CN101205420A - Magnetic inorganic nano-particle/ordered meso-porous silica core-shell microspheres and preparation thereof - Google Patents
Magnetic inorganic nano-particle/ordered meso-porous silica core-shell microspheres and preparation thereof Download PDFInfo
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Abstract
The invention belongs to the nano-composite material technology field, in particular to a magnetic inorganic nano-particle/ordered mesoporous silica core-shell microsphere and a preparation method thereof. The invention first utilizes sol-gel chemical synthesis method, coats a layer of amorphous silica on the surface of a plurality of magnetic inorganic nano-particles, then utilizes self-assembly of an organic surfactant as structure-directing agent and inorganic species in the solution, coats a layer of ordered meso-structured silica/surfactant composite material on the surface of the magnetic inorganic nano-particle/ silica composite microsphere, removes the surfactant through solvent extraction, and obtains the ordered mesoporous magnetic inorganic nano-particle/silica core-shell structure composite microsphere material. The composite microsphere has high specific surface area, strong magnetic responsiveness, and wide application prospect in bioseparation and bioabsorption. The invention is simple in method, easy in obtaining raw materials, and suitable for large scale production.
Description
Technical field
The invention belongs to advanced nano composite material and technical field, be specifically related to a kind of magnetic inorganic nano-particle/ordered meso-porous silica core-shell microballoon and preparation method thereof.
Technical background
In recent years, along with people are solidified in bioanalysis separation, enzyme, needs aspect the medical diagnosis on disease, have magnetic iron oxide particle as nuclear, earth silicon material is subjected 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, and can be by the group of chemically modified in the different functionalization of silica sphere grafting, thereby increases its Application Areas.
Than traditional earth silicon material, the characteristic of the mesopore orbit of the high-ratio surface that the ordered mesoporous silica dioxide material has, high pore volume, homogeneous is with a wide range of applications at aspects such as catalysis, fractionation by adsorption.As fully visible, the complex microsphere with magnetic response performance, order mesoporous structure can make full use of the advantage of above-mentioned two class materials, has more wide application prospect in the compartment analysis field.But up to the present, being nuclear with the magnetic oxide particle, is that the synthesizing of nucleocapsid composite nano-microsphere of shell also rarely has report with the ordered mesoporous material.In the existing report, institute's synthetic matrix material have magnetic response weak effect, matrix material shape inhomogeneous, deficiency such as can't finely in water, disperse.In addition, it is unordered or be parallel to the mesoporous of microsphere surface that institute's synthetic material is had, has certain deficiency aspect mass transfer.(Kim，J.；Lee，J.E.；Lee，J.；Yu，J.H.；Kim，B.C.；An，K.；Hwang，Y.；Shin，C.H.；Park，J.G..；Kim，J.；Hyeon，T.；J.Am.Chem.Soc.，2006，128，688-689.Lin，Y.S.；Wu，S.H.；Hung，Y.；Chou，Y.H.；Chang，C.；LIn，M.L.；Tsai，C.P.；Mou，C.Y.；Chem.Mater.，2006，18，5170-5172.Giri，S.；Trewyn，B.G.；Stellmaker，M.P.；Lin，V.S.Y.；Angew.Chem.Int.Ed.，2005，44，5038-5044.Zhao，W.R.；Gu，J.L.；Zhang，L.X.；Chen，H.R.；Shi，J.L.；J.Am.Chem.Soc.，2005，127，8916-8917.)
Different and various magnetic particles/meso-porous titanium dioxide silicon composite particles of being reported before, the magnetic inorganic nano-particle with ordered mesoporous pore canals/silicon dixoide nucleocapsid structure complex microsphere that the present invention reported have the corresponding height of magnetic, microballoon shape homogeneous, mesoporous in order and be easy to the characteristic of mass transfer diffusion.In the synthetic method that the present invention reported, make full use of the characteristic of magneticsubstance, adopted magnet to separate, had the characteristic that raw material is easy to get, method is simple rapidly, synthetic materials purity is high, be suitable for scale operation.Because high-ratio surface, high pore volume, the mesoporous characteristic of uniform and ordered that it had have important application prospects in the fractionation by adsorption 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 magnetic inorganic nano-particle/silica core-shell microspheres of ordered mesoporous pore canals and preparation method thereof.
A kind of magnetic inorganic nano-particle/ordered meso-porous silica core-shell microballoon proposed by the invention, make by following method: with the magnetic inorganic nanoparticle as seed grain, utilize the principle of sol-gel chemistry, adopt silicon source presoma hydrolysis, at first coat the last layer soft silica on the magnetic particle surface, utilize in sol-gel chemistry and the solution self-assembly behavior then as the tensio-active agent and the inorganic silicon species of structure directing agent, coat tensio-active agent and the silicon dioxide composite material that one deck has orderly mesoscopic structure at the soft silica laminar surface, remove organic surface active agent by solvent extraction at last, promptly obtain having the inorganic nano-particle/silica core-shell complex microsphere of magnetic and ordered mesoporous pore canals.The size of institute's synthetic complex microsphere is 200nm～1 μ m, specifically by regulating size, the amorphous silica thickness of coating and the thickness control of organic surface active agent and silicon dioxide composite material of magnetic inorganic nanoparticle, cross the thickness of the organic surface active agent/inorganic silicon dioxide matrix material of the silicon-dioxide layer thickness of controlling initial magnetic microsphere size, coating and coating and realize that the specific surface area of microballoon is 100m
2/ g～600m
2/ g, pore volume are 0.1cm
3/ g～0.8cm
3Between/the g, the mesoporous aperture size that microballoon had is 2nm～10nm.
In the microballoon, inorganic nano-particle is of a size of 100nm～800nm, and the amorphous silica layer thickness is 10nm～820nm, and the thickness of organic surface active agent/inorganic silicon dioxide matrix material is 20nm～880nm.The size of microballoon is 200nm～1 μ m.
Among the present invention, described inorganic nano-particle disperses in polar solvent easily, has magnetic.Particulate is of a size of 100nm～800nm, and the material of this particulate can be Z 250 (Fe
3O
4), γ-ferric oxide (γ-Fe
2O
3), NiFe
2O
4, CuFe
2O
4, wherein one or more of nano iron particles, nanometer nickel, nanometer cobalt.
Among the present invention, employed silicon source is one or more in water glass, tetraethoxysilance (TEOS), the methyl silicate (TMOS).
Among the present invention, the silicon source employed catalyzer of presoma hydrolysis is an acidic catalyst or basic catalyst.Basic catalyst is sodium hydroxide (NaOH), potassium hydroxide (KOH) or strong aqua (NH
3H
2O).Acid an acidic catalyst is one or more in acetic acid, acetate, the dilute hydrochloric acid (HCl).
Among the present invention, employed tensio-active agent is nonionic surface active agent or ionogenic surfactant.Nonionic surface active agent is the small molecules C that contains polyethers
nH
2n+1EO
mIn one or more (n=5-12, m=10-20).Ionogenic surfactant is alkyl quaternaries tensio-active agent C
nAmong the TAB one or more (n=12-18).
Among the present invention, employed solvent is the mixing solutions of alkyl alcohol and water, and alkyl alcohol wherein is one or more classes of methyl alcohol, ethanol, Virahol.The mass ratio of alkyl alcohol and water is 9: 1～1: 9.
Among the present invention, coat in the colloidal sol-gel chemistry synthetic system of amorphous silica on the inorganic nanoparticles surface, inorganic magnetic nanoparticle mass percent is 0.50wt%～5wt%, silicon source quality per-cent is 0.1wt%～0.5wt%, catalyst quality per-cent is 0.5wt～3wt%, and other are pure water mixed solvent.Continue to coat in the synthetic system of organic surfactivity and silicon dioxide composite material on the surface of amorphous silica, surface deposition the mass percent of inorganic nanoparticles of silicon-dioxide be in 0.50wt%～5wt% colloidal sol-gel chemistry synthetic system, inorganic magnetic nanoparticle mass percent is 0.5wt%～5wt%, the tensio-active agent mass percent is 0.5wt～2wt%, silicon source quality per-cent is 0.2wt%～0.5wt%, catalyst quality per-cent is 0.5wt～3wt%, and other are pure water mixed solvent.
Among the present invention, the order mesoporous structure of silicon-dioxide comprises various meso-hole structures with tubulose duct, spherical duct in the prepared composite microsphere material.Its pore passage structure can be p6mm on spacer,
P6
3/ mmc,
One or several mixed structure wherein.
Embodiment
Embodiment 1:
(1) size is dispersed in 80ml ethanol at the 0.1g of about 300nm magnetic ferroferric oxide particulate, in 20ml deionized water and the 1ml strong aqua (28wt%), add 0.3g tetraethoxysilance (TEOS), stir 6h under the room temperature, the magnetic composite microsphere of layer of silicon dioxide that obtained surface deposition, product separated with magnet and with the mixing solutions washing of second alcohol and water, wash after the after product drying at room temperature stand-by.
(2) with the magnetic ferroferric oxide complex microsphere ultra-sonic dispersion after the surface deposition layer of silicon dioxide in containing 60ml ethanol, the 80ml deionized water, 1.00g in the mixing solutions of strong aqua and 0.30g cetyl trimethyl ammonia bromide (CTAB), after stirring 0.5h makes solution evenly, dropwise add 0.40g tetraethoxysilance (TEOS), drip follow-up continuous stirring 6h fully, obtain magnetic ferroferric oxide/the contain SiO 2 composite microsphere of tensio-active agent, magnet is collected product, and washs with the mixing solutions of second alcohol and water.
(3) with the above-mentioned complex microsphere that obtains in 60ml acetone 80 ℃ of extraction 48h three times to remove tensio-active agent, deionized water wash, drying.The products therefrom magnetic saturation intensity is 40.8emu/g, and particle diameter is 410nm, and mesoporous aperture is 2.1nm.
Embodiment 2:
(1) size is dispersed in 100ml ethanol at the 0.1g of about 500nm magnetic ferroferric oxide particulate, in 10ml deionized water and the 1ml strong aqua (28wt%), add 0.25g tetraethoxysilance (TEOS), stir 7h under the room temperature, the magnetic composite microsphere of layer of silicon dioxide that obtained surface deposition, product separated with magnet and with the mixing solutions washing of second alcohol and water, wash after the after product drying at room temperature stand-by.
(2) with the magnetic ferroferric oxide complex microsphere ultra-sonic dispersion after the surface deposition layer of silicon dioxide in containing 90ml ethanol, the 60ml deionized water, 1.00g in the mixing solutions of strong aqua and 0.30g cetyl trimethyl ammonia bromide (CTAB), after stirring 0.8h makes solution evenly, dropwise add 0.40g tetraethoxysilance (TEOS), drip follow-up continuous stirring 5h fully, obtain magnetic ferroferric oxide/the contain SiO 2 composite microsphere of tensio-active agent, magnet is collected product, and washs with the mixing solutions of second alcohol and water.
(3) with the above-mentioned complex microsphere that obtains in 60ml acetone 80 ℃ of extraction 48h three times to remove tensio-active agent, deionized water wash, drying.The products therefrom magnetic saturation intensity is 38.0emu/g, and particle diameter is 620nm, and mesoporous aperture is 2.4nm.
Embodiment 3:
(1) with size at the 0.1g of about 300nm magnetic NiFe
2O
4Particulate is dispersed in 90ml ethanol, in 10ml deionized water and the 1ml strong aqua (28wt%), add 0.5g tetraethoxysilance (TEOS), stir 10h under the room temperature, the magnetic composite microsphere of layer of silicon dioxide that obtained surface deposition, product separated with magnet and with the mixing solutions washing of second alcohol and water, wash after the after product drying at room temperature stand-by.
(2) with the magnetic NiFe after the surface deposition layer of silicon dioxide
2O
4The complex microsphere ultra-sonic dispersion is in containing 30ml ethanol, 110ml deionized water, 1.00g aqueous hydrochloric acid (1.0M) and 0.30g Brij 56 (C
16H
33EO
10) mixing solutions in, after stirring 0.4h and making solution evenly, dropwise add 0.40g tetramethoxysilance (TEOS), drip follow-up continuous stirring 8h fully, obtain magnetic NiFe
2O
4/ containing the SiO 2 composite microsphere of tensio-active agent, magnet is collected product, and washs with the mixing solutions of second alcohol and water.
(3) with the above-mentioned complex microsphere that obtains in 60ml acetone 80 ℃ of extraction 36h three times to remove tensio-active agent, deionized water wash, drying.The products therefrom magnetic saturation intensity is 52.7emu/g, and particle diameter is 440nm, and mesoporous aperture is 2.0nm.
Embodiment 4:
(1) size is dispersed in 80ml ethanol at the 0.1g of about 700nm magnetic γ-ferric oxide particulate, in 20ml deionized water and the 1ml strong aqua (28wt%), add 0.03g tetraethoxy (TEOS), stir 6h under the room temperature, the magnetic composite microsphere of layer of silicon dioxide that obtained surface deposition, product separated with magnet and with the mixing solutions washing of second alcohol and water, wash after the after product drying at room temperature stand-by.
(2) with the magnetic γ-ferric oxide complex microsphere ultra-sonic dispersion of surface deposition layer of silicon dioxide in containing the 60ml Virahol, the 80ml deionized water, 1.00g in the mixing solutions of strong aqua and 0.30g cetyl trimethyl ammonia bromide (CTAB), after stirring 1.5h makes solution evenly, dropwise add 0.40g tetraethoxysilance (TEOS), drip follow-up continuous stirring 8h fully, obtain magnetic γ-ferric oxide particulate/contain SiO 2 composite microsphere of tensio-active agent, magnet is collected product, and washs with the mixing solutions of second alcohol and water.
(3) with the above-mentioned complex microsphere that obtains in 60ml acetone 80 ℃ of extraction 48h three times to remove tensio-active agent, deionized water wash, drying.The products therefrom magnetic saturation intensity is 60.8emu/g, and particle diameter is 900nm, and mesoporous aperture is 2.2nm.
Claims (3)
1. magnetic inorganic nano-particle/ordered meso-porous silica core-shell microballoon, it is characterized in that making by following method: with the magnetic inorganic nanoparticle as seed grain, utilize the principle of sol-gel chemistry, adopt silicon source presoma hydrolysis, coat the last layer soft silica on the magnetic particle surface; Utilize in the sol-gel principles of chemistry and the solution self-assembly behavior then as the tensio-active agent and the inorganic silicon species of structure directing agent, coat tensio-active agent and the silicon dioxide composite material that one deck has orderly mesoscopic structure at the soft silica laminar surface, remove organic surface active agent by solvent extraction at last, promptly obtain having the magnetic inorganic nano-particle/silica core-shell complex microsphere of magnetic and ordered mesoporous pore canals; The size of institute's synthetic complex microsphere is 200nm～1 μ m, and specific surface is 100m
2/ g～600m
2/ g, pore volume are 0.1cm
3/ g～0.8cm
3/ g, mesoporous aperture size is 2nm～10nm; Wherein:
Described magnetic inorganic nanoparticle is of a size of 100nm～800nm, and this microparticle material is Z 250, γ-ferric oxide, NiFe
2O
4, CuFe
2O
4, nano iron particles, nanometer nickel, wherein a kind of of nanometer cobalt; Employed silicon source is one or more in water glass, tetraethoxysilance, the methyl silicate;
The employed catalyzer of presoma hydrolysis is acid matter agent or basic catalyst in the synthesizing mesoporous silicon dioxide materials process, wherein basic catalyst be sodium hydroxide, potassium hydroxide or strong aqua one or more; An acidic catalyst be in acetic acid, acetate or the dilute hydrochloric acid one or more;
Employed tensio-active agent is nonionic surface active agent or ionogenic surfactant, and wherein nonionic surface active agent is the small molecules C that contains polyethers
nH
2n+1EO
mIn one or more, n=5-12, m=10-20; Ionogenic surfactant is alkyl quaternaries tensio-active agent C
nAmong the TAB one or more, n=12-18;
Employed solvent is the mixing solutions of alkyl alcohol and water, and alkyl alcohol wherein is one or more in methyl alcohol, ethanol or the Virahol, and the mass ratio of alkyl alcohol and water is 9: 1～1: 9.
2. the preparation method of a magnetic inorganic nano-particle/ordered meso-porous silica core-shell microballoon, it is characterized in that concrete steps are as follows: with the magnetic inorganic nanoparticle as the initial seed grain, utilize the sol-gel principles of chemistry, adopt silicon source presoma hydrolysis, at first coat the last layer soft silica on the inorganic nano-particle surface; Utilize in the sol-gel principles of chemistry and the solution self-assembly behavior then, coat organic surface active agent and the inorganic silicon dioxide matrix material that one deck has orderly mesoscopic structure on the amorphous silica surface as the tensio-active agent and the inorganic silicon species of structure directing agent; Obtain by organic solvent extraction at last and remove organic surface active agent, promptly obtain order mesoporous and inorganic nano-particle/silica core-shell microspheres magnetic, institute's synthetic complex microsphere size is 200nm～1 μ m, and specific surface is 100m
2/ g～600m
2/ g, pore volume are 0.1cm
3/ g～0.8cm
3/ g, mesoporous aperture size is 2nm～10nm; Wherein:
Described magnetic inorganic nanoparticle is of a size of 100nm～800nm, and this microparticle material is Z 250, γ-ferric oxide, NiFe
2O
4, CuFe
2O
4, wherein a kind of of nano iron particles, nanometer nickel or nanometer cobalt;
Employed silicon source is one or more in water glass, tetraethoxysilance, the methyl silicate;
The employed catalyzer of presoma hydrolysis is acid matter agent or basic catalyst in the synthesizing mesoporous silicon dioxide materials process, basic catalyst be sodium hydroxide, potassium hydroxide or strong aqua one or more, an acidic catalyst be in acetic acid, acetate or the dilute hydrochloric acid one or more;
Employed tensio-active agent is nonionic surface active agent or ionogenic surfactant, and wherein nonionic surface active agent is the small molecules C that contains polyethers
nH
2n+1EO
mIn one or more, n=5-12, m=10-20; Ionogenic surfactant is alkyl quaternaries tensio-active agent C
nAmong the TAB one or more, n=12-18;
Employed solvent is the mixing solutions of alkyl alcohol and water, and alkyl alcohol wherein is one or more of methyl alcohol, ethanol or Virahol, and the mass ratio of alkyl alcohol and water is 9: 1～1: 9;
Coat in the colloidal sol-gel chemistry synthetic system of amorphous silica on the inorganic nanoparticles surface, inorganic magnetic nanoparticle mass percent is 0.50wt%～5wt%, silicon source quality per-cent is 0.1wt%～0.5wt%, catalyst quality per-cent is 0.5wt～3wt%, and other are pure water mixed solvent; Continue to coat in the synthetic system of organic surfactivity and silicon dioxide composite material on the surface of amorphous silica, surface deposition the mass percent of inorganic nanoparticles of silicon-dioxide be 0.5wt%～5wt%, the tensio-active agent mass percent is 0.5wt～2wt%, silicon source quality per-cent is 0.2wt%～0.5wt%, catalyst quality per-cent is 0.5wt～3wt%, and other are pure water mixed solvent.
3. magnetic inorganic nano-particle/ordered meso-porous silica core-shell microballoon according to claim 1, it is characterized in that the order mesoporous meso-hole structure of mesoporous silicon oxide in the described complex microsphere comprises the meso-hole structure in tubulose duct, spherical duct, be p6mm on the spacer of its pore passage structure
P6
3/ mmc,
One or several mixed structure wherein.
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