CN102616792A

CN102616792A - Method for preparing hollow spherical silicon dioxide with mesoporous shell

Info

Publication number: CN102616792A
Application number: CN2012100814941A
Authority: CN
Inventors: 张丹; 李君华
Original assignee: Liaoning University of Technology
Current assignee: Liaoning University of Technology
Priority date: 2012-03-26
Filing date: 2012-03-26
Publication date: 2012-08-01

Abstract

The invention discloses a method for preparing hollow spherical silicon dioxide with a mesoporous shell. The method includes: adding pure silica-based spherical mesoporous molecular sieves with template agent unremoved into deionized water, adjusting the system pH (potential of hydrogen) to range from 8 to 14, transferring into a reaction kettle after stirring, performing hydro-thermal treatment for 2-72h at 80-200 DEG C, taking out the reaction kettle to separate products in the kettle, subjecting the products to ethanol washing before water washing, vacuum drying for 4-48h at 40-80 DEG C, and roasting the obtained powder for 3-8h at 400-700 DEG C to obtain a hollow mesoporous spherical silicon dioxide material with the mesoporous shell. The obtained hollow mesoporous silicon balls with mesoporous shells are high in dispersibility, simple in preparation process, easy in expanded industrial production and applicable to medicine slow release, adsorptive separation and the like.

Description

Preparing method with hollow sphere silicon-dioxide of mesoporous lamella

Technical field

The present invention relates to a kind of preparation method, belong to mesoporous materials field with hollow sphere silicon-dioxide of mesoporous lamella.

Background technology

The researchist of Mobile company in 1992 [Natrue, 1992,359,710] has first reported that the research of mesoporous material becomes one of research focus of material circle since the M41S series mesoporous material of high-specific surface area, high-sequential property.Researchist and the mesoporous material that has synthesized different-shape, mesoporous material receives extensive concern in the application in fields such as catalysis, separation, transmitter, medicament slow release.Usually the structure and the pattern of mesoporous material have significant effects to its application.The hollow mesoporous material has specific pore passage structure; Have characteristics such as hollow, density is little, specific surface area is big; Thereby it has perviousness, adsorptivity, screening molecule ability and optical property preferably; And hollow structure can increase substantially the charge capacity of guest molecule, and mesoporous lamella also helps the inside and outside diffusion transport of guest molecule, so the hollow mesoporous material is with a wide range of applications.

At present, hollow mesoporous sphere earth silicon material preparation method mainly contains two kinds: and hard template method [J.Am.Chem.Soc. 2001,123, and 7723; J. Phy.Chem.B 2005,109, and 7040.] and soft template method [Nanotechnology 2005,16, and 2633; Micropor. Mesopor. Mater. 2005,84, and 218; Langmuir 2006,22,6.].Hard template method is to select the solid monodisperse particles of uniform particle diameter for use, and it is carried out after the surface treatment forming a nucleocapsid structure at its surface production SiO2 mesoporous lamella, removes hard template nuclear then and promptly obtains the hollow mesoporous silicon sphere.This method need be carried out suitable surface modification treatment to the hard template particle, and process is loaded down with trivial details consuming time.Soft template method is to utilize template and co-template under specific solution condition; Form a spherical micelle; Silicon species hydrolytie polycondensation on this micella constitutes a nucleocapsid structure then; Remove template and promptly obtain the hollow mesoporous silicon sphere, but this approach needs strict control solution condition, processing condition are harsh.

Summary of the invention

The object of the present invention is to provide that a kind of technology is simple, a kind of preparation method with hollow sphere silicon-dioxide of mesoporous lamella of mild condition.

Technical scheme of the present invention is to add the not mesoporous silicon sphere of template agent removing in the alkalitropism solution; Stirring at room is after press the still hydrothermal treatment consists certainly, product filters, make after the washing, dry, roasting size evenly, have a hollow sphere earth silicon material of mesoporous lamella.

Preparing method of the present invention comprises the steps:

1, with 0.5-4.5 g not the pure silicon base spherical mesoporous molecular sieve of template agent removing join in the 10-100 ml deionized water, to 8-14, stir 0.5-24 h with alkaline substance solution regulation system pH value;

2, the product after will stirring changes in the closed reactor, handles 4-72 h at 100-200 ℃ of following constant temperature;

3, take out reaction kettle, naturally cooling in air;

4, white precipitate in the reaction kettle is separated, used washing 2-5 time, 40-80 ℃ of vacuum-drying 4-48 h then after first ethanol is washed 2-4 time again;

5, with dry gained white powder at 400-700 ℃ of following roasting 3-8 h, obtain having the hollow mesoporous silicon sphere material of mesoporous shell;

Aforesaid pure silicon spherical mesoporous molecular sieve is spherical MCM-41 mesopore molecular sieve or SBA-15 mesopore molecular sieve or MCM-48 mesopore molecular sieve; The synthetic of them can be with reference to following document: J. Phys. Chem. C 2007,111,1093; Chem. Commun. 1999,2047; Solid State Sciences 2004,6,489; J. Chromato. A, 2006,112,13; Stud. Surf. Sci. Catal. 2007,17,861;

Aforesaid alkaline substance solution is 2mol/L ammoniacal liquor or the 1 mol/L NaOH aqueous solution or the 25 wt % tetraethyl ammonium hydroxide aqueous solution.

Advantage of the present invention is,

1, the big I of ball is regulated through the size of pure silicon base mesoporous silicon sphere, and the hollow sphere silicon oxide dimensions that gained has mesoporous lamella is even, good dispersivity;

2, the mesoporous even size distribution of mesoporous shell, and mesoporously have a through hole;

3, need not the strict hierarchy of control condition or the surface treatment process of traditional method, the preparation process is simple, favorable reproducibility.

Description of drawings

Fig. 1 is the small angle X-ray diffraction spectrogram of the material of embodiment 1 preparation;

Fig. 2 is the stereoscan photograph of embodiment 1 gained material;

Fig. 3 is the transmission electron microscope photo of embodiment 1 gained material.

Embodiment

The present invention combines following instance to be further described.

Embodiment 1

Get 0.5g not the spherical MCM-41 mesopore molecular sieve of pure silicon base of template agent removing join in the 15 ml water, with 2mol/L ammoniacal liquor regulation system pH to 9, behind stirring at room 1 h; Change in the tetrafluoroethylene reaction kettle; Put into 100 ℃ of constant temperature ovens after the sealing and handle 4 h, take out reaction kettle then, naturally cooling in air; White precipitate spinning in the still; After washing 2 times again after washing 2 times with absolute ethyl alcohol earlier, behind 40 ℃ of baking oven vacuum-drying 6 h, must have the hollow sphere silicon-dioxide of mesoporous lamella in 500 ℃ of roasting 4 h.

Embodiment 2

Get 1.5 g not the spherical MCM-48 mesopore molecular sieve of pure silicon base of template agent removing join in the 45 ml water, with 1 mol/L NaOH aqueous solution regulation system pH to 10, behind the stirring at room 4h; Change in the tetrafluoroethylene reaction kettle; Put into 120 ℃ of constant temperature ovens after the sealing and handle 12 h, take out reaction kettle then, naturally cooling in air; White precipitate spinning in the still; After washing 4 times again after earlier washing 3 times with absolute ethyl alcohol, 50 ℃ of baking oven vacuum-drying 24 h must have the hollow sphere silicon-dioxide of mesoporous lamella in 550 ℃ of roasting 6 h.

Embodiment 3

Get 4.2 g not the spherical SBA-15 mesopore molecular sieve of pure silicon base of template agent removing join in the 65 ml water, with 25 wt % tetraethyl ammonium hydroxide aqueous solution regulation system pH to 14, stir 12 h after; Change in the tetrafluoroethylene reaction kettle; Put into 140 ℃ of constant temperature ovens after the sealing and handle 36h, take out reaction kettle then, naturally cooling in air; White precipitate spinning in the still; After washing 5 times again after earlier washing 4 times with absolute ethyl alcohol, 80 ℃ of baking oven vacuum-drying 48 h must have the hollow sphere silicon-dioxide of mesoporous lamella in 600 ℃ of roasting 8 h.

Embodiment 4

Get 3.0 g not the spherical MCM-41 mesopore molecular sieve of pure silicon base of template agent removing join in the 85 ml water, with 25 wt % tetraethyl ammonium hydroxide aqueous solution regulation system pH to 11, stir 24 h after; Change in the tetrafluoroethylene reaction kettle; Put into 180 ℃ of constant temperature ovens after the sealing and handle 70 h, take out reaction kettle then, naturally cooling in air; White precipitate spinning in the still; After washing 2 times again after earlier washing 3 times with absolute ethyl alcohol, 50 ℃ of baking oven vacuum-drying 24 h must have the hollow sphere silicon-dioxide of mesoporous lamella in 550 ℃ of roasting 5 h.

Claims

1. the preparation method with hollow sphere silicon-dioxide of mesoporous lamella is characterized in that, as follows preparation:

A, with 0.5-4.5 g not the pure silicon base spherical mesoporous molecular sieve of template agent removing join in the 10-100 ml deionized water, to 8-14, stir 0.5-24 h with alkaline substance solution regulation system pH value;

B, the product after will stirring change in the closed reactor, handle 4-72 h at 100-200 ℃ of following constant temperature;

C, taking-up reaction kettle, naturally cooling in air;

D, white precipitate in the reaction kettle is separated, after first ethanol is washed 2-4 time again with washing 2-5 time, 40-80 ℃ of vacuum-drying 4-48 h then;

E, with dry gained white powder at 400-700 ℃ of following roasting 3-8 h, obtain having the hollow mesoporous silicon sphere material of mesoporous shell;

Aforesaid pure silicon spherical mesoporous molecular sieve is spherical MCM-41 mesopore molecular sieve or SBA-15 mesopore molecular sieve or MCM-48 mesopore molecular sieve;

2. have the preparation method of the hollow sphere silicon-dioxide of mesoporous lamella according to one kind of claim 1, it is characterized in that, get 0.5g not the spherical MCM-41 mesopore molecular sieve of pure silicon base of template agent removing join in the 15 ml water; With 2mol/L ammoniacal liquor regulation system pH to 9, behind stirring at room 1 h, change in the tetrafluoroethylene reaction kettle; Put into 100 ℃ of constant temperature ovens after the sealing and handle 4 h, take out reaction kettle then, naturally cooling in air; White precipitate spinning in the still; After washing 2 times again after washing 2 times with absolute ethyl alcohol earlier, behind 40 ℃ of baking oven vacuum-drying 6 h, must have the hollow sphere silicon-dioxide of mesoporous lamella in 500 ℃ of roasting 4 h.

3. have the preparation method of the hollow sphere silicon-dioxide of mesoporous lamella according to one kind of claim 1, it is characterized in that, get 1.5 g not the spherical MCM-48 mesopore molecular sieve of pure silicon base of template agent removing join in the 45 ml water; With 1 mol/L NaOH aqueous solution regulation system pH to 10, behind the stirring at room 4h, change in the tetrafluoroethylene reaction kettle; Put into 120 ℃ of constant temperature ovens after the sealing and handle 12 h, take out reaction kettle then, naturally cooling in air; White precipitate spinning in the still; After washing 4 times again after earlier washing 3 times with absolute ethyl alcohol, 50 ℃ of baking oven vacuum-drying 24 h must have the hollow sphere silicon-dioxide of mesoporous lamella in 550 ℃ of roasting 6 h.

4. have the preparation method of the hollow sphere silicon-dioxide of mesoporous lamella according to one kind of claim 1, it is characterized in that, get 4.2 g not the spherical SBA-15 mesopore molecular sieve of pure silicon base of template agent removing join in the 65 ml water; With 25 wt % tetraethyl ammonium hydroxide aqueous solution regulation system pH to 14; After stirring 12 h, change in the tetrafluoroethylene reaction kettle, put into 140 ℃ of constant temperature ovens after the sealing and handle 36h; Take out reaction kettle then; Naturally cooling in air, white precipitate spinning in the still, wash 5 times again after earlier washing 4 times with absolute ethyl alcohol after; 80 ℃ of baking oven vacuum-drying 48 h must have the hollow sphere silicon-dioxide of mesoporous lamella in 600 ℃ of roasting 8 h.

5. have the preparation method of the hollow sphere silicon-dioxide of mesoporous lamella according to one kind of claim 1, it is characterized in that, get 3.0 g not the spherical MCM-41 mesopore molecular sieve of pure silicon base of template agent removing join in the 85 ml water; With 25 wt % tetraethyl ammonium hydroxide aqueous solution regulation system pH to 11; After stirring 24 h, change in the tetrafluoroethylene reaction kettle, put into 180 ℃ of constant temperature ovens after the sealing and handle 70 h; Take out reaction kettle then; Naturally cooling in air, white precipitate spinning in the still, wash 2 times again after earlier washing 3 times with absolute ethyl alcohol after; 50 ℃ of baking oven vacuum-drying 24 h must have the hollow sphere silicon-dioxide of mesoporous lamella in 550 ℃ of roasting 5 h.