CN112938992B - Preparation method of silicon dioxide nanometer bowl - Google Patents

Preparation method of silicon dioxide nanometer bowl Download PDF

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CN112938992B
CN112938992B CN202110263736.8A CN202110263736A CN112938992B CN 112938992 B CN112938992 B CN 112938992B CN 202110263736 A CN202110263736 A CN 202110263736A CN 112938992 B CN112938992 B CN 112938992B
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solution
weight
stirring
silica
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CN112938992A (en
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王晟
石敏
王騊
纪律律
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Hangzhou Tong King Environment Technology Co ltd
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Zhejiang Sci Tech University ZSTU
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    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00Silicon; Compounds thereof
    • C01B33/113Silicon oxides; Hydrates thereof
    • C01B33/12Silica; Hydrates thereof, e.g. lepidoic silicic acid
    • C01B33/18Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00Particle morphology
    • C01P2004/01Particle morphology depicted by an image
    • C01P2004/03Particle morphology depicted by an image obtained by SEM

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Abstract

The invention discloses a preparation method of a silicon dioxide nanometer bowl, which comprises the following steps: 1) sequentially adding 90-99.9 parts by weight of water and 0.1-10 parts by weight of PAANa into a reactor, and stirring to obtain a solution 1; 2) sequentially adding 0.1-10 parts of hydroxide and 0.3-10 parts (by weight) of ammonia water into 100ml of water, and stirring to obtain a solution 2; 3) adding 1-10 parts (by weight) of solution 1 into 150 parts of ethanol/water mixed solution with the concentration of 40-80%, and stirring to obtain solution 3; 4) slowly adding 0.3-30 parts by weight of the solution 2 and 3-25 parts by weight of tetraethoxysilane into the solution 3, and stirring; 5) slowly dripping inorganic acid into the solution obtained in the step 4), stirring, and adjusting the pH value of the solution to 2.0-3.0; 6) and after stirring is finished, drying to obtain the silicon dioxide nanometer bowl. The invention utilizes different dissolution characteristics of acid-base environments to obtain the silicon dioxide nanometer bowl material which is used as a carrier of the catalyst and is convenient to release.

Description

Preparation method of silicon dioxide nanometer bowl
Technical Field
The invention relates to a preparation method of a silicon dioxide nanometer bowl.
Background
Silica is commonly called glass, and has unique properties in aspects of extremely stable physical and chemical properties, large specific surface area, strong surface adsorption force, large surface energy, high chemical purity, good dispersion performance, thermal resistance, electric resistance and the like, so that the silica has an irreplaceable effect in various subjects and fields, and is widely used in various fields of catalyst carriers, petrochemical industry, decolorants, flatting agents, rubber reinforcing agents, plastic filling agents, ink thickening agents, metal soft polishing agents, insulating and heat insulating filling agents, high-grade daily cosmetic filling agents and spraying materials, medicine, environmental protection and the like. In particular, the nano-silica spheres can be applied to the fields of catalysis, stabilizers, reinforcing agents, additives, adsorbents, photoelectricity, biology and the like, and application number 201810674615.0 discloses a preparation method of the nano-silica spheres, which comprises the steps of mixing ammonia water, tetraethoxysilane and alcoholic solution to obtain a nano-silica sphere suspension; and (4) centrifugally washing the nano silicon dioxide ball suspension, and drying the precipitate to obtain the nano silicon dioxide ball.
On the other hand, nanoshell structures may generally exhibit superior properties as compared to solid nanomaterials and thus have broader application value. The hollow structure can be used as an inner space, and more possibilities are provided for the superposition, storage, transportation and the like of the magnetic, optical, mechanical, thermal, electrical and catalytic functions of the material.
At present, one of the simplest and most effective methods for removing the hollow core-shell material by the hard template method is widely applied due to the characteristics of simple method, high repetition rate, good predictability, uniform product form, stable performance and the like. Carbon spheres, silicon spheres or PS spheres are generally used as templates, a shell structure is coated on the carbon spheres, silicon spheres or PS spheres, and then a core is removed by a certain means, so that a hollow structure is obtained. However, such methods generally require a large number of steps and are not suitable for mass production.
The present invention has been made to solve the above problems.
Disclosure of Invention
The invention aims to provide a preparation method of a silicon dioxide nanometer bowl. By utilizing the characteristic that sodium polyacrylate (PAANa) is precipitated in an alkaline solution and the pH value is dissolved at a specific value (the pH value is about 2.5), the nano-silica spheres are induced to self-assemble into the silica nano bowl by controlling the process of converting the precipitation (alkaline) of the sodium polyacrylate into the dissolution (acidic).
The purpose is realized by the following technical scheme:
a preparation method of a silicon dioxide nanometer bowl comprises the following steps:
1) sequentially adding 90-99.9 parts by weight of water and 0.1-10 parts by weight of PAANa into a reactor, and stirring to obtain a solution 1;
2) sequentially adding 0.1-10 parts by weight of hydroxide and 0.3-10 parts by weight of ammonia water into 100ml of water, and stirring to obtain a solution 2;
3) adding 1-10 parts by weight of solution 1 into 150 parts by weight of 40-80% ethanol/water mixed solution, and stirring to obtain solution 3;
4) slowly adding 0.3-30 parts by weight of the solution 2 and 3-25 parts by weight of tetraethoxysilane into the solution 3, and stirring;
5) slowly dripping inorganic acid into the solution obtained in the step 4), stirring, adjusting the pH value of the solution to 2.0-3.0, and fully stirring to obtain the silicon dioxide nanometer bowl.
Preferably, the stirring in step 1) is performed in a dark/non-light condition.
Further, the hydroxide in the step 2) is magnesium hydroxide.
Preferably, the inorganic acid in step 5) is hydrochloric acid, and the PH of the solution is 2.5.
Further, in the step 5), after the full stirring is finished, the silica nanometer bowl is obtained by centrifuging, washing with absolute ethyl alcohol and drying.
Preferably, the stirring in step 5) is carried out for 30 to 150 minutes.
In one embodiment, in step 1), the weight ratio of water to PAANa is 95 parts: 5 parts of the raw materials.
Preferably, in step 2), the weight ratio of the hydroxide to the ammonia water is 5 parts to 5 parts.
Preferably, in step 3), the weight ratio of the 60% ethanol/water mixture to the solution 1 obtained in step 1) is 150 parts: 5 parts of the raw materials.
Preferably, in the step 4), the weight ratio of the solution 2 obtained in the step 2) to the solution 3 obtained in the step 3) is 15 parts: 14 parts of the raw materials.
The beneficial technical effects are as follows:
1. the silicon dioxide nanometer bowl prepared by the invention has an open structure, can be used as a carrier of a catalyst, is used for carrying a large-capacity catalytic substance, is easy to load and is convenient to release.
2. The silicon dioxide nanometer bowl prepared by the invention can be filled with other functional substances, the application value and the range are widened, the preparation process of the product is simple, the conditions are easy to control, and the large-scale industrial production is easy to realize.
Drawings
FIG. 1 is a scanning electron microscope image of a silicon dioxide nanometer bowl, wherein the scale size in the image is 1 μm, and the magnification is 20.00K.
FIG. 2 is a scanning electron microscope image of the silica nanometer bowl, wherein the scale size is 1 μm, and the magnification is 10.00K.
Detailed Description
The present invention will be further described in conjunction with the following detailed description and accompanying drawings so as to enable those skilled in the art to better understand the technical solutions of the present invention.
Example 1
A preparation method of a silicon dioxide nanometer bowl comprises the following steps:
1) adding 90 parts by weight of water and 0.1 part by weight of PAANa into a reactor in sequence, and stirring for 5 minutes to obtain a solution 1;
2) adding 0.1 part by weight of magnesium hydroxide and 0.3 part by weight of ammonia water into 100ml of water in sequence, and stirring for 5 minutes to obtain a solution 2;
3) adding 1 part of solution 1 into 150 parts of ethanol/water mixed solution with the concentration of 40% (weight ratio), and stirring for 5 minutes to obtain solution 3;
4) slowly adding 0.3 part by weight of the solution 2 and 3 parts by weight of Tetraethoxysilane (TEOS) into the solution 3, and stirring for 3 hours;
5) slowly dripping hydrochloric acid into the solution obtained in the step 4), stirring, adjusting the pH value of the solution to 2.5, fully stirring and drying to obtain the silicon dioxide nanometer bowl.
The method utilizes the characteristic that sodium polyacrylate (PAANa) is precipitated in an alkaline solution and dissolved at the PH value of 2.5, and induces the nano silicon dioxide spheres to self-assemble into a bowl-shaped structure with an open end, namely a silicon dioxide nano bowl by regulating the process of converting sodium polyacrylate precipitation (alkalinity) into dissolution (acidity).
Referring to fig. 1, a scanning electron microscope image of the silica nanometer bowl prepared in this example is shown, wherein the scale size is 1 μm, and the magnification is 20.00K.
Referring to fig. 2, a scanning electron microscope image of the silica nanometer bowl prepared in this example is shown, wherein the scale size is 1 μm, and the magnification is 10.00K.
Example 2
A preparation method of a silicon dioxide nanometer bowl comprises the following steps:
1) adding 99.9 parts by weight of water and 10 parts by weight of PAANa into a brown bottle coated with tinfoil paper in a shading mode, and stirring for 15 minutes to obtain a solution 1;
2) adding 10 parts by weight of magnesium hydroxide and 10 parts by weight of ammonia water into 100ml of water in sequence, and stirring for 15 minutes to obtain a solution 2;
3) adding 10 parts by weight of solution 1 into 150 parts by weight of 80% ethanol/water mixed solution, and stirring for 15 minutes to obtain solution 3;
4) slowly adding 30 parts by weight of the solution 2 and 25 parts by weight of Tetraethoxysilane (TEOS) into the solution 3, and stirring for 13 hours;
5) slowly dripping hydrochloric acid into the solution obtained in the step 4), stirring, adjusting the pH value of the solution to 2.0, fully stirring and drying to obtain the silicon dioxide nanometer bowl.
Example 3
A preparation method of a silicon dioxide nanometer bowl comprises the following steps:
1) adding 95 parts by weight of water and 5 parts by weight of PAANa into a brown bottle coated with tinfoil paper in a shading mode, and stirring for 10 minutes to obtain a solution 1;
2) sequentially adding 5 parts by weight of potassium hydroxide and 5 parts by weight of ammonia water into 100ml of water, and stirring for 10 minutes to obtain a solution 2;
3) adding 5 parts by weight of solution 1 into 150 parts by weight of 60% ethanol/water mixed solution, and stirring for 10 minutes to obtain solution 3;
4) slowly adding 15 parts by weight of the solution 2 and 14 parts by weight of Tetraethoxysilane (TEOS) into the solution 3, and stirring for 13 hours;
5) slowly dripping hydrochloric acid into the solution obtained in the step 4), stirring, adjusting the pH value of the solution to 3.0, fully stirring and drying to obtain the silicon dioxide nanometer bowl.
Example 4
A preparation method of a silicon dioxide nanometer bowl comprises the following steps:
1) adding 90 parts by weight of ultrapure water and 0.1 part by weight of PAANa into a brown bottle coated with tinfoil paper in a shading mode, and stirring for 5 minutes to obtain a solution 1;
2) sequentially adding 10 parts by weight of calcium hydroxide and 0.3 part by weight of ammonia water into 100ml of ultrapure water, and stirring for 5 minutes to obtain a solution 2;
3) adding 1 part by weight of the solution 1 into 150 parts by weight of an ethanol/ultrapure water mixed solution with the concentration of 80%, and stirring for 5 minutes to obtain a solution 3;
4) slowly adding 0.3 part by weight of the solution 2 and 25 parts by weight of Tetraethoxysilane (TEOS) into the solution 3, and stirring for 13 hours;
5) slowly dripping hydrochloric acid into the solution obtained in the step 4), stirring, adjusting the pH value of the solution to 2.2, centrifuging, washing for 3 times by using absolute ethyl alcohol, and drying to obtain the silicon dioxide nanometer bowl.
Example 5
A preparation method of a silicon dioxide nanometer bowl comprises the following steps:
1) adding 99.9 parts by weight of ultrapure water and 10 parts by weight of PAANa into a brown bottle coated with tinfoil paper in a shading mode, and stirring for 15 minutes to obtain a solution 1;
2) adding 0.1 part by weight of magnesium hydroxide and 10 parts by weight of ammonia water into 100ml of ultrapure water in sequence, and stirring for 15 minutes to obtain a solution 2;
3) adding 10 parts by weight of solution 1 into 150 parts by weight of 40% ethanol/ultrapure water mixed solution, and stirring for 15 minutes to obtain solution 3;
4) slowly adding 30 parts by weight of the solution 2 and 3 parts by weight of tetraethoxysilane into the solution 3, and stirring for 3 hours;
5) slowly dripping hydrochloric acid into the solution obtained in the step 4), stirring, adjusting the pH value of the solution to 2.8, centrifuging, washing for 3 times by using absolute ethyl alcohol, and drying to obtain the silicon dioxide nanometer bowl.
Example 6
A preparation method of a silicon dioxide nanometer bowl comprises the following steps:
1) adding 90 parts by weight of ultrapure water and 10 parts by weight of PAANa into a brown bottle coated with tinfoil paper in a shading mode, and stirring for 5 minutes to obtain a solution 1;
2) adding 0.1 part by weight of magnesium hydroxide and 10 parts by weight of ammonia water into 100ml of ultrapure water in sequence, and stirring for 15 minutes to obtain a solution 2;
3) adding 10 parts of solution 1 into 150 parts of ethanol/ultrapure water mixed solution with the concentration of 40% (weight ratio), and stirring for 15 minutes to obtain solution 3;
4) slowly adding 30 parts by weight of the solution 2 and 3 parts by weight of tetraethoxysilane into the solution 3, and stirring for 13 hours;
5) slowly dripping hydrochloric acid into the solution obtained in the step 4), stirring, adjusting the pH value of the solution to 2.1, centrifuging, washing for 3 times by using absolute ethyl alcohol, and drying to obtain the silicon dioxide nanometer bowl.

Claims (10)

1. A preparation method of a silicon dioxide nanometer bowl is characterized by comprising the following steps: the method comprises the following steps:
1) sequentially adding 90-99.9 parts by weight of water and 0.1-10 parts by weight of PAANa into a reactor, and stirring to obtain a solution 1;
2) sequentially adding 0.1-10 parts by weight of hydroxide and 0.3-10 parts by weight of ammonia water into 100ml of ultrapure water, and stirring to obtain a solution 2;
3) adding 1-10 parts by weight of solution 1 into 150 parts by weight of ethanol/water mixed solution with the concentration of 40-80%, and stirring to obtain solution 3;
4) slowly adding 0.3-30 parts by weight of the solution 2 and 3-25 parts by weight of ethyl orthosilicate into the solution 3, and stirring;
5) slowly dripping inorganic acid into the solution obtained in the step 4), stirring, adjusting the pH value of the solution to 2.0-3.0, and fully stirring to obtain the silicon dioxide nanometer bowl.
2. The method for preparing silica nanobowl according to claim 1, wherein the stirring in step 1) is performed under dark/no light condition.
3. The method for preparing the silica nanobowl according to claim 2, wherein the hydroxide in the step 2) is magnesium hydroxide.
4. The method for preparing a silica nanobowl according to claim 3, wherein the inorganic acid in step 5) is hydrochloric acid, and the pH of the solution is 2.5.
5. The method for preparing the silica nanometer bowl according to claim 4, wherein in the step 5), the silica nanometer bowl is obtained by centrifuging, washing with absolute ethyl alcohol and drying after the complete stirring.
6. The method for preparing a silica nanobowl according to claim 5, wherein the stirring in step 5) is carried out for 30 to 150 minutes.
7. The method for preparing the silica nanometer bowl according to claim 1, which is characterized by comprising the following steps: in the step 1), the weight ratio of water to PAANa is 95 parts: 5 parts of the raw materials.
8. The method for preparing the silica nanometer bowl as claimed in claim 7, wherein in the step 2), the weight ratio of the hydroxide to the ammonia water is 5 parts to 5 parts.
9. The method for preparing a silica nanobowl according to claim 8,
in the step 3), the weight ratio of the 60% ethanol/water mixed solution to the solution 1 obtained in the step 1) is 150 parts: 5 parts of the raw materials.
10. The method for preparing a silica nanobowl according to claim 9,
in the step 4), the weight ratio of the solution 2 obtained in the step 2) to the solution 3 obtained in the step 3) is 15 parts: 14 parts of (A).
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3114493A1 (en) * 1981-04-10 1982-10-28 Degussa Ag, 6000 Frankfurt "FELLING SILICONES AND METHOD FOR THE PRODUCTION THEREOF"
CA2087911C (en) * 1992-01-24 1999-06-29 Kiyoshi Abe Spherical granules of porous silica or silicate, process for the production thereof, and applications thereof
CN100494057C (en) * 2006-10-09 2009-06-03 中国科学技术大学 Preparation process of hollow silica ball
CN104138733B (en) * 2013-05-08 2016-02-03 中国石油天然气股份有限公司 Silica hollow microsphere with through macropores on surface and preparation method thereof
WO2015133606A1 (en) * 2014-03-06 2015-09-11 国立大学法人名古屋工業大学 Method for producing nano hollow particles composed of silica shell
CN104787769B (en) * 2015-03-21 2017-10-13 北京化工大学 A kind of method that silicon dioxide hollow microsphere is prepared with template
JP6967256B2 (en) * 2016-08-31 2021-11-17 国立大学法人 名古屋工業大学 Manufacturing method of nanosilica hollow particles
CN110734070A (en) * 2019-11-07 2020-01-31 贵州大学 mesoporous silicon nanoparticles with controllable morphology and preparation method thereof

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