnetic composite microsphere of sandwich structure, and interlayer is silicon dioxide;
(3) the coated method of sol-gel that then adopts surfactant to get involved, the composite shell being formed by surfactant and silicon dioxide at coated one deck of appearance of sandwich structure magnetic composite microsphere;
(4) finally by roasting, remove organic surface active agent and macromolecule layer, obtain thering is magnetic, inorganic nano-particle/silicon dioxide Yolk-Shell structure composite microballoon of cavity structure and ordered mesoporous pore canals; The size of this complex microsphere is 200 nm～1 μ m, and cavity size is 10 ~ 300 nm, and specific surface is 100 m
2/ g ~ 1000 m
2/ g, pore volume is 0.1 cm
3/ g ~ 0.8 cm
3/ g, mesoporous lamella thickness is 30-300nm, mesoporous aperture size is 2 nm ~ 10 nm.Its cavity size is adjustable with polymer resin macromolecule layer gauge.
In complex microsphere prepared by the present invention, inorganic nano-particle is of a size of 50 nm ~ 800 nm, amorphous silica layer thickness is 10 nm ~ 200 nm, and cavity size is 10 ~ 300 nm, and the thickness of organic surface active agent/inorganic silicon dioxide composite material is 30 nm ~ 300 nm.The size of microballoon is 200 nm～1 μ m.
In the present invention, the magnetic nano-particle of use easily disperses in polar solvent, has magnetic.Size is between 50 nm ~ 800 nm.This microparticle material is tri-iron tetroxide (Fe
3o
4), γ-di-iron trioxide (γ-Fe
2o
3), NiFe
2o
4, CuFe
2o
4, nano iron particles, nano nickel, wherein a kind of of nanometer cobalt.
In the present invention, the synthetic silicon source of using of material is one or more in sodium metasilicate, tetraethoxysilance (TEOS), methyl silicate (TMOS).
In the present invention, the polymer resin macromolecule layer using is phenolic resins, or wherein a kind of of melamine resin; The resinae raw material that parcel polymer resin macromolecule layer is used is phenol, Resorcino, and phloroglucinol, amino-phenol, a kind of in melamine, or a kind of in same formaldehyde, urotropine; Coated polymer resin is used base catalyst, and this base catalyst can be one or more in NaOH, potassium hydroxide, concentrated ammonia liquor.
In the present invention, the surfactant using is nonionic surface active agent or ionic surfactant.Nonionic surface active agent is containing one or more (n=5-12, m=10-20) in the little molecule CnH2n+1EOm of polyethers.Ionic surfactant is alkyl quaternaries surfactant (C
ntAB) one or more in (n=12-18).
In the present invention, the solvent using is the mixed solution of alkylol and water, and alkylol is wherein one or more classes of methyl alcohol, ethanol, isopropyl alcohol.The mass ratio of alkyl alcohol and water is 9:1 ~ 1:9.
In the present invention, during the hydrolysis of silicon source presoma, using catalyst, this catalyst is acidic catalyst or base catalyst.Base catalyst is NaOH (NaOH), potassium hydroxide (KOH), concentrated ammonia liquor (NH
3h
2o).Acid acidic catalyst is one or more in acetic acid, acetic acid, watery hydrochloric acid (HCl) etc.
In the present invention, in prepared composite microsphere material, the order mesoporous structure of silicon dioxide comprises the various meso-hole structures with tubulose duct, spherical duct.Its pore passage structure, in space group, can be p6mm, Fm
m, Im
m, Pm
n, Pm
m, Fd
m, P6
3/ mmc, Ia
d is one or several mixed structure wherein
In the present invention, in the sol-gel chemistry synthetic system of the coated amorphous silica in inorganic nanoparticles surface, inorganic magnetic nanoparticle mass percent is 0.50wt% ~ 5wt%, silicon source quality percentage is 0.1 wt% ~ 0.5 wt%, catalyst quality percentage is 0.5wt ~ 3wt%, and other are alcohol water mixed solvent.On the surface of amorphous silica, continue in the synthetic system of coated polymer resin macromolecule layer, resin raw material mass percent is 0.1 wt% ~ 1.0 wt%, formaldehyde mass percent is 0.1 wt% ~ 1.0 wt%, catalyst quality percentage is 0.5wt ~ 5wt%, on polymer resin surface, continue in the synthetic system of coated organic surface activity and silicon dioxide composite material, surface deposition the mass percent of inorganic nanoparticles of silicon dioxide be 0.5wt% ~ 5 wt%, surfactant mass percent is 0.5wt ~ 2wt%, silicon source quality percentage is 0.2wt% ~ 0.5 wt %, catalyst quality percentage is 0.5wt ~ 3wt%, other are alcohol water mixed solvent.
Before being different from, report, in the present invention, to have magnetic response high for the prepared electrodeless nano particle/silicon dioxide of the magnetic with ordered mesoporous pore canals and larger adjustable cavity Yolk-Shell structure composite microballoon, even adjustable cavity, uniform morphology and better dispersed, orderly mesopore orbit and be easy to the characteristic of mass transfer diffusion.In synthetic method of the present invention, take full advantage of the characteristic of magnetic material, adopt magnet separated, have the characteristic that raw material is easy to get, method is simple rapidly, synthetic material purity is high, method is simple, is suitable for large-scale production.Due to its even adjustable large cavity having, quick magnetic response, and high-ratio surface, high pore volume, the characteristic that uniform and ordered is mesoporous, in absorption, separation, catalysis, medicament slow release, the fields such as nano-reactor have important application prospect.
Accompanying drawing explanation
Fig. 1 is that the present invention prepares magnetic mesoporous silica composite microsphere material structure and a shape appearance figure with Yolk-Shell structure.Wherein, (a) being 200nm:1, is (b) 50nm:1 enlarged drawing.
Embodiment
Below by specific embodiment, further describe the present invention.
embodiment 1:
(1) the 0.1 g magnetic ferroferric oxide particulate of the about 150nm of size is dispersed in to 80 mL ethanol, in 20 mL deionized waters and 1 mL concentrated ammonia liquor (28 wt%), add 0.3 g tetraethoxysilance (TEOS), under room temperature, stir 6 h, the magnetic composite microsphere of layer of silicon dioxide that obtained surface deposition, product is separated also with the mixed solution washing of second alcohol and water with magnet, stand-by after washing afterproduct drying at room temperature.
(2) ultrasonic being scattered in of the magnetic ferroferric oxide complex microsphere after surface deposition layer of silicon dioxide contained to 30 mL ethanol, 15 mL deionized waters, 1.25 g concentrated ammonia liquors, mechanical agitation 10 min, add 0.2 g Resorcino, stir 20 min, add 0.30 ml formaldehyde.Continue to stir 4h, product is separated also with the mixed solution washing of second alcohol and water with magnet, obtain the complex microsphere of magnetic ferroferric oxide/silica/phenolic resins sandwich structure.
(3) complex microsphere obtained above is scattered in and contains 60 mL ethanol, 80 mL deionized waters, in the mixed solution of 1.00 g concentrated ammonia liquors and 0.30 g cetyl trimethyl ammonia bromide (CTAB), after stirring 0.5 h and making solution evenly, dropwise add 0.20 g tetraethoxysilance (TEOS), drip follow-up continuous stirring 6 h completely, obtain magnetic ferroferric oxide/silica/phenolic resins/containing the SiO 2 composite microsphere of surfactant, magnet is collected product, and washs with the mixed solution of second alcohol and water.Drying at room temperature, and roasting in air, heating rate 1
oc/min, rises to 500
oc, roasting 3 h.Products therefrom magnetic saturation intensity is 42.1 emu/g, and particle diameter is 510nm, and cavity size is 85 nm, and mesoporous aperture is 2.0 nm.
embodiment 2:
(1) by the 0.1 g magnetic NiFe of the about 250nm of size
2o
4particulate is dispersed in 70 mL ethanol, in 30 mL deionized waters and 1 mL concentrated ammonia liquor (28 wt%), add 0.2 g tetraethoxysilance (TEOS), under room temperature, stir 6 h, the magnetic composite microsphere of layer of silicon dioxide that obtained surface deposition, product is separated also with the mixed solution washing of second alcohol and water with magnet, stand-by after washing afterproduct drying at room temperature.
(2) by the magnetic NiFe after surface deposition layer of silicon dioxide
2o
4ultrasonic being scattered in of complex microsphere contained 60 mL ethanol, 30 mL deionized waters, and 1.25 g concentrated ammonia liquors, mechanical agitation 10 min, add 0.2 g amino-phenol, stir 20 min, add 0.30 ml formaldehyde.Continue to stir 4h, product is separated also with the mixed solution washing of second alcohol and water with magnet, obtain magnetic NiFe
2o
4the sandwich structure complex microsphere of/silica/phenolic resins.
(3) complex microsphere obtained above is scattered in and contains 60 mL ethanol, 80 mL deionized waters, in the mixed solution of 1.00 g concentrated ammonia liquors and 0.30 g cetyl trimethyl ammonia bromide (CTAB), after stirring 0.5 h and making solution evenly, dropwise add 0.40 g tetraethoxysilance (TEOS), drip follow-up continuous stirring 6 h completely, obtain magnetic NiFe
2o
4/ silica/phenolic resins/containing the SiO 2 composite microsphere of surfactant, magnet is collected product, and washs with the mixed solution of second alcohol and water.Drying at room temperature, and roasting in air, heating rate 1
oc/min, rises to 500
oc, roasting 3 h.Products therefrom magnetic saturation intensity is 51.5 emu/g, and particle diameter is 600nm, and cavity size is 50 nm, and mesoporous aperture is 2.2 nm.
embodiment 3:
(1) 0.1 g magnetic γ-di-iron trioxide particulate of the about 400nm of size is dispersed in to 90 mL ethanol, in 10 mL deionized waters and 1 mL concentrated ammonia liquor (28 wt%), add 0.05 g tetraethoxysilance (TEOS), under room temperature, stir 6 h, the magnetic composite microsphere of layer of silicon dioxide that obtained surface deposition, product is separated also with the mixed solution washing of second alcohol and water with magnet, stand-by after washing afterproduct drying at room temperature.
(2) by the ultrasonic 90 mL deionized waters that are scattered in of the magnetic γ after surface deposition layer of silicon dioxide-di-iron trioxide complex microsphere, 0.35 ml formaldehyde, stirs and is heated to 80
oc, adds 0.2 g melamine, adds 0.10 ml formic acid after dissolving, stirs 4h, and product is separated also with the mixed solution washing of second alcohol and water with magnet, obtains the sandwich structure complex microsphere of magnetic γ-di-iron trioxide/silica/melamine resin.
(3) complex microsphere obtained above is scattered in and contains 60 mL ethanol, 80 mL deionized waters, in the mixed solution of 1.00 g concentrated ammonia liquors and 0.30 g cetyl trimethyl ammonia bromide (CTAB), after stirring 0.5 h and making solution evenly, dropwise add 0.50 g tetraethoxysilance (TEOS), drip follow-up continuous stirring 6 h completely, obtain magnetic γ-di-iron trioxide/silica/melamine resin/containing the SiO 2 composite microsphere of surfactant, magnet is collected product, and washs with the mixed solution of second alcohol and water.Drying at room temperature, and roasting in air, heating rate 1
oc/min, rises to 500
oc, roasting 3 h.Products therefrom magnetic saturation intensity is 63.2 emu/g, and particle diameter is 780nm, and cavity size is 20 nm, and mesoporous aperture is 2.2 nm.
embodiment 4:
(1) the 0.1 g magnetic ferroferric oxide particulate of the about 300nm of size is dispersed in to 80 mL ethanol, in 20 mL deionized waters and 1 mL concentrated ammonia liquor (28 wt%), add 0.3 g tetraethoxysilance (TEOS), under room temperature, stir 6 h, the magnetic composite microsphere of layer of silicon dioxide that obtained surface deposition, product is separated also with the mixed solution washing of second alcohol and water with magnet, stand-by after washing afterproduct drying at room temperature.
(2) ultrasonic being scattered in of the magnetic ferroferric oxide complex microsphere after surface deposition layer of silicon dioxide contained to 40 ml deionized waters, add 0.10 g phenol, 0.05 mg urotropine.Stir 10 min, reactant liquor is transferred to water heating kettle, 160
oc hydro-thermal reaction 3 h, product is separated also with the mixed solution washing of second alcohol and water with magnet, obtain the complex microsphere of magnetic ferroferric oxide/silica/phenolic resins sandwich structure.
(3) complex microsphere obtained above is scattered in and contains 60 mL ethanol, 80 mL deionized waters, in the mixed solution of 1.50 g concentrated ammonia liquors and 0.30 g cetyl trimethyl ammonia bromide (CTAB), after stirring 0.5 h and making solution evenly, dropwise add 0.50 g tetraethoxysilance (TEOS), drip follow-up continuous stirring 6 h completely, obtain magnetic ferroferric oxide/silica/phenolic resins/containing the SiO 2 composite microsphere of surfactant, magnet is collected product, and washs with the mixed solution of second alcohol and water.Drying at room temperature, and roasting in air, heating rate 1
oc/min, rises to 500
oc, roasting 3 h.Products therefrom magnetic saturation intensity is 38.9 emu/g, and particle diameter is 870nm, and cavity size is 120 nm, and mesoporous aperture is 2.0 nm.
Claims (5)
1. a preparation method with the magnetic mesoporous silica composite microsphere material of Yolk-Shell structure, is characterized in that concrete steps are as follows:
(1) take magnetic inorganic nanoparticle as core, utilize the principle of sol-gel chemistry, first adopt the presoma hydrolysis of silicon source at the coated last layer amorphous silica in magnetic particle surface;
(2) at silica surface, utilize sol-gel chemistry principle, the macromolecule layer of coated one layer of polymeric resin, as cavity template, obtains having the magnetic composite microsphere of sandwich structure, and interlayer is silicon dioxide;
(3) the coated method of sol-gel that then adopts surfactant to get involved, the composite shell being formed by surfactant and silicon dioxide at coated one deck of appearance of sandwich structure magnetic composite microsphere;
(4) finally by roasting, remove organic surface active agent and macromolecule layer, obtain thering is magnetic, inorganic nano-particle/silicon dioxide Yolk-Shell structure composite microballoon of cavity structure and ordered mesoporous pore canals; The size of this complex microsphere is 200 nm～1 μ m, and cavity size is 10 ~ 300 nm, and specific surface is 100 m
2/ g ~ 1000 m
2/ g, pore volume is 0.1 cm
3/ g ~ 0.8 cm
3/ g, mesoporous lamella thickness is 30-300nm, mesoporous aperture size is 2 nm ~ 10 nm;
Wherein:
Described magnetic inorganic nanoparticle is of a size of 100 nm ~ 800 nm, and this microparticle material is tri-iron tetroxide, γ-di-iron trioxide, NiFe
2o
4, CuFe
2o
4, nano iron particles, nano nickel, a kind of in nanometer cobalt; The silicon source of using is one or more in sodium metasilicate, tetraethoxysilance, methyl silicate;
Coated polymer resin macromolecule layer material is a kind of in phenolic resins, melamine resin; The resinae raw material that parcel polymer resin macromolecule layer is used is a kind of in phenol, Resorcino, phloroglucinol, amino-phenol, melamine, or a kind of in same formaldehyde, urotropine; During coated polymer resin, use base catalyst, base catalyst be NaOH, potassium hydroxide, concentrated ammonia liquor one or more;
Acidic catalyst or base catalyst are used in the presoma hydrolysis of silicon source; Wherein base catalyst is one or more in NaOH, potassium hydroxide, concentrated ammonia liquor, and acidic catalyst is one or more in acetic acid, acetic acid, watery hydrochloric acid;
The surfactant using is nonionic surface active agent or ionic surfactant, and wherein nonionic surface active agent is the little molecule CnH containing polyethers
2n+1one or more in EOm, n=5-12, m=10-20; Ionic surfactant is one or more in alkyl quaternaries surfactant, n=12-18; The solvent using is the mixed solution of alkylol and water, and alkylol is wherein one or more in methyl alcohol, ethanol or isopropyl alcohol; The mass ratio of alkyl alcohol and water is 9:1 ~ 1:9.
2. preparation method according to claim 1, it is characterized in that, in the sol-gel chemistry synthetic system of the coated amorphous silica in inorganic nanoparticles surface, inorganic magnetic nanoparticle mass percent is 0.50wt% ~ 5wt%, silicon source quality percentage is 0.1 wt% ~ 0.5 wt%, catalyst quality percentage is 0.5wt ~ 3wt%, and other are alcohol water mixed solvent.
3. preparation method according to claim 1, it is characterized in that, on the surface of amorphous silica, continue in the synthetic system of coated polymer resin macromolecule layer, resin raw material mass percent is 0.1 wt% ~ 1.0 wt%, formaldehyde mass percent is 0.1 wt% ~ 1.0 wt%, and catalyst quality percentage is 0.5wt ~ 5wt%.
4. preparation method according to claim 1, it is characterized in that, on polymer resin surface, continue in the synthetic system of coated organic surface activity and silicon dioxide composite material, surface deposition the mass percent of inorganic nanoparticles of silicon dioxide be 0.5wt% ~ 5 wt%, surfactant mass percent is 0.5wt ~ 2wt%, silicon source quality percentage is 0.2wt% ~ 0.5 wt %, and catalyst quality percentage is 0.5wt ~ 3wt%, and other are alcohol water mixed solvent.
5. the magnetic mesoporous silica composite microsphere material with Yolk-Shell structure being obtained by the described preparation method of one of claim 1-4, it is characterized in that, the order mesoporous structure of complex microsphere intermediary hole silicon dioxide comprises the meso-hole structure in tubulose duct, spherical duct, in the space group of its pore passage structure, be p6mm, Fm
m, Im
m, Pm
n, Pm
m, Fd
m, P6
3/ mmc, Ia
d is one or several mixed structure wherein.
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