CN108483453B - Preparation method of SBA-15 type mesoporous silica microspheres - Google Patents
Preparation method of SBA-15 type mesoporous silica microspheres Download PDFInfo
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- CN108483453B CN108483453B CN201810367463.XA CN201810367463A CN108483453B CN 108483453 B CN108483453 B CN 108483453B CN 201810367463 A CN201810367463 A CN 201810367463A CN 108483453 B CN108483453 B CN 108483453B
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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
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Abstract
A preparation method of SBA-15 type mesoporous silica microspheres comprises the following steps: (1) mixing P123, concentrated hydrochloric acid, PVA and water to prepare a mixed aqueous solution; (2) adding a silicon dioxide precursor into the mixed aqueous solution at the temperature of 15-45 ℃ and stirring; (3) standing for 3-36 hours at 15-30 ℃; (4) stirring or standing for 3-36 hours at the temperature of 30-55 ℃; (5) carrying out hydrothermal treatment in a high-pressure kettle, filtering, washing and drying the obtained precipitate, and roasting to prepare the SBA-15 type mesoporous silica microsphere. The method has simple system and good reproducibility, can be used for mass production, and has cheap raw materials; the prepared product has microspherical particles with micron-sized size, long-range two-dimensional hexagonal mesoporous structure, high specific surface area and high pore volume, and can meet the requirements of equal fixation for chromatographic separation.
Description
Technical Field
The invention relates to the technical field of mesoporous materials, in particular to a preparation method of SBA-15 type mesoporous silica microspheres.
Background
Since the scientists of Mobil corporation (Mobil) in 1992 successfully synthesized a novel M41S mesoporous molecular sieve by using an alkyl quaternary ammonium salt cationic surfactant as a template, the research heat of mesoporous materials by people in the scientific community has been raised; the mesoporous material has an ordered mesostructure, a high specific surface area and a large pore volume, and has huge application prospects in the aspects of adsorption, catalysis, separation and the like.
The principle of the preparation of ordered mesoporous materials is based on the self-assembly process between inorganic species and surfactants, among the many surfactants that have been used, non-ionic block copolymer surfactants (such as P123) allow the preparation of mesoporous materials with larger pore size and more flexible structural design, among which SBA-15 with two-dimensional hexagonal mesoporous structure prepared with classical P123/silicon source/dilute hydrochloric acid system is most interesting, with adjustable pore size and particle morphology, such as fibrous, etc.
In application, the spherical SBA-15 mesoporous silica not only has larger and adjustable specific surface area, regular pore structure and higher mechanical strength, but also has higher modifiable capacity and lower mass transfer resistance, thereby having important application value in the fields of chromatographic separation, catalysts, drug carriers and the like; according to literature research, the problems of difficult control of morphology, poor long-range orderliness of an ordered structure, complex preparation system and the like still exist in the preparation of the SBA-15 type microspheres at present; the main reasons are that: (1) the added organic additive influences the self-assembly process of P123 and silicon species, so that the mesoporous structure has no long-range order, and a vermicular structure is generally obtained, even a mesoporous foam structure (mesocellular) is formed; (2) the preparation conditions (e.g., temperature) are outside the preferred range of formation conditions for the SBA-15 type silica in order to obtain a spherical morphology.
Disclosure of Invention
The invention aims to provide a preparation method of SBA-15 type mesoporous silica microspheres, which utilizes polyvinyl alcohol as an additive and utilizes a classic P123/silicon source/dilute hydrochloric acid system to prepare the SBA-15 microspheres with a two-dimensional hexagonal mesoporous structure, so that the SBA-15 microspheres have higher long-range order, micron-sized spherical particle appearance and higher specific surface area and pore volume.
The method of the invention comprises the following steps:
1. mixing a surfactant P123, concentrated hydrochloric acid, PVA and water to prepare a mixed aqueous solution, wherein the mass ratio of P123, HCl, PVA and water in the mixed aqueous solution is 1 (1-3) to 1-7 (40-140); the mass concentration of the concentrated hydrochloric acid is 37 percent;
2. adding a silicon dioxide precursor into the mixed aqueous solution at the temperature of 15-45 ℃, and stirring and mixing for 5-60 minutes to obtain a primary solution; the silicon dioxide precursor is sodium silicate, ethyl orthosilicate or methyl orthosilicate; the adding amount of the silicon dioxide precursor is according to SiO in the silicon dioxide precursor2The mass ratio of the components to P123 in the mixed aqueous solution is 0.5-2;
3. standing the primary solution for 3-36 hours at the temperature of 15-30 ℃ to obtain a secondary solution;
4. stirring or standing the secondary solution for 3-36 hours at the temperature of 30-55 ℃ to obtain a tertiary solution;
5. and carrying out hydrothermal treatment on the third solution in a high-pressure kettle, filtering, washing and drying the obtained precipitate, and roasting to prepare the SBA-15 type mesoporous silica microspheres.
The molecular weight of the PVA is 60-160K.
In the step 1, the preferred mass ratio of the P123, HCl, PVA and water in the mixed aqueous solution is 1 (1.5-2): (3-6): 60-90).
In the step 2, the preferable temperature is 30-40 ℃, and the preferable stirring and mixing time is 5-20 minutes.
In the step 3, the preferable temperature condition is 20-25 ℃, and the preferable standing time is 6-24 hours.
In the step 4, the preferable temperature condition is 32-40 ℃, and the preferable stirring or standing time is 6-24 hours.
The particle size of the SBA-15 type mesoporous silica microsphere is 1-20 mu m.
The SBA-15 type mesoporous silica microsphere has a long-range two-dimensional hexagonal mesoporous structure, and the pore diameter of a mesoporous is 6-12 nm.
The SBA-15 type mesoporous silica microsphere has the specific surface area of 500-800 m2g-1Pore volume of 0.6-1.0 cm3g-1。
Compared with the existing preparation method, the invention has the characteristics and beneficial effects that:
(1) the system is simple, the reproducibility is good, the mass production can be realized, and the raw materials are cheap;
(2) the particles of the prepared product are microspherical, the size is in micron order, and the requirements of fixation and the like for chromatographic separation are met;
(3) the prepared product has a long-range two-dimensional hexagonal mesoporous structure, and has high specific surface area and high pore volume.
Drawings
FIG. 1 is a scanning electron microscope image of an SBA-15 type mesoporous silica microsphere in example 1 of the present invention;
FIG. 2 is a graph showing the particle size distribution of the SBA-15 type mesoporous silica microspheres in example 1 of the present invention;
FIG. 3 is a low-angle X-ray diffraction chart of SBA-15 type mesoporous silica microspheres in example 1 of the present invention;
FIG. 4 is a high-power scanning electron microscope image of an SBA-15 type mesoporous silica microsphere in example 1 of the present invention;
fig. 5 is a scanning nitrogen adsorption isotherm and a pore size distribution curve chart of the SBA-15 type mesoporous silica microsphere in example 1 of the present invention.
Detailed Description
In the embodiment of the invention, the temperature of the hydrothermal reaction is 80-160 ℃ and the time is 6-48 hours.
In the embodiment of the invention, the roasting temperature is 450-650 ℃, and the roasting time is 2-6 hours.
The molecular weight of the surfactant P123 in the examples of the present invention was 5800.
The molecular weight of PVA (polyvinyl alcohol) in the embodiment of the invention is 60-160K.
The adding amount of the silicon dioxide precursor is that the silicon component in the silicon dioxide precursor is converted into SiO2Then, according to SiO2Mass ratio to P123.
In the embodiment of the invention, when the sodium silicate is added, the sodium silicate is added in the form of a sodium silicate solution, and the mass concentration of the selected sodium silicate solution is 30-50%.
In the embodiment of the invention, the influence of the introduced water on the reaction system is ignored when the sodium silicate solution is added.
The present invention is described in detail below with reference to examples, which are intended to illustrate the present invention and not to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention will occur to those skilled in the art after reading the present disclosure, and such equivalents will fall within the scope of the appended claims.
Example 1
Mixing a surfactant P123, concentrated hydrochloric acid, PVA and water to prepare a mixed aqueous solution, wherein the mass ratio of P123, HCl, PVA and water in the mixed aqueous solution is 1:1.66:3.2: 71; the mass concentration of the concentrated hydrochloric acid is 37 percent;
adding a silicon dioxide precursor into the mixed aqueous solution at the temperature of 35 ℃, and stirring and mixing for 10 minutes to obtain a primary solution; the silicon dioxide precursor is sodium silicate; the adding amount of the silicon dioxide precursor is according to SiO in the silicon dioxide precursor2The mass ratio of the component (D) to P123 in the mixed aqueous solution was 0.63;
standing the primary solution for 24 hours at the temperature of 20 ℃ to obtain a secondary solution;
stirring the secondary solution for 24 hours at the temperature of 35 ℃ to obtain a tertiary solution;
carrying out hydrothermal treatment on the third solution in a high-pressure kettle at 100 ℃ for 24 hours, filtering the obtained precipitate, washing until the filtrate is neutral, drying to remove water, and roasting at 550 ℃ for 4 hours to prepare SBA-15 type mesoporous silica microspheres; the SBA-15 type mesoporous silica microsphere has a long-range two-dimensional hexagonal mesoporous structure, the pore diameter of a mesoporous is 8.8nm, and the specific surface area is 634m2g-1Pore volume 0.66cm3g-1；
The obtained SBA-15 type mesoporous silica microspheres have good sphericity, the scanning of a low power electron microscope is shown in figure 1, the average size of the particle diameters is 12.2 mu m according to the statistical analysis result, the distribution is relatively narrow, and the distribution curve is shown in figure 2; the LA-XRD spectrum shows that the product has long-range order and is a two-dimensional hexagonal structure, the low-angle X-ray diffraction result is shown in figure 3 (at least three diffraction peaks (100) (110) (200) can be seen), and the high-magnification electronic microscope scanning image is shown in figure 4 and can correspond to the content of figure 3; n is a radical of2The adsorption-desorption isotherms are shown in fig. 5, and the type IV isotherm displayed indicates the presence of the mesoporous structure, indicating that the quality of the obtained mesoporous structure is good.
Example 2
The method is the same as example 1, except that:
(1) the mass ratio of P123, HCl, PVA and water in the mixed aqueous solution is 1:2:6: 90;
(2) adding at a temperature of 40 DEG CStirring and mixing the silicon dioxide precursor for 8 minutes; the silicon dioxide precursor is tetraethoxysilane; the adding amount of the silicon dioxide precursor is SiO2The mass ratio of the components to P123 is 0.5;
(3) standing the primary solution at 25 ℃ for 8 hours;
(4) standing the secondary solution at 40 ℃ for 8 hours;
(5) carrying out hydrothermal treatment on the third solution at 160 ℃ for 6 hours, and roasting the third solution at 650 ℃ for 2 hours; the average grain diameter of the SBA-15 type mesoporous silicon dioxide microspheres is 15.4 mu m, the average pore diameter of mesopores is 11.5nm, and the specific surface area is 522m2g-1Pore volume 0.95cm3g-1。
Example 3
The method is the same as example 1, except that:
(1) the mass ratio of P123, HCl, PVA and water in the mixed aqueous solution is 1:1.8:5: 80;
(2) adding a silicon dioxide precursor at the temperature of 30 ℃, and stirring and mixing for 15 minutes; the silicon dioxide precursor is methyl orthosilicate; the adding amount of the silicon dioxide precursor is SiO2The mass ratio of the components to P123 is 1;
(3) standing the primary solution at 22 ℃ for 16 hours;
(4) stirring the secondary solution at 36 ℃ for 16 hours;
(5) carrying out hydrothermal treatment on the third solution at 100 ℃ for 24 hours, and roasting at 550 ℃ for 4 hours; the average grain diameter of the SBA-15 type mesoporous silicon dioxide microspheres is 8.3 mu m, the average pore diameter of mesopores is 6.5nm, and the specific surface area is 780m2g-1Pore volume 0.84cm3g-1。
Example 4
The method is the same as example 1, except that:
(1) the mass ratio of P123, HCl, PVA and water in the mixed aqueous solution is 1:1.6:4.5: 75;
(2) adding a silicon dioxide precursor at the temperature of 32 ℃, and stirring and mixing for 12 minutes; the silicon dioxide precursor is methyl orthosilicate; the adding amount of the silicon dioxide precursor is SiO2The mass ratio of the components to P123 is 1.5;
(3) standing the primary solution at 23 ℃ for 12 hours;
(4) standing the secondary solution at 38 ℃ for 12 hours;
(5) carrying out hydrothermal treatment on the third solution at 120 ℃ for 12 hours, and roasting at 500 ℃ for 5 hours; the average grain diameter of the SBA-15 type mesoporous silicon dioxide microspheres is 9.6 mu m, the average pore diameter of the mesopores is 9.2nm, and the specific surface area is 769m2g-1Pore volume 0.73cm3g-1。
Example 5
The method is the same as example 1, except that:
(1) the mass ratio of P123, HCl, PVA and water in the mixed aqueous solution is 1:1.5:3: 60;
(2) adding a silicon dioxide precursor at the temperature of 38 ℃, and stirring and mixing for 9 minutes; the silicon dioxide precursor is methyl orthosilicate; the adding amount of the silicon dioxide precursor is SiO2The mass ratio of the components to P123 is 2;
(3) standing the primary solution at 24 ℃ for 15 hours;
(4) standing the secondary solution at 35 ℃ for 9 hours;
(5) carrying out hydrothermal treatment on the third solution at 160 ℃ for 6 hours, and roasting the third solution at 450 ℃ for 6 hours; the average grain diameter of the SBA-15 type mesoporous silicon dioxide microspheres is 2.2 mu m, the average pore diameter of mesopores is 8.4nm, and the specific surface area is 634m2g-1Pore volume 0.71cm3g-1。
Claims (3)
1. A preparation method of SBA-15 type mesoporous silica microspheres is characterized by comprising the following steps:
(1) mixing a surfactant P123, concentrated hydrochloric acid, PVA and water to prepare a mixed aqueous solution, wherein the mass ratio of P123, HCl, PVA and water in the mixed aqueous solution is 1 (1.66-1.8) to 3.2-5 to 71-80; the mass concentration of the concentrated hydrochloric acid is 37 percent; the molecular weight of the PVA is 60-160K;
(2) adding a silicon dioxide precursor into the mixed aqueous solution at the temperature of 30-35 ℃, and stirring and mixing for 10-15 minutes to obtain a primary solution; the silicon dioxide precursor is sodium silicate or methyl orthosilicate; the adding amount of the silicon dioxide precursor is according to SiO in the silicon dioxide precursor2The mass ratio of the components to P123 in the mixed aqueous solution is 0.63-1;
(3) standing the primary solution at the temperature of 20-22 ℃ for 16-24 hours to obtain a secondary solution;
(4) stirring the secondary solution at the temperature of 35-36 ℃ for 16-24 hours to obtain a tertiary solution;
(5) and carrying out hydrothermal treatment on the third solution in a high-pressure kettle, filtering, washing and drying the obtained precipitate, and roasting to prepare the SBA-15 type mesoporous silica microspheres with the particle size of 8.3-12.2 microns.
2. The preparation method of the SBA-15 type mesoporous silica microsphere according to claim 1, wherein the SBA-15 type mesoporous silica microsphere has a long-range two-dimensional hexagonal mesoporous structure, and the mesoporous diameter is 6.5-8.8 nm.
3. The preparation method of the SBA-15 type mesoporous silica microsphere according to claim 1, wherein the SBA-15 type mesoporous silica microsphere has a specific surface area of 634-780 m2g-1Pore volume of 0.66-0.84 cm3g-1。
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| CN1872684A (en) * | 2006-06-16 | 2006-12-06 | 清华大学 | Method for synthesizing microspheres of high ordered mesoporous silicon dioxide |
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Patent Citations (4)
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|---|---|---|---|---|
| CN1872684A (en) * | 2006-06-16 | 2006-12-06 | 清华大学 | Method for synthesizing microspheres of high ordered mesoporous silicon dioxide |
| CN101157454A (en) * | 2007-09-15 | 2008-04-09 | 太原理工大学 | Spherical heteroatom mesopore molecular sieve and preparation method thereof |
| CN104556106A (en) * | 2015-01-14 | 2015-04-29 | 陕西理工学院 | SBA-15 molecular sieve with bimodal mesopores as well as preparation method thereof |
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