CN113264534B - Preparation method of silicon dioxide hollow microspheres - Google Patents
Preparation method of silicon dioxide hollow microspheres Download PDFInfo
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- CN113264534B CN113264534B CN202110687200.9A CN202110687200A CN113264534B CN 113264534 B CN113264534 B CN 113264534B CN 202110687200 A CN202110687200 A CN 202110687200A CN 113264534 B CN113264534 B CN 113264534B
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- 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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- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
- C01P2004/34—Spheres hollow
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- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/16—Pore diameter
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
Abstract
The invention discloses a preparation method of silicon dioxide hollow microspheres, which comprises the steps of dispersing a silicon source into a water-alcohol mixed solution containing a catalyst to prepare a slurry, diluting the slurry with the water-alcohol mixed solution to obtain a diluted mixed solution, adding the silicon source into the diluted mixed solution to obtain a secondary slurry, and finally drying and calcining the secondary slurry to obtain the silicon dioxide hollow microspheres. The obtained silica hollow microsphere has extremely high purity, each metal impurity can be controlled below 1ppm, the sphericity ratio of the silica hollow microsphere is up to more than 98%, the internal hollow core structure is mesoporous hollow, the hollow is formed by various small holes, and the small holes form a honeycomb structure and have higher effect of supporting a shell.
Description
Technical Field
The invention belongs to the field of inorganic material science, and particularly relates to a preparation method of a silicon dioxide hollow microsphere.
Background
In recent years, mesoporous silica has attracted people's attention in the field of nanomaterial science due to its advantages of large specific surface area and pore volume, good thermal stability, adjustable pore diameter, controllable morphology, low cytotoxicity and the like. But the application development is limited due to the limited pore size capacity. The silica hollow microspheres not only have the advantages of mesoporous silica, but also can contain a large number of guest molecules or large-size molecules in the hollow part, and become a research hotspot of many scholars.
At present, the preparation method of the silicon dioxide hollow microsphere is mainly a sacrificial template method, including a hard template method and a soft template method. The hard template method mainly uses nano particles as a template, wraps a silicon dioxide shell on the outer layer, and then adds an etching agent under the acidic or alkaline condition to selectively etch the inner core of the template. The method is a multi-step synthesis, and thus has low yield and more byproducts. The soft template method is usually a one-step synthesis, and is simpler than the hard template method, and the common soft template methods comprise oil-in-water (O/W) type microemulsion, surfactant vesicles, high molecular polymers and the like.
Chinese patent CN104445214A reports a preparation method of a mesoporous silica hollow sphere, and the spherical shell of the product silica is formed by aggregating mesoporous silica nanoparticles with the particle size of 5-50 nm. In the experimental process, polystyrene spheres used as hard templates need to be reversely prepared in advance, a certain amount of amination reagent (3-aminopropyltriethoxysilane) needs to be added into a reaction system, the method has strict requirements on the material composition of the reaction system, the preparation process is complicated, the reaction period is long, nitrogen protection is needed in the experimental process, and the conditions are harsh.A preparation method of an ordered mesoporous silica hollow sphere is reported in Chinese patent CN102153094A, and the experiment is carried out in order to obtain the ordered mesoporous silica hollow sphere
The prepared silicon dioxide ball is used as a template, a core-shell type precursor is synthesized in advance under the action of a surfactant (long-chain organic quaternary ammonium salt), and finally, anhydrous carbonic acid is addedSodium is used for selectively etching the inner core, the experimental process is complicated, and the particle size of the product particles is limited to a certain extent by the particle size of the silicon dioxide spheres used as the hard template. Jatupaibonon et al prepare hollow silica spheres by one-step reverse microemulsion method at room temperature, the reverse microemulsion system is relatively complex and consists of Aminopropyltrimethoxysilane (APS) -polyethylene glycol octylphenyl ether-n-hexanol-cyclohexane-water, the wall thickness of the prepared hollow silica spheres is adjustable, but the thickness is not uniform, and the volume of the silicon spheres cavity is small (A)<50 nm) are not favorable for the encapsulation of a large number of guest molecules, which severely limits its applications.
The most main problems of the existing preparation of the silica hollow microspheres are that 1, the surfaces of the microspheres are not completely closed, cavities are formed on the surfaces of shells, the inner hollow space is not a closed space 2, the thicknesses of the surfaces of the shells are insufficient, the thicknesses of the shells are too thin, the surfaces of the shells are easy to break, the mechanical properties of the shells are poor, and the like. In view of the defects of the hollow silica microspheres prepared by the prior art, a preparation method of hollow silica spheres with simple synthesis process, controllable particle size and larger pore diameter is urgently needed.
Disclosure of Invention
The invention aims to provide a silicon dioxide hollow microsphere and a preparation method thereof, and the prepared product has the advantages of controllable particle size, adjustable surface thickness, larger pore diameter, uniform particle size distribution and the like.
In order to achieve the purpose, the invention provides the following technical scheme:
a preparation method of silica hollow microspheres comprises the following steps:
(1) Preparation of slurry: slowly adding a silicon source into a water-alcohol mixture containing a catalyst under the stirring condition to prepare slurry;
(2) Diluting: diluting the slurry obtained in the step (1) with a water-alcohol mixture to obtain a diluted mixed solution;
(3) Preparing secondary slurry: slowly adding a silicon source into the diluted mixed solution obtained in the step (2) under the stirring condition to obtain secondary slurry;
(4) And (3) drying: drying the secondary slurry obtained in the step (3) to obtain a powder material;
(5) And (3) calcining: and (4) calcining the powder material obtained in the step (4) to obtain the silicon dioxide hollow microspheres.
Preferably, in step (1), the silicon source is one or more of n-octyltrimethoxysilane, n-octyltriethoxysilane, dodecyltrimethoxysilane, hexadecyltrimethoxysilane, phenyltrimethoxysilane or their hydrolysates.
Preferably, the catalyst in step (1) is acid or alkali, wherein the acid is one or more of hydrochloric acid, acetic acid, oxalic acid or formic acid, and the alkali is one or more of ammonia water, ethylenediamine, ethanolamine, dimethylamine or hexamethyltetramine.
Preferably, in the hydroalcoholic mixture in the step (1) and the step (2), the alcohol is a mixture of one or more of methanol, ethanol or isopropanol and water, and the hydroalcoholic mass ratio is about 0.01-100; in the step (2), the dilution ratio is 1-10 times.
Preferably, in the steps (1) and (3), the stirring conditions are as follows: the stirring speed is 5-100r/min, the temperature is 10-40 ℃, and the time is 0.5-6 hours.
Preferably, the amount of the silicon source used in the step (1) is 1-10 parts; the amount of the catalyst is 0.01-5 parts; the amount of the water alcohol is 1 to 100 parts.
Preferably, in the step (3), the silicon source is one or more of ethyl orthosilicate, methyl orthosilicate, butyl orthosilicate or hydrolysates thereof, and the using amount of the silicon source is 1-10 parts.
Preferably, the preparation method of the hollow silica microspheres is characterized in that in the step (4), the drying temperature is 30-150 ℃, and the drying time is 1-24 hours.
Preferably, the preparation method of the silica hollow microspheres is characterized in that in the step (5), the calcining temperature is 400-1000 ℃, and the calcining time is 1-15 hours.
Compared with the prior art, the invention has the following beneficial effects:
the spherical silicon oxide hollow powder prepared by the two-step sol-gel process has extremely high purity, each metal impurity can be controlled below 1ppm, the sphericity rate of the silicon oxide hollow microsphere is up to more than 98 percent, the internal hollow core structure is mesoporous hollow, the hollow is formed by various small holes, and the small holes form a honeycomb structure and have higher effect of supporting a shell.
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FIG. 1 is a scanning electron microscope image of silica hollow microspheres at 5000 times in example 1 of the present invention;
FIG. 2 is a scanning electron microscope image of the hollow silica microspheres at 1000 times in example 1 of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
A preparation method of silica hollow microspheres comprises the following steps:
(1) Preparation of slurry: slowly adding 5g of n-octyltrimethoxysilane into 50g of a hydroalcoholic mixture (the mass ratio of water to alcohol is 1) containing 1g of ammonia water at the stirring speed of 20r/min and the temperature of 25 ℃, and stirring for 1 hour to prepare slurry;
(2) Diluting: diluting the slurry obtained in the step (1) by using a water-alcohol mixture (the water-alcohol mass ratio is 1) with the mass of 5 times that of the slurry to obtain a diluted mixed solution;
(3) Preparing secondary slurry: slowly adding 5g of tetraethoxysilane into the diluted mixed solution obtained in the step (2) at the stirring degree of 20r/min and the temperature of 25 ℃, and stirring for 1 hour to obtain secondary slurry;
(4) And (3) drying: drying the secondary slurry obtained in the step (3) at 50 ℃ for 5 hours to obtain a powder material;
(5) And (3) calcining: and (4) calcining the powder material obtained in the step (4) at 600 ℃ for 5 hours to obtain the silicon dioxide hollow microspheres.
As can be seen from the scanning electron microscope picture of the silicon dioxide hollow microsphere of FIG. 1 under 5000 times, the appearance of the sample is a sphere with the particle size range of 3-10 μm, the particle size is uniform, and the sphericity is high; the scanning electron microscope picture of the hollow silica microsphere of fig. 2 under 1000 times can show that the hollow structure is formed by various pores, the pores form a honeycomb structure, the pore diameter of the pores is 20-500nm, and the sphericity of the hollow silica microsphere is more than 98%.
Example 2
A preparation method of silica hollow microspheres comprises the following steps:
(1) Preparing slurry: slowly adding 3g of n-octyltrimethoxysilane into 50g of a hydroalcoholic mixture (the mass ratio of water to alcohol is 5) containing 2g of ammonia water at the stirring speed of 40r/min and the temperature of 20 ℃, and stirring for 1 hour to prepare a slurry;
(2) Diluting: using a water-alcohol mixture (the water-alcohol mass ratio is 5) with the mass of 5 times of that of the slurry obtained in the step (1) to obtain a diluted mixed solution;
(3) Preparing secondary slurry: slowly adding 3g of tetraethoxysilane into the diluted mixed solution obtained in the step (2) at the stirring speed of 40r/min and the temperature of 20 ℃ to obtain secondary slurry;
(4) And (3) drying: drying the secondary slurry obtained in the step (3) at 50 ℃ for 5 hours to obtain a powder material;
(5) And (3) calcining: and (4) calcining the powder material obtained in the step (4) at 600 ℃ for 5 hours to obtain the silicon dioxide hollow microspheres.
The particle size range of the hollow silica microspheres prepared by the embodiment is 4-9 μm, the pore diameter of the pores is 100-400nm, and the sphericity ratio is more than 98%.
Example 3
A preparation method of silica hollow microspheres comprises the following steps:
(1) Preparation of slurry: slowly adding 5g of dodecyl trimethyl oxysilane into 60g of water-alcohol mixture (the water-alcohol mass ratio is 3) of 0.5g of acetic acid at the stirring speed of 40r/min and the temperature of 30 ℃, and stirring for 2 hours to prepare slurry;
(2) Diluting: diluting the slurry obtained in the step (1) by using a water-alcohol mixture (the water-alcohol mass ratio is 3) with the mass of 5 times that of the slurry to obtain a diluted mixed solution;
(3) Preparing secondary slurry: slowly adding 5g of n-butyl silicate into the diluted mixed solution obtained in the step (2) at the stirring speed of 40r/min and the temperature of 30 ℃, and stirring for 2 hours to obtain secondary slurry;
(4) And (3) drying: drying the secondary slurry obtained in the step (3) at 50 ℃ for 5 hours to obtain a powder material;
(5) And (3) calcining: and (5) calcining the powder material obtained in the step (4) at 600 ℃ for 5 hours to obtain the silicon dioxide hollow microspheres.
The particle size range of the silica hollow microsphere prepared by the embodiment is 3-8 μm, the aperture of the small hole is 60-450nm, and the sphericity ratio is more than 98%.
Example 4
A preparation method of silica hollow microspheres comprises the following steps:
(1) Preparing slurry: slowly adding 8g of phenyltrimethoxysilane into 80g of a hydroalcoholic mixture (the mass ratio of the hydroalcoholic is 0.5) containing 0.5g of ammonia water at the stirring speed of 80r/min and the temperature of 15 ℃, and stirring for 1 hour to prepare slurry;
(2) Diluting: diluting the slurry obtained in the step (1) with a water-alcohol mixture (the water-alcohol mass ratio is 0.5) with the mass of 2 times that of the slurry to obtain a diluted mixed solution;
(3) Preparing secondary slurry: slowly adding 3g of tetraethoxysilane into the diluted mixed solution obtained in the step (2) at the stirring speed of 80r/min and the temperature of 15 ℃, and stirring for 1 hour to obtain secondary slurry;
(4) And (3) drying: drying the secondary slurry obtained in the step (3) at 80 ℃ for 3 hours to obtain a powder material;
(5) And (3) calcining: and (4) calcining the powder material obtained in the step (4) at 800 ℃ for 5 hours to obtain the silicon dioxide hollow microspheres.
The particle size range of the silica hollow microsphere prepared by the embodiment is 5-9 μm, the aperture of the small hole is 80-500nm, and the sphericity ratio is more than 98%.
Example 5
A preparation method of silica hollow microspheres comprises the following steps:
(1) Preparation of slurry: slowly adding 8g of n-octyltrimethoxysilane into 100g of a water-alcohol mixture (the water-alcohol mass ratio is 0.1) of 0.5g of ammonia water at the stirring speed of 50r/min and the temperature of 30 ℃, and stirring for 1 hour to prepare a slurry;
(2) Diluting: diluting the slurry obtained in the step (1) with a water-alcohol mixture (the water-alcohol mass ratio is 0.1) with the mass of 3 times that of the slurry to obtain a diluted mixed solution;
(3) Preparing secondary slurry: slowly adding 2g of tetraethoxysilane into the diluted mixed solution obtained in the step (2) at the stirring speed of 50r/min and the temperature of 30 ℃, and stirring for 1 hour to obtain secondary slurry;
(4) And (3) drying: drying the secondary slurry obtained in the step (3) at 70 ℃ for 10 hours to obtain a powder material;
(5) And (3) calcining: and (4) calcining the powder material obtained in the step (4) at 550 ℃ for 10 hours to obtain the silicon dioxide hollow microspheres.
The particle size range of the hollow silica microspheres prepared by the embodiment is 5-10 μm, the pore diameter of the pores is 50-400nm, and the sphericity ratio is more than 98%.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (7)
1. The preparation method of the silica hollow microsphere is characterized by comprising the following steps:
(1) Preparing slurry: slowly adding a silicon source into a water-alcohol mixture containing a catalyst under the stirring condition to prepare slurry;
(2) Diluting: diluting the slurry obtained in the step (1) with a water-alcohol mixture to obtain a diluted mixed solution;
(3) Preparing secondary slurry: slowly adding a silicon source into the diluted mixed solution obtained in the step (2) under the stirring condition to obtain secondary slurry;
(4) And (3) drying: drying the secondary slurry obtained in the step (3) to obtain a powder material;
(5) And (3) calcining: calcining the powder material obtained in the step (4) to obtain the silicon dioxide hollow microspheres;
wherein in the step (1), the silicon source is one or more of n-octyltrimethoxysilane, n-octyltriethoxysilane, dodecyl-trimethoxysilane, hexadecyl-trimethoxysilane, phenyl-trimethoxysilane or hydrolysates thereof;
in the step (3), the silicon source is one or more of ethyl orthosilicate, methyl orthosilicate and butyl orthosilicate or hydrolysates thereof, and the using amount of the silicon source is 1-10 parts;
in the step (5), the calcining temperature is 400-1000 ℃, and the calcining time is 1-15 hours.
2. The method for preparing hollow silica microspheres according to claim 1, wherein the catalyst in step (1) is an acid or a base, wherein the acid is one or more selected from hydrochloric acid, acetic acid, oxalic acid and formic acid, and the base is one or more selected from ammonia, ethylenediamine, ethanolamine, dimethylamine and hexamethyltetramine.
3. The preparation method of the hollow silica microspheres according to claim 1, wherein the alcohol in the hydroalcoholic mixture in the steps (1) and (2) is a mixture of one or more of methanol, ethanol or isopropanol and water, and the mass ratio of the hydroalcoholic is 0.01-100; the dilution ratio in the step (2) is 1 to 10 times.
4. The method for preparing hollow silica microspheres according to claim 1, wherein in the steps (1) and (3), the stirring conditions are as follows: the stirring speed is 5-100r/min, the temperature is 10-40 ℃, and the time is 0.5-6 hours.
5. The method for preparing the hollow silica microspheres according to claim 1, wherein the amount of the silicon source used in the step (1) is 1 to 10 parts; the dosage of the catalyst is 0.01-5 parts; the amount of the water alcohol is 1 to 100 parts.
6. The method for preparing hollow silica microspheres according to claim 1, wherein in the step (4), the drying temperature is 30-150 ℃ and the drying time is 1-24 hours.
7. A silica hollow microsphere produced by the production method according to any one of claims 1 to 6.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101966994A (en) * | 2010-11-03 | 2011-02-09 | 陕西师范大学 | Preparation method of porous silicon dioxide hollow microspheres |
| CN102020283A (en) * | 2010-12-03 | 2011-04-20 | 宁波大学 | Preparation method of silicon dioxide nano hollow sphere with adjustable inner diameter |
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| CN101186301B (en) * | 2007-09-17 | 2010-05-26 | 浙江理工大学 | Method for preparing polysilicon oxide microsphere of uniform size with active group |
| CN106044788B (en) * | 2016-05-26 | 2017-11-10 | 齐鲁工业大学 | A kind of hollow silica ball nano material of size tunable and preparation method thereof |
| CN107128935A (en) * | 2017-05-23 | 2017-09-05 | 苏州纳迪微电子有限公司 | A kind of preparation method of high-purity preparing spherical SiO 2 micro mist |
| KR102201589B1 (en) * | 2017-06-12 | 2021-01-11 | 주식회사 엘지화학 | Preparation method of hollow silicon-based particles |
| US11242256B2 (en) * | 2018-06-01 | 2022-02-08 | Imam Abdulrahman Bin Faisal University | Multi-stage calcination method for making hollow silica spheres |
| CN110015666A (en) * | 2019-04-29 | 2019-07-16 | 江苏辉迈粉体科技有限公司 | A kind of preparation method of high-purity Submicron spherical silica micropowder |
| CN111892060A (en) * | 2020-09-11 | 2020-11-06 | 江苏辉迈粉体科技有限公司 | Preparation method of mesoporous silica microspheres |
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| CN101966994A (en) * | 2010-11-03 | 2011-02-09 | 陕西师范大学 | Preparation method of porous silicon dioxide hollow microspheres |
| CN102020283A (en) * | 2010-12-03 | 2011-04-20 | 宁波大学 | Preparation method of silicon dioxide nano hollow sphere with adjustable inner diameter |
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