KR-102964614-B1 - SILICA NANOSTRUCTURE, MESOSCALE ASSEMBLY INCLUDING THE SAME, METHOD OF MANUFACTURING THEREOF, AND METHOD OF MANUFCATURING MESOSCALE ASSEMBLY INCLUDING THE SAME

Abstract

The present invention relates to a silica nanostructure according to one embodiment, a mesoscale assembly including the same, a method for manufacturing the same, and a method for manufacturing a mesoscale assembly including the same, wherein the silica nanostructure comprises a hollow frame having at least one spherical or polyhedral shape and a filling portion in which a predetermined material is filled within the frame.

Inventors

• 이인수
• 니티 쿠마리
• 최정훈

Assignees

• 포항공과대학교 산학협력단

Dates

Publication Date

20260512

Application Date

20220404

Claims (20)

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3. A hollow frame having at least one polyhedral shape; and It includes a filling portion in which a predetermined material is filled within the above frame, and If the above frame has a polyhedral shape, A silica nanostructure having a frame thickness of 13 to 22 nm.
4. A hollow frame having at least one polyhedral shape; and It includes a filling portion in which a predetermined material is filled within the above frame, and If the above frame has a polyhedral shape, A silica nanostructure having a width of 100 to 120 nm for the above-mentioned filling portion.
5. A hollow frame having at least one polyhedral shape; and It includes a filling portion in which a predetermined material is filled within the above frame, and If the above frame has a polyhedral shape, Silica nanostructures having a length of 120 to 180 nm measured based on a vertical cross-section.
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9. In any one of paragraphs 3 through 5, The above-mentioned filling comprises silicon (Si), nickel (Ni), oxygen (O), and other unavoidable impurities, and The at% of the silicon above is 15 to 25 at%, and A silica nanostructure in which the at% of the nickel is 10 to 20 at%.
10. Comprising a silica nanostructure according to any one of claims 3 to 5, A mesoscale assembly in which at least one of the above silica nanostructures is self-assembled.
11. A step of dispersing at least one amphiphilic polymer in a dispersion; A step of adding nickel nitrate hydrate to the product of the above step and stirring; A step of preparing a ghost template by adding and stirring ammonia water to the result obtained from the above stirring step; A step of adding and stirring a first silica precursor that reacts with the above ghost template at least once; A step of precipitating the reaction product that has undergone the above stirring step; and The above reaction product includes the step of washing and separating, In the step of adding ammonia water and a first silica precursor at least once to the product obtained from the above stirring step and stirring at a stirring speed, The content ratio of the first silica precursor to the ammonia water is 0.3 to 1.0, and A method for manufacturing a silica nanostructure in which a first silica precursor is supplied at least once at intervals of 50 to 70 minutes.
12. In Article 11, The step of adding nickel nitrate hydrate to the result of the above step and stirring is, A method for manufacturing a silica nanostructure comprising the step of dispersing at least one amphiphilic polymer in a dispersion solution, the step of forming a reverse micelle system.
13. In Article 11, A method for preparing a silica nanostructure in which the above-mentioned amphiphilic polymer is a cationic surfactant, anionic surfactant, amphoteric surfactant, nonionic surfactant, or a combination thereof.
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15. In Article 11, In the step of adding ammonia water and a first silica precursor at least once to the product obtained from the above stirring step and stirring at a stirring speed, A method for manufacturing a silica nanostructure by adding the above-mentioned first silica precursor multiple times with different amounts.
16. In Article 11, The step of adding ammonia water and a first silica precursor at least once to the result obtained from the above stirring step and stirring at a second stirring speed is A method for manufacturing a silica nanostructure comprising the step of adding a second silica precursor after adding the first silica precursor at least once.
17. In Article 16, The step of further adding the second silica precursor is, A method for manufacturing silica nanostructures comprising the step of adding at least one silica precursor.
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19. In Article 11, In the step of adding the first silica precursor at least once, and then further adding the second silica precursor, A method for preparing a silica nanostructure in which the content ratio of the second silica precursor to the ammonia water is 0.2 to 1.0.
20. In Article 11, A method for manufacturing a silica nanostructure, wherein, in the step of adding a second silica precursor after adding the first silica precursor at least once, the content ratio of the second silica precursor to the first silica precursor is less than 1.0 to 2.0.

Description

Silica nanostructure, mesoscale assembly including the same, method of manufacturing the same, and method of manufacturing a mesoscale assembly including the same The present invention relates to nanostructures, and more specifically, to silica nanostructures, mesoscale assemblies containing the same, a method for manufacturing the same, and a method for manufacturing mesoscale assemblies containing the same. Silica-based nanomaterials have demonstrated applicability for drug delivery, controllable release, catalysts, gas storage devices, lithium-ion batteries, and nanodevices due to structural properties favorable to them, such as colloidal stability, controllable surface area, pores, cavity volume, size, and a wide range of surface chemistry, which enable their use as biocompatible interfaces. Various methods have been proposed as synthesis methods for silica-based nanomaterials. For example, assembled molecular template-based methods can create well-aligned mesopores/channels in bulk silicate materials, but they have limitations due to access to only a limited number of crystal phases, poor reaction kinetic control, and a narrow range of post-synthesis structural deformation. Furthermore, scalable and easy-to-perform hydrothermal, flame synthesis, or spray drying and rapid melting and crystallization-based methods can generate thermodynamically stable spherical shapes with minimal surface energy, resulting in inferior nanostructure control. On the other hand, other sol-gel chemistry-based methods allow for easier reaction-kinetic control of nanostructures by utilizing soft polymers or micelles, hard solid cores, or self-templating strategies. However, until now, they have been limited to forming closed and inaccessible internal structures, such as smooth or rough isotropic spherical mesoporous silica nanoparticles (NPs), simple coatings of conformal shells, or core nanoparticle forms. Furthermore, additional template removal, chemical etching, calcination, or hydrolysis hollowing steps present complex and difficult-to-control problems. Unlike crystalline metal/metal oxide counterparts, where atoms can be easily packed and aligned in an ordered manner under appropriate reaction kinetic control, or modified by post-synthesis through chemical reactions based on the Kirkendall effect, ion exchange, and galvanic replacement, examples of hollow non-spherical polygonal amorphous silica nanostructures (h-SiNS) are rare due to the defect-rich covalently interconnected polymeric silica networks. These fundamental synthesis problems limit the diversity and application range of nanoscale amorphous materials, and new synthesis strategies are required to achieve high structural complexity with excellently controlled shapes. FIG. 1 illustrates a silica nanostructure according to one embodiment of the present invention. FIG. 2a illustrates a method for synthesizing a silica nanostructure (h-SiOh-NF) of a hollow octahedral frame according to an embodiment of the present invention, FIG. 2b illustrates an HR-TEM image of the h-SiOh-NF, FIG. 2c illustrates an SEM image of the h-SiOh-NF, FIG. 2d illustrates an octahedral frame model of the h-SiOh-NF, FIG. 2e illustrates the size and thickness of the h-SiOh-NF, FIG. 2f illustrates an energy-dispersive X-ray spectroscopic line profile of the h-SiOh-NF, and FIG. 2g illustrates an EF-TEM image of the h-SiOh-NF. FIG. 3a illustrates a method for synthesizing a silica nanostructure (h-SiOh-NS) having closed faces according to an embodiment of the present invention, FIG. 3b illustrates an HR-TEM image of the h-SiOh-NS, FIG. 3c illustrates an SEM image of the h-SiOh-NS, FIG. 2d illustrates an octahedral frame model of the h-SiOh-NS, FIG. 3e illustrates the size and thickness of the h-SiOh-NS, FIG. 3f illustrates an energy-dispersive X-ray spectroscopic line profile of the h-SiOh-NS, and FIG. 3g illustrates an EF-TEM image of the h-SiOh-NS. Figures 4a to 4c illustrate the effect of the nanostructure shape according to the supply rate of TMSD. Figure 5a shows XRD peaks according to the concentration change of the inverse micelle structure and the nano-limited environment, and Figures 5b and 5c show the NH3 arrangement on different sides of the Ni octahedral crystal and the DFT results for calculating the dissociation energy of NH3 from different sides of the Ni octahedral crystal. Figure 6a shows an SEM image of Ni( NH3 ) 6 ( NO3 ) 2 , Figure 6b shows the state of TMSD added to Ni( NH3 ) 6 ( NO3 ) 2 , Figure 6c shows an EDS configuration mapping showing the distribution of silicon (Si) at the corners and edges, and Figure 6d shows the SiO2 frame structure after the Ni template has dissociated. FIGS. 7A and 7B illustrate a method for synthesizing hollow silica nanosphere-shaped silica nanostructures (h-SiNPs) according to an embodiment of the present invention, FIG. 7B illustrates an HR-TEM image of the h-SiNPs, FIG. 7C illustrates an SEM image of the h-SiNPs, FIG. 7D illustrates an oct