TWI799268B - Preparation method of mesoporous silica nanoparticles - Google Patents

Abstract

A method for preparing mesoporous silicon dioxide nanoparticles, comprising the following steps: in the presence of a basic catalyst, surface surface element, a siloxane compound, water and an alkyl alcohol solvent are carried out under the condition of 20°C to 30°C for 1 The hydrolytic polymerization reaction of more than 1 hour and less than 20 hours, to obtain a colloid solution comprising a complex bound by the surface element and silicon oxide; subjecting the colloid solution to a treatment procedure, wherein the treatment procedure includes calcination treatment, so that the surface The element is removed from the composite to produce a plurality of mesopores, and the calcination temperature ranges from 450°C to 600°C in the calcination process. By using the surfin as a template, the method for preparing mesoporous silicon dioxide nanoparticles has the advantage of rapidly obtaining silicon dioxide nanoparticles with several mesoporous pores.

Description

Preparation method of mesoporous silica nanoparticles

The invention relates to a method for preparing silicon dioxide nanoparticles, in particular to a method for preparing mesoporous silicon dioxide nanoparticles.

A scientific journal of RSC Advances , 2012 , 2 , 7449-7455 revealed that oleylamine, N,N -dimethyloleylamine, N-oleyl-1,3-propanediamine or N,N -di( A method for synthesizing mesoporous silica with oleylamine surfactant of 2-hydroxyethyl) oleylamine as a template, and the method comprises adding tetraethoxysilane to a mixed solution containing the template, water and ethanol, and The hydrolytic polymerization reaction was carried out at 25° C., 45° C. and 60° C. for 20 hours, followed by filtration treatment, drying treatment and calcination treatment in sequence, wherein the temperature of the calcination treatment was 600° C. and the time was 4 hours.

A scientific journal J Sol-Gel Sci Technol , 2011, 58 , 170-174 reveals that L-Glutamic acid (L-Glutamic acid) or L-leucine (L-Leucine) is used as a template to synthesize mesoporous two A method for silicon oxide, and the method includes adding sodium silicate to a solution containing a template, and performing a polymerization reaction at room temperature for 72 hours, followed by sequentially performing filtration treatment, centrifugation treatment, drying treatment and calcination treatment, Wherein, the temperature of the calcination treatment is 600°C.

Although the preparation methods of these scientific journals can obtain mesoporous silica materials, they have the disadvantage of time-consuming preparation in the polymerization reaction.

Therefore, the object of the present invention is to provide a preparation method capable of rapidly obtaining mesoporous silica nanoparticles.

Therefore, the preparation method of mesoporous silica nanoparticles of the present invention comprises the following steps: in the presence of an alkaline catalyst, make surfactin (surfactin, also known as subtilisin), siloxane compound, water and alkyl Under the condition of 20°C to 30°C, the hydrolysis polymerization reaction is carried out for more than 1 hour and less than 20 hours in an alcohol solvent to obtain a colloidal solution containing a complex bound by the surfin and silicon oxide; applying a treatment procedure to the colloidal solution, Wherein, the treatment procedure includes calcination treatment, so that the surface element is removed from the composite to generate a plurality of mesopores, and the calcination temperature range of the calcination treatment is 450°C to 600°C.

The effect of the present invention is that by using the surfin as a template, the preparation method of the mesoporous silicon dioxide nanoparticles has the advantage of rapidly obtaining silicon dioxide nanoparticles with several mesoporous pores.

The present invention will be described in detail below.

The preparation method of mesoporous silicon dioxide nanoparticles of the present invention comprises the following steps: in the presence of an alkaline catalyst, make surfactin (surfactin, also known as subtilisin), siloxane compound, water and alkyl alcohol solvent Under the condition of 20°C to 30°C, the hydrolysis polymerization reaction is carried out for more than 1 hour and less than 20 hours, and a colloid solution containing a complex bound by the surfin and silicon oxide is obtained; a treatment procedure is applied to the colloid solution, wherein, The treatment procedure includes calcination treatment to remove the surface element from the composite to generate a plurality of mesopores, and the calcination temperature range of the calcination treatment is 450°C to 600°C.

The basic catalyst is used to promote the hydrolysis reaction between the water and the siloxane compound. In some embodiments of the present invention, the basic catalyst such as but not limited to ammonia water, sodium hydroxide, alkali metal salts, alkaline earth metal salts, rare earth metal salts, alkali metal oxides, alkaline earth metal oxides, or rare earth metal oxides things etc. The alkali metal salt is for example but not limited to sodium carbonate. In some embodiments of the present invention, the basic catalyst is ammonia water.

In some embodiments of the present invention, the surfin is, for example but not limited to, surfin produced by Bacillus subtilis BBK006 and the like. The surfin is not limited to the production of surfin by using Bacillus subtilis , and can also be purchased directly, for example, surfin with CAS No. 24730-31-2 purchased from Sigma-Aldrich. In some embodiments of the present invention, the surfin is a surfin produced by Bacillus subtilis BBK006. In the present invention, the surfin is used as a template for synthesizing mesoporous silica nanoparticles, and because the surfin is a surfactant, it can make the mesoporous The shape of the porous silica nanoparticles is granular, and when the surface element is removed through the calcination process, several mesopores can be left on the surface of the mesoporous silica nanoparticles.

In some embodiments of the present invention, the siloxane compound is such as but not limited to tetraethoxysilane (Tetraethoxysilane, referred to as TEOS), tetramethoxysilane (Tetramethoxysilane, referred to as TMOS), or (3-amine Propyl) triethoxysilane [(3-Aminopropyl) triethoxysilane, referred to as APTES] and so on. In some embodiments of the present invention, the siloxane compound is selected from tetraethoxysilane, tetramethoxysilane, (3-aminopropyl)triethoxysilane, or any combination thereof. In some embodiments of the present invention, the siloxane compound is tetraethoxysilane.

The water is used to hydrolyze the siloxane compound to form silicic acid.

The alkanol solvent is used to dissolve the basic catalyst. In some embodiments of the present invention, the alkanol solvent is such as but not limited to methanol or ethanol. In some embodiments of the present invention, the alkyl alcohol solvent is selected from methanol, ethanol, or any combination of the above.

The complex is that the siloxane compound undergoes a hydrolysis reaction to form silicic acid, and then, the silicic acid reacts with the surfin and combines through chemical bonding to form an intermediate with a silicon oxide structure (-Si-O-), and then , which is formed by polymerization.

In some embodiments of the present invention, the temperature range of the hydrolytic polymerization reaction is 22°C to 25°C. In some implementation aspects of the present invention, the time range of the hydrolytic polymerization reaction is 1 hour to 10 hours. In some implementation aspects of the present invention, the time range of the hydrolytic polymerization reaction is 1.5 hours to 2 hours. In some embodiments of the present invention, the temperature range of the hydrolysis polymerization reaction is 25° C., and the time range of the hydrolysis polymerization reaction is 1.75 hours.

In some implementation aspects of the present invention, the temperature of the calcination treatment is 550°C.

In some embodiments of the present invention, the treatment procedure further includes centrifuging the colloid solution before the calcination treatment, so as to remove the colloid containing the complex from the colloid solution. In some embodiments of the present invention, under the condition that the ambient temperature is 25° C., the rotation speed of the centrifugation treatment is 5000 rpm and the time is 10 minutes.

In some embodiments of the present invention, the treatment procedure further includes drying the colloid after the centrifugation treatment and before the calcination treatment. The purpose of the drying treatment is to remove the residual ammonia, water and alkanol solvent in the colloid to obtain the composite. The drying treatment is, for example but not limited to, heat treatment or freeze-drying treatment. In some embodiments of the present invention, the drying treatment is heat treatment, and the temperature of the heat treatment is 70° C. and the time is 24 hours.

In some embodiments of the present invention, the particle diameter of the mesoporous silica nanoparticles ranges from 61 nm to 400 nm. In some embodiments of the present invention, the average particle diameter of the mesoporous silica nanoparticles ranges from 240 nm to 300 nm. In some embodiments of the present invention, the diameter of the mesopores ranges from 14 nm to 30 nm. In some embodiments of the present invention, the specific surface area of the mesoporous silica nanoparticles ranges from 6.5 m ² g ^-1 to 8.3 m ² g ^-1 .

The present invention will be further described with reference to the following examples, but it should be understood that these examples are for illustrative purposes only and should not be construed as limitations on the implementation of the present invention.

[Cultivation of Preparation Example 1 Bacillus subtilis ]

Na ₂ HPO ₄ , KH ₂ PO ₄ , NaCl, NH ₄ Cl, MgSO ₄ . 7H ₂ O and CaCl ₂ were dissolved in double deionized water to obtain M9 growth medium (M9 broth media). In this M9 growth medium, the concentration of Na ₂ HPO ₄ is 6.78 g/L, the concentration of KH ₂ PO ₄ is 3.0 g/L, the concentration of NaCl is 0.5 g/L, and the concentration of NH ₄ Cl is 1.0 g/L , MgSO ₄ . The concentration of 7H ₂ O was 0.493 g/L, and the concentration of CaCl ₂ was 0.011 g/L.

Wrap the above-mentioned M9 growth medium with aluminum foil, then place it in an autoclave whose temperature and pressure are respectively set to 121° C. and 15 atm to sterilize for 20 minutes, then take it out from the autoclave and cool it to 25 ±5°C, then place it in a laminar flow hood, and inoculate Bacillus subtilis (source: isolated from the soil in Chiayi County), then add 300mL of 0.4% glucose aqueous solution (including water and Glucose, and in this glucose aqueous solution, the concentration of this glucose is 0.4wt%). Then, place it in a rotary oscillating constant temperature incubator (brand: Rishun; model: JSL-530) with the temperature set at 37°C and the shaking speed at 200rpm for 24 hours of culture treatment to obtain a bacterial solution containing Bacillus subtilis colonies , wherein, utilize ultraviolet-visible spectrophotometer (brand: Prema; Model: PRO-739; Light source: halogen bulb), and be 2500nm/min and scan wavelength be 320nm to 1100nm to analyze this bacterial liquid with scanning rate, this subtilis The number of bacillus colonies was 1×10 ⁶ CFU/mL to 1×10 ⁷ CFU/mL, and the optical density (OD) value at a wavelength of 600 nm was 1.2.

[Preparation of Preparation Example 2 Surfactin]

Place the bacterial solution of Preparation Example 1 in a high-speed refrigerated centrifuge (brand: Hitachi, Japan; model: Himac CR-22G, used in conjunction with R20A2 Rotor) and rotate at 10,000 rpm at an ambient temperature of 25°C (centrifugal force: 12000×g) was centrifuged for 15 minutes to obtain a Bacillus subtilis-free supernatant. Use 5M hydrochloric acid aqueous solution to adjust the pH value of the supernatant to less than 2, then place the temperature in a shaking incubator set at 25±5°C and shake it at 200±20rpm for 12 hours to obtain the following: A mixture of precipitates, wherein the precipitates include surfin. Then, the mixture was centrifuged at 5000 rpm for 12 minutes at 25±5° C. to obtain the precipitate. Next, the precipitate was dried for 24 hours in a hot air circulation oven (brand: Rishun; model: JA-72) set at 65° C. to obtain a light brown powdery surface protein. In addition, it should be noted that this surfin can also be obtained commercially, and its CAS No. is 24730-31-2.

[Example 1]

Mix 0.57 g of Surfactin of Preparation Example 2 with 50 mL of secondary deionized water and keep stirring until it becomes clear to obtain a clear solution. 11 mL of ammonia water (including ammonia and water, wherein the ammonia concentration is 25 wt %) and 76 mL of ethanol were simultaneously added to the clear solution to obtain a mixed solution. At the same time, 10 mL of tetraethoxysilane was added dropwise to the mixed solution, and the stirring was continued, followed by a hydrolysis polymerization reaction at 25° C. for 1.75 hours to obtain a colloidal solution, wherein the colloidal solution contained colloidal And the supernatant liquid, and the colloid includes ammonia, water, ethanol and the white spherical complex combined by the surfin and silicon oxide.

The colloid solution was placed in a centrifuge (brand: Hsiang Tai; model: CN-3302-091281), and centrifuged at 5000 rpm for 10 minutes at 25°C to obtain the colloid.

The colloid was washed three times with deionized water and methanol in sequence, and then dried at 70°C for 24 hours to remove the ammonia, ethanol, water and methanol from the colloid to obtain the composite things.

The composite was placed in a muffle furnace (brand: Rishun; model: B0619) and calcined at 450°C for 5 hours to obtain a plurality of amorphous SiO2 nanospheres.

[Embodiments 2 to 4]

Examples 2 to 4 were carried out in the same steps as in Example 1, the difference being that the temperature of the calcination treatment was changed, and the results are shown in Table 1.

[Comparative Example 1]

Using the method described in the section of mesostructure synthesis (mesostructure synthesis) in the scientific journal RSC Advances , 2012 , 2 , 7449-7455, wherein tetraethoxysilane and oleylamine were mixed at 45 ° C, and carried out 20 hours of hydrolytic polymerization.

[Comparative Example 2]

Adopt J Sol-Gel Sci Technol , 2011 , 58 , 170-174 The method described in the section "Preparation and characterization of hybrid-silica based materials" of scientific journals, wherein, Sodium silicate and L-glutamic acid were mixed at room temperature and polymerized for 72 hours.

evaluation item

Particle size measurement (unit: nm): use a field emission scanning electron microscope (Field Emission Scanning Electron Microscope; brand: Hitachi; model: S4800-I) to measure the mesoporous silica nanospheres of Examples 1 to 4 Measurements were performed and the results are presented in Table 1.

Specific surface area (unit: m ² g ^-1 ), pore volume (unit: cm ³ g ^-1 ) and pore diameter (unit: nm) measurement: BET method (Brunauer, Emmett, and Teller method) and surface area analyzer ( Brand: American Micromeritics; Model: ASAP 2020 Plus), and in the presence of liquid nitrogen at a temperature of 77K, the mesoporous silica nanospheres of Examples 1 to 4 were measured, and the results are shown in Table 1 .

Table 1 "-" means no measurement Calcination temperature (℃) Specific surface area (m ² g ^-1 ) Pore volume (cm ³ g ^-1 ) Aperture (nm) Particle size range (nm) Average particle size (nm) Example 1 450 6.5179 0.015763 29.7070 71.36 to 384.31 248.87 2 500 7.7300 0.017399 20.2166 71.36 to 387.61 291.38 3 550 8.2616 0.020407 14.8516 61.8 to 394.12 289.71 4 600 7.9856 0.017394 16.5246 107.04 to 377.62 264.87 comparative example 1 600 1008 0.93 2.5 - 4.17 2 600 - - 3.4 - - Note: The data source of Comparative Example 1 is RSC Advances , 2012 , 2 , 7449–7455; the data source of Comparative Example 2 is J Sol-Gel Sci Technol , 2011 , 58 , 170–174.

As can be seen from the above, in the preparation method of mesoporous silica nanoparticles of the present invention, the surface element is used and subjected to a hydrolysis polymerization reaction at 25° C. for 1.75 hours to obtain mesoporous silica nanoparticles. In the method of Comparative Example 1, the oleylamine was used and hydrolysis polymerization was carried out at 45°C for 20 hours to obtain mesoporous silica, and in the method of Comparative Example 2, the L-glutamic acid was used The polymerization reaction was carried out at room temperature for 72 hours to obtain mesoporous silica. It can be seen that the method of the present invention can rapidly obtain mesoporous silica nanoparticles by using surfin as a template. Furthermore, since surfin is produced by Bacillus subtilis, the preparation method of the mesoporous silica nanoparticles of the present invention is non-toxic and environmentally friendly.

Although the particle size distribution range of the mesoporous silica nanospheres of the present invention is wide and there are large and small mesoporous silica nanospheres, the average of the mesoporous silica nanospheres The particle size is 240nm to 300nm, which means that the particle size distribution of the mesoporous silica nanoparticles is relatively concentrated, so the preparation method of the mesoporous silica nanoparticles of the present invention also has particle size homogeneity. In addition, since the surfin has the property of reducing the surface tension of the silicon dioxide nanoparticles gradually generated during the hydrolytic polymerization reaction, the preparation method of the mesoporous silicon dioxide nanoparticles of the present invention also has the ability to reduce the surface tension of the silicon dioxide nanoparticles. Advantages of the Agglomeration Phenomena Between Mesoporous Silica Nanoparticles.

In summary, by using the surfin as a template, the preparation method of mesoporous silica nanoparticles has the advantage of rapidly obtaining silica nanoparticles with several mesoporous pores, so it can indeed achieve the goal of the present invention. Purpose.

But the above-mentioned ones are only embodiments of the present invention, and should not limit the scope of the present invention. All simple equivalent changes and modifications made according to the patent scope of the present invention and the content of the patent specification are still within the scope of the present invention. Within the scope covered by the patent of the present invention.

none.

Claims (10)

A method for preparing mesoporous silicon dioxide nanoparticles, comprising the following steps: In the presence of a basic catalyst, the surface element, siloxane compound, water and alkanol solvent are subjected to a hydrolysis polymerization reaction at 20°C to 30°C for more than 1 hour and less than 20 hours, and the surface containing A colloidal solution of a complex of element and silicon oxide; Subjecting the colloidal solution to a treatment procedure, wherein the treatment procedure includes calcination treatment, so that the surface element is removed from the complex to generate a plurality of mesopores, and the calcination temperature range of the calcination treatment is 450°C to 600°C . The preparation method of mesoporous silica nanoparticles as claimed in item 1, wherein the basic catalyst is selected from ammonia water, sodium hydroxide, alkali metal salts, alkaline earth metal salts, rare earth metal salts, alkali metal oxides, Alkaline earth metal oxides, or rare earth metal oxides. The preparation method of mesoporous silica nanoparticles as described in Claim 1, wherein the siloxane compound is selected from tetraethoxysilane, tetramethoxysilane, (3-aminopropyl) triethyl Oxysilane, or any combination of the above. The preparation method of mesoporous silica nanoparticles according to claim 1, wherein the alkyl alcohol solvent is selected from methanol, ethanol, or any combination of the above. The method for preparing mesoporous silica nanoparticles according to claim 1, wherein the treatment procedure further includes centrifuging the colloidal solution before the calcination, so as to remove the complex from the colloidal solution. The method for preparing mesoporous silica nanoparticles as claimed in Claim 1, wherein the calcination temperature is 550°C. The method for preparing mesoporous silica nanoparticles according to Claim 1, wherein the particle diameter of the mesoporous silica nanoparticles ranges from 61 nm to 400 nm. The method for preparing mesoporous silica nanoparticles according to Claim 1, wherein the average particle diameter of the mesoporous silica nanoparticles ranges from 240nm to 300nm. The method for preparing mesoporous silicon dioxide nanoparticles as claimed in Claim 1, wherein the diameter of the mesoporous pores ranges from 14nm to 30nm. The method for preparing mesoporous silica nanoparticles according to Claim 1, wherein the specific surface area of the mesoporous silica nanoparticles ranges from 6.5m ² g ^-1 to 8.3m ² g ^-1 .