CN103310935A - Silicon dioxide nano magnetic microsphere and preparation method thereof - Google Patents
Silicon dioxide nano magnetic microsphere and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a silicon dioxide nano magnetic microsphere. The particle size is 50-600 nm, an inner core is a magnetic nanoparticle with the particle size of 10-500 nm, compact silicon dioxide with the thickness of 1-10 nm is arranged in a middle layer, mesoporous silicon dioxide is arranged in an outer layer, the specific surface area of the nano magnetic microsphere is 10-500 m<2>/g, and the average aperture is 2-50 nm. A preparation method for the silicon dioxide nano magnetic microsphere comprises the steps as follows: dispersing the magnetic nanoparticle in a solvent, adding a compact silicon dioxide precursor, stirring for reaction, and coating the outer surface of the magnetic nanoparticle with a layer of compact silicon dioxide; adding a mesoporous silicon dioxide precursor and stirring for reaction; and separating and carrying out mesoporous formation to obtain the silicon dioxide nano magnetic microsphere with a mesoporous structure. The silicon dioxide nano magnetic microsphere has the functions of large specific surface area, adjustable aperture and capability of loading molecules with different sizes, and is widely applied to the aspects of cell separation, enzyme immobilization, protein separation, immunodetection, immunodiagnosis of water body pollutants and the like.
Description
Technical field
The invention belongs to the inorganic nano-particle technical field, be specifically related to a kind of silica nanometer magnetic microsphere and preparation method thereof.
Background technology
Magnetic nano-particle can magnetize under the effect of externally-applied magnetic field, is widely studied at biological field, such as magnetic resonance imaging, drug delivery, biology sensor, bio-separation and pyromagnetic diagnosis and treatment etc.; And, adding under the magnetic fields, can from solvent, separate fast.The method is responsive, and is simple and efficient.Therefore, the magnetic mesoporous material that has magnetic and high-specific surface area concurrently is considered to a kind of large molecule support materials that application potential is arranged very much.In sewage disposal, the bio-molecular separation enrichment, there is good application prospect in the fields such as heterocatalysis agent carrier.Yet, exposed magnetic nano-particle such as Fe
3O
4Unstable, structure is easily destroyed under acid and higher temperature.So in general, magnetic composite is the magnetic nuclear of tool and nonmagnetic surperficial coating all, comprises macromolecule, carbon and silicon dioxide etc., and high adsorption specific surface area and chemical stability can be provided.Compare SiO
2Because stable performance, and the surface easily by some functional groups such as functionalization such as amino, sulfydryl, carboxyls, be considered to desirable clad material.Can coat one deck inert material in the magnetic nano particle sub-surface if some scholar is verified, such as SiO
2, in the aqueous solution, can prevent the reunion of magnetic nano-particle, improve their chemical stability.
At present, the CN200910219335 patent discloses a kind of silicon dioxide magnetic composite microballoon, comprises the nuclear of a magnetic oxide and the silica shell of a dense non-porous.A critical function of the dense non-porous silica shell of inertia is to coat to have high chemism iron oxide, and it can be used safely under different condition.Yet because the silicon dioxide structure of dense non-porous causes the specific area of silicon dioxide magnetic composite microballoon little, the molecular amounts of load is limited, greatly reduces its application efficiency.A solution is to wrap up the silicon dioxide structure of one deck porous outside the dense non-porous silicon dioxide layer again.Chinese patent ZL200710055604 and ZL200810050222.9 disclose a kind of preparation method of magnetic microsphere of nano core-shell structure of porous surface.The inventor utilizes softex kw to be template, prepares the material that shell is the porous silica structure.But softex kw is very expensive on the one hand, and its use amount and pore structure are proportional, and preparation cost is too high; The hole that obtains on the other hand is very little, only has 2～4nm, and the aperture that specifically prepares all is no more than 3.8nm, and practical application is not strong.So synthetic silica nanometer magnetic microsphere with high-specific surface area, macropore volume, homogeneous aperture just becomes urgent problem under lower cost.
Summary of the invention
The present invention is directed to that the specific area of magnetic composite microsphere is little in the prior art, the aperture is little and the main technical problem such as skewness, purpose is to provide a kind of technology of preparing of low-cost preparation porous silicon dioxide nano magnetic microsphere.
The particle diameter of nano-magnetic microsphere of the present invention is 50～600nm, its kernel is the magnetic nano-particle of the single dispersed structure of particle diameter between 10～500nm, the middle level is that thickness is at the compact silicon dioxide of 1～10nm, skin is mesoporous silicon oxide, wherein, the specific area of described nano-magnetic microsphere is 10～500m
2/ g, the average pore size of mesoporous silicon oxide is 2～50nm.Aperture according to the outer silicon dioxide of the controlled preparation of the large molecular dimension of required load.Nano-magnetic microsphere of the present invention is single dispersed structure, can make the compact silicon dioxide in middle level closely be coated on the magnetic nano particle sub-surface, thereby guarantor unit's quality nano-magnetic microsphere magnetic is stronger, and its specific area is larger, and more reaction active groups can be provided.
A preferred embodiment of the present invention is that the present invention specifically provides the nano-magnetic microsphere that a kind of aperture is little, specific area is large, and its specific area is 120～280m
2/ g, preferred 130～180m
2/ g, the average pore size of mesoporous silicon oxide is 2～8nm, preferred 4.2～6nm.Another preferred embodiment is that the present invention specifically provides the nano-magnetic microsphere that a kind of aperture is large, specific area is little, and specific area is 30～90m
2/ g, preferred 40～70m
2/ g, the average pore size of mesoporous silicon oxide is 10～50nm, preferred 15～25nm.
Be preferably, the particle diameter of described nano-magnetic microsphere is 50～100nm, preferred 50～90nm, its kernel is that particle diameter is at the magnetic nano-particle of the single dispersed structure between preferred 30～80nm between 50～200nm, the middle level be thickness at the compact silicon dioxide of 5～10nm, skin is that thickness is at the preferred 3～8nm mesoporous silicon oxide of 3～20nm.
Described magnetic nano-particle is preferably ferrite, such as Fe
3O
4, γ-Fe
2O
3Or CoFe
2O
4Deng.
Another object of the present invention is to provide a kind of method for preparing silica nanometer magnetic microsphere of the present invention, it comprises the steps:
Step 1) be that the magnetic nano-particle of 10～500nm is scattered in the solvent with particle diameter, making it concentration is 0.1～10mg/mL, adds compact silicon dioxide presoma and stirring reaction, makes the outer surface of magnetic nano-particle coat one deck compact silicon dioxide;
Step 2) adding the meso-porous titanium dioxide silicon precursor in step 1) outer surface that obtains is coated with in the magnetic nano-particle of compact silicon dioxide, and stirring reaction; Separate and mesoporousization, obtain having the silica nanometer magnetic microsphere of meso-hole structure.
Be preferably, in step 1) in, after magnetic nano-particle is scattered in solvent, ultrasonic dispersion 0.5～3h, stir, then example such as watery hydrochloric acid, dilute sulfuric acid, acetic acid etc. are regulated pH to 2～5 or are used ammoniacal liquor, NaOH, potassium hydroxide etc. to transfer pH to 9～14, add compact silicon dioxide presoma such as tetraethoxysilane (TEOS), and stirring reaction 3～12h, thereby so that compact silicon dioxide presoma such as tetraethoxysilane (TEOS) are hydrolyzed to be coated on the surface of magnetic nano-particle under acidity or alkaline environment.Magnetic nano-particle: the mass ratio of tetraethoxysilane is 0.05～1, is preferably 0.08～0.5.Like this consumption, thus the thickness that can control the compact silicon dioxide layer is at 1～10nm.
With step 1) outer surface that the obtains magnetic nano-particle that is coated with compact silicon dioxide separates first and for example can be magnetism separate method, and use solvent such as ethanol and water washing for several times, be scattered in again in the solvent and stirring, making it concentration is 0.1～10mg/mL, in step 2) in, regulating step 1) outer surface that obtains is coated with the pH to 2 of the magnetic nano-particle of compact silicon dioxide～5 or 9～14, the method that for example can use step 1) to regulate pH is carried out, dropwise add again meso-porous titanium dioxide silicon precursor and stirring reaction 3～24h, many carbon organic chain silane that described meso-porous titanium dioxide silicon precursor comprises 1 parts by volume is dodecyltrimethoxysilane for example, the cetyl trimethoxy silane, octadecyl trichlorosilane alkane, the tetraethoxysilane of tri-phenyl-silane etc. and 0～4 parts by volume, described meso-porous titanium dioxide silicon precursor: the mass ratio of magnetic nano-particle is 2～12:1; So thereby the consumption of control long chain alkyl silane can be controlled the thickness of mesoporous silicon oxide layer, uses different many carbon organic chain silane can control mesoporous aperture, for example the preferred C12 of many carbon organic chain silane more than the C10 and above many carbon organic chain silane.
Step 2) in, with the water-alcohol solvent washing for several times, oven dry carry out mesoporousization at last again after separating; Described mesoporousization refers to that calcination is to remove alkyl in air.
Step 1) and step 2) in solvent be that volume ratio is 0.05～0.5 water and pure mixed solvent.The lower alcohol of described alcohol for dissolving each other with water, as be methyl alcohol, ethanol, ethylene glycol and/or glycerol, described separation can for making arbitrarily the method for magnetic particle and fluid separation applications, for example can be magnetism separate method.
Method of the present invention also further comprises step 3) regulation and control step 2) aperture of the silica nanometer magnetic microsphere intermediary hole silicon dioxide with meso-hole structure of gained.Step 3) described regulation and control refer to step 2) the silica nanometer magnetic microsphere with meso-hole structure of gained is to carry out back flow reaction 3～24h in 2～12 cushioning liquid such as sodium tetraborate, Potassium Hydrogen Phthalate, Tris, barbitol buffer solution, ammonium phosphate buffer solution etc. in the pH value, to regulate and control the aperture of outer mesoporous silicon oxide.Then separate, wash, dry and to get the silica nanometer magnetic microsphere that changes to the aperture.
Use the silica nanometer magnetic microsphere of method preparation of the present invention to be single dispersed structure, specific area is greatly up to 10～500m
2Between/the g, the aperture can hold the molecule that adsorbs multiple different size between 2～50nm, comprises pollution such as organic substance in the water body, azo acid, Microcystin and heavy metal etc.Silica nanometer magnetic microsphere after the reaming is because aperture size is larger in addition, and specific area is higher, aspect the separation and concentration of large biological molecule such as IgG antibody, also is that huge application potential is arranged.The method that can replace traditional splitter, the suspension of use silica nanometer magnetic microsphere, the joint efficiency of raising mesoporous silicon oxide surface p rotein A and IgG makes the separation process Simple fast.
The invention has the advantages that:
1) the silica nanometer magnetic microsphere of the present invention with meso-hole structure has multi-layer core-shell structure, kernel is the magnetic nano-particle of monodispersity, monodispersity can make the compact silicon dioxide in middle level closely be coated on the magnetic nano particle sub-surface, thereby guarantor unit's quality nano-magnetic microsphere magnetic is stronger, skin is mesoporous silicon oxide, specific area is large, and is high to large molecule load capacity;
2) the present invention prepares the method for silica nanometer magnetic microsphere, specific area and the aperture that can control nano-magnetic microsphere by kind and the amount of long chain alkyl silane presoma easily, and specific area is up to 10～500m
2Between/the g, pore diameter range is between 2～10nm, and the molecular dimension of load is regulated and control as required in addition, and the aperture can be regulated and control between 2～50nm, and method of operation is simple, environmental protection.
Description of drawings
Fig. 1 is the structural representation of silica nanometer magnetic microsphere of the present invention;
Fig. 2 is the transmission electron microscope TEM figure of silica nanometer magnetic microsphere of the present invention;
Fig. 3 is the N of silica nanometer magnetic microsphere of the present invention
2Adsorption curve figure, wherein, C
16TMS is the cetyl trimethoxy silane;
Fig. 4 is the graph of pore diameter distribution of silica nanometer magnetic microsphere of the present invention, wherein, and C
16TMS is the cetyl trimethoxy silane.
Embodiment
As shown in Figure 1, the structural representation for silica nanometer magnetic microsphere 10 of the present invention has multi-layer core-shell structure, and particle diameter is 50～600nm.Its kernel 11 is the magnetic nano-particle of single dispersed structure, and particle diameter can be ferrite at 10～500nm, such as Fe
3O
4, γ-Fe
2O
3Or CoFe
2O
4Deng.Outer surface at kernel 12 coats one deck compact silicon dioxide layer 14, and thickness is at 1～10nm.The outer surface of compact silicon dioxide layer 12 coats one deck meso-porous titanium dioxide silicon layer 16 again, has countless in irregular shape mesoporous (not shown) on the meso-porous titanium dioxide silicon layer 16, and average pore size is 2～50nm.It provides high specific area for silica nanometer magnetic microsphere 10, as is 10～500m
2/ g, and reached the aperture according to the adjustable effect of size that is adsorbed molecule.
The Fe of hydrothermal synthesis method preparation
3O
4Nanosphere 0.5g, ultrasonic 10min in 250mL0.1M HCl, magnetic separates, use deionized water washing 3 times, then be dispersed in 400mL ethanol and the 100mL water mixed solvent, add concentrated ammonia liquor 6mL and regulate pH to 11, add again the TEOS(tetraethoxysilane) 6mL, stir 6h under the room temperature, magnetic separates, use second alcohol and water cyclic washing, again be scattered in 170mL ethanol and the 30mL water, add ammoniacal liquor 8mL, dropwise add meso-porous titanium dioxide silicon precursor (the cetyl trimethoxy silane of volume ratio 1:4 and tetraethoxysilane mixture), add 6mL, stir 12h.Magnetic separates, deionized water and ethanol washing several, 60 ℃ of vacuumizes.To obtain powder 550 ℃ of calcinations to remove alkyl, obtain the silica nanometer magnetic microsphere of meso-hole structure.The specific surface that the silica nanometer magnetic microsphere of gained is tested with micrometrics ASAP2020 specific surface instrument when temperature 77K is 171.9m
2/ g, average pore size 3.3nm.
The Fe of hydrothermal synthesis method preparation
3O
4Nanosphere 0.5g is ultrasonic 10min in 250mL0.1M HCl, magnetic separates, use deionized water washing 3 times, then, be dispersed in 400mL ethanol and the 100mL water mixed solvent, add concentrated ammonia liquor 6mL and regulate pH to 11, add again TEOS6mL, stir 6h under the room temperature, magnetic separates, and uses second alcohol and water cyclic washing, again be scattered in 170mL ethanol and the 30mL water, add ammoniacal liquor 8mL, dropwise add altogether 6mL of silicon dioxide presoma cetyl trimethoxy silane and tetraethoxysilane mixture (volume ratio 1:1), stir 16h.Magnetic separates, deionized water and ethanol washing several, 60 ℃ of vacuumizes.To obtain powder 550 ℃ of calcinations to remove alkyl, obtain the silica nanometer magnetic microsphere of meso-hole structure.The specific surface that the silica nanometer magnetic microsphere of gained is tested with micrometrics ASAP2020 specific surface instrument when temperature 77K is 274.3m
2/ g, average pore size 3.3nm.
Embodiment 3
The Fe of hydrothermal synthesis method preparation
3O
4Nanosphere 0.5g is ultrasonic 10min in 250mL0.1M HCl, and magnetic separates, and uses deionized water washing 3 times, then, be dispersed in 400mL ethanol and the 100mL water mixed solvent, add concentrated ammonia liquor 6mL and regulate pH to 11, add again TEOS6mL, stir 6h under the room temperature, magnetic separates, and uses second alcohol and water cyclic washing, again be scattered in 170mL ethanol and the 30mL water, add ammoniacal liquor 8mL, dropwise add silicon dioxide presoma cetyl trimethoxy silane 6mL, stir 16h.Magnetic separates, deionized water and ethanol washing several, 60 ℃ of vacuumizes.To obtain powder 550 ℃ of calcinations to remove alkyl, obtain the silica nanometer magnetic microsphere of meso-hole structure.The specific surface that the silica nanometer magnetic microsphere of gained is tested at the micrometrics of temperature 77K ASAP2020 specific surface instrument is 168.3m
2/ g, average pore size 4.2nm.
The Fe of hydrothermal synthesis method preparation
3O
4Nanosphere 0.5g is ultrasonic 10min in 250mL0.1M HCl, magnetic separates, use deionized water washing 3 times, then, be dispersed in 400mL ethanol and the 100mL water mixed solvent, add concentrated ammonia liquor 4mL and regulate pH to 10, add again TEOS4mL, stir 6h under the room temperature, magnetic separates, and uses second alcohol and water cyclic washing, again be scattered in 200mL ethanol and the 50mL water, add ammoniacal liquor 6mL, dropwise add altogether 5mL of silicon dioxide presoma octadecyl trimethoxy silane and tetraethoxysilane mixture (volume ratio 4:1), stir 24h.Magnetic separates, deionized water and ethanol washing several, 60 ℃ of vacuumizes.To obtain powder 550 ℃ of calcinations to remove alkyl, obtain the silica nanometer magnetic microsphere of meso-hole structure.The silica nanometer magnetic microsphere of the gained specific surface that micrometrics ASAP2020 specific surface instrument is tested when temperature 77K is 146.3m
2/ g, average pore size 4.5nm.
Embodiment 5
The Fe of hydrothermal synthesis method preparation
3O
4Nanosphere 0.5g is ultrasonic 10min in 250mL0.1M HCl, magnetic separates, use deionized water washing 3 times, then, be dispersed in 400mL ethanol and the 100mL water mixed solvent, add concentrated ammonia liquor 4mL and regulate pH to 10, add again TEOS4mL, stir 6h under the room temperature, magnetic separates, and uses second alcohol and water cyclic washing, again be scattered in 200mL ethanol and the 50mL water, add ammoniacal liquor 6mL, dropwise add altogether 6mL of silicon dioxide presoma octadecyl trimethoxy silane and tetraethoxysilane mixture (volume ratio 2:1), stir 24h.Magnetic separates, deionized water and ethanol washing several, 60 ℃ of vacuumizes.To obtain powder 550 ℃ of calcinations to remove alkyl, obtain the silica nanometer magnetic microsphere of meso-hole structure.The silica nanometer magnetic microsphere of the gained specific surface that micrometrics ASAP2020 specific surface instrument is tested when temperature 77K is 173.5m2/g, average pore size 4.6nm.
The Fe of hydrothermal synthesis method preparation
3O
4Nanosphere 0.5g is ultrasonic 10min in 250mL0.1M HCl, and magnetic separates, and uses deionized water washing 3 times, then, be dispersed in 400mL ethanol and the 100mL water mixed solvent, add concentrated ammonia liquor 4mL and regulate pH to 10, add again TEOS4mL, stir 6h under the room temperature, magnetic separates, and uses second alcohol and water cyclic washing, again be scattered in 200mL ethanol and the 50mL water, add ammoniacal liquor 6mL, dropwise add silicon dioxide presoma octadecyl trimethoxy silane 5mL, stir 24h.Magnetic separates, deionized water and ethanol washing several, 60 ℃ of vacuumizes.To obtain powder 550 ℃ of calcinations to remove alkyl, obtain the silica nanometer magnetic microsphere of meso-hole structure.The silica nanometer magnetic microsphere of the gained specific surface that micrometrics ASAP2020 specific surface instrument is tested when temperature 77K is 131.8m
2/ g, average pore size 5.9nm.
Embodiment 7
The silica nanometer magnetic microsphere 2g with meso-hole structure with embodiment 2 synthesizes is scattered in 50mL sodium carbonate-sodium acid carbonate, and the pH value is about 10.5, and at 80 ℃ of heating return stirring 20h, magnetic separates, and uses deionized water washing several, 60 ℃ of vacuumizes.The silica nanometer magnetic microsphere of the gained specific surface that micrometrics ASAP2020 specific surface instrument is tested when temperature 77K is 63.2m2/g, average pore size 17.3nm.
Silica nanometer magnetic microsphere 5g with embodiment 3 synthesising mesoporous structures is scattered in 100mL acetic acid/ammonium acetate buffer solution, and the pH value is about 3.7, and at 100 ℃ of heating return stirring 24h, magnetic separates, and uses the deionized water washing for several times, 60 ℃ of vacuumizes.The silica nanometer magnetic microsphere of the gained specific surface that micrometrics ASAP2020 specific surface instrument is tested when temperature 77K is 43.4m2/g, average pore size 21.8nm.
Embodiment 9
Silica nanometer magnetic microsphere 5g with embodiment 3 synthesising mesoporous structures is scattered in 100mLTris cushioning liquid, and the pH value is about 8.0, and at 100 ℃ of heating return stirring 16h, magnetic separates, and uses the deionized water washing for several times, 60 ℃ of vacuumizes.The silica nanometer magnetic microsphere of the gained specific surface that micrometrics ASAP2020 specific surface instrument is tested when temperature 77K is 55.4m
2/ g, average pore size 23.6nm.
With the silica nanometer magnetic microsphere 5g of embodiment 4 synthesising mesoporous structures, be scattered in the Potassium Hydrogen Phthalate cushioning liquid of 100mLpH=4, at 100 ℃ of heating return stirring 24h, magnetic separates, and uses the deionized water washing for several times, 60 ℃ of vacuumizes.The silica nanometer magnetic microsphere of the gained specific surface that micrometrics ASAP2020 specific surface instrument is tested when temperature 77K is 61.4m
2/ g, average pore size 20.1nm.
Embodiment 11
With the silica nanometer magnetic microsphere 5g of embodiment 5 synthesising mesoporous structures, be scattered in the Potassium Hydrogen Phthalate cushioning liquid of 100mLpH=4, at 100 ℃ of heating return stirring 16h, magnetic separates, and uses the deionized water washing for several times, 60 ℃ of vacuumizes.The silica nanometer magnetic microsphere of the gained specific surface that micrometrics ASAP2020 specific surface instrument is tested when temperature 77K is 55.9m
2/ g, average pore size 22.3nm.
Performance test embodiment
The silica nanometer magnetic microsphere of embodiment 1 gained is carried out microscope or the TEM mirror is observed, as shown in Figure 2, nano-magnetic microsphere single dispersed structure spherical in shape, each nano-magnetic microsphere kernel is fine and close, middle one deck compact silicon dioxide layer that coats, skin is the meso-porous titanium dioxide silicon layer.The size of nano-magnetic microsphere is between 50～100 nanometers, and the compact silicon dioxide layer is about 5～10nm, and the meso-porous titanium dioxide silicon layer is about 3～8nm.
With embodiment 1～3 gained the silica nanometer magnetic microsphere carry out N according to conventional method
2Adsorption test and test pore-size distribution, and with the Fe of hydrothermal synthesis method preparation
3O
4Nanosphere is magnetic nano-particle and coats fine and close SiO
2Magnetic nano-particle compares, respectively shown in Fig. 3 and 4.As shown in the figure, Fe
3O
4Nanosphere is that the specific area of magnetic nano-particle and the magnetic nano-particle that only coats the compact silicon dioxide layer is very little, all less than 20m
2Specific surface increases obviously after the/g, coating mesoporous silicon dioxide layer, all reaches 100m
2More than/the g, wherein specific area reaches 274m when the volume ratio of tetraethoxysilane/cetyl trimethoxy silane is 1:1
2/ g.Fig. 4 illustrates that not reaming is about 4.2nm in the aperture of the nano-magnetic microsphere of coating mesoporous silicon dioxide layer before.
Claims (10)
1. silica nanometer magnetic microsphere, it is characterized in that: the particle diameter of described nano-magnetic microsphere is 50～600nm, its kernel is the magnetic nano-particle of the single dispersed structure of particle diameter between 10～500nm, the middle level is that thickness is at the compact silicon dioxide of 1～10nm, skin is mesoporous silicon oxide, wherein, the specific area of described nano-magnetic microsphere is 10～500m
2/ g, the average pore size of mesoporous silicon oxide is 2～50nm.
2. silica nanometer magnetic microsphere as claimed in claim 1, it is characterized in that: the specific area of described nano-magnetic microsphere is 30～90m
2/ g, preferred 40～70m
2/ g, the average pore size of mesoporous silicon oxide is 10～50nm, preferred 15～25nm; Perhaps, the specific area of described nano-magnetic microsphere is 120～280m
2/ g, preferred 130～180m
2/ g, the average pore size of mesoporous silicon oxide is 2～8nm, preferred 4.2～6nm.
3. silica nanometer magnetic microsphere as claimed in claim 1, it is characterized in that: the particle diameter of described nano-magnetic microsphere is 50～100nm, preferred 50～90nm, its kernel is the magnetic nano-particle of the single dispersed structure of particle diameter between 30～80nm, the middle level be thickness at the compact silicon dioxide of 5～10nm, skin is that thickness is at the mesoporous silicon oxide of the preferred 3～8nm of 3～20nm.
4. method for preparing silica nanometer magnetic microsphere claimed in claim 1, it comprises the steps:
Step 1) be that the magnetic nano-particle of 10～500nm is scattered in the solvent with particle diameter, making it concentration is 0.1～10mg/mL, adds compact silicon dioxide presoma and stirring reaction, makes the outer surface of magnetic nano-particle coat one deck compact silicon dioxide;
Step 2) adding the meso-porous titanium dioxide silicon precursor in step 1) outer surface that obtains is coated with in the magnetic nano-particle of compact silicon dioxide, and stirring reaction; Separate and mesoporousization, obtain having the silica nanometer magnetic microsphere of meso-hole structure.
5. method as claimed in claim 4, it is characterized in that in step 1) in, magnetic nano-particle is scattered in ultrasonic dispersion 0.5～3h behind the solvent, stir, regulate pH to 2～5 or 9～14, add compact silicon dioxide presoma and stirring reaction 3～12h, described compact silicon dioxide presoma is tetraethoxysilane, magnetic nano-particle: the mass ratio of tetraethoxysilane is 0.05～1, is preferably 0.08～0.5.
6. method as claimed in claim 4, it is characterized in that: in step 2) in, regulating step 1) outer surface that obtains is coated with the pH to 2 of the magnetic nano-particle of compact silicon dioxide～5 or 9～14, dropwise add again meso-porous titanium dioxide silicon precursor and stirring reaction 3～24h, many carbon organic chain silane that described meso-porous titanium dioxide silicon precursor comprises 1 parts by volume is dodecyltrimethoxysilane for example, the cetyl trimethoxy silane, octadecyl trichlorosilane alkane, the tetraethoxysilane of tri-phenyl-silane etc. and 0～4 parts by volume, described meso-porous titanium dioxide silicon precursor: the mass ratio of magnetic nano-particle is 2～12:1; Described mesoporousization refers to that calcination is to remove alkyl in air.
7. method as claimed in claim 6, it is characterized in that: in step 2) in, with step 1) outer surface that the obtains magnetic nano-particle that is coated with compact silicon dioxide separates first and washs, be scattered in again in the solvent, making it concentration is 0.1～10mg/mL, stir, then regulating step 1) outer surface that obtains is coated with the pH to 2 of the magnetic nano-particle of compact silicon dioxide～5 or 9～14; Step 1) and step 2) in solvent be that volume ratio is 0.05～0.5 water and pure mixed solvent.
8. method as claimed in claim 7, it is characterized in that: described alcohol is methyl alcohol, ethanol, ethylene glycol and/or glycerol, the described magnetism separate method that is separated into.
9. method as claimed in claim 4 is characterized in that also further comprising step 3) regulation and control step 2) aperture of the silica nanometer magnetic microsphere intermediary hole silicon dioxide with meso-hole structure of gained.
10. method as claimed in claim 9, it is characterized in that step 3) described regulation and control refer to step 2) the silica nanometer magnetic microsphere with meso-hole structure of gained is to carry out back flow reaction 3～24h in 2～12 cushioning liquid such as sodium tetraborate, Potassium Hydrogen Phthalate, Tris, barbitol buffer solution, ammonium phosphate buffer solution etc. in the pH value, to regulate and control the aperture of outer mesoporous silicon oxide.
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