CN103143305A - Method for synthesizing magnetic mesoporous silica nanoparticle microsphere with core-shell structure in acidic conditions - Google Patents
Method for synthesizing magnetic mesoporous silica nanoparticle microsphere with core-shell structure in acidic conditions Download PDFInfo
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Abstract
The invention provides a method for synthesizing a magnetic mesoporous silica nanoparticle microsphere with a core-shell structure in acidic conditions and relates to a preparation method of microsphere with the core-shell structure. The invention aims at solving the problem that the magnetic mesoporous silica with the core-shell structure prepared by the existing alkaline condition path method is small in aperture and low in surface area. According to the method, the acidic conditions are adopted, the magnetic Fe3O4 synthesized by a solvent evaporation self-assembly method is the core, a compact SiO2 layer is an interlayer, and a mesoporous SBA-15 type SiO2 layer is the magnetic mesoporous silica material with the core-shell structure of the external layer. The magnetic mesoporous silica nanoparticle microsphere with the core-shell structure provided by the invention has a large aperture of 5.61nm, a high specific surface area of 839m<2>/g, a large pore volume of 0.9cm<3>/g and a magnetic saturation of 8.52emu/g, and can be applied to the fields such as water treatment, catalyst carrier, drug delivery and controlled release.
Description
Technical field
The present invention relates to a kind of preparation method of core-shell structure magnetic mesoporous silicon dioxide nano microballoon.
Background technology
The core-shell structure magnetic mesoporous silicon oxide is a kind of with magnetic Fe
3O
4Be kernel, the compact silicon dioxide layer is the intermediate layer, and high-specific surface area, large pore volume, homogeneous aperture meso-porous titanium dioxide silicon layer is the nano material of shell, has a wide range of applications in fields such as absorption, catalysis, biology, medicine controlled releasings.Its core Fe
3O
4Have superparamagnetism, can add slewing separation under magnetic fields; Outer shell meso-porous titanium dioxide silicon layer has high-specific surface area, large pore volume, homogeneous aperture, thereby satisfies practical application request.The synthetic alkali condition that all adopts of core-shell structure magnetic Metaporous silicon dioxide material prepares the mesoporous layer of MCM-41 type at present, and its aperture is less, surface area hangs down and limited its further application in fields such as macromolecules adsorption, medicament slow releases.
Summary of the invention
The objective of the invention is to prepare in order to solve existing alkali condition Path Method the problem that core-shell structure magnetic mesoporous silicon oxide aperture is little and surface area is lower, and the method for the magnetic mesoporous silicon dioxide nanosphere of a kind of acid condition synthetic kernel shell structure is provided.
The method of the magnetic mesoporous silicon dioxide nanosphere of a kind of acid condition synthetic kernel shell structure of the present invention, carry out according to following steps:
A, magnetic Fe
3O
4The preparation of nano particle: one, take the source of iron of 1~2 weight portion, join under the condition of magnetic agitation in 40~60 weight portion reducing agents and mix, get mixed solution; Two, the precipitating reagent of 2~3 weight portions and 0.8~1.0 weight portion polyethylene glycol are joined under stirring condition in the mixed solution that step 1 obtains, after mixing, get mixed liquid; Three, the mixed liquid of step 2 being transferred in reactor, be heated to 200 ℃ of crystallization 8h, be cooled to room temperature, clearly respectively wash 6 times with deionized water and absolute ethyl alcohol successively, is dry 12h in 60 ℃ of baking ovens in temperature, namely gets Fe
3O
4Nano particle;
B, Fe
3O
4@nSiO
2Preparation: the Fe that four, gets 0.1 weight portion that steps A makes
3O
4Nano particle is scattered in mixed liquor, ultrasonic processing 15min; Five, with the Fe after the ultrasonic processing of step 4
3O
4Separate under the effect of nano particle outside magnetic field, collect solid formation, respectively wash 3 times with deionized water and absolute ethyl alcohol successively, then add 80~100 weight portion absolute ethyl alcohols, 20 parts by weight of deionized water and 1 weight portion concentrated ammonia liquor, stir 60min under room temperature, get even mixed liquor; Six, in the even mixed liquor that obtains to step 5, dripping 0.6 weight portion silicon source with the speed of 0.1 drops/sec, is then under the condition of 800~1000rpm at rotating speed, mechanical agitation 12h; Separating under the outside magnetic field effect, collect solid formation, respectively clean 6 times with deionized water and absolute ethyl alcohol successively, is dry 12h in 60 ℃ of baking ovens in temperature, gets Fe
3O
4@nSiO
2Wherein, the described mixed liquor of step 4 is that the 0.2M hydrochloric acid solution makes by the concentration of 30~40 weight portion absolute ethyl alcohols and 5~8 weight portions;
C, Fe
3O
4@nSiO
2@mSiO
2Preparation: seven, with step B gained Fe
3O
4@nSiO
2Be scattered in mixed liquor ultrasonic processing 15min; Eight, the solution after the ultrasonic processing of step 7 is stirred and evenly mixed, after adding 0.02 weight account polyethylene pyrrolidones, stir 2h, get mixed liquor; Nine, the absolute ethyl alcohol and stirring that the surfactant of 1 weight portion is dissolved in 10~15 weight portions adds in the mixed liquor of step 8 to clarification, at room temperature stirs 2h, gets solution; Ten, add 0.8 weight portion silicon source in the solution of step 9, after stirring 2d under room temperature, oven dry; 11, step 10 being dried the product grinding and change in reactor, add the deionized water of 15~20 weight portions, be placed in 100 ℃ of baking oven crystallization 24h, after Magnetic Isolation goes out solid formation, is dry 12h in 60 ℃ of baking ovens in temperature; 12, the dry thing of step 11 gained is changed in tube furnace, at N
2Under atmosphere, temperature is to calcine 5~6h under 550 ℃ of conditions, after then being cooled to the room temperature grinding, namely gets Fe
3O
4@nSiO
2@mSiO
2Wherein, the mixed liquor described in step 7 is that the hydrochloric acid solution that absolute ethyl alcohol and 5 weight portion concentration by 20~30 weight portions are 0.2M is made.
The present invention comprises following beneficial effect:
The present invention adopts acid condition (pH is in 1~2 scope), and the solvent evaporates self-assembling method can access the core-shell structure magnetic mesoporous silicon dioxide nano microballoon of high-specific surface area, large aperture, large pore volume.The synthetic material in the more alkaline path of resulting materials has larger aperture (5.61nm), high specific area (839m
2/ g) and large pore volume (0.9cm
3/ g), magnetic saturation is 8.52emu/g.
The present invention adopts acid condition, solvent evaporates self-assembling method synthesizing magnetic Fe
3O
4Be kernel, with fine and close SiO
2Layer is the intermediate layer, with mesoporous SiO
2Layer is outer field core-shell structure magnetic Metaporous silicon dioxide material.
Solvent evaporates self assembly of the present invention is the method for block macromolecular self assembly in solution of inducing by solvent evaporates.
Description of drawings
Fig. 1 is the little angle XRD diffraction pattern of test 1 core-shell structure magnetic mesoporous silicon oxide;
Fig. 2 is the wide-angle XRD diffraction pattern of test 1 core-shell structure magnetic mesoporous silicon oxide;
Fig. 3 is the N of test 1 core-shell structure magnetic mesoporous silicon oxide
2The adsorption-desorption isollaothermic chart; Wherein, ◆ expression desorption curve, ■ represents adsorption curve;
Fig. 4 is the graph of pore diameter distribution of test 1 core-shell structure magnetic mesoporous silicon oxide;
Fig. 5 is the IR figure of test 1 core-shell structure magnetic mesoporous silicon oxide;
Fig. 6 is the SEM figure of test 1 core-shell structure magnetic mesoporous silicon oxide;
Fig. 7 is the TEM figure of test 1 core-shell structure magnetic mesoporous silicon oxide;
Fig. 8 is the shell HRTEM figure of test 1 core-shell structure magnetic mesoporous silicon oxide;
Fig. 9 is the M-H curve of test 1 core-shell structure magnetic mesoporous silicon oxide.
The specific embodiment
Technical solution of the present invention is not limited to the following cited specific embodiment, also comprises any combination between each specific embodiment.
The specific embodiment one: under a kind of acid condition of present embodiment, the method for the magnetic mesoporous silicon dioxide nanosphere of synthetic kernel shell structure is carried out according to following steps:
A, magnetic Fe
3O
4The preparation of nano particle: one, take the source of iron of 1~2 weight portion, join under the condition of magnetic agitation in 40~60 weight portion reducing agents and mix, get mixed solution; Two, the precipitating reagent of 2~3 weight portions and 0.8~1.0 weight portion polyethylene glycol are joined under stirring condition in the mixed solution that step 1 obtains, after mixing, get mixed liquid; Three, the mixed liquid of step 2 being transferred in reactor, be heated to 200 ℃ of crystallization 8h, be cooled to room temperature, clearly respectively wash 6 times with deionized water and absolute ethyl alcohol successively, is dry 12h in 60 ℃ of baking ovens in temperature, namely gets Fe
3O
4Nano particle;
B, Fe
3O
4@nSiO
2Preparation: the Fe that four, gets 0.1 weight portion that steps A makes
3O
4Nano particle is scattered in mixed liquor, ultrasonic processing 15min; Five, with the Fe after the ultrasonic processing of step 4
3O
4Separate under the effect of nano particle outside magnetic field, collect solid formation, respectively wash 3 times with deionized water and absolute ethyl alcohol successively, then add 80~100 weight portion absolute ethyl alcohols, 20 parts by weight of deionized water and 1 weight portion concentrated ammonia liquor, stir 60min under room temperature, get even mixed liquor; Six, in the even mixed liquor that obtains to step 5, dripping 0.6 weight portion silicon source with the speed of 0.1 drops/sec, is then under the condition of 800~1000rpm at rotating speed, mechanical agitation 12h; Separating under the outside magnetic field effect, collect solid formation, respectively clean 6 times with deionized water and absolute ethyl alcohol successively, is dry 12h in 60 ℃ of baking ovens in temperature, gets Fe
3O
4@nSiO
2Wherein, the described mixed liquor of step 4 is that the 0.2M hydrochloric acid solution makes by the concentration of 30~40 weight portion absolute ethyl alcohols and 5~8 weight portions;
C, Fe
3O
4@nSiO
2@mSiO
2Preparation: seven, with step B gained Fe
3O
4@nSiO
2Be scattered in mixed liquor ultrasonic processing 15min; Eight, the solution after the ultrasonic processing of step 7 is stirred and evenly mixed, after adding 0.02 weight account polyethylene pyrrolidones, stir 2h, get mixed liquor; Nine, the absolute ethyl alcohol and stirring that the surfactant of 1 weight portion is dissolved in 10~15 weight portions adds in the mixed liquor of step 8 to clarification, at room temperature stirs 2h, gets solution; Ten, add 0.8 weight portion silicon source in the solution of step 9, after stirring 2d under room temperature, oven dry; 11, step 10 being dried the product grinding and change in reactor, add the deionized water of 15~20 weight portions, be placed in 100 ℃ of baking oven crystallization 24h, after Magnetic Isolation goes out solid formation, is dry 12h in 60 ℃ of baking ovens in temperature; 12, the dry thing of step 11 gained is changed in tube furnace, at N
2Under atmosphere, temperature is to calcine 5~6h under 550 ℃ of conditions, after then being cooled to the room temperature grinding, namely gets Fe
3O
4@nSiO
2@mSiO
2Wherein, the mixed liquor described in step 7 is that the hydrochloric acid solution that absolute ethyl alcohol and 5 weight portion concentration by 20~30 weight portions are 0.2M is made.
Present embodiment comprises following beneficial effect:
Present embodiment adopts acid condition, and the solvent evaporates self-assembling method can access the core-shell structure magnetic mesoporous silicon dioxide nano microballoon of high-specific surface area, large aperture, large pore volume.The synthetic material in the more alkaline path of resulting materials has larger aperture (5.61nm), high specific area (839m
2/ g) and large pore volume (0.9cm
3/ g), magnetic saturation is 8.52emu/g.
Present embodiment adopts acid condition, solvent evaporates self-assembling method synthesizing magnetic Fe
3O
4Be kernel, with fine and close SiO
2Layer is the intermediate layer, with mesoporous SiO
2Layer is outer field core-shell structure magnetic Metaporous silicon dioxide material.
The solvent evaporates self assembly of present embodiment is the method for block macromolecular self assembly in solution of inducing by solvent evaporates.
The specific embodiment two: what present embodiment was different from the specific embodiment one is: the source of iron described in steps A is FeCl
36H
2O or Fe (NO
3)
39H
2O。Other is identical with the specific embodiment one.
The specific embodiment three: what present embodiment was different from the specific embodiment one or two is: the reducing agent described in steps A is ethylene glycol or ammoniacal liquor.Other is identical with the specific embodiment one or two.
The specific embodiment four: what present embodiment was different from one of specific embodiment one to three is: the precipitating reagent described in steps A is sodium acetate or NaOH.Other is identical with one of specific embodiment one to three.
The specific embodiment five: what present embodiment was different from one of specific embodiment one to four is: the silicon source described in step B and step C is tetraethyl orthosilicate.Other is identical with one of specific embodiment one to four.
The specific embodiment six: what present embodiment was different from one of specific embodiment one to five is: the surfactant described in step C is that polyoxyethylene-poly-oxypropylene polyoxyethylene triblock copolymer P123 (molecular formula is EO20PO7PEO20) or F127(molecular formula are EO106PO70EO106).Other is identical with one of specific embodiment one to five.
By following verification experimental verification beneficial effect of the present invention:
Under acid condition in this test, the method for the magnetic mesoporous silicon dioxide nanosphere of synthetic kernel shell structure is carried out according to following steps:
(1) magnetic Fe
3O
4The preparation of nano particle
One, with the FeCl of 1.08g
36H
2O is dissolved under the condition of magnetic agitation in the ethylene glycol of 40mL, then adds sodium acetate and the 0.8g polyethylene glycol of 2.88g, at room temperature mixes 4h, changes in reactor, is heated to 200 ℃ of crystallization 8h; Two, after the step 1 reaction finishes, being cooled to room temperature, getting black particle, respectively clean 6 times with deionized water and absolute ethyl alcohol successively, is dry 12h in 60 ℃ of baking ovens in temperature, namely gets magnetic Fe
3O
4Nano particle;
(2) Fe
3O
4@nSiO
2Preparation
Three, get the prepared magnetic Fe of step 2
3O
4Nano particle 0.1g is scattered in mixed liquor, is under the condition of 40KHz in supersonic frequency, ultrasonic dispersion 15min; Four, with the product after the ultrasonic dispersion of step 3, after adopting the effect of permanent magnet outside magnetic field to separate, respectively wash 3 times with deionized water and absolute ethyl alcohol successively, change 250mL three neck round-bottomed flasks over to, then add the 80mL absolute ethyl alcohol, 20mL distilled water and 1mL concentrated ammonia liquor stir 60min under room temperature, get even mixed liquor; Five, drip 0.6mL tetraethyl orthosilicate (TEOS) in the even mixed liquor that obtains in the step 4 with the speed of 0.1 drops/sec, then with the speed of 1000rpm, mechanical agitation 12h, separate under external magnetic field, gained black product, respectively cleaning 6 times with deionized water and absolute ethyl alcohol successively, is dry 12h in 60 ℃ of baking ovens in temperature, gets Fe
3O
4@nSiO
2Wherein, the described mixed liquor of step 3 is to be that the 0.2M hydrochloric acid solution makes by the absolute ethyl alcohol of 20mL and the concentration of 5mL;
(3) Fe
3O
4@nSiO
2@mSiO
2Preparation
Six, with gained Fe
3O
4@nSiO
2Be scattered in mixed liquor, after ultrasonic dispersion 15min, mechanical agitation makes and is uniformly dispersed; Continue to stir 2h after adding 0.01g polyvinylpyrrolidone (PVP), get mixed liquor; Seven, the P123 with 1g is dissolved in the 10mL absolute ethyl alcohol, joins after stirring to clarify in the mixed liquor that step 6 obtains, after at room temperature stirring 2h, drip the TEOS of 0.8mL with the speed of 0.1 drops/sec, at room temperature stir solvent flashing after dropwising, after stirring 2d, get the grume solid formation; Eight, the grume solid formation that step 7 is obtained is in the baking oven of 60 ℃ after oven dry 12h in temperature, changes over to after grinding in the 30mL reactor, adds 15mL distilled water, is placed in 100 ℃ of baking oven crystallization 24h; Nine, with the product after the step 8 crystallization, after adopting Magnetic Isolation, be dry 12h in 60 ℃ of baking ovens in temperature, will obtain gray product and change in tube furnace, at N
2Under atmosphere, temperature is that under 550 ℃ of conditions, calcining 6h removes template, be chilled to and namely get Fe after room temperature grinds
3O
4@nSiO
2@mSiO
2Wherein, the described mixed liquor of step 6 is made by 20mL absolute ethyl alcohol and 5mL concentration 0.2M hydrochloric acid solution;
The core-shell structure magnetic mesoporous silicon dioxide nano microballoon that this test is made carries out following detection:
1, the little angle of XRD and wide-angle detect
The core-shell structure magnetic mesoporous silicon dioxide nano microballoon that this test is obtained carries out the detection of XRD diffraction, and result as depicted in figs. 1 and 2.As can be seen from Figure 1, the little angle XRD figure of core-shell structure magnetic mesoporous silicon dioxide nano microballoon has clearly illustrated three diffraction maximums, corresponding to (100), (110), (200) crystal face diffraction, shows that this sample has the P6mm structure.
As shown in Figure 2, in the wider diffraction maximum of 2 θ=22.81 ° appearance, this shows the existence of amorphous silica.In addition, in 2 θ=30.1 °, 35.61 °, 43.04 °, 53.7 °, 57.29 °, 63.19 ° of diffraction maximums of locating correspond respectively to Fe
3O
4(220), (311), (400), (422), (511), (440) crystal face diffraction, this has very well shown Fe
3O
4@nSiO
2@mSiO
2In have the magnetic Fe of face-centered cubic spinel structure
3O
4Existence.
2, nitrogen adsorption--desorption isotherm test
The core-shell structure magnetic mesoporous silicon dioxide nano microballoon that this test is obtained carries out N
2Absorption--desorption detects, and result as shown in Figure 3.Can find out Fe in figure
3O
4@nSiO
2@mSiO
2Nitrogen adsorption desorption curve at P/P
0=0.4-0.8 place is hysteresis loop, belongs to H1 type hysteresis loop, and typical IV adsorption isotherm has shown the existence of the meso-hole structure in homogeneous duct.Its BET specific area is 838.5m
2g
-1Found out by Fig. 4 graph of pore diameter distribution, its aperture is concentrated and is distributed in 5.61nm, and pore volume is 0.9cm
3g
-1Higher specific area, large aperture and large pore volume make Fe
3O
4@nSiO
2@mSiO
2Material has potential application in fields such as absorption, catalysis, medicine controlled releasings.
3, IR detects
The resulting core-shell structure magnetic mesoporous silicon dioxide nano of this test microballoon is carried out IR to be detected as shown in Figure 5.Wherein at 3300cm
-1The stretching vibration peak of the broad peak correspondence-OH at place; 570cm
-1The place shows Fe for the Fe-O stretching vibration peak
3O
4Existence; 1220,1090,801 and 457cm
-1The spectrum peak at place is corresponding to the Si-O symmetrical stretching vibration; At 958cm
-1The asymmetric stretching vibration of the corresponding Si-O in spectrum peak, place.
4, SEM and TEM detect
Can be found out the Fe that makes by scanning electron microscope sem Fig. 6
3O
4@nSiO
2@mSiO
2Material is spherical in shape, and pattern is even, and particle diameter is about 390nm.And can find out from Fig. 7 transmission electron microscope TEM figure, the gained particle presents obvious nucleocapsid structure.Black part is divided into magnetic Fe
3O
4, particle diameter is about 250nm.Outsourcing SiO
2Layer, shell thickness is about 70nm.Fig. 8 is the high power transmission electron microscope picture HRTEM in shell zone, can find out the existence of ordered mesoporous pore canals preferably.
5, M-H detects
The core-shell structure magnetic mesoporous silicon dioxide nano microballoon that this test is obtained carries out the magnetic saturation detection, and result as shown in Figure 9.
The magnetic saturation of magnetic mesoporous silicon dioxide nanosphere is 8.52emu/g, occurs without any hysteresis loop in curve, and this has shown prepared Fe
3O
4@nSiO
2@mSiO
2Sample has superparamagnetism.Nano composite material with superparamagnetism feature and high saturation rate can produce response to external magnetic field rapidly, and disappear with external magnetic field, can again be scattered in solution again, and this separates, recycles very favourable for adsorbent.
In sum, in conjunction with the experimental result shown in Fig. 1 to 9, the core-shell structure magnetic mesoporous silicon dioxide nano microballoon of high-specific surface area, large mesoporous size has successfully been prepared in this test under acid condition as can be known, is expected to be widely used in fields such as absorption, catalysis, medicine controlled releasings.
Claims (6)
1. the method for the magnetic mesoporous silicon dioxide nanosphere of acid condition synthetic kernel shell structure is characterized in that the method for the magnetic mesoporous silicon dioxide nanosphere of acid condition synthetic kernel shell structure is carried out according to following steps:
A, magnetic Fe
3O
4The preparation of nano particle: one, take the source of iron of 1~2 weight portion, join under the condition of magnetic agitation in 40~60 weight portion reducing agents and mix, get mixed solution; Two, the precipitating reagent of 2~3 weight portions and 0.8~1.0 weight portion polyethylene glycol are joined under stirring condition in the mixed solution that step 1 obtains, after mixing, get mixed liquid; Three, the mixed liquid of step 2 being transferred in reactor, be heated to 200 ℃ of crystallization 8h, be cooled to room temperature, clearly respectively wash 6 times with deionized water and absolute ethyl alcohol successively, is dry 12h in 60 ℃ of baking ovens in temperature, namely gets Fe
3O
4Nano particle;
B, Fe
3O
4@nSiO
2Preparation: the Fe that four, gets 0.1 weight portion that steps A makes
3O
4Nano particle is scattered in mixed liquor, ultrasonic processing 15min; Five, with the Fe after the ultrasonic processing of step 4
3O
4Separate under the effect of nano particle outside magnetic field, collect solid formation, respectively wash 3 times with deionized water and absolute ethyl alcohol successively, then add 80~100 weight portion absolute ethyl alcohols, 20 parts by weight of deionized water and 1 weight portion concentrated ammonia liquor, stir 60min under room temperature, get even mixed liquor; Six, in the even mixed liquor that obtains to step 5, dripping 0.6 weight portion silicon source with the speed of 0.1 drops/sec, is then under the condition of 800~1000rpm at rotating speed, mechanical agitation 12h; Separating under the outside magnetic field effect, collect solid formation, respectively clean 6 times with deionized water and absolute ethyl alcohol successively, is dry 12h in 60 ℃ of baking ovens in temperature, gets Fe
3O
4@nSiO
2Wherein, the mixed liquor described in step 4 is that the 0.2M hydrochloric acid solution makes by the concentration of 30~40 weight portion absolute ethyl alcohols and 5~8 weight portions;
C, Fe
3O
4@nSiO
2@mSiO
2Preparation: seven, with step B gained Fe
3O
4@nSiO
2Be scattered in mixed liquor ultrasonic processing 15min; Eight, the solution after the ultrasonic processing of step 7 is stirred and evenly mixed, after adding 0.02 weight account polyethylene pyrrolidones, stir 2h, get mixed liquor; Nine, the absolute ethyl alcohol and stirring that the surfactant of 1 weight portion is dissolved in 10~15 weight portions adds in the mixed liquor of step 8 to clarification, at room temperature stirs 2h, gets solution; Ten, add 0.8 weight portion silicon source in the solution of step 9, after stirring 2d under room temperature, oven dry; 11, step 10 being dried the product grinding and change in reactor, add the deionized water of 15~20 weight portions, be placed in 100 ℃ of baking oven crystallization 24h, after Magnetic Isolation goes out solid formation, is dry 12h in 60 ℃ of baking ovens in temperature; 12, the dry thing of step 11 gained is changed in tube furnace, at N
2Under atmosphere, temperature is to calcine 5~6h under 550 ℃ of conditions, after then being cooled to the room temperature grinding, namely gets Fe
3O
4@nSiO
2@mSiO
2Wherein, the mixed liquor described in step 7 is that the hydrochloric acid solution that absolute ethyl alcohol and 5 weight portion concentration by 20~30 weight portions are 0.2M is made.
2. the method for the magnetic mesoporous silicon dioxide nanosphere of a kind of acid condition synthetic kernel shell structure according to claim 1, is characterized in that the source of iron described in steps A is FeCl
36H
2O or Fe (NO
3)
39H
2O。
3. the method for the magnetic mesoporous silicon dioxide nanosphere of a kind of acid condition synthetic kernel shell structure according to claim 1, is characterized in that the reducing agent described in steps A is ethylene glycol or ammoniacal liquor.
4. the method for the magnetic mesoporous silicon dioxide nanosphere of a kind of acid condition synthetic kernel shell structure according to claim 1, is characterized in that the precipitating reagent described in steps A is sodium acetate or NaOH.
5. the method for the magnetic mesoporous silicon dioxide nanosphere of a kind of acid condition synthetic kernel shell structure according to claim 1 is characterized in that the silicon source described in step B and step C is tetraethyl orthosilicate.
6. the method for the magnetic mesoporous silicon dioxide nanosphere of a kind of acid condition synthetic kernel shell structure according to claim 1, is characterized in that the surfactant described in step C is polyoxyethylene-poly-oxypropylene polyoxyethylene triblock copolymer P123 or F127.
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