CN110203936B - Nano silicon dioxide microsphere with surface topological structure and preparation method thereof - Google Patents
Nano silicon dioxide microsphere with surface topological structure and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a preparation method of nano silicon dioxide microspheres with surface topological structures, which comprises the following steps: under the condition of stirring, firstly mixing a silicon source and deionized water according to a certain proportion; then, adding a small molecular surface active substance (R-X) to obtain a clear and transparent mixed solution; then, adding an alkaline catalyst, and reacting to generate silica sol (a); then, adding an ammonia solution, and reacting to generate silica sol (b); and finally, carrying out solid-liquid separation and washing on the silica sol (b) to obtain the nano silica microspheres with the surface topological structure. The preparation method has the characteristics of simplicity, mild conditions, controllable particle size, large reaction batch and the like, is an environment-friendly synthesis method, and has wide application prospect.
Description
Technical Field
The invention relates to a preparation method of nano-silica microspheres with surface topological structures, in particular to green and batch nano-silica microspheres with surface topological structures and a preparation method thereof, belonging to the technical field of chemistry and inorganic materials.
Background
Classic
The method is used for preparing the monodisperse silicon dioxide microspheres, alcohol is used as a solvent, water is used as a reactant, and ammonia water is used as a catalyst. Generally, alcohol, water and catalyst are mixed to obtain alcohol-water-ammonia solution, then the silicon source/alcohol solution is dropped into the alcohol-water-ammonia solution under the condition of stirring, and the silicon source is hydrolyzed to obtain (Si (OH) 4 )，Si(OH) 4 And (4) performing condensation polymerization-growth to obtain the solid silica microspheres with smooth surfaces. It can be widely used in paint, ceramics, cosmetics, colloidal crystal, catalysis, etc. However, the solid silica microspheres with smooth surfaces have limited specific surface area and internal cavities, and are difficult to apply in the aspects of adsorption, catalysis, biomedicine and the like.
The nano material with surface topological structure is used for the targeted delivery of the medicine,The preparation method has wide potential application in the biomedical fields of drug carriers, gene carriers, contrast agents, cancer treatment and the like. The organic material carrier has the inherent defects of poor thermal and chemical stability, so that the coated drug is easy to generate explosive release of the drug in a human body due to the decomposition of the organic carrier, and the organic carrier has the defect of low drug coating amount. The inorganic nano-drug carrier with the pore structure has high drug loading capacity, easily modified internal and external pores, good thermal and chemical stability, and has shown specific advantages in early diagnosis of serious diseases and targeted drug delivery. In particular silicon oxide (SiO) 2 ) The mesoporous material has good biocompatibility and degradability (inorganic material science, 2013, 28,1-11.). The surface topological structure nano-silica microsphere has certain surface structure characteristics, physical and mechanical strength and larger specific surface area, and has attracted extensive research interest (adv. Mater.2013, DOI: 10.1002/adam.201302189).
The synthesis work of the nano silicon dioxide nano microsphere with the surface topological structure has made some progress. However, in the synthesis of the surface topological structure nano-silica nanospheres, a plurality of surfactants (CN 103663478) are used, the synthesis process is complex, and the batch preparation is difficult.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides a preparation method of nano silicon dioxide microspheres with surface topological structures, which does not need to add a surfactant. Firstly, mixing a silicon source, water and a micromolecular surface active substance medium according to a certain proportion to obtain a clear and transparent mixed solution; on the basis, adding an alkaline catalyst, starting a reaction to generate silica sol (a), and adding an ammonia water solution into the sol to react to generate silica sol (b); and (c) carrying out solid-liquid separation and washing on the obtained silica sol (b) to obtain the nano silica microspheres with the surface topological structure. The target product prepared by the invention has high specific surface area (84.91-426.02 m) 2 And/g) has wide application prospect in the aspects of adsorption, catalysis and biomedicine and has surface topological structure nano silicon dioxide microspheres.
In order to achieve the above purpose, the invention adopts the technical scheme that:
a preparation method of nano-silica microspheres with surface topological structures comprises the following steps:
(1) Silicon source/H 2 Preparation of O emulsion: mixing silicon source with deionized water to obtain silicon source/H 2 O emulsion;
(2) Silicon source/R-X/H 2 Preparing an O mixed solution: under the stirring condition, mixing the micromolecular surface active substance with the silicon source/H obtained in the step (1) 2 Mixing the O emulsion to obtain a clear and transparent silicon source/R-X/H 2 O mixed solution;
(3) Preparation of silica sol: adding an alkaline catalyst into the silicon source/R-X/H obtained in the step (2) 2 Reacting in the O mixed solution for a certain time to generate silica sol (a);
(4) Preparation of silica sol with topological structure: adding an ammonia water solution into the silica sol (a) obtained in the step (3) under the conditions of certain temperature and stirring, and reacting for a certain time to obtain silica sol (b);
(5) And (4) carrying out solid-liquid separation and washing on the silica sol (b) obtained in the step (4) to obtain the nano silica microspheres with the surface topological structure.
In the step (1), the silicon source and the deionized water are mixed under the condition of stirring, wherein the stirring speed is 200-300 rpm; preferably, 200rpm, 250rpm, 300rpm.
In the step (1), the mixing temperature is 15-30 ℃; preferably, it is room temperature (20 ℃ C.), 30 ℃.
In the step (1), the mixing time is 1-3 hours; preferably, from 1 to 2 hours; further preferably, it is 2 hours.
In step (1) of the present invention, the silicon source comprises one or more of silicate ester (including but not limited to methyl silicate, ethyl silicate, propyl silicate, etc.), silane coupling agent (including but not limited to γ -aminopropyl triethoxysilane (KH 550), γ - (2,3-glycidoxy) propyl trimethoxysilane (KH 560), γ - (methacryloyloxy) propyl trimethoxysilane (KH 570), γ -mercaptopropyl triethoxysilane (KH 580), γ -mercaptopropyl trimethoxysilane (KH 590), vinyl triethoxysilane (KH 151), vinyl trimethoxysilane (KH 171), etc.); preferably, it is ethyl silicate (TEOS).
In step (1) of the present invention, the volume ratio of the silicon source to the deionized water is: v is more than or equal to 1:50 Silicon source ∶V H2O Less than or equal to 1: 5; preferably 1:5, 1: 10, 1:50 or 3: 50.
In the step (2), the stirring speed is 200 to 300rmp; preferably, 200rpm, 250rpm, 300rpm.
In the step (2) of the invention, the mixing temperature is 15-30 ℃; preferably, it is room temperature (20 ℃).
In the step (2), the mixing time is 1-3 hours; preferably, it is 2 hours.
In the step (2), the small molecule surface active substance is an organic small molecule substance which is mutually soluble with water and does not dissociate; the molecular formula is R-X, wherein R is alkyl; x is hydroxyl, keto, aldehyde group, etc.
Wherein the organic small molecule substance comprises alcohol, aldehyde, ketone and the like; preferably, it is a C1-C4 alkyl alcohol; further preferably, it is methanol (CH) 3 OH), ethanol (C) 2 H 5 OH), isopropyl alcohol ((CH) 3 ) 2 CHOH), sec-butanol (CH) 3 CH 2 CH(OH)CH 3 ) Tert-butyl alcohol ((CH) 3 ) 3 COH); further preferably, ethanol.
In step (2) of the present invention, the small molecule surfactant may be, but not limited to, analytically pure.
In step (2) of the present invention, the small molecule surface active substance and the silicon source/H 2 The volume ratio of the O emulsion is 1: 2-8: 5; preferably, 3: 5 to 8:5; further preferably 10: 11, 32: 33, 50: 33.
In step (2) of the present invention, the silicon source is silicon source/R-X/H 2 The concentration of the O mixed solution is 0.05-0.5M; preferably, 0.05E0.42M; further preferably, it is 0.05M, 0.19M, 0.36M.
In the step (3), the reaction is carried out at 20-60 ℃; preferably, the temperature is 20-40 ℃ and 40-60 ℃; further preferably, it is room temperature (20 ℃), 40 ℃ or 60 ℃.
In the step (3), the reaction time is 2-5 hours; preferably, it is 3 hours.
In the step (3), the reaction is carried out under the condition of stirring, and the rotating speed of the stirring is 200-300 rpm; preferably, 200rpm, 250rpm, 300rpm.
In the step (3), the alkaline catalyst is a weakly alkaline catalyst selected from ammonia water and Na 2 CO 3 NaAc; preferably, ammonia; further preferably, it is a 28% (mass fraction) aqueous ammonia solution.
In the step (3), the alkaline catalyst is added into the silicon source/R-X/H obtained in the step (2) 2 And starting the reaction in the O mixed solution. The concentration of the alkaline catalyst in the whole reaction system is 0.2-2.0 mol/L; preferably, the concentration is 0.2mol/L, 0.3mol/L, 0.4 to 1.5mol/L, or 2.0mol 1/L. Further preferably, the concentration of the ammonia water catalyst in the whole reaction system is 0.4-1.5 mol/L; further preferably, the concentration of the ammonia catalyst is 0.44mol/L, 0.59mol/L, 0.74mol/L, 1.48mol/L.
In step (3) of the present invention, the silicon source/R-X/H prepared in step (2) is preferably added before the reaction with the catalyst 2 Heating the O mixed solution to the reaction temperature, and keeping the temperature for 15-25 min; preferably, the incubation is carried out for 15min or 25min.
In the step (4), the certain temperature is 15-30 ℃; preferably, it is room temperature (20 ℃ C.), 30 ℃.
In the step (4) of the invention, the stirring speed is 200-300 rpm; preferably, 200rpm, 250rpm, 300rpm.
In the step (4), the volume ratio of the added ammonia water to the silica sol (a) is 3: 1-6: 1; preferably 17: 5, 50: 11, 11: 2.
In the step (4), the concentration of the ammonia water is 3.5% -2.5%; preferably 3.3%, 2.8%, 3.0%.
In the step (4), the certain reaction time is 8-12 hours; preferably, it is 10 hours.
In the step (5), the solid-liquid separation comprises centrifugal separation, spray drying and freeze spray drying; preferably, centrifugation.
In step (5) of the present invention, the conditions of centrifugal separation in the solid-liquid separation are as follows: the rotation speed can be more than 8000 rmp; preferably, 8000 to 15000rmp; further preferably 8000rmp, 9000rmp, 10000rmp, 12000rmp, 13000rmp, 15000rmp.
In the step (5), the temperature of centrifugal separation in the solid-liquid separation is 20-30 ℃; preferably, it is room temperature (25 ℃).
In the step (5), the centrifugal separation time in the solid-liquid separation is 10-30 min; preferably, 10min, 20min, 30min.
In the step (5), after centrifugal separation in the solid-liquid separation, the method can also comprise a step of washing the prepared nano-silica microspheres with the surface topological structure by using an organic solvent; preferably, the nano-silica microspheres with surface topology are washed with deionized water for 3 times, and then washed with ethanol for 3 times.
In the invention, the conditions of the preparation method are different, and the prepared surface topological structure nano-silica microspheres are different, but the surface topological structure nano-silica microspheres prepared by adopting the specific conditions of the invention have uniform size, the particle size range of the surface topological structure nano-silica microspheres which can be prepared is between 100 nm and 250nm (for example, the particle size range can be 103nm, 110nm, 115nm, 122nm, 225nm, 227nm and 250 nm), and the silica microspheres have surface topological structures (such as TEM images of the silica microspheres obtained in examples 1 to 7, see figures 1 to 7).
The invention also provides the nano silicon dioxide microsphere with the surface topological structure prepared by the preparation method.
Wherein the particle size of the nano silicon dioxide microsphere with the surface topological structure is 100-250nm; preferably 103nm, 110nm, 115nm, 122nm, 225nm, 227nm, 250nm.
The invention also provides application of the nano silicon dioxide microspheres with the surface topological structure in the biomedical fields of adsorption, catalyst carriers, drug targeted delivery, drug carriers, gene carriers, contrast agents, cancer treatment and the like.
Compared with the prior art, the preparation method of the nano silicon dioxide microspheres with the surface topological structure has the following advantages:
(1) The invention mainly uses the aqueous medium as the solvent to prepare the nano silicon dioxide microspheres with surface topological structures, does not use a surfactant, can effectively reduce the production cost and reduce the pollutant discharge.
(2) The invention is in the classic
On the basis of the method, the method has the characteristics of simplicity, mild conditions, controllable particle size, large reaction batch and the like.
(3) The nano silicon dioxide microspheres with the surface topological structure prepared by the invention have wide application prospects in the aspects of adsorption and catalysis, and have wide potential applications in the aspects of biomedicine such as targeted delivery of medicines, medicine carriers, gene carriers, contrast agents, cancer treatment and the like.
Drawings
FIG. 1 is a TEM image of nano-silica microspheres with surface topology prepared in example 1.
FIG. 2 is a TEM image of nano-silica microspheres with surface topology prepared in example 2.
FIG. 3 is a TEM image of nano-silica microspheres with surface topology prepared in example 3.
FIG. 4 is a TEM image of nano-silica microspheres with surface topology prepared in example 4.
FIG. 5 is a TEM image of nano-silica microspheres with surface topology prepared in example 5.
FIG. 6 is a TEM image of nano-silica microspheres with surface topology prepared in example 6.
FIG. 7 is a TEM image of nano-silica microspheres with surface topology prepared in example 7.
Detailed Description
The present invention will be described in further detail with reference to the following specific examples and drawings, and the present invention is not limited to the following examples. Variations and advantages that may occur to those skilled in the art may be incorporated into the invention without departing from the spirit and scope of the inventive concept, and the scope of the appended claims is intended to be protected. The procedures, conditions, reagents, experimental methods and the like for carrying out the present invention are general knowledge and common general knowledge in the art except for the contents specifically mentioned below, and the present invention is not particularly limited.
The ethanol, ethyl silicate and ammonia used in the following examples were all analytically pure, and water was deionized water.
Example 1:50 mL of water and 1mL of TEOS are injected into a 250mL conical flask at room temperature of 20 ℃ under stirring, and stirred (rotating speed of 300 rmp) for 2 hours; adding 40ml ethanol into a conical flask, and stirring (rotating speed of 300 rmp) for 2 hours at room temperature of 20 ℃ until the concentration of TEOS is 0.05M; adding an ammonia water solution with the mass fraction of 28% into a conical flask to enable the concentration of ammonia to reach 0.44mol/L, reacting for 2 hours under the condition of stirring (the rotating speed is 200 rmp), adding a certain volume of 3.3% ammonia water solution (the volume ratio of the added ammonia water to the original sol is 17: 5), and reacting for 12 hours to obtain the silica sol. The silica sol is centrifugally separated at the room temperature of 20 ℃ (the rotating speed is 15000rmp, the time is 30 min), and the silica sol is washed for 3 times by ethanol, so that the silica microspheres with the surface topological structure and the average particle size of 103nm can be obtained (see figure 1).
Example 2: 30mL of water and 3mL of TEOS are injected into a 250mL conical flask at room temperature of 20 ℃ under stirring, and stirred (rotating speed of 300 rmp) for 2 hours; adding 40ml ethanol into a conical flask, and stirring (rotating speed of 300 rmp) for 2 hours at room temperature of 20 ℃ until the concentration of TEOS is 0.19M; adding an ammonia water solution with the mass fraction of 28% into a conical flask to enable the concentration of ammonia to reach 1.48mol/L, reacting for 2 hours under the condition of stirring (the rotating speed is 250 rmp), adding an ammonia water solution with the certain volume of 2.8% (the volume ratio of the added ammonia water to the original sol is 50: 11), and reacting for 11 hours to obtain the silica sol. The silica sol was centrifuged at 20 ℃ at room temperature (speed 5000rmp for 10 min) and washed with ethanol 3 times to obtain silica microspheres with an average particle size of 250nm and uniform size (see FIG. 2).
Example 3: injecting 25mL of water and 5mL of TEOS into a 250mL conical flask at room temperature of 20 ℃ under the stirring condition, and stirring (rotating speed of 300 rmp) for 2 hours; adding 35ml ethanol into a conical flask, stirring (rotating speed of 300 rmp) for 2 hours at room temperature of 20 ℃ and enabling the TEOS concentration to be 0.36M; adding an ammonia water solution with the mass fraction of 28% into a conical flask to enable the concentration of ammonia to reach 1.48mol/L, reacting for 2 hours under the condition of stirring (the rotating speed is 300 rmp), adding a certain volume of 2.8% ammonia water solution (the volume ratio of the added ammonia water to the original sol is 50: 11), and reacting for 10 hours to obtain the silica sol. The silica sol was centrifuged at 20 ℃ at room temperature (4000 rmp for 20 min), and washed with ethanol 3 times to obtain silica microspheres with an average particle size of 225nm (see FIG. 3).
Example 4: 50mL of water and 3mL of TMOS were introduced into a 250mL Erlenmeyer flask at room temperature of 20 ℃ with stirring, and stirred (rotation speed 300 rmp) for 2 hours; 28ml of ethanol was added to the flask and stirred (rotation speed 300 rmp) at room temperature 20 ℃ for 2 hours with TMOS concentration of 0.15M; adding an ammonia water solution with the mass fraction of 28% into a conical flask to enable the concentration of ammonia to reach 0.59mol/L, reacting for 2 hours under the condition of stirring (the rotating speed is 200 rmp), adding a certain volume of 3.0% ammonia water solution (the volume ratio of the added ammonia water to the original sol is 11: 2), and reacting for 10 hours to obtain the silica sol. The silica sol was centrifuged at 20 ℃ at room temperature (13000 rmp for 30 min), and washed with ethanol 3 times to obtain silica microspheres with an average particle size of 110nm and uniform size (see FIG. 4).
Example 5: 30mL of water and 3mL of TEOS are injected into a 150mL conical flask at room temperature of 20 ℃ under stirring, and stirred (rotating speed of 300 rmp) for 2 hours; 32ml of an alcohol mixed solution (methanol: t-butanol = 1: 1 v/v) was added to the flask, and stirred (rotation speed 300 rmp) at room temperature and 20 ℃ for 2 hours, with a TEOS concentration of 0.21M; adding an ammonia water solution with the mass fraction of 28% into a conical flask to ensure that the concentration of ammonia reaches 0.44mol/L, reacting for 2 hours under the condition of stirring (the rotating speed is 200 rmp), adding a certain volume of 3.0% ammonia water solution (the volume ratio of the added ammonia water to the original sol is 11: 2), and reacting for 10 hours to obtain the silica sol. The silica sol was centrifuged at 20 ℃ at room temperature (6000rmp, 20min), and washed with ethanol for 3 times to obtain silica microspheres with an average particle size of 115nm and uniform size (see FIG. 5).
Example 6: 30mL of water and 3mL of TEOS are injected into a 250mL conical flask at room temperature of 20 ℃ under stirring, and stirred (rotating speed of 300 rmp) for 2 hours; 40ml of ethanol was added to the flask and stirred (300 rmp) at room temperature and 20 ℃ for 2 hours, TEOS concentration 0.19M. And (3) keeping the temperature of the mixed solution at 40 ℃ for 15min, adding an ammonia water solution with the mass fraction of 28% to ensure that the concentration of ammonia reaches 0.74mol/L, reacting for 1.5h under the condition of stirring (the rotating speed is 250 rmp), adding a certain volume of 2.8% ammonia water solution (the volume ratio of the added ammonia water to the original sol is 50: 11), and reacting for 12 h to obtain the silica sol. The silica sol was centrifuged at 20 ℃ at room temperature (10000 rmp for 20 min), and washed with ethanol 3 times to obtain silica microspheres with an average particle size of 227nm and uniform size (see FIG. 6).
Example 7: 30mL of water and 3mL of TEOS are injected into a 250mL conical flask at room temperature of 20 ℃ under stirring, and stirred (rotating speed of 300 rmp) for 2 hours; 40ml of ethanol were added to the flask and stirred (300 rmp) at room temperature and 20 ℃ for 2 hours, the TEOS concentration being 0.19M. And (3) keeping the mixed solution at the constant temperature of 60 ℃ for 25min, adding an ammonia water solution with the mass fraction of 28% to ensure that the concentration of ammonia reaches 0.59mol/L, reacting for 1h under the condition of stirring (the rotating speed is 300 rmp), adding a certain volume of 2.8% ammonia water solution (the volume ratio of the added ammonia water to the original sol is 50: 11), and reacting for 11 h to obtain the silica sol. The silica sol was centrifuged at 20 ℃ at room temperature (13000 rmp for 20 min), and washed with ethanol 3 times to obtain silica microspheres with an average particle size of 122nm and a uniform size (see FIG. 7).
The protection content of the present invention is not limited to the above embodiments. Variations and advantages that may occur to those skilled in the art are intended to be included within the invention without departing from the spirit and scope of the inventive concept, and the scope of the invention is to be determined by the appended claims.
Claims (9)
1. A preparation method of nano silica microspheres with surface topological structures is characterized by comprising the following steps:
(1) Mixing silicon source with deionized water to obtain silicon source/H 2 O emulsion;
(2) Under the stirring condition, mixing the micromolecular surface active substance with the silicon source/H obtained in the step (1) 2 Mixing the O emulsion to obtain a clear and transparent silicon source/R-X/H 2 O mixed solution; the micromolecular surface active substance is an organic micromolecular substance which is mutually soluble with water and does not dissociate, and the structural formula of the micromolecular surface active substance is R-X, wherein R is alkyl; x is hydroxyl, ketone group or aldehyde group; the micromolecule surface active substance and silicon source/H 2 The volume ratio of the O emulsion is 1 to 2 to 8;
(3) Adding an alkaline catalyst into the silicon source/R-X/H obtained in the step (2) under the conditions of certain temperature and stirring 2 Reacting for a certain time in the O mixed solution to obtain silicon dioxide sol (a); the reaction temperature is 20 to 60 ℃; the reaction time is 2~5 hours; the reaction is carried out under the condition of stirring, and the rotating speed of the stirring is 200 to 300rpm; the alkaline catalyst is a weakly alkaline catalyst, and the concentration of the weakly alkaline catalyst is 0.2-2.0 mol/L;
(4) Adding an ammonia water solution into the silica sol (a) obtained in the step (3) under the conditions of certain temperature and stirring, and reacting for a certain time to obtain silica sol (b); the temperature is 15 to 30 ℃; the rotation speed of the stirring is 200 to 300rpm; the volume ratio of the added ammonia water to the silica sol is 3 to 1; the concentration of the ammonia water is 3.5% -2.5%; the reaction time is 8 to 12 hours;
(5) And (4) carrying out solid-liquid separation and washing on the silica sol (b) obtained in the step (4) to obtain the nano silica microspheres with the surface topological structure.
2. The method for preparing the nano-silica microspheres with the surface topological structure according to claim 1, wherein in the step (1), the silicon source and the deionized water are mixed under a stirring condition, and the stirring rotation speed is 200 to 300rpm; and/or the mixing temperature is 15 to 30 ℃; and/or the mixing time is 1~3 hours.
3. The method for preparing nano-silica microspheres with surface topology according to claim 1, wherein in the step (1), the silicon source comprises one or two of silicate ester and silane coupling agent.
4. The method for preparing nano silica microspheres with surface topology according to claim 1, wherein in the step (1), the volume ratio of the silicon source to the deionized water is: v is more than or equal to 50 Silicon source ：V H2O ≤1:5。
5. The method for preparing nano silica microspheres with surface topology according to claim 1, wherein in the step (2), the stirring speed is 200 to 300rpm; and/or the mixing temperature is 15 to 30 ℃; and/or the mixing time is 1~3 hours.
6. The method for preparing nanosilica microspheres with a surface topology according to claim 1, wherein in step (5), the solid-liquid separation comprises centrifugation, spray drying and freeze spray drying.
7. The method for preparing nano silica microspheres with surface topology according to claim 1, wherein in the step (5), the washing is performed by washing with deionized water for 3 times and then washing with absolute ethyl alcohol for 3 times.
8. Nanosilica microspheres having surface topology made by the method of any one of claims 1~7.
9. The nanosilica microspheres with surface topology of claim 8 for use in adsorption, catalytic vectors, targeted delivery of drugs, drug vectors, gene vectors, contrast agents, cancer therapy.
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| CN108341414A (en) * | 2017-01-22 | 2018-07-31 | 华东师范大学 | A kind of uniform silicon dioxide microsphere and its preparation method and application |
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