CN110759348B - Preparation method of silicon dioxide material with hierarchical pore structure - Google Patents
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Abstract
The invention belongs to the field of nano materials, and relates to a preparation method of a silicon dioxide material with a hierarchical pore structure. The invention takes tetraethyl orthosilicate as a silicon source, triethanolamine as an alkaline catalyst and sodium salicylate and hexadecyl trimethyl ammonium bromide as a structure directing agent and a template agent to prepare the silicon dioxide material with a hierarchical pore structure in aqueous solution. The silicon dioxide material prepared by the method has uniform particle size and larger pore volume, not only has a dendritic macroporous channel structure with an emission shape from inside to outside, but also has a mesoporous structure with smaller size. The method disclosed by the invention is simple to prepare, low in cost, good in repeatability, environment-friendly, adjustable in particle size ranging from 50 to 500 nm, and capable of realizing large-scale preparation. The silicon dioxide material with the hierarchical pore structure prepared by the invention can be used for a drug delivery carrier, and particularly has remarkable advantages for the common loading of small-molecular drugs and large-molecular-weight proteins.
Description
Technical Field
The invention relates to a functional material and a preparation method thereof, in particular to a silicon dioxide material with a hierarchical pore structure and a preparation method thereof.
Background
In recent years, dendritic mesoporous silica materials have attracted more and more attention as drug delivery carriers for applications in the fields of biology and medicine. As a mesoporous silicon material with a novel structure, the dendritic mesoporous silicon dioxide material not only has the advantages of large specific surface, high stability, good biocompatibility and the like of the traditional mesoporous silicon material, but also has larger pore volume, higher pore permeability and better particle inner surface accessibility due to the dendritic macroporous channel structure which emits from inside to outside. The mesoporous material as a drug delivery carrier has remarkable advantages for loading drugs or proteins with different molecular weights. In particular, the dendritic mesoporous silica material having a hierarchical pore structure not only has a dendritic macroporous structure with a relatively large pore diameter, but also has small-sized mesopores with a uniform pore diameter, and has attracted a great deal of attention as a drug or protein delivery carrier. However, to date, the controlled synthesis and preparation of dendritic mesoporous silicas with hierarchical pore structures remains a challenge.
To date, some progress has been made in the synthesis of dendritic mesoporous silica materials. Yu Chengzhong et al prepared a series of mesoporous silicon and organic mesoporous silicon materials (Small, 2015, 11, 5949-5955) with dendritic structures by using chlorobenzene and water as a two-phase layering system, CTAC as a surfactant, TEA as an alkaline catalyst, TEOS or TEOS and organosilicon precursors as silicon sources. Xin Du et al prepared a dendritic mesoporous silicon material with a hierarchical pore structure (adv. Mater. 2013, 25, 5981-5985) with ether-water as a system and CTAB as a surfactant; vivek Polshettiwar et al prepared a dendritic mesoporous silicon material with a hierarchical pore structure with a particle size range of 250-450 nm (angelw. Chem. Int. Ed. 2010, 49, 9652-9656) by using cyclohexane-n-amyl alcohol-water as a two-phase layering system, CPB as a template and urea as a catalyst; zhao Dongyuan et al, by adopting an oil-water (cyclohexane/water, 1-octadecene/water, decahydronaphthalene/water) two-phase layering system and a strategy of step-by-step iterative synthesis, prepare a mesoporous silicon material (Nano Lett 2014, 14, 923-932) with a multi-generation adjustable central radial multi-level pore structure. Although the synthesis and preparation of the dendritic mesoporous silicon material have been advanced to some extent, the synthesis of the dendritic mesoporous silicon material with a hierarchical pore structure is still a difficult problem. Moreover, the controllable synthetic particle size range is 50-500 nm, and the dendritic mesoporous silicon material suitable for the drug delivery carrier still needs further research. In addition, in the synthesis process of the materials, organic solvents and water are mostly used as two-phase layered systems, and the use of the organic solvents not only causes potential harm to the environment, but also causes harsher synthesis conditions, increases the production cost, and makes large-scale preparation difficult.
Chinese patent CN201510269402.6 discloses a method for synthesizing mesoporous silica nanoparticles by an alkali-free method, which utilizes a cationic surfactant as a template agent, dicarboxylic acid salts with different carbon chains as co-surfactants, tetraalkyl silicate as a silicon source, deionized water as a water source and synthesizes the mesoporous silica nanoparticles under the condition that a hetero-metal atom compound exists or does not exist under the condition that an alkali source is not additionally introduced; the molar composition of the materials is that a silicon source, a cationic surfactant, dicarboxylate with different carbon chains, water and a hetero metal atom compound = 1. The method is carried out under the condition that the pH value of a reaction system is close to neutral, does not use an additional inorganic or organic alkali source which has great pollution to the environment, and has the advantages of simple synthesis method, short period, low cost, good repeatability, easy scale production and controllable product particle size. However, the factors for regulating and controlling the particle size of the product are more and relatively complex, and the size of the obtained mesoporous of the product is relatively large.
The mesoporous silica nanoparticles prepared by the prior art mostly obtain the same type of pores, and can obtain two pores, namely multi-level pores, in the same material under fewer conditions. The synthesis method with the hierarchical pore structure reported at present is complex and cannot be prepared on a large scale.
The method is environment-friendly in development and suitable for large-scale production, can be controlled to synthesize the mesoporous silicon material with the grain diameter of 50-500 nm and a hierarchical pore structure, is used as a drug or protein delivery carrier, and has important significance in the fields of vaccines, biology, medicine and the like.
Disclosure of Invention
The invention provides a silicon dioxide material with a hierarchical pore structure and a preparation method of the material.
The silica material with the hierarchical pore structure is spherical particles with the particle size of 50 nm-500 nm, and the spherical particles are provided with two types of mesopores, wherein one type of the mesopore structure is a dendritic pore channel structure with the pore diameter of 10-100 nm and the other type of the mesopore structure is secondary pores distributed on the dendritic pore channel structure and the pore diameter of 0-3 nm.
Preferably, the specific surface area of the silicon dioxide material with the hierarchical pore structure is 280-490 m 2 Between/g, the total pore volume is 0.7-1.6 cm and the weight is high.
The preparation method of the silicon dioxide material with the hierarchical pore structure comprises the following steps:
(1) Respectively dissolving sodium salicylate and hexadecyl trimethyl ammonium bromide of sodium salicylate in deionized water at room temperature, and fully stirring at a constant temperature of 60 ℃ to form a uniform solution;
(2) Adding an alkaline catalyst into the solution, and continuously and fully stirring;
(3) Adding silicate ester as silicon source into the solution, and stirring at constant temperature for reaction in an oil bath at 60 ℃;
(4) Centrifuging the product obtained in the step (3), collecting precipitate, and washing the obtained precipitate;
(5) And (4) calcining the precipitate obtained in the step (4) at 600 ℃ for 6 hours to obtain the dendritic silica target material with the hierarchical pore structure.
Preferably, the preparation method of the hierarchical pore structure silica material is characterized by comprising the following steps:
(1) Dissolving 100-1000 mg of sodium salicylate and 200-2000 mg of hexadecyl trimethyl ammonium bromide in 60 ml of deionized water at room temperature, and stirring at the constant temperature of 60 ℃ for 1 hour to form a uniform solution;
(2) Adding 200 mg of triethanolamine into the solution, and continuously stirring for 0.5 hour;
(3) Adding 9 ml of tetraethyl orthosilicate into the solution, and stirring the mixture in an oil bath at the constant temperature of 60 ℃ for 12 hours;
(4) Centrifuging the product obtained in the step (3) at 10000 rpm for 10 minutes, collecting precipitate, and washing the precipitate with ethanol for 3 times;
(5) And (4) calcining the product obtained in the step (4) at 600 ℃ for 6 hours to obtain the dendritic silica material with the hierarchical pore structure.
Corresponding experiments also show that the particle size of the product can be regulated and controlled by adjusting the content of the sodium salicylate used in the preparation method of the silicon dioxide material with the hierarchical pore structure. The silicon dioxide material with the hierarchical pore structure has two different types of mesopores, and the pore diameters of the two types of mesopores are different, so that the silicon dioxide material is more favorable for simultaneously loading small-molecular drugs and proteins with large molecular weight. The preparation method disclosed by the invention has the advantages of simple preparation procedure, high yield and environmental friendliness, can be used for large-scale production, avoids environmental pollution due to the fact that water is used for replacing an organic solvent and water two-phase layered system, and is more beneficial to large-scale preparation and production.
Drawings
FIG. 1 is a Transmission Electron Microscope (TEM) image of the synthesized dendritic mesoporous silicon material with a hierarchical pore structure;
FIG. 2 is a Scanning Electron Microscope (SEM) image of the synthesized dendritic mesoporous silicon material with a hierarchical pore structure;
fig. 3 is a distribution diagram of the specific surface area and the pore volume of the synthesized dendritic mesoporous silicon material with a hierarchical pore structure.
Detailed Description
The invention is further illustrated by the following examples, which are intended only for a better understanding of the contents of the study and are not intended to limit the scope of the invention.
Example 1
100 mg of sodium salicylate and 1000 mg of cetyltrimethylammonium bromide were weighed, added to 60 ml of deionized water, and stirred at a constant temperature of 60 ℃ for 1 hour to form a uniform solution. 200 mg of triethanolamine were added to the solution and stirring was continued for 0.5 hour. 9 ml of tetraethyl orthosilicate was added and stirred in an oil bath at 60 ℃ for 12 hours at a constant temperature. After cooling to room temperature, centrifuging at 10000 rpm for 10 minutes, collecting the precipitate, and washing the precipitate with ethanol for 3 times; drying; the resulting solid was calcined at 600 ℃ for 6 hours to give 2.113 g of a hierarchical porous dendritic silica material with a particle size of 50 nm, at 88.0% yield.
Example 2
500 mg of sodium salicylate and 1000 mg of cetyltrimethylammonium bromide were weighed, added to 60 ml of deionized water, and stirred at a constant temperature of 60 ℃ for 1 hour to form a uniform solution. 200 mg of triethanolamine were added to the above solution and stirring was continued for 0.5 hours. 9 ml of tetraethyl orthosilicate was added and stirred in an oil bath at 60 ℃ for 12 hours at a constant temperature. After cooling to room temperature, centrifuging at 10000 rpm for 10 minutes, collecting the precipitate, and washing the precipitate with ethanol for 3 times; drying; the solid obtained was calcined at 600 ℃ for 6 hours, giving 2.169 g of a dendritic silica material with a hierarchical pore structure having a particle size of 300 nm, with a yield of 90.3%.
Example 3
1000 mg of sodium salicylate and 1000 mg of cetyltrimethylammonium bromide were weighed, added to 60 ml of deionized water, and stirred at a constant temperature of 60 ℃ for 1 hour to form a uniform solution. 200 mg of triethanolamine were added to the solution and stirring was continued for 0.5 hour. 9 ml of tetraethyl orthosilicate was added and stirred in an oil bath at 60 ℃ for 12 hours at a constant temperature. After cooling to room temperature, centrifuging at 10000 rpm for 10 minutes, collecting the precipitate, and washing the precipitate with ethanol for 3 times; drying; the solid obtained was calcined at 600 ℃ for 6 hours to give 2.215 g of a 500 nm particle size dendritic silica material with a hierarchical pore structure with a yield of 92.3%.
Example 4
50 g of sodium salicylate and 158 g of cetyltrimethylammonium bromide were weighed, added to 10 l of deionized water, and stirred at a constant temperature of 60 ℃ for 1 hour to form a uniform solution. 25 g triethanolamine was added to the above solution and stirring was continued for 0.5 hour. 1.5 liters of tetraethyl orthosilicate was added and stirred in an oil bath at 60 ℃ for 12 hours at a constant temperature. After cooling to room temperature, centrifuging at 10000 rpm for 10 minutes, collecting the precipitate, and washing the precipitate with ethanol for 3 times; drying; the solid obtained was calcined at 600 ℃ for 6 hours to give 373 g of a dendritic silica material with a hierarchical pore structure having a particle size of 230 nm, in a yield of 92.9%.
Claims (4)
1. A silica material having a hierarchical pore structure, characterized in that: the material is spherical particles with the particle size of 50 nm-500 nm, the spherical particles are provided with two kinds of mesopores, wherein one kind of mesopore structure is a dendritic pore channel structure with the pore diameter of 10-100 nm and the pore diameter of 0-3 nm, which is distributed on the dendritic pore channel structure, the preparation method of the silicon dioxide material comprises the following steps:
(1) Respectively taking 100-1000 mg of sodium salicylate and 200-2000 mg of hexadecyl trimethyl ammonium bromide at room temperature, dissolving in 60 ml of deionized water, and stirring for 1 hour at the constant temperature of 60 ℃ to form a uniform solution;
(2) Adding 200 mg of triethanolamine into the solution, and continuously stirring for 0.5 hour;
(3) Adding 9 ml of tetraethyl orthosilicate into the solution, and stirring the mixture for 12 hours at constant temperature in an oil bath at 60 ℃;
(4) Centrifuging the product obtained in the step (3) at 10000 rpm for 10 minutes, collecting precipitate, and washing the precipitate with ethanol for 3 times;
(5) And (4) calcining the product obtained in the step (4) at 600 ℃ for 6 hours to obtain the dendritic silica material with the hierarchical pore structure.
2. The silica material with hierarchical pore structure according to claim 1, characterized in that the specific surface area of the material is 280-490 m 2 And/g, the total pore volume is 0.7-1.6 cm weight division/g.
3. A method for preparing a hierarchical pore structured silica material according to claim 1 or 2, characterized in that:
(1) Dissolving 100-1000 mg of sodium salicylate and 200-2000 mg of hexadecyl trimethyl ammonium bromide in 60 ml of deionized water at room temperature, and stirring at the constant temperature of 60 ℃ for 1 hour to form a uniform solution;
(2) Adding 200 mg of triethanolamine into the solution, and continuously stirring for 0.5 hour;
(3) Adding 9 ml of tetraethyl orthosilicate into the solution, and stirring the mixture for 12 hours at constant temperature in an oil bath at 60 ℃;
(4) Centrifuging the product obtained in the step (3) at 10000 rpm for 10 minutes, collecting precipitate, and washing the precipitate with ethanol for 3 times;
(5) And (4) calcining the product obtained in the step (4) at 600 ℃ for 6 hours to obtain the dendritic silica material with the hierarchical pore structure.
4. The method for preparing a hierarchical pore structure silica material according to claim 3, wherein the particle size of the product can be controlled by adjusting the content of sodium salicylate used.
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| CN111595800A (en) * | 2020-06-08 | 2020-08-28 | 吉林大学 | Immobilized glucose oxidase with aminated dendritic mesoporous silica as carrier and application of immobilized glucose oxidase in detection of glucose |
| CN113401913A (en) * | 2021-07-30 | 2021-09-17 | 陕西科技大学 | Hierarchical pore SiO2Microsphere material and preparation method and application thereof |
| CN113578326A (en) * | 2021-08-18 | 2021-11-02 | 哈尔滨工业大学（深圳） | SiO2Ni-loaded double-layer core-shell catalyst and preparation method and application thereof |
| CN113998704A (en) * | 2021-10-29 | 2022-02-01 | 上海唯可生物科技有限公司 | Silica nanoparticles, method for the production thereof, use thereof, composite and use thereof |
| CN114975942B (en) * | 2022-06-08 | 2023-06-13 | 陕西科技大学 | Micro/nano structure silicon-carbon negative electrode material and preparation method thereof |
| CN114975943B (en) * | 2022-06-08 | 2023-06-16 | 陕西科技大学 | Preparation method for constructing gelatin/silicon nanoparticle microspheres based on emulsification self-assembly method |
| CN115920115A (en) * | 2022-12-12 | 2023-04-07 | 安徽韶华生物科技有限公司 | Hemostatic gel based on mesoporous silica and preparation method thereof |
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