CN110371991A - The preparation method of core-shell structure silica spherical shape nano particle - Google Patents
The preparation method of core-shell structure silica spherical shape nano particle Download PDFInfo
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- CN110371991A CN110371991A CN201910604612.4A CN201910604612A CN110371991A CN 110371991 A CN110371991 A CN 110371991A CN 201910604612 A CN201910604612 A CN 201910604612A CN 110371991 A CN110371991 A CN 110371991A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
- C01B33/18—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
Abstract
The present invention relates to a kind of preparation methods of core-shell structure silica spherical shape nano particle, comprising: TEOS and APTES is added in O/W type surfactant-free microemulsion, after being completely dissolved, under the existence condition of ammonium hydroxide, condensation forms SiO2, collect solid SiO2Particle；Etching is to get core-shell structure silica spherical shape nano particle.It compares using TEOS and APTES synthetic silica spheric granules, and by the result etched with warm water with HF etching result.The present invention does not use surfactant, by O/W surfactant-free microemulsion, has not only synthesized that pattern is good, spheric granules of uniform size, and synthesis process is easy, fast.Therefore method provided herein has the characteristics that environmental-friendly, inexpensive, efficient and exploitativeness.
Description
Technical field
The invention belongs to field of nano material preparation, and in particular to a kind of core-shell structure silica nanosphere shape particle
Preparation method.
Background technique
Disclosing the information of the background technology part, it is only intended to increase understanding of the overall background of the invention, without certainty
It is considered as recognizing or implying in any form that information composition has become existing skill well known to persons skilled in the art
Art.
Nano material drug delivery, catalysis and in terms of have important application, with conventional surface activity
Agent microemulsion is that the research of template preparation nano material is more and more.Mesoporous, hollow, core-shell structure nano silica is available
In many fields such as drug delivery, catalysis and biological detection, cause the extensive concern of people.The nanometer titanium dioxide of core-shell structure
Silicon has biggish surface area, uniform pore diameter and unique vestibule distribution space, is applicable to separation and catalyst carrier
Deng.
To the preparation of this new type structure of hud nano particle, there are many reports in recent years.The conjunction of Core-shell Structure Nanoparticles
There are self-template methods, soft, hard template method and selective etch process etc. at method.The method of template auxiliary is typically based on to prepare
The nano particle of core-shell structure.Soft template method, it is most using micella, vesica and lotion etc. as template, but soft template method
The control of reaction condition is required more harsh.Hard template method, mostly to calcine or etch away by polymer or full particle
To form nucleocapsid particles even hollow bead after interior section structure.Self-template methods differ markedly from hard template, are made
The template later period used will not be removed instead for creating hollow structure inside and can be as the integral part of the mesoporous shell in outside.
Yu-Shen Lin et al. is based on template, and the nano SiO 2 particle of core-shell structure is prepared for using classical microemulsion.Xun
Wang et al. then utilizes hydro-thermal method and acid etch technology etc., also obtains the uniform nucleocapsid (SiO of structure2-SiO2) particle.Also have
People is prepared for nucleocapsid silica dioxide granule using surfactant mixture as soft template.Although the synthesis of core-shell structure particles
There are reports for method, but big multi-method is more complex and preparation cost is higher.
Summary of the invention
In order to overcome the above problem, the present invention provides a kind of silica dioxide granules of self-template methods synthesis core shell structure.
It is opposite with HF etching result using TEOS and APTES synthetic silica spheric granules, and by the result etched with warm water
Than.The present invention does not use surfactant, and by O/W surfactant-free microemulsion, it is good not only to have synthesized pattern, size
Uniform spheric granules, and synthesis process is easy, fast.Therefore method provided herein has environmental-friendly, inexpensive, high
The features such as effect and exploitativeness.
To realize the above-mentioned technical purpose, The technical solution adopted by the invention is as follows:
A kind of preparation method of core-shell structure silica spherical shape nano particle, comprising:
In O/W type surfactant-free microemulsion be added TEOS and APTES, after being completely dissolved, ammonium hydroxide there are items
Under part, condensation forms SiO2, collect solid SiO2Particle；Etching is to get core-shell structure silica spherical shape nano particle.
The application research discovery: after constructing the O/W drop of surfactant-free microemulsion, microresponse is formd
Device.The oil soluble material TEOS and APTES of addition enter the reactor.Under the catalytic action of ammonium hydroxide, because of the concentration of TEOS
Much larger than APTES, so that the condensation reaction rate of APTES is far smaller than the condensation reaction of TEOS, (EtO)4Si+2H2O=SiO2+
EtOH.Therefore, preliminary TEOS hydrolysis forms the harder SiO of structure2；With the reduction two silicon source substance at this time of TEOS content
Reaction rate is about the same, and the SiO of organic and inorganic is formed between core-shell structure copolymer2；Last a small amount of APTES is preferentially depleted, is remained
Remaining TEOS continues to hydrolyze to form harder SiO2Shell.By etching, HF aqueous solution or 40 DEG C of H2O can penetrate shell
The mesoporous of surface enters SiO2Inside, the SiO that then intermediate soft portion is divided2Be etched dissolution, ultimately forms core-shell structure
SiO2。
The composition of O/W type surfactant-free microemulsion can pattern to the silica dioxide granule of synthesis and uniformity generate
Large effect.Therefore, in some embodiments, the O/W type surfactant-free microemulsion is by diethyl malonate, ethyl alcohol
It is formed with water, which can form microresponse device, react the TEOS being added and APTES wherein, be formed between core-shell structure copolymer
The inorganic SiO of machine-2, prepared silica dioxide granule is with rule, uniform spherical nucleocapsid, regular appearance, stability
It is good.
When using Synthesis of Nanomaterials by Microemulsion, extreme influence of the structure and performance of material by technological factor is special
It is not that the condensation reaction that microemulsion matches TEOS and APTES in comparison O/W system has vital influence.Therefore, in some realities
It applies in example, the mass ratio of the diethyl malonate, second alcohol and water are as follows: 1:9~10:0.65~0.75, prepared nucleocapsid knot
Structure silica spherical shape nano particle, is uniformly dispersed, size uniformity.
Method proposed in this paper carries out in normal temperature and pressure, does not use without containing surfactant and high-temperature process.For
From solid silica dioxide granule to hollow or yolk eggshell structure silica dioxide granule, the selectivity of sphere middle section is lost
Quarter is particularly important.Method forms solid dioxy using tetraethyl orthosilicate (TEOS) under the catalytic action of ammonium hydroxide
SiClx spheric granules.But the addition meeting of 3-aminopropyltriethoxysilane (APTES) so that silicon skeleton by pure inorganic transformation
For inorganic-organic skeleton, by the regulation to each drug addition sequence and etch period etc., so that the internal junction of silica
Structure and surface layer generate difference.Therefore, in some embodiments, the molar ratio of the APTES, TEOS, ammonium hydroxide are as follows: 1:14~16:
133~135, prepared silica dioxide granule has core-shell structure.
In order to guarantee the orderly progress of condensation, the application optimizes the condition of condensation reaction, therefore, in some implementations
In example, the condensation reaction carries out under mechanical agitation, and the time is 60~62h, to guarantee that TEOS hydrolysis forms knot
The harder SiO of structure2Afterwards；The SiO of organic and inorganic is formed between core-shell structure copolymer2；Last remaining TEOS continues to hydrolyze to form harder
SiO2Shell.
In some embodiments, the etching uses HF solution or warm water, and the temperature of the warm water is 40 DEG C~45 DEG C.It is logical
The discovery of comparison etching mode is crossed, although the green cleaning of warm water lithographic method, bad control structure, the etching of short time is not
It is enough to form whole core-shell structure particles, but etching for a long time, it will lead to the rupture of partial particulate；The quarter of HF aqueous solution
Etching method greatly shortens the reaction time, and it is preferable to etch result.
Research is found: if HF solution concentration is excessively high, easily to shell structure generate destruction, it is too low if HF solution concentration, if can
Cause part of silica nanosphere that can not form core-shell structure.Therefore, in some embodiments, the quality of the HF solution is dense
Degree is 10~12%, and prepared core-shell structure silica spherical shape nano particle is uniformly dispersed, size uniformity.
In some embodiments, the condensation forms SiO2It uses afterwards and white precipitate, again washed, drying is collected by centrifugation,
Obtain solid SiO2Particle improves solid SiO2The purity of particle eliminates the reaction solution for remaining in its surface；
In some embodiments, the specific steps of warm water etching are as follows: take solid SiO2Sample particle is dissolved in ultrapure water,
Ultrasound is kept for 40 DEG C, then is centrifuged, and is washed, is dried, obtains part core-shell structure SiO2Granular solids.The method of warm water etching
Etching effect is poor, is only capable of preparing part core-shell structure SiO2Granular solids.
In some embodiments, the specific steps of HF solution etches are as follows: above-mentioned solid SiO2Sample is dissolved in ultrapure water,
HF aqueous solution is added, is uniformly mixed, centrifugation, washing, drying obtain core-shell structure SiO2Particle.With warm water etching phase ratio, using HF
The lithographic method of aqueous solution greatly shortens the reaction time, and it is preferable to etch result.
The present invention also provides the core-shell structure silica spherical shape nano particle of any above-mentioned method preparation, core it is straight
Diameter be 130-160nm, shell with a thickness of 20-30nm.
The present invention also provides above-mentioned core-shell structure silica spherical shape nano particles in drug delivery, catalysis and biology
The application of detection field.
The beneficial effects of the present invention are:
(1) self-template methods compared to tradition containing surfactant do not contain a large amount of surfactant in the method.
Therefore be conducive to save that experimental cost, material final wash process are simple, do not damage to environment and raw material can be with
Recycling.
(2) APTES addition so that initial stage synthesis nano SiO 2 particle, structural difference is obvious, is anaphase nucleus
The necessary condition that shell structure is formed.
(3) by comparing different lithographic methods, it has been found that two methods all have feasibility, but utilize HF solution
Obtained core-shell structure silica spherical shape nano particle is handled, is uniformly dispersed, size uniformity and preparation are easy.
(4) nano SiO 2 particle of core-shell structure, surface area is big, surface is meso-hole structure in sides such as catalysis, absorption
Face is with important application prospects.
(5) operating method of the application it is simple, it is at low cost, have universality, be easy to large-scale production.
Detailed description of the invention
The accompanying drawings constituting a part of this application is used to provide further understanding of the present application, and the application's shows
Meaning property embodiment and its explanation are not constituted an undue limitation on the present application for explaining the application.
Solid nano SiO 2 particle field emission scanning electron microscope (SEM) picture prepared by Fig. 1 embodiment of the present invention 1；
Nucleocapsid silica transmission electron microscope (TEM) picture prepared by 2 medium temperature water etching 144h of Fig. 2 embodiment of the present invention；
Nucleocapsid silica transmission electron microscope (TEM) picture prepared by 3 medium temperature water etching 216h of Fig. 3 embodiment of the present invention；
Nucleocapsid silica transmission electron microscope (TEM) picture prepared by HF solution etches in Fig. 4 embodiment of the present invention 4；
Fig. 5 present invention prepares the route map of core-shell structure silica spherical shape nano particle.
Specific embodiment
It is noted that following detailed description is all illustrative, it is intended to provide further instruction to the application.Unless another
It indicates, all technical and scientific terms used in this application have logical with the application person of an ordinary skill in the technical field
The identical meanings understood.
It should be noted that term used herein above is merely to describe specific embodiment, and be not intended to restricted root
According to the illustrative embodiments of the application.As used herein, unless the context clearly indicates otherwise, otherwise singular
Also it is intended to include plural form, additionally, it should be understood that, when in the present specification using term "comprising" and/or " packet
Include " when, indicate existing characteristics, step, operation, device, component and/or their combination.
It is complicated, at high cost for current nucleocapsid silica dioxide granule preparation method to ask as background technique is introduced
Topic.Therefore, an object of the present invention is: providing one kind and the microemulsion of surfactant is utilized to come the two of synthesis core shell structure
The method of silica spherical nanoparticle, the method are easy, efficient and environmentally protective.Core-shell structure silica nanosphere shape
The preparation method of grain, comprising:
(1) O/W type diethyl malonate/ethanol/water surfactant-free microemulsion is prepared: by diethyl malonate, second
Alcohol and water is configured to the microemulsion of clear according to a certain percentage；
(2) O/W type diethyl malonate/ethanol/water surfactant-free microemulsion under magnetic stirring, be added TEOS and
APTES, they will be dissolved in oily core, form the microenvironment of reaction.Then, ammonium hydroxide is added as catalyst, reactant contracting
Conjunction forms SiO2, white depositions are collected by centrifugation.After respectively being washed twice with ultrapure water and ethyl alcohol, white solid is put into 60 DEG C of bakings
Case dries 12h.Obtain solid SiO2Sample particle；
(3) appropriate solid SiO is taken2Sample particle is dissolved in ultrapure water, and ultrasound is kept for 40 DEG C, then is centrifuged, and is washed with ethyl alcohol
It washs once, solid is put into 60 DEG C of baking ovens and dries 12h.Obtain part core-shell structure SiO2Granular solids save, to be measured；
(4) above-mentioned appropriate solid SiO is taken2Sample is dissolved in ultrapure water, addition HF aqueous solution, after magnetic agitation, centrifugation,
It is washed with water three times, is put into 60 DEG C of baking ovens and dries 12h.Obtain core-shell structure SiO2Particle saves, to be measured；
The mass ratio of diethyl malonate, second alcohol and water in step (1) are as follows: 1.00:9.00:0.65；
The molar ratio of step (2) APTES, TEOS, ammonium hydroxide are as follows: 1.00:14.40:133.20, magnetic agitation react 60h；
40 DEG C of processing about 216h in step (3).In the present invention, as a result, it has been found that the warm water immersion of 144h can't obtain whole
The particle of core-shell structure, the warm water processing of 216h, obtains the silica dioxide granule of core-shell structure.But the shell quilt of partial particulate
It destroys.Therefore select suitable warm water etching period critically important to the pattern of final granule.
Magnetic agitation 10min after addition HF solution, finally obtains uniform core-shell structure SiO in step (4)2Ball shaped nano
Particle.
The second object of the present invention is to: the present invention utilizes surfactant-free, both after silicon source TEOS and APTES are added
Substance is all dissolved in oily core.Under the catalytic action of ammonium hydroxide, TEOS is because condensation reaction occurs greatly first for concentration:
(EtO)4Si+2H2O=SiO2+EtOH
Then internal harder SiO is formed2Particle；But with the reduction of TEOS reactant, APTES and TEOS is same at this time
Shi Jinhang reaction, in the SiO for forming organic and inorganic close to sphere stone outer section2Partially (this part is softer)；Finally
APTES is depleted that TEOS forms the SiO compared with hard shell in the shell condensation reaction of sphere first2.Therefore step (2) let us
Obtain the SiO of architectural difference2Spheric granules.
The third object of the present invention is: being compared with the lithographic method of medicine ball in document.It was found that when molten by HF
Liquid etching obtains the SiO of core-shell structure2When spheric granules, etch period can be greatly shortened.So that reaction process becomes quick, letter
Just.
The fourth object of the present invention is: the SiO of core-shell structure prepared by the present invention2Spherical nanoparticle material has straight
Diameter is the core of 130-160nm and the shell with a thickness of 20-30nm.Process of the present invention provides experiment base to control the size of nucleocapsid
Plinth.
The fourth object of the present invention is: the SiO of core-shell structure provided by the invention2Spherical nanoparticle material, in drug
Transmitting, absorption, biological medicine etc. have powerful application potential.
It is illustrated below by way of technical solution of the specific embodiment to the application.
In following embodiment, APTES ethanol solution the preparation method comprises the following steps: take 0.5mL APTES be added 2.75mL ethyl alcohol it is molten
In liquid, be uniformly mixed to get.
Embodiment 1
(1) in reaction flask, 4.0g ultrapure water and 36.0g second the preparation of O/W type surfactant-free microemulsion: is added
Alcohol, magnetic agitation effect is lower to be added 2.6g diethyl malonate, and 30min is stirred at room temperature in holding, until solution mixes.
(2) preparation of solid nano SiO 2 particle
1mL ethyl orthosilicate is added in microemulsion, then 0.4mL APTES ethanol solution is added, keeps magnetic force
Stirring.So that two kinds of substances are all dissolved in oily core.
(3) reaction flask is placed in magnetic agitation 2h in ice-water bath, 1.5mL ammonium hydroxide (25%wt) then is added, keep ice water
After bath 30 minutes, switch to room temperature magnetic agitation reaction 60h.
(4) after having reacted, white depositions are centrifuged to obtain, are respectively washed 2 times with water and ethyl alcohol.It obtains it after white powder
It is placed in 60 DEG C of baking ovens and dries 12h.
Embodiment 2
Appropriate white powder prepared by Example 1 is dissolved in 40 DEG C of ultrapure waters, constant temperature, is centrifuged after maintaining 144h, is used water
It respectively washed once with ethyl alcohol, obtain white solid, place it in 60 DEG C of baking ovens and dry 12h.It saves, it is to be measured.
Embodiment 3
Appropriate white powder prepared by Example 1 is dissolved in 40 DEG C of ultrapure waters, constant temperature, is centrifuged whole samples after maintaining 216h
Product respectively washed once with water and ethyl alcohol, obtain white solid, place it in 60 DEG C of baking oven drying 12h.It saves, it is to be measured.
Embodiment 4
Appropriate white powder prepared by Example 1 is dissolved in ultrapure water, stirs 10 points after 10% HF aqueous solution is added
Clock is centrifuged whole samples, is washed with water three times, obtains white solid, places it in 60 DEG C of baking ovens and dries 12h.It saves, it is to be measured.
The pattern comparison of the nucleocapsid silica prepared by Fig. 2-4 different etching mode is it is found that the application discovery, warm water
Although the green cleaning of lithographic method, the etching of bad control structure, short time are not enough to be formed whole core-shell structures
Particle, but prolonged etching, will lead to the rupture of partial particulate；The lithographic method of HF aqueous solution, when greatly shortening reaction
Between, and it is preferable to etch result.
Finally it should be noted that the foregoing is only a preferred embodiment of the present invention, it is not limited to this hair
It is bright, although the present invention is described in detail referring to the foregoing embodiments, for those skilled in the art, still
It can modify to technical solution documented by previous embodiment, or part is equivalently replaced.It is all in this hair
Within bright spirit and principle, any modification, equivalent replacement, improvement and so on should be included in protection scope of the present invention
Within.Above-mentioned, although specific embodiments of the present invention have been described, and it is not intended to limit the protection scope of the present invention, institute
Category field technical staff should be understood that based on the technical solutions of the present invention those skilled in the art do not need to pay wound
The various modifications or changes that the property made labour can be made are still within protection scope of the present invention.
Claims (10)
1. a kind of preparation method of core-shell structure silica spherical shape nano particle characterized by comprising
TEOS and APTES is added in O/W type surfactant-free microemulsion, after being completely dissolved, under the existence condition of ammonium hydroxide,
Condensation forms SiO2, collect solid SiO2Particle；Etching is to get core-shell structure silica spherical shape nano particle.
2. the preparation method of core-shell structure silica spherical shape nano particle as described in claim 1, which is characterized in that the O/
W type surfactant-free microemulsion is made of diethyl malonate, second alcohol and water.
3. the preparation method of core-shell structure silica spherical shape nano particle as claimed in claim 2, which is characterized in that described third
The mass ratio of diethyl adipate, second alcohol and water are as follows: 1:9~10:0.65~0.75.
4. the preparation method of core-shell structure silica spherical shape nano particle as described in claim 1, which is characterized in that described
The molar ratio of APTES, TEOS, ammonium hydroxide are as follows: 1:14~16:133~135.
5. the preparation method of core-shell structure silica spherical shape nano particle as described in claim 1, which is characterized in that the contracting
It closes reaction to carry out under mechanical agitation, the time is 60~62h.
6. the preparation method of core-shell structure silica spherical shape nano particle as described in claim 1, which is characterized in that the quarter
Erosion uses HF solution or warm water, and the temperature of the warm water is 40 DEG C~45 DEG C.
7. the preparation method of core-shell structure silica spherical shape nano particle as claimed in claim 6, which is characterized in that the HF
The mass concentration of solution is 10~12%.
8. the preparation method of core-shell structure silica spherical shape nano particle as claimed in claim 6, which is characterized in that
The condensation forms SiO2Afterwards using white precipitate, again washed, drying is collected by centrifugation, solid SiO is obtained2Particle；
Or the specific steps of warm water etching are as follows: take solid SiO2Sample particle is dissolved in ultrapure water, ultrasound, 40 DEG C of holding, then from
The heart, washing, drying, obtains part core-shell structure SiO2Granular solids；
Or the specific steps of HF solution etches are as follows: above-mentioned solid SiO2Sample is dissolved in ultrapure water, and HF aqueous solution, mixing is added
Uniformly, it is centrifuged, washing, drying obtain core-shell structure SiO2Particle.
9. the core-shell structure silica spherical shape nano particle of the described in any item method preparations of claim 1-8, feature exist
In, which is characterized in that the diameter of core be 130-160nm, shell with a thickness of 20-30nm.
10. core-shell structure silica spherical shape nano particle as claimed in claim 9 is led in drug delivery, catalysis and biological detection
The application in domain.
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