CN1792788A

CN1792788A - Process for preparing silicon dioxide hollow ball material with hexagonal phase penetrating mesopore orbit

Info

Publication number: CN1792788A
Application number: CN 200510112407
Authority: CN
Inventors: 朱钰方; 施剑林
Original assignee: Shanghai Institute of Ceramics of CAS
Current assignee: Shanghai Institute of Ceramics of CAS
Priority date: 2005-12-30
Filing date: 2005-12-30
Publication date: 2006-06-28
Anticipated expiration: 2025-12-30
Also published as: CN100355654C

Abstract

A process for preparing the hollow balls of hexagonal-phase meso-porous SiO2 includes such steps as dissolving cosurfactant and surfactant in deionized water, regulating pH value by NaOH, adding Si source, stirring, ageing, filtering, washing, drying and heat treating.

Description

A kind of silicon dioxide hollow sphere preparation methods of hexagonal phase penetrating mesopore orbit

Technical field

The present invention relates to a kind of silicon dioxide hollow sphere preparation methods, belong to inorganic mesoporous material field with hexagonal phase penetrating mesopore orbit.

Technical background

The investigator of U.S. Mobil company in 1992 has reported the specific surface area height first on Nature, since the high M41S of the degree of order series mesoporous material, people to it synthetic and its in catalysis, absorption, application facet such as medicament slow release have been carried out increasingly extensive research.Usually the structure and morphology of material has material impact to its application.The hollow ball structure that shell has penetrating mesopore orbit not only can increase substantially the loading capacity of guest molecule, and more helps the inside and outside transmission of guest molecule.Therefore, such mesoporous hollow ball has more wide application prospect as the solid support material of catalyzer and drug delivery system.

At present, about the existing bibliographical information of the preparation method of the silica spheres of hollow core/mesoporous shell structure.As (J.Am.Chem.Soc.2001 such as G.Zhu, 123:7723-7724) polystyrene (PSS) microballoon that adopts surperficial sulfidizing to cross is a hard template, at the mesoporous shell of its outside self-assembly formation layer of silicon dioxide, remove the silica spheres that PSS obtains hollow core/mesoporous shell structure then.This method is the common method of preparation hollow structure, but hard template at first needs suitable surface modification treatment, the processing condition harshness.H.-P.Lin (Chem.Mater.1998,10:3772), S.Schacht (Science, 1996,273:768), D.Zhao (Chem.Lett.2002,62), M.Stephen propositions such as (Chem.Comm.2001,2028) control reaction microenvironment obtains oil-in-water microemulsion, and tensio-active agent and silicon source tetraethoxy (TEOS) form mesoporous shell in the self-assembly at the interface of microemulsion then.This method technology is simple, and single stage method obtains hollow core/mesoporous shell structure, but its mesopore orbit of mesoporous shell of this material is parallel with weft direction, causes guest molecule inside and outsidely not transmit.

Summary of the invention

The object of the present invention is to provide a kind of technology simple, mild condition, good dispersity, mesoporous shell has the preparation method of the silicon dioxide hollow sphere material in hexagonal phase penetrating duct.

Mesoporous silicon oxide hollow ball material with hexagonal phase penetrating duct provided by the invention is to prepare by technological process shown in Figure 1:

(1) with cosurfactant polyvinylpyrrolidone (PVP, k ₃₀) be dissolved in the deionized water, its concentration range is: 1.7～17.0mg/ml.

(2) add NaOH.Regulating the pH value is 10.5-12.

(3) adding tensio-active agent is 16 (14,12,20) alkyl trimethyl ammonium bromides (CTAB) or 16 (14,12,20) alkyl trimethyl ammonium chlorides (CTAC),, the mass ratio of its add-on and PVP is between 0.7～7.0.

(4) adding silicon source material is tetraethoxy (TEOS) or methyl silicate (TMOS), and the mass ratio of its add-on and tensio-active agent is 3.0～4.7.

(5) stirring ageing handled 12～24 hours.

(6) with deionized water and washing with alcohol several, filter, drying is 12 hours under 100 ℃ of air.

(7) under air atmosphere, calcine removal organic surface active agent, calcining temperature: 400-700 ℃, calcination time: 2-8 hour at last.

Silicon dioxide hollow sphere material that the mesoporous shell that the present invention relates to has the hexagonal phase penetrating duct and preparation method thereof has following characteristics:

(1) mesoporous lamella of hollow silica ball has the hexagonal phase penetrating duct.

(2) this hollow structure helps the micromolecular inside and outside transmission of object, improves the reserves of guest molecule and realizes sustained release.

(3) hollow ball material good dispersity.

(4) this preparation method can a step realize that directly preparation technology is simple, mild condition under the normal temperature and pressure aqueous solution state.

Description of drawings

The technical process of the silicon dioxide hollow sphere material of Fig. 1 preparation hexagonal phase penetrating mesopore orbit provided by the invention.

Fig. 2 presses the small angle X-ray diffraction collection of illustrative plates of the mesoporous SiO 2 hollow ball material of embodiment 1-5 prepared.Curve 1-3 shows as three diffraction peaks, and its collection of illustrative plates is indicated as typical six side's phase structures.The mesoporous shell that mesoporous hollow ball is described has six side's phase mesopore orbits.Curve 4-5 shows as the diffraction peak of a broadening, and the mesoporous order of illustrative material descends.

Fig. 3 is by the low power and the high power transmission electron microscope photo of the mesoporous SiO 2 hollow ball with six side's phase mesopore orbits of embodiment 1 prepared.The ratio of product that the low power electromicroscopic photograph can obtain having hollow structure is very high, and the high power transmission electron microscope photo can show that the mesopore orbit of shell is inside and outside and be communicated with.

Fig. 4 presses the low power transmission electron microscope photo of the mesoporous SiO 2 hollow ball material of embodiment 3 prepared.

Embodiment

Embodiment 1:

Cosurfactant is polyvinylpyrrolidone (PVP, k ₃₀); The silicon source is a tetraethoxy, Si (OC ₂H ₅) ₄Tensio-active agent is cetyl trimethylammonium bromide CTAB; Adjust the pH value of solution with sodium hydroxide.According to formula rate (mass ratio): 0.5PVP: 0.7CTAB: 0.23NaOH: 2.6TEOS: 60H ₂O adds various reactive material, through stir, the ageing after-filtration, with deionized water and washing with alcohol repeatedly after, under 100 ℃ of air dry 12 hours; Tensio-active agent was removed in calcining in 6 hours under 550 ℃ of air atmospheres at last.

Its small angle X-ray diffraction result is shown in curve among Fig. 21; Its low power and high power transmission electron microscope photo are shown in Fig. 3 a and b, and its product is the mesoporous hollow ball with through hole, and hollow ball size 300～400nm is about hollow core size 200nm.As seen this method can obtain having the mesoporous SiO 2 hollow ball in hexagonal phase penetrating duct.

Embodiment 2-5 primitive reaction substance classes is constant, only changes the add-on of various reactive material, obtains following several different embodiments:

Embodiment 2

Formula rate: 0.25PVP: 0.7CTAB: 0.23NaOH: 2.6TEOS: 60H ₂O, its small angle X-ray diffraction collection of illustrative plates is shown in curve among Fig. 22.

Embodiment 3

Formula rate: 0.1PVP: 0.7CTAB: 0.23NaOH: 2.6TEOS: 60H ₂O, its small angle X-ray diffraction collection of illustrative plates is shown in curve among Fig. 23.The low power transmission electron microscope photo has the ratio minimizing of the silica spheres of hollow structure as shown in Figure 4 in its product.

Embodiment 4

0.5PVP: 0.5CTAB: 0.23NaOH: 2.6TEOS: 60H ₂O, its small angle X-ray diffraction collection of illustrative plates is shown in curve among Fig. 24.

Embodiment 5

0.5PVP: 0.7CTAB: 0.23NaOH: 2.2TEOS: 60H ₂O, its small angle X-ray diffraction collection of illustrative plates is shown in curve among the figure 5.

Claims

1, a kind of silicon dioxide hollow sphere preparation methods of hexagonal phase penetrating mesopore orbit comprises the steps:

(1) cosurfactant and tensio-active agent are dissolved in deionized water, and with NaOH regulator solution pH value;

(2) stirring ageing behind the material of adding silicon source handles;

(3) filter, washing is heat-treated after the drying.

2, by the silicon dioxide hollow sphere preparation methods of the described a kind of hexagonal phase penetrating mesopore orbit of claim 1, it is characterized in that

Described cosurfactant kind is polyvinylpyrrolidone (PVP, k ₃₀), concentration is 1.7～17.0mg/ml;

Described kinds of surfactants is 16 (14,12,20) alkyl trimethyl ammonium bromides (CTAB) or 16 (14,12,20) alkyl trimethyl ammonium chlorides (CTAC), and the mass ratio of add-on and PVP is between 0.7～7.0.

3, by the silicon dioxide hollow sphere preparation methods of the described a kind of hexagonal phase penetrating mesopore orbit of claim 1, it is characterized in that with NaOH regulator solution pH value be 10.5-12.

4, press the silicon dioxide hollow sphere preparation methods of claims 1,2 or 3 described a kind of hexagonal phase penetrating mesopore orbits, it is characterized in that the silicon source material that adds is tetraethoxy (TEOS) or methyl silicate (TMOS), the mass ratio of add-on and tensio-active agent is 3.0～4.7.

5, press the silicon dioxide hollow sphere preparation methods of claims 1,2 or 3 described a kind of hexagonal phase penetrating mesopore orbits, it is characterized in that heat-treat condition be under air atmosphere 400-700 ℃ calcination time 2-8 hour.