CN102583404A - Mesoporous silicon dioxide nanometer particle and preparation method - Google Patents
Mesoporous silicon dioxide nanometer particle and preparation method Download PDFInfo
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- CN102583404A CN102583404A CN2012100687448A CN201210068744A CN102583404A CN 102583404 A CN102583404 A CN 102583404A CN 2012100687448 A CN2012100687448 A CN 2012100687448A CN 201210068744 A CN201210068744 A CN 201210068744A CN 102583404 A CN102583404 A CN 102583404A
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Abstract
The invention relates to a mesoporous silicon dioxide nanometer particle and a preparation method. The method comprises the steps as follows: 1, resolving 0.2 to 2 parts of surface active agent into 300 parts of deionized water, and heating and mixing to obtain clear solution; 2, adding 10 to 250 parts of hydrophobic component, 0.1 to 18 parts of organic monomer, 0.1 to 18 parts of silicon source, 20 to 100 parts of catalyst and 1 to 9 parts of initiator into the system obtained in step 1 sequentially, and reacting for 2 to 4 hour at the temperature of 60 to 80 DEG C under the protection of argon gas; and 3, stopping heating the reaction system of step 2, cooling to ambient temperature, washing centrifugally, and calcining at the temperature of 500 DEG C to 800 DEG C to removing organic components so as to obtain the mesoporous silicon dioxide nanometer particle. The mesoporous silicon dioxide nanometer has a favorable dispersivity and adopts a spherical porous structure that the average pore diameter is 4 to 15 nm and the outside diameter is 50 to 150 nm. The invention has the advantages that preparation process is simple, the reaction is uniform, and troublesome isolation and purification processes are not required.
Description
Technical field
The present invention relates to a kind of mesoporous material that can be applicable to biomedical sector, especially relate to mesoporous silicon dioxide nano particle and preparation method that a kind of preparation has less external diameter and larger aperture simultaneously.
Background technology
In recent years, the mesoporous material development has attracted more and more researchists' concern rapidly.Mesoporous material is the type material with huge surface area and three-dimensional open-framework of a kind of aperture between micropore and macropore.It has the excellent specific property that other porous material does not have: the pore passage structure of high-sequential; The single distribution in aperture, and aperture size can change at relative broad range; Mesoporous shape is various, and hole wall composition and character are adjustable; Can obtain high thermal stability and chemicalstability through optimizing synthesis condition.The research and development of mesoporous material is all significant for theoretical investigation and actual production, can be widely used in comprising the field such as targeted therapy, delivery of drug of chemical sensor, medicine.
In in the past 10 years, using maximum mesoporous materials is silica nano material.Nano silicon is a unformed white powder, nontoxic, tasteless; Thereby the surface exists hydroxyl to have excellent biological compatibility; Have the advantages that particle diameter is little, purity is high, specific surface area is big, dispersing property is good, and superior stability, be many investigators' first-selection therefore.
Reported the preparation method of the meso-porous nano earth silicon material (serial with SBA) of various morphological structures (film like, fibrous, powdery, spherical etc.), for example dried preparation method, sol-gel method, microemulsion organic formwork method and overweight force method like MCM series at present.But, because nano silicon be prone to reunite, be difficult for the dispersiveness that keeps good, its application is very limited, and since the harmful chemical in the traditional preparation process method (for example: ammoniacal liquor, N
2H
4As catalyzer), they possibly become the difficult problem on the biologic applications, the most important thing is that the external diameter that these methods prepare particle is difficult to less than diameter 200nm, and the aperture also only limits to below the 3nm.Therefore how to prepare size distribution evenly, the meso-porous nano silicon-dioxide of good dispersibility, become a focal issue in the Application Areas.
We improve on the basis of spraying method, adopt microemulsion organic formwork method at oily aqueous phase.This method forms oil-in-water system in reaction system; In micella, be hydrolyzed simultaneously and polyreaction, make and prepare uniform particle diameter, good dispersivity, the nanoparticle that does not have deposition or reunite; And particle diameter can control to 50～150nm, and the aperture can control to 4～15nm.
Summary of the invention
The purpose of this research aims to provide a kind of method for preparing mesoporous silicon dioxide nano particle, and emphasis has solved mesoporous silicon dioxide nano particle can have littler external diameter simultaneously, and has more wide-aperture problem.Use the preparation of organic formwork method at oily aqueous phase, particle good dispersivity in reaction process does not have deposition or agglomeration.And adopt Methionin to make catalyzer, and reduce preparation toxicity, and can effectively control nano particle diameter, stop and reunite.Its aperture of Nano particles of silicon dioxide of preparation is at 4～15nm, and its external diameter has good selective adsorption and catalytic activity at 50～150nm, has expanded the application of mesoporous silicon dioxide nano particle at biomedical sector.
The preparation method of mesoporous silicon dioxide nano particle of the present invention, its characterization step is following:
1) with 0.2～2 part of surfactant dissolves in 300 parts of deionized waters, heating mixes and to obtain settled solution;
2) 10～250 parts of hydrophobic components, 0.1～18 part of organic monomer, 0.1～18 part of silicon source, 20～100 parts of catalyzer, 1～9 part of initiator are added in the system of step 1) successively; Under argon shield, 2～4h is carried out in 60～80 ℃ of following reactions;
3) reaction system step 2) stops heating, reduces to room temperature, centrifuge washing; Organic constituent is removed in 500 ℃～800 ℃ calcinings, makes mesoporous silicon dioxide nano particle.
Described mesoporous silicon dioxide nano particle, be meant mean pore size at 4～15nm and external diameter at 50～150nm, have mesoporous silicon dioxide nano particle of spherical porous structure, good dispersibility.
Described tensio-active agent comprises one or both the combination in cetyl trimethylammonium bromide (CTAB), the dodecyl trimethylammonium amine bromide (DTAB).
Described hydrophobic components is one or both the combination in octane, the octane-iso.
Described organic monomer is one or both the combination in vinylbenzene, the TEB 3K.
Described silicon source is one or both the combination in tetraethoxy (TEOS), the silicon tetrachloride.
Described catalyzer is one or both the combination in Lysine acid, the dextrorotation Methionin.
Described initiator is for being one or both the combination in the azo diisobutyl amidine salt (AIBA), azo two different (N-amine ethyl) fourth amidine (ABEA).
Preparation process of the present invention all is under argon shield, to carry out.
The present invention compared with prior art is characterised in that: the first, adopt the organic formwork method, and form water in oil micellar system, make the particle good dispersivity of preparation, there are not deposition or agglomeration, but the nanoparticle of prepared sizes homogeneous.The second, mesoporous silicon dioxide nano particle of preparing, its aperture is at 4～15nm, and its external diameter has solved mesoporous silicon dioxide nano particle and has had the problem of less external diameter and larger aperture simultaneously at 50～150nm.The 3rd, adopt Methionin to make catalyzer, have the following advantages: 1) growth of silicon-dioxide can be controlled, can obtain littler external diameter and more wide-aperture silicon dioxide nanosphere; 2) can avoid reuniting; 3) be different from like ammonia, N
2H
4These traditional catalyst, Methionin make in the preparation process nontoxic.The 4th, can control external diameter through changing hydrophobic components concentration, control the aperture through changing organic monomer concentration.
Advantage of the present invention is that mainly hydrolytic condensation tetraethoxy (TEOS) forms the reaction of silicon-dioxide and the polyreaction of organic monomer all occurs in the micella, and its advantage is that process is simple, and the reaction homogeneous does not need loaded down with trivial details isolation and purge process.
Description of drawings
The transmission electron microscope photo of mesoporous silicon dioxide nano particle described in Fig. 1: the embodiment 5.
Embodiment
Make detailed description in the face of embodiments of the invention down: present embodiment is being to implement under the prerequisite with technical scheme of the present invention, and given detailed embodiment and process are to further specify of the present invention, rather than limit scope of the present invention.
Embodiment 1:
Step 1 is dissolved in 0.2 part of cetyl trimethylammonium bromide (CTAB) in 300 parts of water, and the heating mixing obtains settled solution;
Step 2 is added 130 parts of octanes, 18 parts of styrene monomers, 20 parts of dextrorotation Methionins, 9 parts of silicon tetrachlorides, 0.5 part of azo diisobutyl amidine hydrochloride (AIBA) and 0.5 part of azo two different (N-amine ethyl) fourth amidines (ABEA) in the system of step 1 to; Under argon shield, 2h is carried out in 60 ℃ of following reactions;
Step 3, the reaction system of step 2 stop heating, and suspension-s naturally cooling 12h is to room temperature; Suspension-s under 15000 rev/mins rotating speed, centrifugal twice purifying particle;
Step 4, in 500 ℃ of TRs, organic constituent is removed in calcining, makes mesoporous silicon dioxide nano particle.
The mesoporous silicon dioxide nano particle molecular dispersivity of preparation is good, does not have deposition or agglomeration, and meso-hole structure is clear, and obviously its external diameter is about 50nm, and the aperture is about 4nm.
Embodiment 2:
Step 1 is dissolved in 1.1 parts of cetyl trimethylammonium bromides (CTAB) in 300 parts of water, and the heating mixing obtains settled solution;
Step 2 is added 250 parts of octanes, 0.1 part of MMA MONOMER, 60 parts of dextrorotation Methionins, 18 parts of silicon tetrachlorides, 2.5 parts of azo diisobutyl amidine hydrochlorides (AIBA) and 2.5 parts of azos two different (N-amine ethyl) fourth amidines (ABEA) in the system of step 1 to; Under argon shield, 3h is carried out in 60 ℃ of following reactions;
Step 3, the reaction system of step 2 stop heating, and suspension-s naturally cooling 12h is to room temperature; Suspension-s under 15000 rev/mins rotating speed, centrifugal twice purifying particle;
Step 4, in 600 ℃ of TRs, organic constituent is removed in calcining, makes mesoporous silicon dioxide nano particle.
The mesoporous silicon dioxide nano particle molecular dispersivity of preparation is good, does not have deposition or agglomeration, and meso-hole structure is clear, and obviously its external diameter is about 100nm, and the aperture is about 4nm.
Embodiment 3:
Step 1 is dissolved in 2 parts of cetyl trimethylammonium bromides (CTAB) in 300 parts of water, and the heating mixing obtains settled solution;
Step 2 is added 10 parts of octane-iso, 9 parts of MMA MONOMERs, 100 parts of dextrorotation Methionins, 0.05 part of tetraethoxy (TEOS) and 0.05 part of silicon tetrachloride, 4.5 parts of azo diisobutyl amidine hydrochlorides (AIBA) and 4.5 parts of azos two different (N-amine ethyl) fourth amidines (ABEA) in the system of step 1 to; Under argon shield, 4h is carried out in 60 ℃ of following reactions;
Step 3, the reaction system of step 2 stop heating, and suspension-s naturally cooling 12h is to room temperature; Suspension-s under 15000 rev/mins rotating speed, centrifugal twice purifying particle;
Step 4, in 700 ℃ of TRs, organic constituent is removed in calcining, makes the mesoporous silicon dioxide nano microballoon.
The mesoporous silicon dioxide nano particle molecular dispersivity of preparation is good, does not have deposition or agglomeration, and meso-hole structure is clear, and obviously its external diameter is about 150nm, and the aperture is about 4nm.
Embodiment 4:
Step 1 is dissolved in 0.2 part of dodecyl trimethylammonium amine bromide (DTAB) in 300 parts of water, and the heating mixing obtains settled solution;
Step 2 is added 130 parts of octane-iso, 18 parts of MMA MONOMERs, 10 parts of Lysine acids and 10 parts of dextrorotation Methionins, 4.5 parts of tetraethoxys (TEOS) and 4.5 parts of silicon tetrachlorides, 1 part of azo diisobutyl amidine hydrochloride (AIBA) in the system of step 1 to; Under argon shield, 2h is carried out in 70 ℃ of following reactions;
Step 3, the reaction system of step 2 stop heating, and suspension-s naturally cooling 12h is to room temperature; Suspension-s under 15000 rev/mins rotating speed, centrifugal twice purifying particle;
Step 4, in 800 ℃ of TRs, organic constituent is removed in calcining, makes the mesoporous silicon dioxide nano microballoon.
The mesoporous silicon dioxide nano particle molecular dispersivity of preparation is good, does not have deposition or agglomeration, and meso-hole structure is clear, and obviously its external diameter is about 50nm, and the aperture is about 9nm.
Embodiment 5:
Step 1 is dissolved in 1.1 parts of dodecyl trimethylammonium amine bromides (DTAB) in 300 parts of water, and the heating mixing obtains settled solution;
Step 2 is added 250 parts of octane-iso, 0.05 part of styrene monomer and 0.05 part of MMA MONOMER, 30 parts of Lysine acids and 30 parts of dextrorotation Methionins, 9 parts of tetraethoxys (TEOS) and 9 parts of silicon tetrachlorides, 5 parts of azo diisobutyl amidine hydrochlorides (AIBA) in the system of step 1 to; Under argon shield, 3h is carried out in 70 ℃ of following reactions;
Step 3, the reaction system of step 2 stop heating, and suspension-s naturally cooling 12h is to room temperature; Suspension-s under 15000 rev/mins rotating speed, centrifugal twice purifying particle;
Step 4, in 500 ℃ of TRs, organic constituent is removed in calcining, makes mesoporous silicon dioxide nano particle.
The mesoporous silicon dioxide nano particle molecular dispersivity of preparation is good, does not have deposition or agglomeration, and meso-hole structure is clear, and obviously its external diameter is about 100nm, and the aperture is about 9nm, and is as shown in Figure 1.
Embodiment 6:
Step 1 is dissolved in 2 parts of dodecyl trimethylammonium amine bromides (DTAB) in 300 parts of water, and the heating mixing obtains settled solution;
Step 2 is added 5 parts of octanes and 5 parts of octane-iso, 4.5 parts of styrene monomers and 4.5 parts of MMA MONOMERs, 50 parts of Lysine acids and 50 parts of dextrorotation Methionins, 0.1 part of tetraethoxy (TEOS), 9 parts of azo diisobutyl amidine hydrochlorides (AIBA) in the system of step 1 to; Under argon shield, 4h is carried out in 70 ℃ of following reactions;
Step 3, the reaction system of step 2 stop heating, and suspension-s naturally cooling 12h is to room temperature; Suspension-s under 15000 rev/mins rotating speed, centrifugal twice purifying particle;
Step 4, in 600 ℃ of TRs, organic constituent is removed in calcining, makes mesoporous silicon dioxide nano particle.
The mesoporous silicon dioxide nano particle molecular dispersivity of preparation is good, does not have deposition or agglomeration, and meso-hole structure is clear, and obviously its external diameter is about 150nm, and the aperture is about 9nm.
Embodiment 7:
Step 1 is dissolved in 0.1 part of cetyl trimethylammonium bromide (CTAB) and 0.1 part of dodecyl trimethylammonium amine bromide (DTAB) in 300 parts of water, and the heating mixing obtains settled solution;
Step 2 is added 65 parts of octanes and 65 parts of octane-iso, 9 parts of styrene monomers and 9 parts of MMA MONOMERs, 20 parts of Lysine acids, 9 parts of tetraethoxys (TEOS), 1 part of azo two different (N-amine ethyl) fourth amidines (ABEA) in the system of step 1 to; Under argon shield, 2h is carried out in 80 ℃ of following reactions;
Step 3, the reaction system of step 2 stop heating, and suspension-s naturally cooling 12h is to room temperature; Suspension-s under 15000 rev/mins rotating speed, centrifugal twice purifying particle;
Step 4, in 700 ℃ of TRs, organic constituent is removed in calcining, makes mesoporous silicon dioxide nano particle.
The mesoporous silicon dioxide nano particle molecular dispersivity of preparation is good, does not have deposition or agglomeration, and meso-hole structure is clear, and obviously its external diameter is about 50nm, and the aperture is about 15nm.
Embodiment 8:
Step 1 is dissolved in the mixture of 0.55 part of cetyl trimethylammonium bromide (CTAB) with 0.55 part of dodecyl trimethylammonium amine bromide (DTAB) in 300 parts of water, and the heating mixing obtains settled solution;
Step 2 is added 125 parts of octanes and 125 parts of octane-iso, 0.1 part of styrene monomer, 60 parts of Lysine acids, 18 parts of tetraethoxys (TEOS), 5 parts of azos two different (N-amine ethyl) fourth amidines (ABEA) in the system of step 1 to; Under argon shield, 3h is carried out in 80 ℃ of following reactions;
Step 3, the reaction system of step 2 stop heating, and suspension-s naturally cooling 12h is to room temperature; Suspension-s under 15000 rev/mins rotating speed, centrifugal twice purifying particle;
Step 4, in 800 ℃ of TRs, organic constituent is removed in calcining, makes mesoporous silicon dioxide nano particle.
The mesoporous silicon dioxide nano particle molecular dispersivity of preparation is good, does not have deposition or agglomeration, and meso-hole structure is clear, and obviously its external diameter is about 100nm, and the aperture is about 15nm.
Embodiment 9:
Step 1 is dissolved in the mixture of 1 part of cetyl trimethylammonium bromide (CTAB) with 1 part of dodecyl trimethylammonium amine bromide (DTAB) in 300 parts of water, and the heating mixing obtains settled solution;
Step 2 is added 10 parts of octanes, 9 parts of styrene monomers, 100 parts of Lysine acids, 0.1 part of silicon tetrachloride, 9 parts of azos two different (N-amine ethyl) fourth amidine (ABEA) in the system of step 1 to; Under argon shield, 4h is carried out in 80 ℃ of following reactions;
Step 3, the reaction system of step 2 stop heating, and suspension-s naturally cooling 12h is to room temperature; Suspension-s under 15000 rev/mins rotating speed, centrifugal twice purifying particle;
Step 4, in 800 ℃ of TRs, organic constituent is removed in calcining, makes mesoporous silicon dioxide nano particle.
The mesoporous silicon dioxide nano particle molecular dispersivity of preparation is good, does not have deposition or agglomeration, and meso-hole structure is clear, and obviously its external diameter is about 150nm, and the aperture is about 15nm.
The foregoing description is a preferred implementation of the present invention; But embodiment of the present invention is not restricted to the described embodiments; Other any do not deviate from change, the modification done under spirit of the present invention and the principle, substitutes, combination, simplify; All should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (9)
1. mesoporous silicon dioxide nano particle is characterized in that its aperture of Nano particles of silicon dioxide at 4～15nm, and its external diameter is at 50～150nm; Has spherical porous structure.
2. the preparation method of the mesoporous silicon dioxide nano particle of claim 1 son is characterized in that step is following:
1) with 0.2～2 part of surfactant dissolves in 300 parts of deionized waters, heating mixes and to obtain settled solution;
2) 10～250 parts of hydrophobic components, 0.1～18 part of organic monomer, 0.1～18 part of silicon source, 20～100 parts of catalyzer, 1～9 part of initiator are added in the system of step 1) successively; Under argon shield, 2～4h is carried out in 60～80 ℃ of following reactions;
3) reaction system step 2) stops heating, reduces to room temperature, centrifuge washing; Organic constituent is removed in 500 ℃～800 ℃ calcinings, makes mesoporous silicon dioxide nano particle.
3. preparation method according to claim 2 is characterized in that described tensio-active agent, comprises one or both the combination in cetyl trimethylammonium bromide, the dodecyl trimethylammonium amine bromide.
4. preparation method according to claim 2 is characterized in that described hydrophobic components is one or both the combination in octane, the octane-iso.
5. preparation method according to claim 2 is characterized in that described organic monomer is one or both combination of vinylbenzene, TEB 3K.
6. preparation method according to claim 2 is characterized in that described silicon source is one or both the combination in tetraethoxy, the silicon tetrachloride.
7. preparation method according to claim 2 is characterized in that described catalyzer is one or both the combination in Lysine acid, the dextrorotation Methionin.
8. preparation method according to claim 2 is characterized in that described initiator is for being one or both the combination in the azo diisobutyl amidine salt, azo two different (N-amine ethyl) fourth amidine.
9. preparation method according to claim 2 is characterized in that the preparation process all carries out under argon shield.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105905912A (en) * | 2016-04-05 | 2016-08-31 | 天津大学 | High-yield mesoporous silica nano-particle and folic acid targeting modification method thereof |
| CN105903062A (en) * | 2016-04-12 | 2016-08-31 | 中国人民解放军军事医学科学院卫生装备研究所 | Aperture and particle size monodisperse controllable mesoporous silicon rapid hemostatic powder and preparation method |
| CN109179429A (en) * | 2018-08-30 | 2019-01-11 | 昆明理工大学 | A kind of method that chlorosilane raffinate prepares meso-porous nano silica |
| CN110036077A (en) * | 2017-02-24 | 2019-07-19 | 惠普发展公司，有限责任合伙企业 | Ink-jet priming paint liquid |
| CN112850716A (en) * | 2021-02-04 | 2021-05-28 | 昆明理工大学 | Method for preparing nano-scale porous crystal Si by magnesiothermic reduction |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1355135A (en) * | 2001-12-31 | 2002-06-26 | 天津大学 | Process for preparing mesoporous SiO2 microparticles material |
| CN101786639A (en) * | 2010-03-08 | 2010-07-28 | 天津大学 | Mesoporous silicon dioxide molecular sieve and preparation method thereof |
| CN101857234A (en) * | 2010-06-10 | 2010-10-13 | 天津大学 | Monodisperse mesoporous silicon dioxide hollow nano-microsphere and preparation method |
-
2012
- 2012-03-15 CN CN2012100687448A patent/CN102583404A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1355135A (en) * | 2001-12-31 | 2002-06-26 | 天津大学 | Process for preparing mesoporous SiO2 microparticles material |
| CN101786639A (en) * | 2010-03-08 | 2010-07-28 | 天津大学 | Mesoporous silicon dioxide molecular sieve and preparation method thereof |
| CN101857234A (en) * | 2010-06-10 | 2010-10-13 | 天津大学 | Monodisperse mesoporous silicon dioxide hollow nano-microsphere and preparation method |
Non-Patent Citations (1)
| Title |
|---|
| ASEP BAYU DANI NANDIYANTO ET AL.: "Synthesis of spherical mesoporous silica nanoparticles with nanometer-size controllable pores and outer diameters", 《MICROPOROUS AND MESOPOROUS MATERIALS》 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105905912A (en) * | 2016-04-05 | 2016-08-31 | 天津大学 | High-yield mesoporous silica nano-particle and folic acid targeting modification method thereof |
| CN105903062A (en) * | 2016-04-12 | 2016-08-31 | 中国人民解放军军事医学科学院卫生装备研究所 | Aperture and particle size monodisperse controllable mesoporous silicon rapid hemostatic powder and preparation method |
| CN105903062B (en) * | 2016-04-12 | 2019-06-25 | 中国人民解放军军事医学科学院卫生装备研究所 | A kind of aperture and the controllable mesoporous silicon rapid hemostasis powder and preparation method of the equal monodisperse of partial size |
| CN110036077A (en) * | 2017-02-24 | 2019-07-19 | 惠普发展公司，有限责任合伙企业 | Ink-jet priming paint liquid |
| US11130876B2 (en) | 2017-02-24 | 2021-09-28 | Hewlett-Packard Development Company, L.P. | Inkjet primer fluid |
| CN109179429A (en) * | 2018-08-30 | 2019-01-11 | 昆明理工大学 | A kind of method that chlorosilane raffinate prepares meso-porous nano silica |
| CN109179429B (en) * | 2018-08-30 | 2022-02-22 | 昆明理工大学 | Method for preparing mesoporous nano-silica from chlorosilane residual liquid |
| CN112850716A (en) * | 2021-02-04 | 2021-05-28 | 昆明理工大学 | Method for preparing nano-scale porous crystal Si by magnesiothermic reduction |
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