CN101948139A

CN101948139A - Method for preparing novel mesoporous silica nano balls

Info

Publication number: CN101948139A
Application number: CN2010102910709A
Authority: CN
Inventors: 张海娇; 焦正; 李智勇; 张宗南; 张璐; 李霞
Original assignee: University of Shanghai for Science and Technology
Current assignee: University of Shanghai for Science and Technology
Priority date: 2010-09-21
Filing date: 2010-09-21
Publication date: 2011-01-19

Abstract

The invention relates to a method for preparing novel mesoporous silica nano balls, and belongs to the technical field of inorganic chemistry and material synthesis. The method comprises the following main steps of: mixing a certain amount of diethyl ether, deionized water, ammonia water and tetraethoxysilane for reaction, adding a certain amount of tetraethoxysilane and cetyl trimethyl ammonium bromide (serving as a template agent), putting into a high pressure reactor, and performing reaction at 120 DEG C for 12 to 24 hours; and cleaning with the deionized water and ethanol solution, performing centrifugal separation, drying the sedimentation, and finally obtaining the mesoporous silica nano balls. The material has the advantages of high chemical stability and no toxin, and is expected to be applied to the aspect of biomedicines, such as fields of controlled release of medicines, biosensors and cell marking.

Description

A kind of preparation method of novel mesoporous silicon dioxide nano ball

Technical field

The present invention relates to a kind of preparation method of novel mesoporous silicon dioxide nano ball, belong to inorganic chemistry and field of material synthesis technology.

Background technology

Since 1992, the scientist of U.S. Mobil company uses the nanostructure self-assembling technique first, with the quaternary cationics is template, prepare have even duct, since the MCM-41 that the aperture is adjustable, mesoporous material is because it has internal surface and the higher specific surface area that is easy to modify, the characteristics such as handiness that the duct of narrow pore size distribution, rule is arranged and formed, the ability that good penetrating quality, absorption property and screening molecule are arranged, thus in catalysis, absorption and separate, field such as drug delivery has extremely application prospects.At present, the direct embedding of medicine and controlled release are the good Application Areass of ordered mesoporous material, and this is that mainly ordered mesoporous material has very big specific surface area and specific pore volume, can be in the duct of material fixing various medicines of embedding, and can play controlled-release function to medicine, improve the persistence of drug effect; Also can utilize the bio-guide effect, hit target cell and diseased region efficiently and accurately, give full play to the curative effect of medicine, therefore, this field has attracted numerous scientists' concern.

Wherein, in the family, the nanometer ball of porous silica structure is one of drug molecule carrier ideal material because of having advantages such as Stability Analysis of Structures, nontoxicity and biocompatibility in mesoporous material.Thereby get more and more people's extensive concerning.At present, various synthetic methods have been used to synthesizing porous nano ball and nanocapsule as hard template method, vesica method and microemulsion method etc.In the currently known methods, under the anti-phase environment of oil-water, form nano silicon material by template and the self-assembly of inorganic silicon species and be considered to a kind of very effective method, cause investigators' very big interest.Yet, how to obtain the porous nano capsule and the nanometer ball of size and pattern controlled and medicine carrier band and slowly-releasing superior performance, remain the challenge of a greatness.Therefore, exploring the method for synthesizing good pattern and controllable size mesoporous silicon sphere is very important.

Summary of the invention

The preparation method who the purpose of this invention is to provide a kind of novel mesoporous silicon dioxide nano ball

The preparation method of a kind of novel mesoporous silicon dioxide nano ball of the present invention is characterized in that having following preparation process and step

A. get a certain amount of ether and a certain amount of deionized water is put into container, the volume ratio of ether and deionized water is 4: 1～6: 1; Stir at the constant temperature lower magnetic force, make to mix;

B. add proper ammonia and tetraethoxy (TEOS) then successively in above-mentioned solution, the volume ratio of ammoniacal liquor and tetraethoxy is 1: 1～1: 4; Continued stirring reaction 1～3 hour;

C. progressively slowly add tetraethoxy (TEOS) and cetyl trimethylammonium bromide (CTAB) in above-mentioned solution for continuous; Both consumptions recently measure with volume weight, i.e. TEOS: CTAB=1: (0.35～1.0) that is to say that every 1mL tetraethoxy needs the cetyl trimethylammonium bromide of adapted 0.35～1.0g; Slow then stirring reaction 3～6 hours;

D. the autoclave of above-mentioned mixed solution being packed into is put into 120 ℃ of baking ovens, reacts 12～24 hours;

E. take out mixed solution and use deionized water and ethanol repetitive scrubbing respectively repeatedly, centrifugation then obtains precipitation; This precipitation is placed in 60 ℃ of baking ovens dries, finally obtain the mesoporous silicon dioxide nano ball.In the technological process of the present invention, as template, water is solvent with cetyl trimethylammonium bromide, and ether after stirring, can make solution form reverse microemulsion system as cosolvent; In addition, ether has played the effect of auxiliary template agent simultaneously; The nano-structure porous silicon ball that obtains of the inventive method not only has the pattern of dispersing at the center but also has meso-hole structure.

The present invention adopts simple reverse microemulsion method, prepare the new pattern porous silicon dioxide nano sphere of novel chrysanthemum shape of emission around the mind-set therefrom first, this material is expected to be applied to the biological medicine aspect, as the controllable release of medicine, fields such as biosensor and cell marking.

Compared with prior art, the technology of the present invention has following remarkable advantage:

This novel porous SiO that the present invention makes ₂Nanometer ball is the new pattern porous SiO that disperses growth around a kind of therefrom mind-set ₂Nanometer ball.The inventive method is simple to operate, good reproducibility; The porous SiO that obtains ₂Nanometer ball have the high and low poison of chemical stability in addition nontoxic, with low cost, be easy to realize characteristics such as physiologically acceptable, through can be used for biological medicine carrying, fluorescent mark etc. after the subsequent disposal such as finishing.

Description of drawings

Fig. 1 is the novel porous SiO of gained in the embodiment of the invention 1 ₂The SEM photo of nanometer ball.

Fig. 2 is the novel porous SiO of gained in the embodiment of the invention 1 ₂The TEM photo of nanometer ball.

Fig. 3 is the novel porous SiO of gained in the embodiment of the invention 1 ₂The XRD figure spectrum of nanometer ball.

Embodiment

After now specific embodiments of the invention being described in.

Embodiment 1

(1) measures 40mL ether (CH respectively with graduated cylinder ₃OCH ₃) and 8mLH ₂O pours in the sealing round-bottomed flask of 100mL band stopper, and the room temperature lower magnetic force mixes;

(2) in solution, slowly add 1mL ammoniacal liquor (NH then successively ₄OH) and 2mL tetraethoxy (TEOS), continued stirring reaction 3 hours;

(3) progressively slowly add TEOS 2mL and cetyl trimethylammonium bromide (CTAB) 1.0g again in above-mentioned solution, slowly stirring reaction is 5 hours;

(4) will go up the step mixed solution autoclave of packing into, put into 120 ℃ baking oven, react 20 hours;

(5) take out mixed solution and take off layer precipitation with centrifugation behind distilled water, the ethanol repetitive scrubbing respectively, at last precipitation is put

In 60 ℃ of baking ovens, dry, obtain porous SiO ₂Nanometer ball.

Embodiment 2

The implementation process step except for the following differences, other are all identical with embodiment 1

In (2) step, in solution, slowly add 1mL ammoniacal liquor (NH successively ₄OH) and 2mL tetraethoxy (TEOS), continued stirring reaction 1 hour;

In (3) step, in solution, progressively slowly add TEOS 2mL, cetyl trimethylammonium bromide (CTAB) 0.8g again, slowly stirring reaction is 3 hours;

The gained result is similar substantially to embodiment 1, and difference is SiO ₂The diameter of nanometer ball is more smaller than embodiment's 1.

Embodiment 3

In (2) step, in solution, slowly add 1mL ammoniacal liquor (NH successively ₄OH) and 1mL tetraethoxy (TEOS), continued stirring reaction 2 hours;

In (3) step, in solution, progressively slowly add TEOS 1mL and cetyl trimethylammonium bromide (CTAB) 1.0g again, slowly stirring reaction is 5 hours;

Result and embodiment 1 broadly similar, difference is to obtain SiO ₂Some descends the output of nanometer ball, the SiO that obtains ₂Nanometer ball is less than normal a bit.

Embodiment 4

In (2) step, in solution, slowly add 1mL ammoniacal liquor (NH then successively ₄OH) and 4mL tetraethoxy (TEOS), continued stirring reaction 3 hours;

In (3) step, in solution, progressively slowly add TEOS 4mL and cetyl trimethylammonium bromide (CTAB) 1.5g again, slowly stirring reaction is 4 hours;

Result and embodiment 1 broadly similar, difference is SiO ₂The output of nanometer ball increases, and particle diameter is bigger than normal slightly.Instrument detecting

Every instrument detecting the results are shown among Fig. 1, Fig. 2 and Fig. 3 of accompanying drawing.

Referring to accompanying drawing, Fig. 1 is the novel porous SiO of gained in the embodiment of the invention 1 ₂The SEM photo of nanometer ball.Sem analysis: adopt Japanese Hitachi S-4800 type sem observation material surface pattern and size-grade distribution.As can be seen from Figure 1: the novel porous SiO of the present invention's preparation ₂Nanometer ball is spheroidal particle of uniform size, and its particle diameter is about 200nm.

Referring to accompanying drawing, Fig. 2 is the novel porous SiO of gained in the embodiment of the invention 1 ₂The TEM photo of nanometer ball.Tem analysis: adopt the JSM-2010F of Jeol Ltd. type transmission electron microscope observation material pattern.Can be clearly seen that novel porous SiO from the TEM picture ₂Nanometer ball is the novel structure as chrysanthemum of emission around the mind-set therefrom, and the particulate size is about 200nm.

Referring to accompanying drawing, Fig. 3 is the novel porous SiO of gained in the embodiment of the invention 1 ₂The XRD figure spectrum of nanometer ball.XRD analysis: on Japanese Rigaku D/max-2550 type X-ray diffractometer, carry out, adopt CuK _αDiffraction.Therefrom as can be known, the novel porous SiO of gained ₂Nanometer ball has good characteristic peak at Small angle, illustrates that it has certain meso-hole structure.

Claims

1. method with the synthesizing porous BiFeO3 nano microcrystalline of P123 assisting sol gel method is characterized in that having following process and step:

A. the preparation of raw material: the Fe (NO that operational analysis is pure ₃) ₃9H ₂O and Bi (NO ₃) ₃5H ₂O is as raw material, according to Fe: after the weighing in 1: 1 of Bi mol ratio that both are mixed, place flask;

B. the preparation of colloidal sol: analytical pure ethylene glycol is added above-mentioned flask as solvent and complexing agent,, inorganic salt raw material is dissolved fully, become even mixed solution by magnetic agitation; Add a certain amount of analytical pure Glacial acetic acid as stablizer, above-mentioned solution is placed oil bath device, stirred 30 minutes at 70 ℃ of constant temperature, will add condensation reflux unit this moment, prevents that solution evaporation is too fast; Add a certain amount of analytical pure P123 as tensio-active agent and pore-forming material, continue 70 ℃ of constant temperature and stirred 2 hours, obtain maroon colloidal sol;

C. the formation of gel: above-mentioned maroon colloidal sol is poured in the culture dish, put into 70 ℃ of baking oven air seasonings 2 days, make it fully aging, form the maroon xerogel; The gained xerogel is fully ground in mortar, obtain yellow dry gel powder;

D. the sintering of gel powder: above-mentioned dry gel powder is put into retort furnace carry out sintering, the control temperature rise rate is 1 ℃/min, reaction environment is that air or protective atmosphere are (as nitrogen, oxygen), the sintering top temperature is 400 ℃～600 ℃, top temperature insulation 30 minutes, cool to room temperature with the furnace, obtain the sinter of a series of various grain sizes and pattern;

E. washing and dry: above-mentioned sinter is washed with deionized water and ethanol, and the baking oven inner drying at 80 ℃ promptly obtains BiFeO ₃Crystallite.