CN112919483B - Method for preparing mesoporous silica nanospheres by double-template method - Google Patents
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Abstract
The invention relates to the technical field of mesoporous silica, and provides a method for preparing mesoporous silica nanospheres by a dual-template method. The invention uses cationic surfactant (CTAB and/or CTAC) and sulfonated calixarene (SC n, n=4 or 8) as template agent, uses tetraethoxysilane as silicon source, adopts one-pot method to react to obtain silicon dioxide nanospheres, and removes the template agent through calcination treatment to obtain mesoporous silicon dioxide nanospheres. According to the invention, the regulation and control of the particle size of the silica nanospheres can be conveniently realized by regulating and controlling the dosage ratio of the cationic surfactant to the sulfonated calixarene, the adjustable range of the particle size of the obtained product is wider, the preparation method is simple, and the yield is higher. The results of the examples show that the mesoporous silica nanospheres with the particle size of 50-160 nm can be prepared by the method of the invention.
Description
Technical Field
The invention relates to the technical field of mesoporous silica, in particular to a method for preparing mesoporous silica nanospheres by a dual-template method.
Background
The mesoporous silica nanospheres are nano materials with porous structures, which are formed by using organic molecules as templates, have the advantages of high specific surface area, easiness in surface functionalization, good biocompatibility, strong thermal stability and the like, and have great application values in catalysis, molecular adsorption, drug delivery and the like. The Kresge team successfully synthesizes the mesoporous silica ordered molecular sieve MCM-41 for the first time in 1992, and causes research hot-air for mesoporous materials.
In the field of drug delivery, it is necessary to regulate the particle size of the carrier according to the drug to be delivered. At present, most of researches on mesoporous material drug carriers are developed around MCM-41, but the adjustable range of the particle size of the MCM-41 is narrow, only mesoporous silica nanospheres with the particle size of 100-200 nm can be prepared, and mesoporous silica nanospheres with the particle size of less than 100nm are difficult to prepare and cannot meet the loading requirements of the carriers on various drug molecules.
Patent CN105236417A discloses a preparation method of spherical mesoporous silica with adjustable particle size, wherein amphiphilic particles are adoptedSiO modified by sexual polymer 2 (SiO 2 -PBA-PDMAEMA), hexadecyl trimethyl ammonium bromide and tetraethoxysilane are used as reaction raw materials, hydrochloric acid and ammonia water are adopted to adjust the pH value of the reaction liquid, mesoporous silica is obtained through self-assembly reaction and calcination, and the adjustment and control of the particle size of the mesoporous silica can be realized by adjusting the addition amount of CTAB. However, in this patent, only mesoporous silica nanospheres having a particle diameter in the range of 25 to 90nm can be produced, and silica nanospheres having a particle diameter of 100nm or more cannot be obtained, and the range of particle diameter controllability is still narrow.
Disclosure of Invention
In view of the above, the invention provides a method for preparing mesoporous silica nanospheres by a dual-template method with a wide adjustable range of particle size. The mesoporous silica nanospheres with adjustable particle size within the range of 50-160 nm can be prepared by adopting the method provided by the invention.
In order to achieve the above object, the present invention provides the following technical solutions:
a method for preparing mesoporous silica nanospheres by a dual-template method comprises the following steps:
mixing a cationic surfactant, sulfonated calixarene, ethyl orthosilicate, an alkaline substance and water for reaction to obtain a product feed liquid;
carrying out solid-liquid separation on the product feed liquid, washing and drying the obtained solid product, and then carrying out calcination treatment to obtain mesoporous silica nanospheres;
the cationic surfactant comprises cetyltrimethylammonium bromide and/or cetyltrimethylammonium chloride; the sulfonated calixarene comprises sulfonated calixarene [4] and/or sulfonated calixarene [8 ];
the mol ratio of the tetraethoxysilane to the cationic surfactant to the sulfonated calixarene is 1 (0.055-0.065) to 0-0.0029.
Preferably, in the mixed feed liquid, the concentration of the cationic surfactant is 21-63 mmol/L, and the concentration of the sulfonated calixarene is 0.0525-2.1 mmol/L.
Preferably, the ratio of the positive charge carried by the cation in the cationic surfactant to the negative charge carried by the sulfonated calixarene is (5-200): 1.
Preferably, the alkaline substance comprises one or more of triethanolamine, triethylamine and ammonia water.
Preferably, the mol ratio of the tetraethoxysilane to the alkaline substance to the water is 1 (0.020-0.030): 75-85); when the alkaline substance is aqueous ammonia, the molar amount of the aqueous ammonia is based on the molar amount of the solute.
Preferably, the reaction temperature is 60-90 ℃ and the reaction time is 1-3 h.
Preferably, the drying temperature is 70-90 ℃ and the drying time is 1-3 h.
Preferably, the temperature of the calcination treatment is 400-700 ℃ and the calcination time is 3-7 h.
Preferably, the particle size of the mesoporous silica nanospheres is 50-160 nm.
The invention provides a method for preparing mesoporous silica nanospheres by a double-template method, which takes a cationic surfactant (CTAB and/or CTAC) and sulfonated calixarene (SC n, n=4 or 8) as a template agent, takes tetraethoxysilane as a silicon source, obtains the silica nanospheres by adopting a one-pot method, and removes the template agent through calcination treatment to obtain the mesoporous silica nanospheres, wherein the molar ratio of the tetraethoxysilane to the cationic surfactant to the sulfonated calixarene is 1 (0.055-0.065) (0-0.0029). In the invention, when the dosage of the sulfonated calixarene is 0, namely, a cationic surfactant is adopted as a single template agent to prepare mesoporous silica nanospheres, silicate oligomer generated by hydrolysis of tetraethoxysilane and the cationic surfactant (CTAB and/or CTAC) are synergistically and self-assembled to form an aggregate, and under the action of the template of the aggregate, the silicate oligomer nucleates and slowly grows to form the silica nanospheres, so that the obtained mesoporous silica nanospheres have smaller particle size; when the dosage of the sulfonated calixarene is not 0, the sulfonated calixarene and a cationic surfactant (CTAB and/or CTAC) form a super-amphiphilic molecule, the super-amphiphilic molecule and a silicate oligomer form a self-assembled aggregate, the hydroxyl exposed at the lower edge of the sulfonated calixarene and a silicon hydroxyl can form a hydrogen bond, silicate generated by induced hydrolysis is deposited on the surface of the aggregate, and the nucleation growth speed of silicon dioxide is improved, so that the particle size of the obtained mesoporous silicon dioxide nanospheres is increased; on the other hand, as the amount of sulfonated calixarene increases, the stoichiometric combination ratio of cationic surfactant (CTAB and/or CTAC) and sulfonated calixarene gradually approaches, the volume of super-amphiphilic molecular aggregate formed by the cationic surfactant and the sulfonated calixarene increases, the apparent charge density decreases, and thus the pore diameter of the mesoporous silica nanosphere increases, and the SC 8 has a larger hydrophobic calix cavity than SC 4, so that the pore diameter of the obtained mesoporous silica nanosphere is also larger.
In the invention, the charge ratio (CTA is recorded as the charge ratio of positive charges carried by cations in the cationic surfactant to negative charges carried by the sulfonated calixarene can be realized by regulating and controlling the dosage of the cationic surfactant and the sulfonated calixarene + /SC[n] n- ) When the dosage of the sulfonated calixarene is not 0, the particle size of the obtained mesoporous silica nanospheres is gradually increased along with the gradual decrease of the charge ratio (namely, along with the gradual increase of the dosage of the sulfonated calixarene), the pore diameter is gradually increased, and the surface roughness is gradually increased. The invention can conveniently realize the regulation and control of the particle size of the mesoporous silica nanospheres by controlling the dosage of the sulfonated calixarene.
The mesoporous silica nanospheres with uniform dispersion, stable structure and adjustable particle size and aperture can be obtained through the compounding of the cationic surfactant and the sulfonated calixarene in different proportions, and the preparation method provided by the invention has the advantages of simple steps, higher yield and wider adjustable range of the particle size of the obtained product. The example results show that the method can be used for preparing the silica nanospheres with the particle size of 50-160 nm, and the pore channels in the mesoporous silica nanospheres are arranged in a highly ordered manner.
Drawings
FIG. 1 is a transmission electron microscope image of mesoporous silica nanospheres obtained in examples 1 to 3;
FIG. 2 is a graph showing the particle size distribution of mesoporous silica nanospheres obtained in example 1;
FIG. 3 is a graph showing the particle size distribution of mesoporous silica nanospheres obtained in example 2;
FIG. 4 is a graph showing the particle size distribution of mesoporous silica nanospheres obtained in example 3;
FIG. 5 is a transmission electron microscope image of mesoporous silica nanospheres obtained in examples 1, 4, and 5;
FIG. 6 is a graph showing the particle size distribution of mesoporous silica nanospheres obtained in example 4;
FIG. 7 is a graph showing the particle size distribution of mesoporous silica nanospheres obtained in example 5.
Detailed Description
The invention provides a method for preparing mesoporous silica nanospheres by a dual-template method, which comprises the following steps:
mixing a cationic surfactant, sulfonated calixarene, ethyl orthosilicate, an alkaline substance and water for reaction to obtain a product feed liquid;
and (3) carrying out solid-liquid separation on the product feed liquid, washing and drying the obtained solid product, and then carrying out calcination treatment to obtain the mesoporous silica nanospheres.
The invention mixes and reacts the cationic surfactant, sulfonated calixarene, tetraethoxysilane, alkaline substance and water to obtain product feed liquid. In the present invention, the cationic surfactant includes Cetyl Trimethyl Ammonium Bromide (CTAB) and/or Cetyl Trimethyl Ammonium Chloride (CTAC), and the sulfonated calixarene includes sulfonated calixarene (SC 4) and/or sulfonated calixarene (SC 8); the mol ratio of the tetraethoxysilane, the cationic surfactant and the sulfonated calixarene is 1 (0.055-0.065): (0-0.0029), preferably 1 (0.058-0.062): (0.0001-0.002), further preferably 1:0.06 (0.001-0.002), and particularly when the sulfonated calixarene is SC < 8 >, the mol ratio of the tetraethoxysilane, the cationic surfactant and the SC < 8 > is further preferably 1 (0.055-0.065): (0-0.0011).
In the present invention, the concentration of the cationic surfactant in the feed solution obtained by the mixing is preferably 21 to 63mmol/L, more preferably 25 to 60mmol/L, and the concentration of the sulfonated calixarene is preferably 0.0525 to 2.1mmol/L, more preferably0.06-1.5 mmol/L; in a specific embodiment of the invention, the concentrations of the cationic surfactant and the sulfonated calixarene are calculated as the ratio of the molar amount of the cationic surfactant (or the sulfonated calixarene) to the volume of water in the mixed feed solution, and the addition amount of other substances is negligible. In the present invention, the ratio of the positive charge of the cation in the cationic surfactant to the negative charge of the sulfonated calixarene (denoted as CTA + /SC[n] n- ) Preferably (5 to 200): 1, more preferably (10 to 180): 1, and still more preferably (50 to 150): 1. The invention can realize CTA by adjusting the mole ratio of the cationic surfactant to the sulfonated calixarene + /SC[n] n- And further realizing the regulation of the particle size of the mesoporous silica nanospheres, wherein the larger the dosage of the sulfonated calixarene is, the larger the particle size of the obtained mesoporous silica nanospheres is, the smaller the specific surface area is, the larger the pore diameter is, and the larger the surface roughness is.
In the present invention, the alkaline substance preferably includes one or more of triethanolamine, triethylamine and ammonia water; the mol ratio of the tetraethoxysilane to the alkaline substance to the water is preferably 1 (0.020-0.030): 75-85%, more preferably 1 (0.022-0.025): 78-82); when the alkaline substance is ammonia water, the molar amount of the ammonia water is calculated by the molar amount of the solute; the invention uses alkaline matter to adjust the pH value of the reaction liquid to 7.5-10, to promote the hydrolysis of tetraethoxysilane.
In the present invention, the temperature of the reaction is preferably 60 to 90 ℃, more preferably 80 ℃, and the time of the reaction is preferably 1 to 3 hours, more preferably 2 hours; the reaction is preferably carried out under stirring, and the stirring speed is preferably 500 to 1500rpm, more preferably 1200rpm. In the specific embodiment of the invention, the cationic surfactant, the sulfonated calixarene, the alkaline substance and the deionized water are preferably mixed firstly, stirred for 1h at the temperature of 60-90 ℃ and the speed of 500-1500 rpm to obtain a premix, and then the ethyl orthosilicate is quickly added into the premix for reaction.
After the reaction is finished, the obtained product liquid is subjected to solid-liquid separation, and the obtained solid product is washed, dried and then subjected to calcination treatment to obtain the Mesoporous Silica Nanospheres (MSNs). In the present invention, the solid-liquid separation method is preferably centrifugal separation, and the rotational speed of the centrifugal separation is preferably 10000rpm; the washing detergent is ethanol preferentially, and the washing times are 3 times preferentially; the drying temperature is preferably 70 to 90 ℃, more preferably 80 ℃, and the drying time is preferably 1 to 3 hours, more preferably 2 hours.
In the present invention, the temperature of the calcination treatment is preferably 400 to 700 ℃, more preferably 550 to 600 ℃, and the calcination time is preferably 3 to 7 hours, more preferably 5 to 6 hours; the rate of temperature rise to the temperature of the calcination treatment is preferably 2 ℃/min, and the calcination treatment is preferably performed in a muffle furnace. The invention removes the template agent in the solid product through calcination treatment, and forms mesoporous pore canals in the silica nanospheres to obtain the mesoporous silica nanospheres.
In the present invention, the particle diameter of the mesoporous silica nanospheres is preferably 50 to 160nm, more preferably 60 to 150nm, and the pore diameter of the mesoporous silica nanospheres is mesoporous (pores having a pore diameter range of 2.0 to 50nm specified by IUPAC classification standards are referred to as mesopores). In a specific embodiment of the invention, when ethyl orthosilicate, cationic surfactant and SC 4]The molar ratio of (2) is 1:0.055 to 0.065: when the particle size of the mesoporous silica nanospheres is 0 to 0.0029, the particle size of the mesoporous silica nanospheres is preferably 52 to 160nm, and the specific surface area is preferably 286 to 85m 2 Preferably, the pore diameter is 2.9-3.3 nm; when tetraethoxysilane, cationic surfactant and SC 4]The molar ratio of (2) is 1:0.055 to 0.065: when the particle size of the mesoporous silica nanospheres is 0 to 0.0011, the particle size of the mesoporous silica nanospheres is preferably 52 to 155nm, and the specific surface area is preferably 286 to 109m 2 Preferably, the pore diameter is 2.9-3.5 nm; when single CTAB is used as a template agent, the particle size of the obtained mesoporous silica nanospheres is 52+/-5 nm, and the specific surface area is 286m 2 And/g, pore diameter of 2.9nm.
The technical solutions of the present invention will be clearly and completely described in the following in connection with the embodiments of the present invention.
Example 1
(1) CTAB 0.38g, triethanolamine 0.068g and deionized water 25mL are mixed, stirred at the speed of 1200rpm for 1h at 80 ℃ to obtain a premix, then 4mL of tetraethoxysilane is rapidly added into the premix, and stirred at the speed of 1200rpm for 2h at 80 ℃ to obtain a product feed liquid. Wherein, the concentration of CTAB in the feed liquid obtained by mixing the components is 42mmol/L.
(2) Centrifugally separating the obtained product feed liquid at a rotating speed of 10000rpm, washing the obtained solid product with ethanol for 3 times, drying the washed white product in a drying oven at 80 ℃ for 2 hours, placing the dried product in a muffle furnace, heating to 550 ℃ at a speed of 2 ℃/min, calcining for 5 hours at 550 ℃, and naturally cooling to obtain the mesoporous silica nanospheres, wherein the yield of the obtained mesoporous silica nanospheres is 1.01g.
Example 2
Otherwise, the same conditions as in example 1 were followed, and only 0.0097g of SC 4 was added to step (1), and the CTAB concentration in the resultant feed solution was 42mmol/L, and the SC 4 concentration was 0.52mmol/L, whereby the yield of the resulting mesoporous silica nanospheres was 1.03g.
Example 3
Other conditions were the same as in example 2, except that the amount of SC 4 was changed to 0.0391g, CTAB concentration was 42mmol/L and SC 4 concentration was 2.1mmol/L in the mixed feed solution, and the yield of the obtained mesoporous silica nanospheres was 0.58g.
The mesoporous silica nanospheres prepared in examples 1 to 3 were subjected to transmission electron microscopy, and the results are shown in fig. 1, wherein (a) to (b) in fig. 1 are transmission electron microscopy pictures of the mesoporous silica nanospheres obtained in example 1, (c) to (d) are transmission electron microscopy pictures of the mesoporous silica nanospheres obtained in example 2, and (e) to (f) are transmission electron microscopy pictures of the mesoporous silica nanospheres obtained in example 3, and the scales of (a), (c) and (e) are 200nm, and the scales of (b), (d) and (f) are 100nm. As can be seen from FIG. 1, the mesoporous silica nanospheres obtained in examples 1 to 3 are all uniform spheres, and the mesoporous silica nanospheres obtained in example 1 have the smallest particle size, and the SC 4 dosage in examples 2 to 3 is gradually increased, and the particle size of the obtained mesoporous silica nanospheres is gradually increased; in addition, in fig. 1 (a) to (f), ordered mesoporous lattice structures can be observed, which indicates that the pore channels of the obtained silica nanospheres are mesoporous.
The particle size distribution of the mesoporous silica nanospheres prepared in examples 1 to 3 was tested, and the obtained results are shown in fig. 2 to 4, and fig. 2 to 4 are the particle size distribution diagrams of the mesoporous silica nanospheres obtained in examples 1 to 3 in order. The test results in FIGS. 2 to 4 show that the mesoporous silica nanospheres obtained in example 1 had a particle size of 52.+ -. 5nm, the mesoporous silica nanospheres obtained in example 2 had a particle size of 72.+ -. 5nm, and the mesoporous silica nanospheres obtained in example 3 had a particle size of 160.+ -. 10nm.
In addition, the specific surface area and pore diameter of the mesoporous silica nanospheres obtained in examples 1 and 3 were tested, and the results showed that: the mesoporous silica obtained in example 1 had a specific surface area of 286m 2 Per g, pore size of 2.9nm, specific surface area of mesoporous silica obtained in example 3 of 85m 2 And/g, pore size of 3.3nm.
Example 4
Otherwise, the same conditions as in example 2 were followed except that SC 4 was replaced with SC 8, the amount of SC 8 was 0.0098g, the CTAB concentration in the mixed solution was 42mmol/L, the SC 8 concentration was 0.2625mmol/L, and the yield of the resulting mesoporous silica nanospheres was 0.98g.
Example 5
Other conditions were the same as in example 4 except that the amount of SC 8 was changed to 0.028g, the CTAB concentration in the mixed feed solution was 42mmol/L, the SC 8 concentration was 0.75mmol/L, and the yield of the resulting mesoporous silica nanospheres was 0.78g.
The mesoporous silica nanospheres prepared in examples 4 to 5 were subjected to transmission electron microscopy, and the transmission electron microscopy images of the mesoporous silica nanospheres obtained in example 1 and the mesoporous silica nanospheres obtained in example 1 are shown together in fig. 5, wherein (a) to (b) are transmission electron microscopy images of the mesoporous silica nanospheres obtained in example 1, (c) to (d) are transmission electron microscopy images of the mesoporous silica nanospheres obtained in example 4, and (e) to (f) are transmission electron microscopy images of the mesoporous silica nanospheres obtained in example 5, and the scales of (a), (c) and (e) are 200nm, and the scales of (b), (d) and (f) are 100nm. As can be seen from FIG. 5, after SC 8 is added, the particle size of the obtained mesoporous silica nanospheres gradually increases with the increase of the amount of SC 8; in addition, in fig. 5 (a) to (f), an ordered mesoporous lattice structure can be observed, which indicates that the pore canal of the obtained silica nanosphere is mesoporous.
The particle size distribution of the mesoporous silica nanospheres prepared in examples 4 to 5 was tested, and the results are shown in fig. 6 to 7, and fig. 6 to 7 are particle size distribution diagrams of the mesoporous silica nanospheres prepared in examples 4 to 5 in order. The test results in FIGS. 4 to 5 show that the mesoporous silica nanospheres obtained in example 4 have a particle size of 80.+ -.5 nm and the mesoporous silica nanospheres obtained in example 5 have a particle size of 155.+ -.10 nm.
In addition, the specific surface area and pore size of the mesoporous silica nanospheres obtained in example 5 were tested, and the results showed that: the mesoporous silica obtained in example 5 had a specific surface area of 109m 2 And/g, pore size of 3.5nm.
The yields of the mesoporous silica nanospheres obtained in examples 1 to 5 were calculated, and the results are shown in table 1, wherein the amounts of ethyl orthosilicate charged in examples 1 to 5 were each 4mL, and the theoretical yield of the mesoporous silica nanospheres was 1.07g, and the yield=actual yield/1.07×100% calculated from the hydrolysis equation of ethyl orthosilicate.
TABLE 1 yields of Mesoporous Silica Nanospheres (MSNs) obtained in examples 1 to 5
As can be seen from the data in Table 1, the mesoporous silica nanospheres prepared by the method provided by the invention have higher yields, which can reach 96.26%, and lower yields in example 3, because the electronegativity of the system increases with increasing amount of sulfonated calixarene, which results in a decrease in yield, but the yield can reach 54.2%.
The results of the above examples show that the invention adopts cationic surfactant (CTAB and/or CTAC) and SC [ n ] as dual-template agent, and the particle size of the mesoporous silica nanospheres can be conveniently controlled by regulating and controlling the ratio of the cationic surfactant (CTAB and/or CTAB) and the SC [ n ], the adjustable range of the particle size of the obtained product is large, the preparation method is simple, and the product yield is high.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (8)
1. The method for preparing the mesoporous silica nanospheres by the double-template method is characterized by comprising the following steps of:
mixing a cationic surfactant, sulfonated calixarene, ethyl orthosilicate, an alkaline substance and water for reaction to obtain a product feed liquid; mixing the obtained feed liquid, wherein the concentration of the cationic surfactant is 21-63 mmol/L, and the concentration of the sulfonated calixarene is 0.0525-2.1 mmol/L;
carrying out solid-liquid separation on the product feed liquid, washing and drying the obtained solid product, and then carrying out calcination treatment to obtain mesoporous silica nanospheres;
the cationic surfactant comprises cetyltrimethylammonium bromide and/or cetyltrimethylammonium chloride; the sulfonated calixarene comprises sulfonated calixarene [4] and/or sulfonated calixarene [8 ];
the mol ratio of the tetraethoxysilane to the cationic surfactant to the sulfonated calixarene is 1 (0.055-0.065) to 0-0.0029.
2. The method of claim 1, wherein the cationic surfactant has a charge ratio of positive charge to negative charge of sulfonated calixarene of (5-200): 1.
3. The method according to claim 1, wherein the alkaline substance comprises one or more of triethanolamine, triethylamine, and ammonia.
4. The method according to claim 1 or 3, wherein the molar ratio of the ethyl orthosilicate, the alkaline substance and the water is 1 (0.020-0.030): 75-85); when the alkaline substance is aqueous ammonia, the molar amount of the aqueous ammonia is based on the molar amount of the solute.
5. The method according to claim 1, wherein the reaction temperature is 60 to 90 ℃ and the reaction time is 1 to 3 hours.
6. The method according to claim 1, wherein the drying temperature is 70 to 90 ℃ and the drying time is 1 to 3 hours.
7. The method according to claim 1, wherein the calcination treatment is performed at a temperature of 400 to 700 ℃ for a calcination time of 3 to 7 hours.
8. The method of claim 1, wherein the mesoporous silica nanospheres have a particle size of 50-160 nm.
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Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011016277A1 (en) * | 2009-08-07 | 2011-02-10 | パナソニック電工株式会社 | Method for producing fine mesoporous silica particles, fine mesoporous silica particles, liquid dispersion of fine mesoporous silica particles, composition containing fine mesoporous silica particles, and molded article containing fine mesoporous silica particles |
| CN102616795A (en) * | 2012-04-23 | 2012-08-01 | 华东师范大学 | Method for preparing pure silicon-based mesoporous silica nanoparticles |
| CN102786061A (en) * | 2012-07-20 | 2012-11-21 | 东华大学 | Preparation method of hollow mesoporous silica nanoparticle |
| CN103663478A (en) * | 2013-11-20 | 2014-03-26 | 华东师范大学 | Preparation method of mesoporous silica spherical nano particles with dendritic pore structure |
| CN103771427A (en) * | 2014-01-28 | 2014-05-07 | 齐鲁工业大学 | Method for preparing sphere-like mesoporous silica |
| CN104787768A (en) * | 2015-03-19 | 2015-07-22 | 华南理工大学 | Preparation method for mesoporous silica material |
| CN105236417A (en) * | 2015-11-06 | 2016-01-13 | 齐鲁工业大学 | Spherical mesoporous silica with controllable particle size and preparation method of spherical mesoporous silica |
| CN108404854A (en) * | 2018-01-19 | 2018-08-17 | 江苏大学 | A kind of preparation method and applications of mackle mark porous silicon film |
| CN109607554A (en) * | 2019-01-23 | 2019-04-12 | 天津医科大学 | The preparation method of macroporous silica nanoparticle |
| CN109666287A (en) * | 2018-12-25 | 2019-04-23 | 陕西科技大学 | A kind of no-solvent type aqueous polyurethane/Sulfonated calixarenes modified hydrotalcite nanocomposite and preparation method thereof |
-
2021
- 2021-04-13 CN CN202110392509.5A patent/CN112919483B/en active Active
- 2021-05-24 AU AU2021102789A patent/AU2021102789A4/en not_active Ceased
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011016277A1 (en) * | 2009-08-07 | 2011-02-10 | パナソニック電工株式会社 | Method for producing fine mesoporous silica particles, fine mesoporous silica particles, liquid dispersion of fine mesoporous silica particles, composition containing fine mesoporous silica particles, and molded article containing fine mesoporous silica particles |
| CN102616795A (en) * | 2012-04-23 | 2012-08-01 | 华东师范大学 | Method for preparing pure silicon-based mesoporous silica nanoparticles |
| CN102786061A (en) * | 2012-07-20 | 2012-11-21 | 东华大学 | Preparation method of hollow mesoporous silica nanoparticle |
| CN103663478A (en) * | 2013-11-20 | 2014-03-26 | 华东师范大学 | Preparation method of mesoporous silica spherical nano particles with dendritic pore structure |
| CN103771427A (en) * | 2014-01-28 | 2014-05-07 | 齐鲁工业大学 | Method for preparing sphere-like mesoporous silica |
| CN104787768A (en) * | 2015-03-19 | 2015-07-22 | 华南理工大学 | Preparation method for mesoporous silica material |
| CN105236417A (en) * | 2015-11-06 | 2016-01-13 | 齐鲁工业大学 | Spherical mesoporous silica with controllable particle size and preparation method of spherical mesoporous silica |
| CN108404854A (en) * | 2018-01-19 | 2018-08-17 | 江苏大学 | A kind of preparation method and applications of mackle mark porous silicon film |
| CN109666287A (en) * | 2018-12-25 | 2019-04-23 | 陕西科技大学 | A kind of no-solvent type aqueous polyurethane/Sulfonated calixarenes modified hydrotalcite nanocomposite and preparation method thereof |
| CN109607554A (en) * | 2019-01-23 | 2019-04-12 | 天津医科大学 | The preparation method of macroporous silica nanoparticle |
Non-Patent Citations (1)
| Title |
|---|
| Hollow mesoporous silica with a hierarchical shell from in situ synergistic soft-hard double templates;Wang Juan;《Nanoscale》;第12卷(第19期);第10863-10871页 * |
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| AU2021102789A4 (en) | 2021-07-08 |
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