CN110371991B - Preparation method of core-shell structure silicon dioxide spherical nano-particles - Google Patents
Preparation method of core-shell structure silicon dioxide spherical nano-particles Download PDFInfo
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Abstract
The invention relates to a preparation method of core-shell structure silicon dioxide spherical nano particles, which comprises the following steps: adding TEOS and APTES into O/W type surfactant-free microemulsion, dissolving completely, and condensing in the presence of ammonia water to obtain the final productSiO2Collecting solid SiO2Particles; and etching to obtain the silicon dioxide spherical nano particles with the core-shell structures. Spherical particles of silica were synthesized using TEOS and APTES, and the results of etching with warm water were compared with those of etching with HF. The invention does not use surfactant, and utilizes O/W microemulsion without surfactant, thereby synthesizing spherical particles with good appearance and uniform size, and the synthesis process is simple, convenient and quick. Therefore, the method provided by the invention has the characteristics of environmental friendliness, low cost, high efficiency, feasibility and the like.
Description
Technical Field
The invention belongs to the field of nano material preparation, and particularly relates to a preparation method of core-shell structure silicon dioxide nano spherical particles.
Background
The information in this background section is only for enhancement of understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art that is already known to a person of ordinary skill in the art.
The nano material has important application in the aspects of drug delivery, catalysis, environmental protection and the like, and the research of preparing the nano material by taking the traditional surfactant microemulsion as a template is more and more. The nano silicon dioxide with mesoporous, hollow and core-shell structures can be used in many fields such as drug delivery, catalysis, biological detection and the like, and attract wide attention of people. The nano silicon dioxide with the core-shell structure has larger surface area, uniform aperture and unique pore cavity distribution space, and can be suitable for separation, catalyst carriers and the like.
In recent years, there have been many reports on the preparation of such novel core-shell structured nanoparticles. The synthesis method of the core-shell structure nano-particles comprises a self-template method, a soft template method, a hard template method, a selective etching method and the like. The preparation of core-shell structured nanoparticles is generally based on a template-assisted method. In the soft template method, micelles, vesicles, emulsions, and the like are often used as templates, but the control of reaction conditions is more demanding in the soft template method. The hard template method is usually used to form core-shell particles or even hollow particles by using polymers or solid particles after calcining or etching off internal partial structures. Self-templating is significantly different from hard templates in that the template used is not later removed but is used to create an internal hollow structure and is an integral part of the outer mesoporous shell. Yu-Shen Lin et al prepared silica nanoparticles with a core-shell structure using a conventional microemulsion based on a template method. Xun Wang et alThe core-Shell (SiO) with uniform structure is obtained by hydrothermal method and acid etching technique2-SiO2) And (3) granules. Core shell silica particles have also been prepared using surfactant mixtures as soft templates. Although some methods for synthesizing the core-shell structure particles have been reported, most methods are complex and have high preparation cost.
Disclosure of Invention
In order to overcome the problems, the invention provides a self-template method for synthesizing silica particles with core-shell structures. Spherical particles of silica were synthesized using TEOS and APTES, and the results of etching with warm water were compared with those of etching with HF. The invention does not use surfactant, and utilizes O/W microemulsion without surfactant, thereby synthesizing spherical particles with good appearance and uniform size, and the synthesis process is simple, convenient and quick. Therefore, the method provided by the invention has the characteristics of environmental friendliness, low cost, high efficiency, feasibility and the like.
In order to achieve the technical purpose, the technical scheme adopted by the invention is as follows:
a preparation method of core-shell structure silicon dioxide spherical nanoparticles comprises the following steps:
TEOS and APTES are added into O/W type surfactant-free microemulsion, and after complete dissolution, SiO is formed by condensation in the presence of ammonia water2Collecting solid SiO2Particles; and etching to obtain the silicon dioxide spherical nano particles with the core-shell structures.
The research of the application finds that: when the O/W droplets of the surfactant-free microemulsion were built, a mini-reactor was formed. The oil soluble materials TEOS and APTES added enter the reactor. Under the catalytic action of ammonia water, the concentration of TEOS is far higher than that of APTES, so that the condensation reaction rate of APTES is far lower than that of TEOS, (EtO)4Si+2H2O=SiO2+ EtOH. Thus, the preliminary TEOS hydrolysis reaction forms SiO with a harder structure2(ii) a As the TEOS content is reduced, the reaction rates of the two silicon source materials are almost the same, and organic-inorganic SiO is formed between the core and the shell2(ii) a Finally, a small amount of APTES is preferentially consumed, and the rest TEOS is continuously hydrolyzed to form harder SiO2A housing. By etching, aqueous HF solution or H at 40 deg.C2O can enter SiO through the mesopores on the surface of the shell2Inner, then middle softer part of SiO2Is etched and dissolved to finally form SiO with a core-shell structure2。
The composition of the O/W type surfactant-free microemulsion has a great influence on the morphology and uniformity of the synthesized silica particles. Thus, in some embodiments, the O/W-type surfactant-free microemulsion is composed of diethyl malonate, ethanol, and water, and the system can be formed into a mini-reactor in which the added TEOS and APTES are allowed to react to form an organic-inorganic SiO between the core and the shell2The prepared silicon dioxide particles have regular and uniform spherical core-shell structures, regular appearance and good stability.
When the microemulsion method is adopted to synthesize the nano material, the structure and the performance of the material are greatly influenced by process factors, and particularly the microemulsion proportion has a crucial influence on the condensation reaction of TEOS and APTES in an O/W system. Thus, in some embodiments, the mass ratio of diethyl malonate, ethanol, and water is: 1: 9-10: 0.65-0.75, and the prepared core-shell structure silicon dioxide spherical nano-particles are uniformly dispersed and uniform in size.
The method provided herein is carried out at normal temperature and pressure, does not contain a surfactant, and does not employ high temperature treatment. The selective etching of the middle portion of the sphere is particularly important for silica particles ranging from solid silica particles to hollow or egg shell structures.The method utilizes tetraethyl orthosilicate (TEOS) to form solid silicon dioxide spherical particles under the catalytic action of ammonia water. However, the addition of 3-Aminopropyltriethoxysilane (APTES) can change the silicon skeleton from a pure inorganic skeleton to an inorganic-organic skeleton, and the internal structure and the surface layer of the silicon dioxide are different by regulating and controlling the addition sequence, etching time and the like of each medicine. Thus, in some embodiments, the molar ratio of APTES, TEOS, and ammonia is: 1: 14-16: 133-135, preparedThe silica particles have a core-shell structure.
In order to ensure the orderly progress of condensation, the conditions of the condensation reaction are optimized, so that in some embodiments, the condensation reaction is carried out under the condition of mechanical stirring for 60-62 hours to ensure that the TEOS hydrolysis reaction forms SiO with a harder structure2Then; formation of organic-inorganic SiO between core and shell2(ii) a Finally, the remaining TEOS is continuously hydrolyzed to form harder SiO2A housing.
In some embodiments, the etching uses an HF solution or warm water at a temperature of 40 ℃ to 45 ℃. The comparison of etching modes shows that the warm water etching method is green and clean, but the structure is not easy to control, short-time etching is not enough to form all core-shell structure particles, but long-time etching can cause the breakage of partial particles; the etching method of the HF aqueous solution greatly shortens the reaction time and has better etching result.
The research finds that: if the concentration of the HF solution is too high, the shell structure is easily damaged, and if the concentration of the HF solution is too low, part of the silicon dioxide nanospheres cannot form the shell structure. Therefore, in some embodiments, the mass concentration of the HF solution is 10-12%, and the prepared core-shell structure silica spherical nanoparticles are uniformly dispersed and uniform in size.
In some embodiments, the condensation forms SiO2Then centrifugally collecting white precipitate, washing and drying to obtain solid SiO2Particles of solid SiO are improved2Purity of the particles, removal of residual reaction solution on the surface thereof;
in some embodiments, the warm water etching comprises the following specific steps: taking solid SiO2Dissolving the sample particles in ultrapure water, performing ultrasonic treatment, keeping the temperature at 40 ℃, centrifuging, washing and drying to obtain partial SiO with the core-shell structure2A particulate solid. The etching effect of the warm water etching method is poor, and only partial SiO with the core-shell structure can be prepared2A particulate solid.
In some embodiments, the specific steps of HF solution etching are: the solid SiO2Dissolving the sample in the solutionAdding HF aqueous solution into pure water, uniformly mixing, centrifuging, washing and drying to obtain SiO with a core-shell structure2And (3) granules. Compared with warm water etching, the etching method adopting the HF aqueous solution greatly shortens the reaction time and has better etching result.
The invention also provides the core-shell structure silicon dioxide spherical nano-particles prepared by any one of the methods, wherein the diameter of the core is 130-160nm, and the thickness of the shell is 20-30 nm.
The invention also provides application of the core-shell structure silicon dioxide spherical nano-particles in the fields of drug delivery, catalysis and biological detection.
The invention has the beneficial effects that:
(1) compared with the traditional self-template method containing the surfactant, the method does not contain a large amount of the surfactant. Therefore, the method is favorable for saving the experimental cost, has simple material later washing process, does not cause damage to the environment and can recycle raw materials.
(2) Due to the addition of APTES, the structural difference of the silicon dioxide nano-particles synthesized in the initial stage is obvious, and the method is a necessary condition for the formation of a later-stage core-shell structure.
(3) By comparing different etching methods, the two methods are feasible, but the core-shell structure silicon dioxide spherical nano-particles obtained by HF solution treatment are uniform in dispersion, uniform in size and simple and convenient to prepare.
(4) The silicon dioxide nano-particles with the core-shell structure have large surface area and mesoporous structure on the surface, and have important application prospects in the aspects of catalysis, adsorption and the like.
(5) The operation method is simple, low in cost, universal and easy for large-scale production.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate embodiments of the application and, together with the description, serve to explain the application and are not intended to limit the application.
FIG. 1 is a field emission Scanning Electron Microscope (SEM) picture of solid silica nanoparticles prepared in example 1 of the present invention;
FIG. 2 is a Transmission Electron Microscope (TEM) picture of core-shell silica prepared by medium temperature water etching for 144h in example 2 of the present invention;
FIG. 3 is a Transmission Electron Microscope (TEM) image of core-shell silica prepared by medium-temperature water etching for 216h in example 3 of the present invention;
FIG. 4 is a Transmission Electron Microscope (TEM) image of core-shell silica prepared by HF solution etching in example 4 of the present invention;
FIG. 5 is a schematic diagram of the preparation of silica spherical nanoparticles with core-shell structure according to the present invention.
Detailed Description
It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the disclosure. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of example embodiments according to the present application. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
As introduced in the background art, the method aims at solving the problems of complex preparation method and high cost of the existing core-shell silicon dioxide particles. Therefore, one of the objects of the present invention is: the method for synthesizing the silicon dioxide spherical nano-particles with the core-shell structure by using the microemulsion of the surfactant is simple, convenient, efficient and environment-friendly. The preparation method of the silicon dioxide nano spherical particles with the core-shell structure comprises the following steps:
(1) preparing O/W type diethyl malonate/ethanol/water surfactant-free microemulsion: preparing clear and transparent microemulsion from diethyl malonate, ethanol and water according to a certain proportion;
(2) O/W type diethyl malonate/ethanol/water surfactant-free microemulsion under magnetic stirringTEOS and APTES are added, and will dissolve in the oil core to form a microenvironment for reaction. Then, ammonia water is added as a catalyst, and reactants are condensed to form SiO2The white precipitate was collected by centrifugation. After washing twice with ultrapure water and ethanol, the white solid was oven-dried at 60 ℃ for 12 hours. Obtaining solid SiO2Sample particles;
(3) taking a proper amount of solid SiO2Dissolving the sample particles in ultrapure water, performing ultrasonic treatment, keeping the temperature at 40 ℃, centrifuging, washing with ethanol once, and drying the solid in an oven at 60 ℃ for 12 hours. Obtaining partial SiO with core-shell structure2Storing the granular solid to be tested;
(4) taking the appropriate amount of solid SiO2Dissolving a sample in ultrapure water, adding an HF aqueous solution, magnetically stirring, centrifuging, washing with water for three times, and drying in an oven at 60 ℃ for 12 hours. Obtaining SiO with a core-shell structure2Particles are stored and are to be detected;
in the step (1), the mass ratio of diethyl malonate, ethanol and water is as follows: 1.00:9.00: 0.65;
the mol ratio of APTES, TEOS and ammonia water in the step (2) is as follows: reacting for 60 hours at a ratio of 1.00:14.40:133.20 by magnetic stirring;
the treatment in step (3) is carried out for about 216h at 40 ℃. In the invention, the result shows that the particles with the core-shell structure can not be obtained by soaking in warm water for 144h, and the silicon dioxide particles with the core-shell structure can be obtained by treating with warm water for 216 h. But the shell of part of the particles is destroyed. The selection of an appropriate warm water etch time is therefore important to the morphology of the final particles.
Adding HF solution in the step (4), and then magnetically stirring for 10min to finally obtain uniform SiO with a core-shell structure2Spherical nanoparticles.
The second purpose of the invention is that: the invention uses surfactant-free, after adding silicon source TEOS and APTES, these two substances are dissolved in oil core. Under the catalytic action of ammonia, TEOS firstly undergoes condensation reaction because of large concentration:
(EtO)4Si+2H2O=SiO2+EtOH
thus forming SiO with harder inner part2Particles; however, as the TEOS reactant is reduced, APT is presentES reacts with TEOS at the same time to form organic-inorganic SiO near the outer layer of the hard core of the sphere2Part (this part is softer); finally APTES is consumed firstly, TEOS is condensed on the outer shell of the sphere to form SiO with a hard shell2. Thus step (2) lets us obtain SiO with structural differences2Spherical particles.
The third purpose of the invention is: compared with the etching method of the solid sphere in the literature. It was found that SiO in the core-shell structure is obtained when etching with the aid of HF solutions2With spherical particles, the etching time is greatly shortened. The reaction process becomes rapid and simple.
The fourth purpose of the invention is: SiO with core-shell structure prepared by the invention2Spherical nanoparticle material having a core with a diameter of 130-160nm and a shell with a thickness of 20-30 nm. The process of the invention provides an experimental basis for controlling the size of the core shell.
The fourth purpose of the invention is: the SiO of the core-shell structure provided by the invention2The spherical nano-particle material has strong application potential in the aspects of drug delivery, adsorption, biological medicine and the like.
The technical solution of the present application will be described below with specific examples.
In the following examples, the preparation of APTES ethanol solution was as follows: adding 0.5mL of APTES into 2.75mL of ethanol solution, and mixing uniformly to obtain the final product.
Example 1
(1) Preparing O/W type microemulsion without surfactant: 4.0g of ultrapure water and 36.0g of ethanol are added into a reaction flask, 2.6g of diethyl malonate is added under the action of magnetic stirring, and the mixture is kept at room temperature and stirred for 30min until the solution is mixed uniformly.
(2) Preparation of solid silica nanoparticles
1mL of tetraethylorthosilicate was added to the microemulsion, followed by 0.4mL of APTES in ethanol, maintaining magnetic stirring. So that both substances are totally dissolved in the oil core.
(3) The reaction flask was placed in an ice-water bath and magnetically stirred for 2h, then 1.5mL of ammonia (25% wt) was added, and after maintaining the ice-water bath for 30min, the reaction was switched to room temperature and magnetically stirred for 60 h.
(4) After the reaction, a white precipitate was obtained by centrifugation, and washed 2 times with water and ethanol, respectively. After obtaining white powder, the white powder is placed in an oven at 60 ℃ for baking for 12 h.
Example 2
An appropriate amount of the white powder prepared in example 1 was dissolved in ultrapure water at 40 ℃, kept at a constant temperature for 144 hours, centrifuged, washed once with water and ethanol to obtain a white solid, and placed in an oven at 60 ℃ for 12 hours. And (5) storing and testing.
Example 3
An appropriate amount of the white powder prepared in example 1 was dissolved in 40 ℃ ultrapure water, the temperature was maintained, all samples were centrifuged after maintaining for 216 hours, and washed once with water and ethanol, respectively, to obtain a white solid, which was placed in a 60 ℃ oven and dried for 12 hours. And (5) storing and testing.
Example 4
An appropriate amount of the white powder prepared in example 1 was dissolved in ultrapure water, a 10% aqueous solution of HF was added thereto, the mixture was stirred for 10 minutes, the whole sample was centrifuged, and the resultant was washed three times with water to obtain a white solid, which was then dried in an oven at 60 ℃ for 12 hours. And (5) storing and testing.
As can be seen from the comparison of the appearances of the core-shell silicon dioxide prepared by different etching modes in fig. 2 to 4, the present application finds that the warm water etching method is green and clean, but is not easy to control the structure, short-time etching is not enough to form all core-shell structure particles, but long-time etching can cause the fracture of part of particles; the etching method of the HF aqueous solution greatly shortens the reaction time and has better etching result.
It should be noted that the above-mentioned embodiments are only preferred embodiments of the present invention, and the present invention is not limited thereto, and although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that modifications and equivalents can be made in the technical solutions described in the foregoing embodiments, or equivalents thereof. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention. Although the present invention has been described with reference to the specific embodiments, it should be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention.
Claims (7)
1. A preparation method of silica spherical nanoparticles with a core-shell structure is characterized by comprising the following steps:
TEOS and APTES are added into O/W type surfactant-free microemulsion, and after complete dissolution, SiO is formed by condensation in the presence of ammonia water2Collecting solid SiO2Particles; etching to obtain the silicon dioxide spherical nano particles with the core-shell structure;
the O/W type surfactant-free microemulsion consists of diethyl malonate, ethanol and water; the mass ratio of the diethyl malonate to the ethanol to the water is as follows: 1: 9-10: 0.65-0.75;
the mol ratio of APTES, TEOS and ammonia water is as follows: 1:14 to 16:133 to 135.
2. The preparation method of the core-shell structure silica spherical nanoparticles according to claim 1, wherein the condensation reaction is performed under a mechanical stirring condition for 60-62 hours.
3. The preparation method of the core-shell structure silica spherical nanoparticle as claimed in claim 1, wherein the etching employs HF solution or warm water, and the temperature of the warm water is 40 ℃ to 45 ℃.
4. The preparation method of the core-shell structure silica spherical nanoparticle as claimed in claim 3, wherein the mass concentration of the HF solution is 10-12%.
5. The method for preparing the core-shell structure silica spherical nanoparticles according to claim 3,
the condensation to form SiO2Then centrifugally collecting white precipitate,Then washing and drying to obtain solid SiO2Particles;
or the specific steps of warm water etching are as follows: taking solid SiO2Dissolving the sample particles in ultrapure water, performing ultrasonic treatment, keeping the temperature at 40 ℃, centrifuging, washing and drying to obtain partial SiO with the core-shell structure2A particulate solid;
or the specific steps of HF solution etching are as follows: the solid SiO2Dissolving a sample in ultrapure water, adding an HF aqueous solution, uniformly mixing, centrifuging, washing and drying to obtain the SiO with the core-shell structure2And (3) granules.
6. The spherical silica nanoparticles having a core-shell structure prepared by the method as set forth in any one of claims 1 to 5, wherein the diameter of the core is 130-160nm and the thickness of the shell is 20-30 nm.
7. The use of the core-shell structured spherical silica nanoparticles of claim 6 in the fields of drug delivery, catalysis, and biological detection.
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CN107879348A (en) * | 2017-08-07 | 2018-04-06 | 山东师范大学 | A kind of preparation method of the monodisperse silica nanosphere of novel green |
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