CN104445215B

CN104445215B - The preparation method of hollow silica nano material

Info

Publication number: CN104445215B
Application number: CN201410614977.2A
Authority: CN
Inventors: 张海娇; 徐慧娟; 朱学栋; 李立昂; 应敏霞; 焦正
Original assignee: University of Shanghai for Science and Technology
Current assignee: University of Shanghai for Science and Technology
Priority date: 2014-11-05
Filing date: 2014-11-05
Publication date: 2016-11-16
Anticipated expiration: 2034-11-05
Also published as: CN104445215A

Abstract

The present invention relates to the preparation method of a kind of hollow silica nano material.The present invention is with Nano carbon balls as hard template, tetraethyl orthosilicate (TEOS) is silicon source, water as solvent, and cetyl trimethylammonium bromide (CTAB) makees structure directing agent, remove the residual organic matter such as carbon ball and CTAB by subsequent heat treatment, obtain pattern uniformly, hollow SiO of surface folding shape₂Nano material.Knowable to TEM picture, the SiO that the present invention prepares₂Nano material, has hollow structure, and wall thickness is about 20 nm, and particle diameter is at about 200 nm.Hollow SiO prepared by this method₂Nano material has potential application prospect in fields such as biomedicines.

Description

The preparation method of hollow silica nano material

Technical field

The present invention relates to the preparation method of a kind of hollow silica nano material.

Background technology

Along with the development of nanotechnology, it is many that nano material has been widely used in catalysis, biomedicine and fine chemistry industry etc. Individual field.Wherein, nano silicon (SiO₂) as one of extremely important New Inorganic Materials, because of its have particle diameter adjustable, Many unrivaled advantages such as specific surface area is high, dispersive property is good and structural stability is high and abundance, with low cost, Various fields has very important effect.

Currently, with respect to the material of the special appearance on different nanostructureds and nano-scale, as nano-particle, nano wire, Nanotube and nanometer rods etc., be widely studied.Wherein, hollow porous nanometer structure is always one of focus of people's research. With traditional Si O₂Material is compared, and this kind of material has porous and hollow dual structure characteristic, and not only density is lower, and specific surface area is more Greatly, and have unique advantages such as good biocompatibility, stable framing structure, higher porosity and easy modification, Therefore all have important application in fields such as chemistry, biological and material science, as catalysis, adsorb and separate, medicine transmission etc..Closely Nian Lai, multiple preparation hollow porous SiO₂Method, including sol-gel process, template, microemulsion method and hydrothermal synthesis method Deng, it is in the news.Wherein, template (soft template and hard template method) is one of important method of nano materials, and technology is relatively For maturation.Soft template method is to utilize surfactant, micelle or polymer vesicle etc. as Flexible formwork assembly to prepare SiO₂Hollow Porous material, but the SiO that the method prepares₂Material shape is irregular, particle diameter is uneven and shell is the most damaged.Used is organic Solvent easily causes environmental pollution, and productivity is low, is not suitable for large-scale production.And hard template method is mainly by its space confinement effect With structure-directing effect, the pattern of material, size, structure etc. are carried out effective cutting.Compared with additive method, hard template method Preparation nano material is workable, and the regulation and control to product are more accurate, the good product dispersibility prepared.

In consideration of it, the present invention is with the pyrogenically prepared Nano carbon balls of glucose as hard template, water is solvent, and tetraethyl orthosilicate is Silicon source, by simple low temperature hydrolysis process, prepares hollow sphere silicon oxide nano material.

Summary of the invention

It is an object of the invention to provide the preparation method of a kind of hollow silica nano material, this method can obtain Pattern rule, uniform particle diameter, surface have hollow SiO of fold₂Nano material.

For reaching above-mentioned purpose, the present invention by the following technical solutions:

The preparation method of a kind of hollow silica nano material, it is characterised in that concretely comprising the following steps of the method:

A. prepared carbon ball is dissolved in 0.20 ~ 0.50 mol/L ethanol solution, adds 3-aminopropyl-triethoxy silicon Alkane, stirring at normal temperature 2 h obtains mixed solution；Wherein, the mass ratio of 3-aminopropyl triethoxysilane and carbon ball be 0.00125 ~ 0.002:1；

B. in step a gained mixed solution, a certain amount of tetraethyl orthosilicate and ammonia (25 ~ 28 wt%) are added, regulation PH value to 11 ~ 12, centrifugation after stirring at normal temperature 12 h；Wherein, the mass ratio of tetraethyl orthosilicate and carbon ball be 0.0018 ~ 0.0025:1；

C. step b products therefrom is dissolved in deionized water, adds cetyl trimethylammonium bromide, and regulate pH value Being 9 ~ 10, stir, be added dropwise over tetraethyl orthosilicate, 55 ° of C stir 2 h；After having reacted, reactant is taken out, often The steps such as being centrifuged, wash of rule, drying, and in 550 ° of C air atmospheres, calcine 6 h, obtain hollow sphere prepared by the present invention Silica nano material；Wherein, the mass ratio of cetyl trimethylammonium bromide and TEOS is 0.20 ~ 1.0:1.

During present invention process, preparing particle diameter at about 180 nm initially with hydro-thermal method, pattern is homogeneous and dispersibility Good carbon ball is hard template, the dealcoholysis polycondensation reaction pair occurred with the methoxyl group in APTES followed by the hydroxyl on carbon ball surface Gained carbon ball carries out organic decoration, then in the alkaline environment that ammonia provides, and the SiO that a small amount of TEOS hydrolysis generates₂Nanometer Particle is in carbon ball superficial growth, thus forms one layer of unbodied SiO₂Thin layer.Subsequently, at sodium hydroxide or the alkaline bar of ammonia In part, the rear TEOS added continues hydrolysis, by the structure-directing effect of Surfactant CTAB, further in amorphous Si O₂ Superficial growth, finally roasting 6 h in 550 ° of C air atmospheres of Muffle furnace, removes the organic miscellaneous of de-carbon template, CTAB and residual After matter, obtain the SiO of hollow porous₂Nano material.

Compared with prior art, the technology of the present invention has following remarkable advantage: the present invention reacts gentle, the product tool prepared There are low-density, pattern and a structure-controllable, and are uniformly dispersed and the advantage such as surface easily modification, additionally, the cavity that ball interior is huge Be conducive to storage and the transport of material, therefore have potential biomedical applications prospect, can be used for the controllable release etc. of medicine.

Accompanying drawing explanation

Fig. 1 is the TEM photo of gained hollow silica nano material in the embodiment of the present invention 1.

Fig. 2 is the SEM photograph of gained hollow silica nano material in the embodiment of the present invention 1.

Fig. 3 is the FT-IR spectrogram of gained hollow silica nano material in the embodiment of the present invention 1.

Detailed description of the invention

All embodiments are all operated by the operating procedure of technique scheme.Carbon ball used in the present invention its prepare Method refers to CrystEngComm, 2012,14,3793-3801.

Embodiment 1

First produce carbon ball by existing known technology: with electronic balance weigh 1.98 g glucoses add 20 mL go from In sub-water, ultrasonic extremely dissolving, is poured in the band teflon-lined autoclave of 100 mL, in 180 ° of C conditions Lower reaction 6 h, after having reacted, takes out product from reactor, is centrifuged with ethanol and deionized water, washs, and Dry under 60 ° of C, obtain the carbon ball that the pattern of particle diameter 180 about nm is homogeneous；

B. take carbon ball prepared for 50 mg to be dissolved in 20 mL ethanol, add 100 μ L 3-aminopropyl triethoxysilanes (APTES), stirring at normal temperature 2 h；

C. in above-mentioned solution, add 100 μ L tetraethyl orthosilicate (TEOS) and 250 μ L ammonia (NH₃·H₂O, 25 ~ 28 Wt%), centrifugal after stirring at normal temperature 12 h；

D. the product after being centrifuged is dissolved in 18 mL deionized waters, adds 0.0364 g cetyl trimethylammonium bromide (CTAB), after adding 0.9 mL 0.001M NaOH, stirring, be added dropwise over 200 μ L TEOS, 55 ° of C stir 2 h；

E., after having reacted, product is taken out, with deionized water and ethanol cyclic washing, centrifugal after, by product at 60 ° of C Lower drying, is finally placed in Muffle furnace air atmosphere, and 550 ° of C calcine 6 h, obtains hollow sphere two prepared by the present invention Silicon oxide nano material.

The product of gained is carried out physical property sign, and its partial results is as shown in drawings.Resulting materials is hollow spheres structure, Wall thickness is about 20 nm, particle diameter 200 about nm, surface irregularity, has a lot of folds.

Embodiment 2: preparation process and the step of the present embodiment are essentially identical with embodiment, difference is b step:

Take carbon ball prepared for 50 mg to be dissolved in 20 mL ethanol, do not add 3-aminopropyl triethoxysilane (APTES), Stirring at normal temperature 2 h.

Acquired results is bigger with embodiment 1 topographical difference, it is impossible to forming complete hollow ball structure, surface folding is many, group Poly-the most serious.

Embodiment 3

Preparation process and the step of the present embodiment are substantially the same manner as Example 1, and difference is Step d:

Being dissolved in 18 mL deionized waters by product after centrifugal, after adding 0.9 mL 0.001M NaOH, stirring is all Even, it is added dropwise over 200 μ L TEOS, stirs 2 h；Do not add cetyl trimethylammonium bromide (CTAB).

Acquired results and embodiment 1 topographical difference are relatively big, and product is the solid silica ball that particle diameter is uneven.

Embodiment 4

Product after centrifugal is dissolved in 18 mL deionized waters, adds 0.0364 g cetyl trimethylammonium bromide (CTAB) 0.9 mL 0.001M NH, is added₃·H₂After O, stir, be added dropwise over 200 μ L TEOS, 55 ° of C stirrings 2 h；

Acquired results and embodiment 1 pattern slightly difference, SiO₂The surface folding of shell becomes apparent from.

Seeing accompanying drawing, Fig. 1 is transmission electron microscope (TEM) figure of the embodiment of the present invention 1 gained hollow silica nano material Sheet.Tem analysis: use Jeol Ltd. JEOL-200CX type transmission electron microscope observation material morphology.From TEM Picture is it can be seen that the hollow silica nano material for preparing of the present invention, and spherical structure is complete, surface folding porous, its grain Footpath is homogeneous controlled at about 200 nm, particle diameter and wall thickness.

Seeing accompanying drawing, Fig. 2 is the embodiment of the present invention 1 gained spherical hollow SiO₂Scanning electron microscope (SEM) figure of nano material Sheet.Sem analysis: use NEC company JSM-6700F type to launch sem observation material morphology.Scheme from SEM Sheet is it can be seen that hollow SiO for preparing of the present invention₂Nano material is regular spherical granule, consistent with TEM result.

Seeing accompanying drawing, Fig. 3 is the embodiment of the present invention 1 gained spherical hollow SiO₂The infrared absorpting light spectra of nano material (Fourier transform infrared spectrometer, FT-IR).FT-IR analyzes: use Thermo Nicolet The infrared absorption spectroscopy of the AVATAR 370 type Fourier transform infrared spectrometer test sample of company, enters sample before test Row infrared drying, uses KBr pressed-disc technique, and spectrogram test scope is 400 ~ 4000 cm^-1.It can be seen that 1066 cm^-1 Absorption belong to Si-O-Si antisymmetric stretching vibration peak, 808 cm^-1The peak at place is Si-O key symmetrical stretching vibration peak, it was demonstrated that Products therefrom is SiO₂Material.

Claims

1. the preparation method of a hollow silica nano material, it is characterised in that concretely comprising the following steps of the method:

A. prepared carbon ball is dissolved in 0.20 ~ 0.50 mol/L ethanol solution, adds 3-aminopropyl triethoxysilane, Stirring at normal temperature 2 h obtains mixed solution；Wherein, 3-aminopropyl triethoxysilane is 0.00125 ~ 0.002 with the mass ratio of carbon ball: 1；

B adds a certain amount of tetraethyl orthosilicate in step a gained mixed solution and concentration is 25 ~ 28 wt% ammonia, regulates pH It is worth to 11 ~ 12, centrifugation after stirring at normal temperature 12 h；Wherein, the mass ratio of tetraethyl orthosilicate and carbon ball be 0.0018 ~ 0.0025:1；

C. step b products therefrom is dissolved in deionized water, adds cetyl trimethylammonium bromide, and regulate pH value be 9 ~ 10, stir, be added dropwise over tetraethyl orthosilicate, 55 ° of C stir 2 h；After having reacted, reactant is taken out, through conventional from The heart, wash, the step such as drying, and in 550 ° of C air atmospheres, calcine 6 h, obtain hollow sphere titanium dioxide prepared by the present invention Silicon nano material；Wherein, the mass ratio of cetyl trimethylammonium bromide and TEOS is 0.20 ~ 1.0:1.