CN108821296A

CN108821296A - A kind of preparation method of mesoporous spherical nano Sio 2 particle

Info

Publication number: CN108821296A
Application number: CN201810608071.8A
Authority: CN
Inventors: 张坤; 彭博; 单冰倩; 林冠峰
Original assignee: East China Normal University
Current assignee: East China Normal University
Priority date: 2018-06-13
Filing date: 2018-06-13
Publication date: 2018-11-16

Abstract

The invention discloses a kind of preparation methods of mesoporous spherical nano Sio 2 particle, this method uses cationic surfactant as template, by hydrolyzing the strategy regulated and controled in advance using silicon source, then unhydrolysed tetraethoxy esters of silicon acis is mixed, pass through the amount of two kinds of silicon source substances of regulation and the type of surfactant, the nucleation rate of final regulation and control particle realizes precisely being combined to for mesoporous spherical nano Sio 2 particle of the particle size within the scope of 25 ~ 100nm.Synthetic method of the present invention is simple, the period is short, at low cost, reproducible, is a kind of environmental-friendly green synthesis method.

Description

A kind of preparation method of mesoporous spherical nano Sio 2 particle

Technical field

The present invention relates to a kind of preparation method of meso-porous nano molecular sieve, relates in particular to a kind of particle size and be less than The preparation method of the silicon-based mesoporous molecular sieve nano particle of 100nm.

Background technique

Mesopore silicon dioxide nano material is a kind of with that high-specific surface area, macropore hold, morphology and size is controllable is novel Inorganic nano material, it is caused in the application study of material science, biological medicine, environmental protection, field of biosensors in recent years Extensive concern.On the one hand, due to its small toxicity, the features such as easily exclusion, the application on medicament slow release and organism is increasingly Extensively；On the other hand, on Solar use, because it possesses lesser index of refraction, more duct is a kind of good anti-reflective It penetrates（AR）Material；But the two applications require its size in 100nm hereinafter, therefore macroblock quantization precisely synthesizes size and is less than The mesoporous silica nano-particle of 100nm is extremely urgent.Currently synthesize small-size meso-porous nano SiO 2 particle（MSN） Main synthetic strategy include：Use single CTAB cationic surfactant（Angew. Chem. Int. Ed., 2002, 2151, 2317.）, early stage reaction, diluted by a large amount of water, particle growth be quenched, has been less than to be prepared for size The mesoporous silica nano-particle of 100 nm, but grain shape is irregular, and size distribution is very inhomogenous；By changing Into St ber method（J. Phys. Chem. B 2004, 108, 20122.）, using ethyl alcohol as CTAB cation surface activating The cosurfactant of agent can prepare the monodispersed mesoporous SiO of height₂Nano particle, but size is commonly greater than 100 nm； Bein is by using triethanolamine（TEAH₃）Replace inorganic base that can synthesize meter ruler cun less than 200 nm mesoporous nano-grains （Adv. Funct. Mater. 2007, 17, 605.）, but triethanolamine（TEAH₃）Dosage it is very big, and need logical Final particle can just be obtained by crossing ultracentrifugal method；Kuroda is recently reported a new synthetic strategy to prepare size SiO mesoporous less than 50nm₂Nano particle, but the molar ratio of CTAB/TMOS is greater than 0.5, the usage amount of water is very big, synthesis Cost is high and surfactant will could remove (Chem. Commu., 2009,5094.) by complicated dialysis process；In State patent CN1923684A makees template using sarcosyl, with（3- aminopropyl）Trimethoxy silane is co-structured leads To agent, SiO uniform in size, that size is controllable has been synthesized₂Nano particle, but the cost synthesized is relatively high；Hybrid template The synthetic strategy of agent may also used to the monodispersed mesoporous nano-grain of synthesis height, but the price of surfactant valuableness It is limited to be widely applied（Chemical Journal of Chinese Universities, 2011,32,560.）.It is examined from particulate nucleation and the angle of growth Consider, according to classical Lamer law, if closing small sized nano SiO 2 particle, the hydrolysis rate of silicon source will use up can Can be fast, outburst forms a large amount of silica sub-nanometer cores, therefore tetramethoxy esters of silicon acis in the short time（TMOS）It is optimal Silicon source, but the silicon source is not only expensive but also easily hydrolysis is difficult to save for a long time in air, thus limit its conduct Use of the silicon source in mesoporous silica nano-particle synthesis.Nearest patent report utilizes organic alkoxide control TEOS's Hydrolysis rate, to efficiently synthesize the mesoporous silica nano-particle that size is less than 50nm.But the introducing of organic alkoxide On the one hand the cost of nano material synthesis is increased, on the other hand also will increase the burden of environment.From above-mentioned report as it can be seen that existing Synthetic method existence condition it is harsh, at high cost, pollution is big and is unfavorable for large-scale production the disadvantages of.Therefore new conjunction is researched and developed It is current mesoporous SiO at technology₂The top priority of nano particle basic research.

Summary of the invention

The purpose of the present invention is to provide the mesoporous SiO that the small size of a kind of quick, low cost, pollution is lower than 100nm₂It receives Rice grain green syt preparation method.

The object of the present invention is achieved like this：

A kind of preparation method of mesoporous spherical nano Sio 2 particle, feature are：This method is with amphiphatic cationic surface Activating agent is template, alkali source, tetraethoxy esters of silicon acis（TEOS）The tetraethoxy esters of silicon acis hydrolyzed in advance be silicon source, Deionized water is as raw material；Mole group of raw material become the tetraethoxy silicic acid ester ︰ sun that hydrolyzes in advance of tetraethoxy-silicane acid ester ︰ from Sub- surfactant ︰ alkali ︰ water=0.03~0.06 ︰ of 0.2-1 ︰ 0.1-0.2 ︰, 0.5~2 ︰ 80~500；Specific preparation includes following Step：

First deionized water, alkali source, template are successively mixed in reaction vessel, 80 DEG C of constant temperature are stirred to solution and clarified, then By the tetraethoxy esters of silicon acis of certain molar weight hydrolyzed in advance（TEOS）It is quickly adding into solution, reacts 5 ~ 60 points Clock；Finally again by no tetraethoxy esters of silicon acis by hydrolyzing in advance（TEOS）It is added dropwise in mixed solution, 80 DEG C of constant temperature continue stirring 2 hours, are directly filtered, washed and dried product after being cooled to room temperature, are handled using roasting or acid By the surfactant removal in duct, the mesoporous spherical nano Sio 2 particle is obtained；Wherein：

The tetraethoxy esters of silicon acis hydrolyzed in advance is that tetraethoxy esters of silicon acis room temperature complete hydrolysis under proper pH value is formed Metasilicic acid species；The amphiphilic cationic surfactant is cetyl trimethyl p-methyl benzenesulfonic acid ammonium or hexadecane Base trimethylammonium bromide；The alkali source includes common inorganic base, and such as sodium hydroxide, ammonium hydroxide also include organic small molecule amine, such as Monoethanolamine, diethanol amine or triethanolamine；The reaction temperature is 30 ~ 80^oC；The roasting is to roast 5 at 550 DEG C Hour；Acid processing is stirred at room temperature 1 hour with the HCl ethanol solution of 1M.

The present invention has the following advantages that compared with existing preparation method：

1）The tetraethoxy esters of silicon acis hydrolyzed in advance（TEOS）It can produce a large amount of metasilicic acid species, directly adsorb in the outer of micella Surface promotes the synthesis speed of silica nanometer core in effective condensation of reaction early stage silicon, and explosion type is nucleated to obtain small ruler Very little nano SiO 2 particle is avoided using expensive and facile hydrolysis tetramethylsilane acid esters TMOS as silicon source, greatly be saved About synthesis cost.

2）From the point of view of the characterization result of product, the product shape that the present invention obtains is regular, aperture is uniform, and particle size is 20 Controllable modulation between ~ 100nm.

3）Surfactant in mesopore orbit is removed by one step of method of direct pickling and high-temperature roasting.

4）Sample, which passes through the method that is simply ultrasonically treated, can be distributed to water, in ethyl alcohol isopolarity protonated solvent, obtain To highly stable colloidal solution.

Detailed description of the invention

Fig. 1 is the mesoporous SiO that the present invention synthesizes₂The scanning electron microscope of nano particle（SEM）Figure；

Fig. 2 is the mesoporous SiO that the present invention synthesizes₂The high-resolution transmission electron microscope of nano particle（TEM）Figure.

Specific embodiment

Below by embodiment, the invention will be further described, and purpose, which is only that, better understands research of the invention The protection scope that content is not intended to limit the present invention.

Embodiment 1

First by 1.05g cetyl trimethylammonium bromide（CTAB）It is added to containing 69.12ml deionized water, tri- second of 0.238g Hydramine（TEAH₃）Beaker in, 80 DEG C of constant temperature are stirred to become to solution for 1 hour and be clarified, the tetraethoxy for then hydrolyzing 1g in advance Esters of silicon acis pours into solution rapidly, 80 DEG C of reactions after ten minutes, then by the unhydrolysed tetraethoxy esters of silicon acis of 9g（TEOS）Dropwise It is added in the beaker, 80 DEG C of constant temperature continue to stir 2 hours, obtain white precipitate, and mole group of the mixture becomes TEOS :The TEOS of prehydrolysis: CTAB : TEAH₃: H₂O = 0.9:0.1:0.06:0.026:80；To obtain mixture directly filter, Washing, drying, obtain mesoporous SiO₂Nano particle, yield 94%, 42 nm of average grain diameter（The SEM figure and Fig. 2 of sample obtained by Fig. 1 The TEM of gained sample schemes）.The surfactant in duct can be removed with a step using the method for high-temperature roasting or acid processing The specific method is as follows：1.0g original powder roasts 6 hours directly in 550 DEG C of muffle furnaces；Or 1.0g original powder is in the salt of 40ml 1M In sour ethanol solution, it is stirred at room temperature 1 hour, is filtered, washed, dries.Finally obtain the specific surface area 650m of particle²/ g, 0.73ml/g, aperture 2.6nm.

Embodiment 2

First by 1.05g cetyl trimethylammonium bromide（CTAB）It is added to containing 69.12ml deionized water, tri- second of 0.238g Hydramine（TEAH₃）Beaker in, 80 DEG C of constant temperature are stirred to become to solution for 1 hour and be clarified, the tetraethoxy for then hydrolyzing 2g in advance Esters of silicon acis pours into solution rapidly, 80 DEG C of reactions after ten minutes, then by the unhydrolysed tetraethoxy esters of silicon acis of 8g（TEOS）Dropwise It is added in the beaker, 80 DEG C of constant temperature continue to stir 2 hours, obtain white precipitate, and mole group of the mixture becomes TEOS :The TEOS of prehydrolysis: CTAB : TEAH₃: H₂O = 0.8:0.2 :0.06:0.026:80；Mixture will be obtained directly to take out Filter, washing, drying, obtain mesoporous SiO₂Nano particle, yield 94%, 30 nm of average grain diameter.

Embodiment 3

Other synthesis conditions are identical, and surfactant is by cetyl trimethylammonium bromide（CTAB）Change cetyl trimethyl into P-methyl benzenesulfonic acid ammonium；It is prepared for the mesoporous SiO that average grain diameter is 85 nm₂Nano particle.

Claims

1. a kind of preparation method of mesoporous spherical nano Sio 2 particle, which is characterized in that this method with it is amphiphatic sun from Sub- surfactant be template, alkali source, tetraethoxy esters of silicon acis and the tetraethoxy esters of silicon acis hydrolyzed in advance be silicon source, go from Sub- water is as raw material；Mole group of raw material becomes the tetraethoxy silicic acid ester ︰ cation form that tetraethoxy-silicane acid ester ︰ is hydrolyzed in advance Face Huo Ji ︰ Jian ︰ water=0.03~0.06 ︰ of 0.2-1 ︰ 0.1-0.2 ︰, 0.5~2 ︰ 80~500；Specific preparation includes following step Suddenly：

First deionized water, alkali source, template are successively mixed in reaction vessel, 80 DEG C of constant temperature are stirred to solution and clarified, then The tetraethoxy esters of silicon acis hydrolyzed in advance is quickly adding into solution, is answered 5 ~ 60 minutes；Finally again by tetraethoxy esters of silicon acis It is added dropwise in mixed solution, 80 DEG C of constant temperature continue stirring 2 hours, are directly filtered, washed product after being cooled to room temperature And it is dry, the surfactant in duct is removed using roasting or acid processing, obtains the mesoporous silica spheres shape nanometer Particle；Wherein：

The tetraethoxy esters of silicon acis hydrolyzed in advance is tetraethoxy esters of silicon acis in room temperature complete hydrolysis formation metasilicic acid species； The amphiphilic cationic surfactant is cetyl trimethyl p-methyl benzenesulfonic acid ammonium or cetyl trimethyl bromine Change ammonium；The alkali source is sodium hydroxide, ammonium hydroxide, monoethanolamine, diethanol amine or triethanolamine；The reaction temperature be 30 ~ 80^oC；The roasting is roasted 5 hours at 550 DEG C；Acid processing is stirred at room temperature 1 hour with the HCl ethanol solution of 1M.