CN101475184A - Preparation of inorganic magnetic material for filling hollow mesoporous silicon dioxide sphere - Google Patents
Preparation of inorganic magnetic material for filling hollow mesoporous silicon dioxide sphere Download PDFInfo
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- CN101475184A CN101475184A CNA2009100763859A CN200910076385A CN101475184A CN 101475184 A CN101475184 A CN 101475184A CN A2009100763859 A CNA2009100763859 A CN A2009100763859A CN 200910076385 A CN200910076385 A CN 200910076385A CN 101475184 A CN101475184 A CN 101475184A
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Abstract
The invention relates to a method for preparing an inorganic magnetic material for filling a hollow mesoporous silicon dioxide ball, which comprises the following steps: (1) preparation of two reaction solutions: A solution, 0.05 to 2g of hexadecyl trimethyl ammonium bromide is dissolved into 12 to 70 ml of ethanol, is stirred for 10 minutes for fully dissolving, and is added with 0.5 to 9 ml of ethyl orthosilicate to be stirred fully, wherein a surfactant is hexadecyl trimethyl ammonium bromide; and B solution is 0.01 to 0.4 M of ammonia solution; (2) preparation of ferric salt solution, the mol ratio of ferrous ions to ferric ions of the ferric salt solution is 1:2, and the ferric salt solution is added into the B solution to be prepared into sol; and the volume ratio of the ferric salt solution to the B solution is 1:2,000-1:200; (3) the A solution is added into the sol generated in the step (2), the stirring speed is reduced, the mixed solution is immediately filtered after pale yellow precipitate is generated, and the volume ratio of the A solution to the sol is 1:4-1:10; and (4) the precipitate is dried at room temperature, and is kept for 1 hour at the temperature of 600 DEG C under the protection of nitrogen.
Description
Technical field:
The present invention relates to a kind of preparation method who fills the inorganic magnetic material of hollow mesoporous silicon dioxide spheres, be specially a kind of compound preparation method of magnetic inorganic nano particle/hollow mesoporous silicon dioxide spheres.Belong to advanced nano composite material technical field.
Background technology:
Magnetic nano-particle is as a kind of important nano material, with its special magnetic property, have broad application prospects in various fields, these are used great majority and require magnetic particle to have the size of particles of chemical stability, homogeneous and good dispersiveness in liquid phase.Because magnetic nano-particle has the high-ratio surface energy, thereby and the anisotropic dipole moment effect of particle be easy to reunite.Some magnetic particle such as Fe, Fe
3O
4Be easy to be oxidized to γ-Fe
2O
3Thereby, cause particle to take place to assemble and precipitation, can not form stable dispersion system, make its application be subjected to very big restriction.Thereby usually to be coated with the surface energy of reduction particle and pass through empty resistance or electrostatic repulsion raising dispersion of particles magnetic particle.Common following several materials can be used as the shell of core-shell magnetic material: organic molecule, organic polymer, SiO
2With other inorganic materials.And mesoporous silicon oxide has higher specific surface area for traditional earth silicon material, is therefore separating absorption, catalysis, and there is wide application prospect in fields such as medicament slow release.Therefore the matrix material of magnetic inorganic nano particle/hollow mesoporous silicon dioxide spheres can possess the advantage of magneticsubstance and mesoporous material simultaneously, possess more wide application prospect aspect separation absorption and the medicine fixed point slowly-releasing.
But up to the present, the synthesis technique of having reported all is that first synthesizing magnetic particle coats mesoporous material again outside particle or the earlier synthetic mesoporous ball of hollow is filled magneticsubstance more therein, and this just makes that technology is loaded down with trivial details, and is consuming time.And the compound of magnetic inorganic nano particle/hollow mesoporous silicon dioxide spheres of having reported all is that magneticsubstance is filled in the cavity of hollow mesoporous silicon dioxide spheres.If this just makes that this material is applied to medicament slow release, then each particulate drug loading amount will significantly reduce.
Summary of the invention:
The object of the present invention is to provide a kind of preparation method who fills the inorganic magnetic material of hollow mesoporous silicon dioxide spheres, to overcome defective of the prior art.
A kind of preparation method who fills the inorganic magnetic material of hollow mesoporous silicon dioxide spheres of the present invention, its technical scheme is: with magnetic nanoparticle as seed grain, by controlling concentration and the granular size of this magnetic-particle in alkaline aqueous solution, make hollow mesoporous silicon dioxide spheres in this alkaline aqueous solution forming process, be coated on one or several magnetic-particles in the mesoporous ball wall but not enter the cavity of hollow mesoporous silicon dioxide spheres.
A kind of preparation method who fills the inorganic magnetic material of hollow mesoporous silicon dioxide spheres of the present invention, concrete preparation process is as follows:
(1). prepare two kinds of reaction solutions:
A liquid is the mixed solution of silicon source, pure and mild tensio-active agent; The cetyl trimethylammonium bromide (CTAB) that is about to 0.05～2g is dissolved in the ethanol of 12～70ml, stirs fully dissolving in ten minutes; The tetraethoxy (TEOS) that then adds 0.5～9ml fully stirs;
Wherein, described tensio-active agent is meant the cetyl trimethyl ammonia bromide;
B liquid is ammonia soln: i.e. the ammonia soln of 0.01～0.4M;
(2). the preparation iron salt solutions, make that the ferrous ion of this iron salt solutions and ferric ion mol ratio are 1:2, iron salt solutions is added in the B solution, be mixed with colloidal sol; Wherein, the volume ratio of iron salt solutions and B solution is 1:2000～1:200;
(3), A liquid is added in the colloidal sol that step (2) generates, reduce stirring velocity, occur filtering immediately after the light-yellow precipitate; Wherein, the volume ratio of A liquid and colloidal sol is 1:4～1:10;
(4), with throw out at room temperature after the drying, 600 ℃ of insulations are one hour under nitrogen protection.
A kind of preparation method who fills the inorganic magnetic material of hollow mesoporous silicon dioxide spheres of the present invention, concrete preparation process is as follows:
(1). prepare two kinds of reaction solutions:
A liquid is the mixed solution of silicon source, pure and mild tensio-active agent; The cetyl trimethylammonium bromide (CTAB) that is about to 0.05～2g is dissolved in the ethanol of 12～70ml, stirs fully dissolving in ten minutes; The tetraethoxy (TEOS) that then adds 0.5～9ml fully stirs;
Wherein, described tensio-active agent is meant the cetyl trimethyl ammonia bromide;
B liquid is ammonia soln: i.e. the ammonia soln of 0.01～0.4M;
(2), the preparation iron salt solutions, make that the ferrous ion of this iron salt solutions and ferric ion mol ratio are 1:2; Iron salt solutions is mixed with A liquid in the step (1), stirred 10～20 minutes; The volume ratio of iron salt solutions and A liquid is: 1:6～1:100;
(3), the mixed solution of step (2) gained is joined in the B liquid of step (1) gained fast, reduce stirring velocity, occur filtering immediately after the light-yellow precipitate; Wherein, the volume ratio of described mixed solution and B liquid is: 1:5～1:30;
(4), with throw out at room temperature after the drying, 600 ℃ of insulations are one hour under nitrogen protection.
Advantage of the present invention and effect: the present invention is embedded in the nanometer ferrite particle of superparamagnetism on the ball wall of hollow mesoporous silicon dioxide spheres first.Like this, both guaranteed to have in the single hollow mesoporous silicon dioxide spheres enough spaces appendix medicine, made to have magnetic again.By the concentration of control ferrum collosol, can be so that coat the ferrite particle of different quantities in the ball wall of each hollow mesoporous silicon dioxide spheres, thus reach the purpose of each particle magnetic power of control.
Description of drawings:
Figure 1 shows that magnetic hollow mesoporous silicon dioxide spheres, scale 50nm by embodiment 1 prepared
Figure 2 shows that magnetic hollow mesoporous silicon dioxide spheres, scale 50nm by embodiment 2 prepared
Figure 3 shows that magnetic mesoporous silica spheres, scale 100nm by embodiment 3 prepared
Figure 4 shows that magnetic mesoporous silica spheres, scale 100nm by embodiment 4 prepared
Figure 5 shows that XRD curve by the magnetic hollow mesoporous silicon dioxide spheres of embodiment 1 prepared
Figure 6 shows that nitrogen adsorption curve by the magnetic mesoporous silica spheres of the magnetic hollow mesoporous silicon dioxide spheres of embodiment 1 prepared and embodiment 3 prepared
Embodiment:
Embodiment 1
At first prepare two kinds of reaction solutions: A liquid is silicon source, pure and mild tensio-active agent, and concrete parameter is a 30ml ethanol, 3ml tetraethoxy, 1g CTAB; B liquid is the 0.05M ammonia soln.Secondly, preparation FeCl
2With FeCl
3Mol ratio is the solution of 1:2, in the iron salt solutions adding 200ml B solution with 2ml, is mixed with colloidal sol.A liquid is added fast in the colloidal sol of generation, reduce stirring velocity, occur after 3 minutes filtering immediately after the light-yellow precipitate.With after the filtering thing drying at room temperature under nitrogen protection 600 ℃ the insulation one hour.Finally obtain being inlaid with magnetic Fe in the brown ball wall
3O
4Hollow mesoporous silicon dioxide spheres.Shown in Fig. 1,5,6.
Embodiment 2
At first prepare two kinds of reaction solutions: A liquid is silicon source, pure and mild tensio-active agent, and concrete parameter is a 30ml ethanol, 3ml tetraethoxy, 1g tensio-active agent; B liquid is the 0.05M ammonia soln.Secondly, preparation Fe (NO
3)
2With Fe (NO
3)
3Mol ratio is the solution of 1:2, in the iron salt solutions adding 200mlB solution with 2ml, is mixed with colloidal sol.A liquid is added fast in the colloidal sol of generation, reduce stirring velocity, occur after 3 minutes filtering immediately after the light-yellow precipitate.With after the filtering thing drying at room temperature under nitrogen protection 600 ℃ the insulation one hour.Finally obtain being inlaid with magnetic Fe in the brown ball wall
3O
4Hollow mesoporous silicon dioxide spheres.Changing the molysite kind makes and is inlaid with magnetic Fe in the ball wall
3O
4Hollow mesoporous silicon dioxide spheres have better pattern.As shown in Figure 2.
Embodiment 3
At first prepare two kinds of reaction solutions: A liquid is silicon source, pure and mild tensio-active agent, and concrete parameter is a 30ml ethanol, 3ml tetraethoxy, 1g CTAB; B liquid is the 0.05M ammonia soln.Secondly, preparation FeCl
2With FeCl
3Mol ratio is the solution of 1:2, stirs after 20 minutes in the iron salt solutions adding A solution with 2ml to join fast in the B liquid, reduces stirring velocity, occurs after 3 minutes filtering immediately after the light-yellow precipitate.With after the filtering thing drying at room temperature under nitrogen protection 600 ℃ the insulation one hour.Finally obtain filling in the brown cavity magnetic Fe
3O
4Mesoporous silica spheres.Shown in Fig. 3,6.
Embodiment 4
At first prepare two kinds of reaction solutions: A liquid is silicon source, pure and mild tensio-active agent, and concrete parameter is a 30ml ethanol, 3ml tetraethoxy, 1g CTAB; B liquid is the 0.05M ammonia soln.Secondly, preparation Fe (NO
3)
2With Fe (NO
3)
3Mol ratio is the solution of 1:2, stirs after 20 minutes in the iron salt solutions adding A solution with 2ml to join fast in the B liquid, reduces stirring velocity, occurs after 3 minutes filtering immediately after the light-yellow precipitate.With after the filtering thing drying at room temperature under nitrogen protection 600 ℃ the insulation one hour.Finally obtain filling in the brown cavity magnetic Fe
3O
4Mesoporous silica spheres.As shown in Figure 4.
Claims (2)
1, a kind of preparation method who fills the inorganic magnetic material of hollow mesoporous silicon dioxide spheres, it is characterized in that: the process of this method is as follows:
(1), two kinds of reaction solutions of preparation:
A liquid is the mixed solution of silicon source, pure and mild tensio-active agent; The cetyl trimethylammonium bromide that is about to 0.05～2g is dissolved in the ethanol of 12～70ml, stirs fully dissolving in ten minutes; The tetraethoxy that then adds 0.5～9ml fully stirs;
Wherein, described tensio-active agent is meant the cetyl trimethyl ammonia bromide;
B liquid is ammonia soln: i.e. the ammonia soln of 0.01～0.4M;
(2), the preparation iron salt solutions, make that the ferrous ion of this iron salt solutions and ferric ion mol ratio are 1:2, iron salt solutions is added in the B solution, be mixed with colloidal sol; Wherein, the volume ratio of iron salt solutions and B solution is 1:2000～1:200
(3), A liquid is added in the colloidal sol that step (2) generates, reduce stirring velocity, occur filtering immediately after the light-yellow precipitate; Wherein, the volume ratio of A liquid and colloidal sol is 1:4～1:10;
(4), with throw out at room temperature after the drying, 600 ℃ of insulations are one hour under nitrogen protection, get product.
2, a kind of preparation method who fills the inorganic magnetic material of hollow mesoporous silicon dioxide spheres,, it is characterized in that: the process of this method is as follows:
(1), two kinds of reaction solutions of preparation:
A liquid is the mixed solution of silicon source, pure and mild tensio-active agent; The cetyl trimethylammonium bromide that is about to 0.05～2g is dissolved in the ethanol of 12～70ml, stirs fully dissolving in ten minutes; The tetraethoxy that then adds 0.5～9ml fully stirs;
Wherein, described tensio-active agent is meant the cetyl trimethyl ammonia bromide;
B liquid is ammonia soln: i.e. the ammonia soln of 0.01～0.4M;
(2), the preparation iron salt solutions, make that the ferrous ion of this iron salt solutions and ferric ion mol ratio are 1:2; Iron salt solutions is mixed with A liquid in the step (1), stirred 10～20 minutes; The volume ratio of iron salt solutions and A liquid is: 1:6～1:100;
(3), the mixed solution of step (2) gained is joined in the B liquid of step (1) gained fast, reduce stirring velocity, occur filtering immediately after the light-yellow precipitate; Wherein, the volume ratio of described mixed solution and B liquid is: 1:5～1:30;
(4), with throw out at room temperature after the drying, 600 ℃ of insulations are one hour under nitrogen protection, get product.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102198929A (en) * | 2010-03-22 | 2011-09-28 | 中国科学院理化技术研究所 | Hollow silicon dioxide sub-microsphere with nanoscale precious metal and silicon dioxide kernel and preparation method thereof |
| CN102247765A (en) * | 2011-07-25 | 2011-11-23 | 复旦大学 | Hollow mesoporous silica bead-polymer hybrid ultrafiltration membrane and preparation method thereof |
| CN102701297A (en) * | 2012-05-29 | 2012-10-03 | 华南师范大学 | Mesoporous silicon dioxide microsphere-loaded zero-valent iron nanoparticle (SiO2@ FeOOH@ Fe) and preparation method and application thereof |
| CN109794216A (en) * | 2019-02-27 | 2019-05-24 | 福建工程学院 | A kind of preparation of nano adsorption material and its application in repairing heavy metal in soil pollution |
| CN110028072A (en) * | 2019-05-06 | 2019-07-19 | 浙江大学 | A kind of preparation method of additive Mn mesoporous silicon dioxide nano particle |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100372763C (en) * | 2006-10-30 | 2008-03-05 | 复旦大学 | Synthetic method for porous silicon dioxide hollow micro ball |
| CN1994879A (en) * | 2006-11-29 | 2007-07-11 | 南开大学 | Process for preparing mesopore silica dioxide hollow sphere |
| CN101195085B (en) * | 2006-12-08 | 2010-05-19 | 北京化工大学 | Method for producing magnetic hollow silicon dioxide particle |
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2009
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102198929A (en) * | 2010-03-22 | 2011-09-28 | 中国科学院理化技术研究所 | Hollow silicon dioxide sub-microsphere with nanoscale precious metal and silicon dioxide kernel and preparation method thereof |
| CN102247765A (en) * | 2011-07-25 | 2011-11-23 | 复旦大学 | Hollow mesoporous silica bead-polymer hybrid ultrafiltration membrane and preparation method thereof |
| CN102701297A (en) * | 2012-05-29 | 2012-10-03 | 华南师范大学 | Mesoporous silicon dioxide microsphere-loaded zero-valent iron nanoparticle (SiO2@ FeOOH@ Fe) and preparation method and application thereof |
| CN109794216A (en) * | 2019-02-27 | 2019-05-24 | 福建工程学院 | A kind of preparation of nano adsorption material and its application in repairing heavy metal in soil pollution |
| CN110028072A (en) * | 2019-05-06 | 2019-07-19 | 浙江大学 | A kind of preparation method of additive Mn mesoporous silicon dioxide nano particle |
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