CN113845117B - Oil-water amphiphilic silicon dioxide nano particle and preparation method thereof - Google Patents

Oil-water amphiphilic silicon dioxide nano particle and preparation method thereof Download PDF

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CN113845117B
CN113845117B CN202010594843.4A CN202010594843A CN113845117B CN 113845117 B CN113845117 B CN 113845117B CN 202010594843 A CN202010594843 A CN 202010594843A CN 113845117 B CN113845117 B CN 113845117B
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CN113845117A (en
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孙灵辉
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Petrochina Co Ltd
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    • C—CHEMISTRY; METALLURGY
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    • C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
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    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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Abstract

The invention discloses an oil-water amphiphilic silicon dioxide nanoparticle and a preparation method thereof. The preparation method comprises the following steps: 1) Adding ammonia water into absolute ethyl alcohol to obtain a solution A; 2) Adding a carbon source into the solution A to obtain a solution B; 3) Adding a silicon source into the solution B to obtain a solution C; 4) Reacting the solution C at a preset temperature for a preset time, and cooling to room temperature; 5) Adding the reacted system into petroleum ether, centrifuging, washing the solid with absolute ethyl alcohol, and drying to obtain the oil-water amphiphilic SiO 2 And (3) nanoparticles. The method solves the problems of the prior oil-water amphipathic SiO 2 The method has the advantages of simple operation, mild condition and short preparation period, is suitable for large-scale production, and has wide application prospect in the fields of energy, electronic industry, aerospace and the like.

Description

Oil-water amphiphilic silicon dioxide nano particle and preparation method thereof
Technical Field
The invention relates to the technical field of nano materials, in particular to an oil-water amphiphilic silicon dioxide nano particle and a preparation method thereof.
Background
SiO 2 Commonly known as white carbon black, is a very important industrial raw material. It is a white powder with many characteristics such as optical shielding, nonlinear resistance, etc. and has very wide application. SiO (SiO) 2 The nano particle is one of extremely important high-tech superfine inorganic new materials, and has wide application value in the fields of high-tech fields such as electronic industry, aerospace technology, novel catalyst carriers and the like, and also in the industries such as high-grade transparent toothpaste, high-grade rubber, synthetic resin, plastics, printing ink, high-grade paint and the like. Recently, as research progresses, siO 2 Nanoparticle in petroleumThe application in industrial tertiary oil recovery is attracting a great deal of attention. The main action principle is that the wetting property of the rock surface of the reservoir and the interaction state of the rock surface of the reservoir and crude oil are changed, so that the crude oil is easy to peel off and flow in the process of flushing a gap by the injection fluid to be displaced, and the recovery ratio is improved. This is for SiO 2 The regulation of the surface properties of the nanoparticles puts high demands. It requires not only SiO 2 The nanoparticle has a hydrophilic or hydrophobic surface and is also required to be capable of oil-water amphiphilicity.
At present, siO is prepared 2 The nanoparticle is mainly prepared from organosilicon such as Tetraethoxysilane (TEOS), 3-aminopropyl triethoxysilane (APTES) and methyl orthosilicate (TMOS) as silicon source, and also from inorganic silicon source such as Si powder or sodium metasilicate. As the method used, a sol-gel method, a precipitation hydrolysis method, a hydrothermal/solvothermal method, etc. are mentioned. Although SiO with good dispersibility can be prepared 2 Nanoparticles, however, are substantially hydrophilic in their surface. SiO can be prepared by the method of post-treatment 2 The surface properties of the nanoparticles are changed from hydrophilic to hydrophobic or hydrophobic/oleophobic. But is expensive, has high condition requirements, and is not suitable for mass production. Moreover, at present, oil-water amphipathic SiO is not prepared basically 2 Nanoparticle methods. Therefore, an oil-water amphipathic SiO with simple operation, high product quality, mild condition and short preparation period is developed 2 The nanoparticle preparation technology has important significance.
Disclosure of Invention
An object of the present invention is to provide an oil-water amphiphilic SiO 2 A method for preparing nano particles. The method has the characteristics of simple operation, high product quality, mild condition, short preparation period, suitability for large-scale production and the like, and the obtained SiO 2 The particle size of the nano particles is between 10 and 50nm, and the nano particles have good oil-water amphipathy.
Another object of the present invention is to provide an oil-water amphiphilic SiO obtained by the above preparation method 2 And (3) nanoparticles.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
in one aspect, the invention provides an oil-water amphiphilic SiO 2 A method of preparing nanoparticles, the method comprising the steps of:
1) Adding ammonia water into absolute ethyl alcohol to obtain a solution A;
2) Adding a carbon source into the solution A to obtain a solution B;
3) Adding a silicon source into the solution B to obtain a solution C;
4) Reacting the solution C at a preset temperature for a preset time, and cooling to room temperature;
5) Adding the reacted system into petroleum ether, centrifuging, washing the solid with absolute ethyl alcohol, and drying to obtain the oil-water amphiphilic SiO 2 And (3) nanoparticles.
The invention utilizes carbon clusters to adjust SiO 2 The wettability of the surface of the nano particles realizes oil-water amphipathy SiO 2 And (3) preparation of nano particles. The preparation method has mild condition and short preparation period, and can be used for mass production.
In some embodiments of the invention, preferably, the carbon source comprises glucose.
In some embodiments of the invention, preferably, the silicon source comprises tetraethyl orthosilicate.
In some embodiments of the invention, preferably, the carbon source is glucose and the silicon source is tetraethyl orthosilicate.
In the preparation method of the present invention, ammonia is used as a catalyst for the reaction and a pH adjustor, and in some embodiments of the present invention, preferably, the concentration of ammonia in the solution C is 0.06mol/L to 1.1mol/L.
In some embodiments of the invention, preferably, the concentration of the carbon source in the solution C is 0.013mol/L to 0.096mol/L.
In some embodiments of the invention, preferably, the concentration of the silicon source in the solution C is 0.08-0.43mol/L.
In some embodiments of the invention, preferably, the predetermined temperature is 150-200 ℃; the preset time is 5-25 h.
In some embodiments of the invention, preferably, the temperature of the drying is 50-100 ℃ for 10-24 hours. For example, 60℃for 12 hours.
In some embodiments of the invention, preferably, the preparation method comprises the steps of:
1) Adding ammonia water into absolute ethyl alcohol at room temperature, and uniformly stirring to obtain a solution A;
2) Adding glucose into the solution A, and stirring for 20min to obtain a solution B, namely an ethanol solution containing glucose;
3) Adding tetraethyl orthosilicate into the solution B, stirring for 30min at the temperature, and transferring the obtained solution C into a high-pressure reaction kettle;
4) Placing the high-pressure reaction kettle in an oven, reacting for 5-25 hours at the temperature of 150-200 ℃, and naturally cooling the reaction kettle to room temperature;
5) Slowly adding the reacted system (comprising solid and liquid) into petroleum ether, centrifuging and washing the solid with absolute ethyl alcohol; and finally, placing the mixture in a 60 ℃ oven for 12 hours and drying the mixture to obtain the product.
In the preparation method, tetraethyl orthosilicate is used as a silicon source, and glucose is used as a carbon source; regulation of SiO using carbon clusters 2 The wettability of the surface of the nano particles realizes oil-water amphipathy SiO 2 Preparation of nano particles, and the obtained oil-water amphiphilic SiO 2 The particle size of the nanoparticle is between 10 and 50nm. The preparation method has mild condition and short preparation period, and can be used for mass production.
In another aspect, the invention provides an oil-water amphiphilic SiO obtained by the preparation method 2 And (3) nanoparticles.
Oil-water amphipathic SiO based on the invention 2 Nanoparticles, preferably, the oil-water amphiphilic SiO 2 The particle size of the nanoparticle is 10nm-50nm.
The invention has the beneficial effects that:
the preparation method has the characteristics of simple operation, mild condition, short preparation period and the like, and solves the problems of the prior oil-water amphipathic SiO 2 The preparation of nanoparticles is problematic. The SiO is 2 The nano particles have narrower size distribution, have good affinity to oil/water,can be produced in large scale.
Drawings
FIG. 1 is a SiO produced in example 1 2 X-ray diffraction pattern of nanoparticles.
FIG. 2 is a SiO produced in example 1 2 TEM photographs of nanoparticles.
FIG. 3 is a SiO produced in example 2 2 TEM photographs of nanoparticles.
FIG. 4 is a SiO produced in example 3 2 TEM photographs of nanoparticles.
FIG. 5 is a SiO produced in example 4 2 TEM photographs of nanoparticles.
FIG. 6 is a SiO produced in example 5 2 TEM photographs of nanoparticles.
FIG. 7 is a SiO produced in example 6 2 TEM photographs of nanoparticles.
FIG. 8 is a SiO produced in example 7 2 TEM photographs of nanoparticles.
FIG. 9 is a SiO produced in example 8 2 TEM photographs of nanoparticles.
FIG. 10 is a SiO produced in example 9 2 TEM photographs of nanoparticles.
FIG. 11 is a SiO produced in example 10 2 TEM photographs of nanoparticles.
FIG. 12 is a SiO produced in example 11 2 TEM photographs of nanoparticles.
FIG. 13 is a SiO of example 1 with water 2 A graph of the spreading on the nanoparticles.
FIG. 14 is a SiO of the oil prepared in example 1 2 A graph of the spreading on the nanoparticles.
FIG. 15 is a SiO of example 2 with water 2 A graph of the spreading on the nanoparticles.
FIG. 16 is a SiO of the oil prepared in example 2 2 A graph of the spreading on the nanoparticles.
FIG. 17 is a SiO of example 3 with water 2 A graph of the spreading on the nanoparticles.
FIG. 18 is a SiO of the oil prepared in example 3 2 A graph of the spreading on the nanoparticles.
FIG. 19 is a SiO of example 4 with water 2 A graph of the spreading on the nanoparticles.
FIG. 20 is a SiO of the oil prepared in example 4 2 A graph of the spreading on the nanoparticles.
FIG. 21 is a SiO of example 5 with water 2 A graph of the spreading on the nanoparticles.
FIG. 22 is a SiO of the oil prepared in example 5 2 A graph of the spreading on the nanoparticles.
FIG. 23 is a SiO of example 6 with water 2 A graph of the spreading on the nanoparticles.
FIG. 24 is a SiO of the oil prepared in example 6 2 A graph of the spreading on the nanoparticles.
FIG. 25 is a SiO of example 7 with water 2 A graph of the spreading on the nanoparticles.
FIG. 26 is a SiO of the oil prepared in example 7 2 A graph of the spreading on the nanoparticles.
FIG. 27 is a SiO of example 8 with water 2 A graph of the spreading on the nanoparticles.
FIG. 28 is a SiO of the oil prepared in example 8 2 A graph of the spreading on the nanoparticles.
FIG. 29 is a SiO of example 9 with water 2 A graph of the spreading on the nanoparticles.
FIG. 30 is a SiO of the oil prepared in example 9 2 A graph of the spreading on the nanoparticles.
FIG. 31 is a SiO of example 10 with water 2 A graph of the spreading on the nanoparticles.
FIG. 32 is a SiO of the oil prepared in example 10 2 A graph of the spreading on the nanoparticles.
FIG. 33 is a SiO of example 11 with water 2 A graph of the spreading on the nanoparticles.
FIG. 34 is a SiO of the oil prepared in example 11 2 A graph of the spreading on the nanoparticles.
Detailed Description
In order to more clearly illustrate the present invention, the present invention will be further described with reference to preferred embodiments. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and that this invention is not limited to the details given herein.
All numerical designations of the invention (e.g., temperature, time, concentration, weight, etc., including ranges for each) can generally be approximations that vary (+) or (-) as appropriate in 0.1 or 1.0 increments. All numerical designations are to be understood as preceded by the term "about".
Example 1
This example prepared an oil-water amphiphilic SiO 2 The nanoparticle specifically comprises the following steps:
1) 0.05mL of ammonia water was added to 20mL of absolute ethanol at room temperature and stirred well.
2) 0.1g of glucose was added to the above solution, and stirred for 20 minutes to obtain a uniform ethanol solution containing glucose.
3) 0.7mL of tetraethyl orthosilicate was added to an ethanol solution containing glucose to obtain a mixture containing 0.17mol/L tetraethyl orthosilicate, 0.06mol/L ammonia water, 0.027mol/L glucose. After stirring at room temperature for 30min, the resulting mixture was transferred to a high-pressure autoclave.
4) The high-pressure reaction kettle is placed in an oven and is naturally cooled to room temperature after being reacted for 18 hours at 180 ℃.
5) The resulting solids and liquids were slowly added to an appropriate amount of petroleum ether, centrifuged and washed with absolute ethanol. Finally, placing the mixture in a 60 ℃ oven for 12 hours and drying the mixture to obtain a product, wherein an X-ray diffraction diagram is shown in a figure 1, and diffraction peaks in the figure are SiO 2 Characteristic diffraction peaks of (2) indicating that the resulting product is SiO 2 。
FIG. 2 is a diagram of the obtained SiO 2 TEM photographs of the nanoparticles, the particle size ranges of which are shown in Table 1.
FIG. 13 is a graph showing that water is present in the SiO 2 The spreading of the nanoparticles, FIG. 14, is a graph of the oil on the SiO 2 As can be seen from FIGS. 13 and 14, the contact angles of oil and water on the nanoparticles are less than 90 DEG, and therefore, the SiO 2 The nano particles have oil-water amphipathy.
Preparation of amphiphilic SiO 2 When preparing nanoparticles, a stepwise preparation method is often adopted, namely, the nanoparticles are prepared first, and then the surfaces of the nanoparticles are modulated into amphiphilicity by a surface modification technology. Where a large amount of surfactant or polymer is required. The amphiphilic nano particles can be obtained by utilizing the method of the invention in one step, and no surfactant is needed. Therefore, compared with the prior art, the technology of the invention has the advantages of simple and convenient operation and short period. Although the preparation method of the invention is carried out at 150-200 ℃, the preparation method still belongs to mild preparation conditions in the field of chemical production.
Example 2
This example prepared an oil-water amphiphilic SiO 2 The nanoparticle specifically comprises the following steps:
1) 0.3mL of ammonia water was added to 20mL of absolute ethanol at room temperature and stirred well.
2) 0.1g of glucose was added to the above solution, and stirred for 20 minutes to obtain a uniform ethanol solution containing glucose.
3) 0.7mL of tetraethyl orthosilicate was added to an ethanol solution containing glucose to obtain a mixture containing 0.17mol/L tetraethyl orthosilicate, 0.36mol/L ammonia water, and 0.027mol/L glucose. After stirring at room temperature for 30min, the resulting mixture was transferred to a high-pressure autoclave.
4) The high-pressure reaction kettle is placed in an oven and is naturally cooled to room temperature after being reacted for 18 hours at 180 ℃.
5) The resulting solids and liquids were slowly added to an appropriate amount of petroleum ether, centrifuged and washed with absolute ethanol. And finally, placing the mixture in a 60 ℃ oven for 12 hours and drying the mixture to obtain the product.
FIG. 3 is a diagram of the obtained SiO 2 TEM photographs of the nanoparticles, the particle size ranges of which are shown in Table 1.
FIG. 15 is a diagram showing the concentration of water in the SiO 2 The spreading of the nanoparticles, FIG. 16 is the oil on the SiO 2 As can be seen from FIGS. 15 and 16, the contact angles of oil and water on the nanoparticles are less than 90 DEG, so that the SiO 2 The nano particles have oil-water amphipathy.
Example 3
This example prepared an oil-water amphiphilic SiO 2 The nanoparticle specifically comprises the following steps:
1) 0.9mL of ammonia water was added to 20mL of absolute ethanol at room temperature and stirred well.
2) 0.1g of glucose was added to the above solution, and stirred for 20 minutes to obtain a uniform ethanol solution containing glucose.
3) 0.7mL of tetraethyl orthosilicate was added to an ethanol solution containing glucose to obtain a mixture containing 0.17mol/L tetraethyl orthosilicate, 1.1mol/L ammonia water, and 0.027mol/L glucose. After stirring at room temperature for 30min, the resulting mixture was transferred to a high-pressure autoclave.
4) The high-pressure reaction kettle is placed in an oven and is naturally cooled to room temperature after being reacted for 18 hours at 180 ℃.
5) The resulting solids and liquids were slowly added to an appropriate amount of petroleum ether, centrifuged and washed with absolute ethanol. And finally, placing the mixture in a 60 ℃ oven for 12 hours and drying the mixture to obtain the product.
FIG. 4 shows the obtained SiO 2 TEM photographs of the nanoparticles, the particle size ranges of which are shown in Table 1.
FIG. 17 is a diagram showing the concentration of water in the SiO 2 The spreading of the nanoparticles, FIG. 18, is a graph of the oil on the SiO 2 As can be seen from FIGS. 17 and 18, the contact angles of oil and water on the nanoparticles are smaller than 90 DEG, and thus, the SiO 2 The nano particles have oil-water amphipathy.
Example 4
This example prepared an oil-water amphiphilic SiO 2 The nanoparticle specifically comprises the following steps:
1) 0.3mL of ammonia water was added to 20mL of absolute ethanol at room temperature and stirred well.
2) 0.27g of glucose was added to the above solution, and stirred for 20 minutes to obtain a uniform ethanol solution containing glucose.
3) 0.7mL of tetraethyl orthosilicate was added to an ethanol solution containing glucose to obtain a mixture containing 0.17mol/L tetraethyl orthosilicate, 0.36mol/L ammonia water, and 0.073mol/L glucose. After stirring at room temperature for 30min, the resulting mixture was transferred to a high-pressure autoclave.
4) The high-pressure reaction kettle is placed in an oven and is naturally cooled to room temperature after being reacted for 18 hours at 180 ℃.
5) The resulting solids and liquids were slowly added to an appropriate amount of petroleum ether, centrifuged and washed with absolute ethanol. And finally, placing the mixture in a 60 ℃ oven for 12 hours and drying the mixture to obtain the product.
FIG. 5 is a diagram of the obtained SiO 2 TEM photographs of the nanoparticles, the particle size ranges of which are shown in Table 1.
FIG. 19 is a graph showing that water is present in the SiO 2 The spreading of the nanoparticles, FIG. 20, is a graph of the oil on the SiO 2 As can be seen from FIGS. 19 and 20, the SiO is formed by a graph of the spreading of nanoparticles 2 The nano particles have oil-water amphipathy.
Example 5
This example prepared an oil-water amphiphilic SiO 2 The nanoparticle specifically comprises the following steps:
1) 0.3mL of ammonia water was added to 20mL of absolute ethanol at room temperature and stirred well.
2) 0.36g of glucose was added to the above solution, and stirred for 20 minutes to obtain a uniform ethanol solution containing glucose.
3) 0.7mL of tetraethyl orthosilicate was added to an ethanol solution containing glucose to obtain a mixture containing 0.17mol/L tetraethyl orthosilicate, 0.36mol/L ammonia water, and 0.096mol/L glucose. After stirring at room temperature for 30min, the resulting mixture was transferred to a high-pressure autoclave.
4) The high-pressure reaction kettle is placed in an oven and is naturally cooled to room temperature after being reacted for 18 hours at 180 ℃.
5) The resulting solids and liquids were slowly added to an appropriate amount of petroleum ether, centrifuged and washed with absolute ethanol. And finally, placing the mixture in a 60 ℃ oven for 12 hours and drying the mixture to obtain the product.
FIG. 6 is a diagram of the obtained SiO 2 NanoparticlesThe particle size ranges are shown in Table 1.
FIG. 21 shows water at the SiO 2 The spreading of the nanoparticles, FIG. 22, is a graph of the oil on the SiO 2 As can be seen from FIGS. 21 and 22, the SiO is formed on the nanoparticles 2 The nano particles have oil-water amphipathy.
Example 6
This example prepared an oil-water amphiphilic SiO 2 The nanoparticle specifically comprises the following steps:
1) 0.3mL of ammonia water was added to 20mL of absolute ethanol at room temperature and stirred well.
2) 0.05g of glucose was added to the above solution and stirred for 20 minutes to obtain a uniform ethanol solution containing glucose.
3) 0.35mL of tetraethyl orthosilicate was added to an ethanol solution containing glucose to obtain a mixture containing 0.08mol/L tetraethyl orthosilicate, 0.36mol/L ammonia water, and 0.013mol/L glucose. After stirring at room temperature for 30min, the resulting mixture was transferred to a high-pressure autoclave.
4) The high-pressure reaction kettle is placed in an oven and is naturally cooled to room temperature after being reacted for 18 hours at 180 ℃.
5) The resulting solids and liquids were slowly added to an appropriate amount of petroleum ether, centrifuged and washed with absolute ethanol. And finally, placing the mixture in a 60 ℃ oven for 12 hours and drying the mixture to obtain the product.
FIG. 7 is a diagram of the obtained SiO 2 TEM photographs of the nanoparticles, the particle size ranges of which are shown in Table 1.
FIG. 23 is a diagram showing the presence of water in the SiO 2 The spreading of the nanoparticles, FIG. 24 is the oil on the SiO 2 As can be seen from FIGS. 23 and 24, the contact angles of oil and water on the nanoparticles are less than 90 DEG, and thus, the SiO 2 The nano particles have oil-water amphipathy.
Example 7
This example prepared an oil-water amphiphilic SiO 2 The nanoparticle specifically comprises the following steps:
1) 0.3mL of ammonia water was added to 20mL of absolute ethanol at room temperature and stirred well.
2) 0.25g of glucose was added to the above solution, and stirred for 20 minutes to obtain a uniform ethanol solution containing glucose.
3) 1.75mL of tetraethyl orthosilicate was added to an ethanol solution containing glucose to give a mixture containing 0.43mol/L tetraethyl orthosilicate, 0.36mol/L ammonia, 0.065mol/L glucose. After stirring at room temperature for 30min, the resulting mixture was transferred to a high-pressure autoclave.
4) The high-pressure reaction kettle is placed in an oven and is naturally cooled to room temperature after being reacted for 18 hours at 180 ℃.
5) The resulting solids and liquids were slowly added to an appropriate amount of petroleum ether, centrifuged and washed with absolute ethanol. And finally, placing the mixture in a 60 ℃ oven for 12 hours and drying the mixture to obtain the product.
FIG. 8 is a diagram of the obtained SiO 2 TEM photographs of the nanoparticles, the particle size ranges of which are shown in Table 1.
FIG. 25 shows water at the SiO 2 The spreading of the nanoparticles, FIG. 26, is a graph of the oil on the SiO 2 As can be seen from FIGS. 25 and 26, the SiO is formed on the nanoparticles 2 The nano particles have oil-water amphipathy.
Example 8
This example prepared an oil-water amphiphilic SiO 2 The nanoparticle specifically comprises the following steps:
1) 0.3mL of ammonia water was added to 20mL of absolute ethanol at room temperature and stirred well.
2) 0.1g of glucose was added to the above solution, and stirred for 20 minutes to obtain a uniform ethanol solution containing glucose.
3) 0.7mL of tetraethyl orthosilicate was added to an ethanol solution containing glucose to obtain a mixture containing 0.17mol/L tetraethyl orthosilicate, 0.36mol/L ammonia water, and 0.027mol/L glucose. After stirring at room temperature for 30min, the resulting mixture was transferred to a high-pressure autoclave.
4) The high-pressure reaction kettle is placed in an oven and is naturally cooled to room temperature after being reacted for 18 hours at 150 ℃.
5) The resulting solids and liquids were slowly added to an appropriate amount of petroleum ether, centrifuged and washed with absolute ethanol. And finally, placing the mixture in a 60 ℃ oven for 12 hours and drying the mixture to obtain the product.
FIG. 9 shows the obtained SiO 2 TEM photographs of the nanoparticles, the particle size ranges of which are shown in Table 1.
FIG. 27 shows water at the SiO 2 The spreading of the nanoparticles, FIG. 28 is the oil on the SiO 2 As can be seen from FIGS. 27 and 28, the SiO is formed by a graph of the spreading of nanoparticles 2 The nano particles have oil-water amphipathy.
Example 9
This example prepared an oil-water amphiphilic SiO 2 The nanoparticle specifically comprises the following steps:
1) 0.3mL of ammonia water was added to 20mL of absolute ethanol at room temperature and stirred well.
2) 0.1g of glucose was added to the above solution, and stirred for 20 minutes to obtain a uniform ethanol solution containing glucose.
3) 0.7mL of tetraethyl orthosilicate was added to an ethanol solution containing glucose to obtain a mixture containing 0.17mol/L tetraethyl orthosilicate, 0.36mol/L ammonia water, and 0.027mol/L glucose. After stirring at room temperature for 30min, the resulting mixture was transferred to a high-pressure autoclave.
4) The high-pressure reaction kettle is placed in an oven and is naturally cooled to room temperature after being reacted for 18 hours at 200 ℃.
5) The resulting solids and liquids were slowly added to an appropriate amount of petroleum ether, centrifuged and washed with absolute ethanol. And finally, placing the mixture in a 60 ℃ oven for 12 hours and drying the mixture to obtain the product.
FIG. 10 shows the obtained SiO 2 TEM photographs of the nanoparticles, the particle size ranges of which are shown in Table 1.
FIG. 29 is a graph of water on the SiO 2 The spreading of the nanoparticles, FIG. 30, is a graph of the oil on the SiO 2 As can be seen from FIGS. 29 and 30, the SiO is formed on the nanoparticles 2 The nano particles have oil-water amphipathy.
Example 10
This example prepared an oil-water amphiphilic SiO 2 The nanoparticle specifically comprises the following steps:
1) 0.3mL of ammonia water was added to 20mL of absolute ethanol at room temperature and stirred well.
2) 0.1g of glucose was added to the above solution, and stirred for 20 minutes to obtain a uniform ethanol solution containing glucose.
3) 0.7mL of tetraethyl orthosilicate was added to an ethanol solution containing glucose to obtain a mixture containing 0.17mol/L tetraethyl orthosilicate, 0.36mol/L ammonia water, and 0.027mol/L glucose. After stirring at room temperature for 30min, the resulting mixture was transferred to a high-pressure autoclave.
4) The high-pressure reaction kettle is placed in an oven and is naturally cooled to room temperature after being reacted for 5 hours at 180 ℃.
5) The resulting solids and liquids were slowly added to an appropriate amount of petroleum ether, centrifuged and washed with absolute ethanol. And finally, placing the mixture in a 60 ℃ oven for 12 hours and drying the mixture to obtain the product.
FIG. 11 is a diagram of the obtained SiO 2 TEM photographs of the nanoparticles, the particle size ranges of which are shown in Table 1.
FIG. 31 is a diagram showing the concentration of water in the SiO 2 The spreading of the nanoparticles, FIG. 32, is a graph of the oil on the SiO 2 As can be seen from FIGS. 31 and 32, the contact angles of oil and water on the nanoparticles are smaller than 90 DEG, and therefore, the SiO 2 The nano particles have oil-water amphipathy.
Example 11
This example prepared an oil-water amphiphilic SiO 2 The nanoparticle specifically comprises the following steps:
1) 0.3mL of ammonia water was added to 20mL of absolute ethanol at room temperature and stirred well.
2) 0.1g of glucose was added to the above solution, and stirred for 20 minutes to obtain a uniform ethanol solution containing glucose.
3) 0.7mL of tetraethyl orthosilicate was added to an ethanol solution containing glucose to obtain a mixture containing 0.17mol/L tetraethyl orthosilicate, 0.36mol/L ammonia water, and 0.027mol/L glucose. After stirring at room temperature for 30min, the resulting mixture was transferred to a high-pressure autoclave.
4) The high-pressure reaction kettle is placed in an oven and is naturally cooled to room temperature after being reacted for 25 hours at 180 ℃.
5) The resulting solids and liquids were slowly added to an appropriate amount of petroleum ether, centrifuged and washed with absolute ethanol. And finally, placing the mixture in a 60 ℃ oven for 12 hours and drying the mixture to obtain the product.
FIG. 12 shows the obtained SiO 2 TEM photographs of the nanoparticles, the particle size ranges of which are shown in Table 1.
FIG. 33 is a diagram showing the presence of water in the SiO 2 The spreading of the nanoparticles, FIG. 34, is a graph of the oil on the SiO 2 As can be seen from FIGS. 33 and 34, the contact angles of oil and water on the nanoparticles are smaller than 90 DEG, and therefore, the SiO 2 The nano particles have oil-water amphipathy.
TABLE 1 morphology and size of the products obtained in examples 1-11
Figure BDA0002557154270000111
Figure BDA0002557154270000121
As is clear from Table 1, siO obtained by the production method of the present invention 2 The nano particles are granular, the size span is only 10nm, and the particle size distribution is narrow.
It should be understood that the foregoing examples of the present invention are provided merely for clearly illustrating the present invention and are not intended to limit the embodiments of the present invention, and that various other changes and modifications may be made therein by one skilled in the art without departing from the spirit and scope of the present invention as defined by the appended claims.

Claims (5)

1. Oil-water amphiphilic SiO 2 A method of preparing nanoparticles, the method comprising the steps of:
1) Adding ammonia water into absolute ethyl alcohol to obtain a solution A;
2) Adding glucose as a carbon source into the solution A to obtain a solution B;
3) Adding silicon source tetraethyl orthosilicate into the solution B to obtain a solution C;
4) Reacting the solution C at 150-200 ℃ for 5h-25h, and cooling to room temperature;
5) Adding the reacted system into petroleum ether, centrifuging, washing the solid with absolute ethyl alcohol, and drying at 50-100 ℃ to obtain the oil-water amphiphilic SiO 2 And (3) nanoparticles.
2. The production method according to claim 1, wherein the concentration of aqueous ammonia in the solution C is 0.06mol/L to 1.1mol/L.
3. The production method according to claim 1 or 2, wherein the concentration of the carbon source in the solution C is 0.013mol/L to 0.096mol/L.
4. The production method according to claim 3, wherein the concentration of the silicon source in the solution C is 0.08 to 0.43mol/L.
5. The method of claim 1, wherein the drying time is 10-24h.
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