KR100644501B1 - Method for producing hollow porous structure and hollow porous structure formed therefrom - Google Patents

Abstract

The present invention relates to a method for manufacturing a hollow porous structure having a large specific surface area and multiple pores and a hollow porous structure formed therefrom, wherein the method for manufacturing a hollow porous carbon-aluminosilicate composite structure of the present invention is (S1). Preparing a carbon-silica composite structure comprising a carbon component and a silica component; (S2) reacting the carbon-silica composite structure with a surfactant in a solvent to form a carbon-aluminosilicate composite structure; And (S3) heat treating the carbon-aluminosilicate composite structure to remove the surfactant component. The hollow porous carbon-aluminosilicate composite structure formed according to the present invention has a multi-pore structure, a large specific surface area and a large pore volume, and due to the characteristics of the organic / inorganic composite structure of carbon and aluminosilicate It can be widely used for a wide range of applications such as catalysts, adsorbents, sensors, electrode materials, separation and purification or for storage of hydrogen and drugs.

Description

Method for manufacturing hollow porous structure and hollow porous structure formed therefrom {preparation process of a porous structure body having a hollow core and a porous structure body having a hollow core formed therefrom}

The accompanying drawings, which are incorporated in and constitute a part of the specification, illustrate the presently preferred embodiments of the invention and, together with the description of the following preferred embodiments, serve to explain the principles of the invention.

1 is a TEM picture of the structure formed by the nano carbon ball and the manufacturing process according to an embodiment of the present invention.

Figure 2 is a SEM photograph of the porous structure composition formed according to the manufacturing process according to an embodiment of the present invention.

FIG. 3A illustrates X-ray diffraction (XRD) patterns of carbon-aluminosilicate composite structures having various Si / Al molar ratios formed according to an embodiment of the present invention. FIG.

FIG. 3B is a diagram illustrating X-ray diffraction (XRD) patterns of hollow porous carbon-alumino composite structures having various Si / Al molar ratios formed according to an embodiment of the present invention.

FIG. 3C is a diagram illustrating X-ray diffraction (XRD) patterns of hollow porous aluminosilicate structures having various Si / Al molar ratios formed according to one embodiment.

4A and 4B illustrate N ₂ adsorption on carbon-aluminosilicate composite structures, hollow porous carbon-aluminosilicate composite structures, and hollow porous aluminosilicate structures formed according to a manufacturing process according to one embodiment of the invention. Figures showing the desorption isotherm and the pore size distribution curves corresponding thereto.

5 is an X-ray diffraction pattern of the carbon-aluminosilicate composite structure, the hollow porous carbon-aluminosilicate composite structure, and the hollow porous aluminosilicate structures formed according to a manufacturing process according to an embodiment of the present invention. XRD) shows the pattern.

6A and 6B illustrate N ₂ adsorption on carbon-aluminosilicate composite structures, hollow porous carbon-aluminosilicate composite structures, and hollow porous aluminosilicate structures formed according to a manufacturing process according to another embodiment of the present invention. A diagram showing desorption isotherms and pore size distribution curves corresponding thereto.

The present invention relates to a method for producing a hollow porous structure having a large specific surface area and pores and a hollow porous structure formed therefrom.

Nanoporous materials with large specific surface areas and uniform pores have been widely used as adsorbents, catalyst supports, separation and purification processes, and ion exchange media [Corma, A. Chem. Re v., 1997 , 97 , 2373.]. In particular, the synthesis of new nanostructured materials with controlled porosity is a new area of research in new materials.

Recently, the synthesis of porous carbon materials using the templating method has been reported by many research groups. For example, nanostructured carbon materials are prepared by chemical vapor deposition (CVD) and / or immersion methods using various types of zeolites as templates, and nanocasting of mesoporous carbon and polymers is carried out using mesoporous molecular sieves, MCM- It has been reported that it is performed using 48 and SBA-15 as a template. A) SB Yoon, JY Kim, J.-S. Yu, Chem. Commun. B) JY Kim, SB Yoon, F. Kooli, J.-S. 2002, 1536. Yu, J. Mater. Chem. 2001, 11, 2912. c] R. Ryoo, SH Joo, S. Jun, J. Phys. Chem. B. 1999, 103, 7743. d] J. Lee, S. Yoon, T. Hyeon, SM Oh, KB Kim, Chem. Commun. 1999. 2177. e] H. Yang, Q. Shi, X. Liu, S. Xie, D. Jiang, F. Zhang, C. Yu, B. Tu, D. Zhao, Chem. Commun. 2002, 2842. f] C. Vix-Cuterl, S. Boulard, J. Parmentier, J. Werckmann, J. Patarin, C hem. Lett . 2002, 106. g] A. Lu, A. Kiefer, W. Schidt, F. Schuth, Chem. Mater. 2004, 16, 100. h] SB Yoon, JY Kim, J.-S. Yu, Chem. Commun. 2003, 1740. i] SH Joo, SJ Choi, I. Oh, J. Kwak, Z. Liu, O. Terasaki, R. Ryoo, Nature 2001, 412,169. j] SS Kim, DK Lee, J. Shah, TJ Pinnavaia, Chem. Commun . 20003, 1436. k] A. Vinu, C. Streb, V. Murugesan, M. Hartman, J. Phys. Chem . B 2003, 107, 8297. l] WH Zhang, C. Liang, H. Sun, Z. Shen, Y. Guan, P. Ying, Can, Li, Adv. Mater. 2002, 14, 1776.]. The porous carbon materials with the new structure thus obtained are more widely used for hydrogen storage and release, drug storage and transport materials, electrode materials and sensors due to their new pore size distribution, large pore volume, large specific surface area and new skeletal structure. Can be used.

As such, the pore size, pore distribution, pore arrangement structure, etc. in the porous material can be an important factor. Generally, porous materials can be divided into microporous (<2nm), mesoporous (2-50nm), and macroporous (> 50nm) materials according to the pore size. Development of porous structures with different materials continues.

Accordingly, the present invention has a large specific surface area and a large pore volume, and a method of preparing a hollow porous carbon-aluminosilicate structure having multiple pore sizes and a hollow porous aluminosilicate structure formed therefrom. To provide.

Another technical problem of the present invention is to provide a hollow porous aluminosilicate structure made of aluminosilicate having a large specific surface area and a large pore volume.

Another technical problem of the present invention is to provide a porous structure composition in which the above-described hollow porous structures and the ZSM-5 type porous aluminosilicate structure are uniformly mixed.

In order to achieve the first object, the method of manufacturing a hollow porous carbon-aluminosilicate composite structure of the present invention (S1) preparing a carbon-silica composite structure in which the carbon component and silica component; (S2) reacting the carbon-silica composite structure with a surfactant in a solvent to form a carbon-aluminosilicate composite structure; And (S3) heat treating the carbon-aluminosilicate composite structure to remove the surfactant component.

The hollow porous carbon-aluminosilicate composite structure formed according to the above-described manufacturing method is composed of a porous carbon capsule having a hollow core portion and a porous aluminosilicate coating layer formed on the surface of the carbon capsule.

In order to achieve the second object, the manufacturing method of the hollow porous aluminosilicate structure of the present invention (S1) preparing a carbon-silica composite structure in which the carbon component and silica component; (S2) reacting the carbon-silica composite structure with a surfactant in a solvent to form a carbon-aluminosilicate composite structure; And (S3) heat treating the carbon-aluminosilicate composite structure to remove both the surfactant component and the carbon component.

In order to achieve the third object of the present invention, the porous structure composition of the present invention comprises (a) a plurality of hollow porous carbon- comprising a porous carbon capsule having a hollow core portion and a porous aluminosilicate coating layer formed on the surface of the carbon capsule. Aluminosilicate composite structures or a plurality of hollow porous aluminosilicate structures having hollow core portions; And (b) a plurality of ZSM-5 type porous aluminosilicate structures.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.

First, the hollow porous carbon-aluminosilicate composite structure and the hollow porous aluminosilicate structure of the present invention will be described in detail.

The carbon-silica composite structure in which the carbon component and the silica component are combined may be prepared by various methods (step S1). As an example, the applicant's patent application No. 10-2003-94009 describes a method for producing such a carbon-silica composite structure in detail. This document is incorporated by reference of the present invention. This is as follows.

Spherical silica particles are prepared. Silica particles are known from known silica precursors such as tetraethoxysilane, tetramethylorthosilicate and tetraethylorthosilicate (Stober, W .; Fink, A .; Bohn, EJ Colloid Inter. Sci. 1968). , 26, 62). In addition to this, various methods for producing silica particles are known, and the size of the silica particles may be variously adjusted, for example, about 10 to 1000 nm depending on the production method.

Subsequently, the spherical silica particles, the silica precursor, and the surfactant are reacted in a solvent to grow a shell portion composed of the silica and the surfactant component on the surface of the spherical silica particles. As a silica precursor, tetraethoxysilane, tetramethyl orthosilicate, tetraethyl orthosilicate, etc. can be used individually or in mixture of 1 or more types, It is not limited to this. Various kinds of surfactants that can be used are known, for example cationic surfactants, nonionic surfactants of oligomers, and block copolymers. For example, the cationic surfactant include a tetraalkylammonium ion ^{_{((C n) 4 A +}} X -; n = 1 ~ 4, X = OH, Cl, Br, I) and an alkyl trimethyl ammonium ions (C ⁺ _n -TMA ^{X -; n = 10 ~ 20} , X = Cl, Br, I) and the like. Nonionic surfactants include Brij52, C ₁₆ H ₃₃ (OCH ₂ CH ₂ ) ₂ OH, designated C ₁₆ EO ₂ , Brij30, C ₁₂ EO ₄ ; Brij 56, C ₁₆ EO ₁₀ ; Brij 58, C ₁₆ EO ₂₀ ; Brij 76, C ₁₈ EO ₁₀ ; Brij ₇₈ , C ₁₆ EO ₂₀ ; Brij97, C ₁₈ H ₃₅ EO ₁₀ ; Brij 35, C ₁₂ EO ₂₃ ; TritonX-100, CH ₃ C (CH ₃ ) ₂ CH ₂ C (CH ₃ ) ₂ C ₆ H ₄ (OCH ₂ CH ₂ ) ₁₀ OH; TritonX-114, such as Brij52, C ₁₆ H ₃₃ (OCH ₂ CH ₂ ) ₂ OH, designated CH ₃ C (CH ₃ ) ₂ CH ₂ C (CH ₃ ) ₂ C ₆ H ₄ (OCH ₂ CH ₂ ) ₅ OH Surfactants of alkyl poly (ethylene oxide) (PEO) oligomers may be used, but are not limited thereto.

Then, the resultant shell portion is heat-treated, for example, 500 to 600 degrees to remove the surfactant component of the shell portion, to obtain silica mold particles having a silica shell portion with pores of a predetermined diameter in the place where the surfactant component is removed. The size of the pores and the thickness of the shell portion can be adjusted by changing the type of surfactant, the type and the molar ratio of the silica precursor, the thickness of the shell portion can be adjusted to about 50 to 500nm, for example.

Subsequently, polymer precursors such as acrylonitrile, phenol-formaldehyde and divinylbenzene are injected into the pores formed in the shell portion and polymerized into silica mold particles having pores formed in the shell portion to form a polymer-silica composite structure. . The polymer precursor is polymerized by a suitable method known in accordance with its properties, and is generally polymerized for about 12 hours at a temperature of 60 to 80 degrees.

Then, the polymer component of the polymer-silica composite structure, which is a silica structure containing the polymer polymer, is carbonized to form a carbon-silica composite structure. The carbonization of the polymer component may be performed in a nitrogen atmosphere at about 1,000 degrees, for example.

As such, the carbon-silica composite structure prepared according to a known method is reacted with a surfactant in a solvent to form a carbon-aluminosilicate composite structure (step S2). The surfactants that can be used are as described above, depending on the surfactants used, but for example, after stirring for 10 to 30 minutes at room temperature, and then 12 hours to 7 at 80 to 250 degrees using a high temperature / high pressure reactor React for days. The silica component of the carbon-silica composite structure reacts with the surfactant to escape to the outside of the structure and grow outside to form an aluminosilicate structure such as ZSM-5 type, and some include the surfactant on the surface of the carbon structure. The aluminosilicate coating layer is formed to form a carbon-aluminosilicate composite structure.

When the obtained carbon-aluminosilicate composite structure is heat-treated to remove the surfactant component (step S3), a hollow porous carbon-aluminosilicate composite structure is obtained. The removal of the surfactant may be performed for 1 to 24 hours at a temperature of 300 to 1000 degrees under an inert gas such as, for example, argon or nitrogen. As a result, a hollow porous carbon-aluminosilicate composite structure composed of a porous carbon capsule having a macropore size hollow core portion and a porous aluminosilicate coating layer formed on the surface of the carbon capsule and having pores of different sizes are obtained. On the contrary, when the obtained carbon-aluminosilicate composite structure is heat-treated to remove both the surfactant component and the carbon component, only the aluminosilicate component remains, thus having a hollow core portion having a macropore size, and having many pores formed therein. A type porous aluminosilicate structure is obtained. In order to remove all the carbon components, for example, heat treatment may be performed at 400 to 1000 degrees in oxygen or air for 1 to 24 hours. As described above, the carbon components may be sequentially removed after the surfactant is first removed by heat treatment under an inert gas. have..

The structures described above are present in the form of a mixture together with a porous aluminosilicate structure such as ZSM-5 type formed by external growth, and the mixture is mixed very uniformly.

Hollow porous structures formed according to the method of the present invention can change the size and shape of the pores formed according to the Si / Al molar ratio of the silica component and the type of surfactant used.

Hereinafter, the present invention will be described in detail with reference to Examples. However, embodiments according to the present invention can be modified in many different forms, the scope of the present invention should not be construed as limited to the embodiments described below. Embodiments of the present invention are provided to more completely explain the present invention to those skilled in the art.

Example 1

Synthesis of silica with mesoporous shells centered on spherical silica particles was carried out using a Stber-Bohn-Fink method in a 1 l polypropylene (PP) bottle. Silica particles (200ml) and water (400ml) were added thereto and stirred for about 5min at room temperature.

Then, 6.59 × 10 ^-3 mol of alkyltrimethylammonium bromide (CnTMABr, n = 12-18), a surfactant, was dissolved in a mixture of absolute ethanol (20ml) and water (40ml), respectively, and this was added to the bottle cap. Stirred at room temperature for about 1 hour while blocking. Then add TEOS (4.3ml) quickly, stir this at room temperature for about 3 ~ 5 min, stop stirring, remove the magnetic bar, leave it in a dry-oven at 70 degrees for 1 day, and then add AlCl ₃ solution. SCMS silica was separated by sedimentation and dried in dry-oven. In order to remove the surfactant, the dried sample has a spherical silica particle through a calcination process at 550 ° C for 7 hours using a tube furnace in air, and has a mesoporous shell of 40 to 60 nm. Silica particles (SCMS silica) were synthesized.

After synthesizing the mesopores of the synthesized SCMS silica nanoparticles using phenol and paraformaldehyde as a carbon precursor, carbon-silica composite structure was synthesized by carbonizing the synthesized polymer-silica composite structure under an inert gas of 700 to 1000 degrees. It was.

10 g (carbon / silica; 2.76 g / 7.24 g) of the synthesized carbon-silica composite structure was uniformly mixed with 50 g of 1.0 M tetrapropylammonium hydroxide (TPAOH), and then placed in a Teflon bottle at 24 ° C. The reaction was carried out for a time. The obtained as-synthesized NCB / ZSM-5 composite was separated by centrifugation or filtering, and then dried in a drying oven. Dried as-synthesized NCB / ZSM-5 composites are used at temperatures of 300 to 1000 degrees under an inert gas such as Ar or N ₂ at an elevated rate of 1 degree / min to 10 degrees / min to remove the surfactant used. Obtained by heat treatment for 24 h.

Example  2

10 g (carbon / silica; 2.76 g / 7.24 g) of the carbon-silica composite structure obtained by the above-described method were added to 271.5 g of distilled water, 9.46 g of cetyltrimethylammonium bromide (CTABr) and 4.83 g of sodium hydroxide (NaOH). After mixing uniformly with the dissolved surfactant solution, it was put in a Teflon bottle and reacted for 2 to 4 days at 90 ~ 100 degrees. The obtained as-synthesized NCB / mesoporous aluminosilicate complex was separated by centrifugation or filtering and then dried in a drying oven. The dried as-synthesized NCB / mesoporous aluminosilicate complex was heat-treated for 1 to 24 h at a temperature of 300 to 1000 degrees under nitrogen gas at an elevated rate of 1 degree / min to 10 degrees / min to remove the surfactant used. Obtained.

Example  3

The as-synthesized NCB / ZSM-5 composite obtained in the manufacturing method of Example 1 was heat-treated at 600 to 700 degrees in air for 5 to 6 hours to remove carbon components.

1 is a transmission electron microscope (TEM) picture according to one embodiment of the invention, (a) is a macroporous hollow center and mesopores obtained by selectively removing the silica in the carbon / silica composite using HF solution TEM image of this uniformly distributed mesoporous carbon capsule, (b) is a carbon obtained after the hydrothermal reaction under high temperature / high pressure using a TPAOH (tetrapropylammonium hydroxide) solution with a carbon-silica complex as a surfactant according to Example 1 -TEM picture of the aluminosilicate composite structure, (c) is a TEM picture of the hollow porous carbon-aluminosilicate composite structure removed by heat treatment of the surfactant component according to Example 1, (d) is shown in Example 3 Therefore, the TEM image of the hollow porous aluminosilicate structure obtained after removing both the surfactant and the carbon component. 2 (a) and 2 (b) are SEM photographs and enlarged views of porous body compositions including a plurality of ZSM-5 type aluminosilicate structures according to the preparation method of Example 1, respectively. 1 and 2, organic / inorganic composites of aluminosilicates having a macrosized hollow core portion, a mesoporous carbon capsule in which mesopores are uniformly distributed, and a microporous structure formed on the surface thereof, and in a general form The resulting ZSM-5 type aluminosilicate structure particles were shown to be very homogeneously mixed and synthesized. 3A, 3B, and 3C show X-ray diffraction (XRD) patterns of various hollow porous carbon-aluminosilicate composite structures formed by controlling the molar ratio of Si / Al. FIG. 3A illustrates X-ray diffraction (XRD) patterns for carbon-aluminosilicate composite structures having various Si / Al molar ratios formed according to a fabrication process in accordance with an embodiment of the present invention. FIG. 3B is a view showing X-ray diffraction (XRD) patterns of hollow porous carbon-alumino composite structures having various Si / Al molar ratios formed according to a manufacturing process according to an embodiment of the present invention. FIG. 3C is a diagram illustrating X-ray diffraction (XRD) patterns for hollow porous aluminosilicate structures having various Si / Al molar ratios formed according to a fabrication process according to an embodiment. FIG.

4A and 4B illustrate N ₂ adsorption on carbon-aluminosilicate composite structures, hollow porous carbon-aluminosilicate composite structures, and hollow porous aluminosilicate structures formed according to a manufacturing process according to Example 1 of the present invention. Figures showing the desorption isotherm and the pore size distribution curves corresponding thereto.

5 is X- for the carbon-aluminosilicate composite structure, the hollow porous carbon-mesoporous aluminosilicate composite structure, and the hollow mesoporous aluminosilicate structures formed according to the manufacturing process according to Example 2 of the present invention. A diagram showing a ray diffraction (XRD) pattern.

Figure 6a and 6b is a carbon-aluminosilicate composite structure, hollow porous carbon-mesoporous alumino composite structure and hollow mesoporous aluminosilicate structures formed according to the manufacturing process according to Examples 2 and 3 of the present invention For N ₂ Figures showing adsorption / desorption isotherms and pore size distribution curves corresponding thereto.

As described above, the hollow porous structures obtained according to the method of the present invention have a large specific surface area and a large pore volume, and because of their structural specificity, they are used for a wide range of applications such as catalysts, adsorbents, sensors, electrode materials and storage materials. It can be widely used.

Claims (12)

(S1) preparing a carbon-silica composite structure comprising a carbon component and a silica component; (S2) reacting the carbon-silica composite structure with a surfactant in a solvent to form a carbon-aluminosilicate composite structure; And (S3) A method of manufacturing a hollow porous carbon-aluminosilicate composite structure, comprising the step of removing the surfactant component by heat-treating the carbon-aluminosilicate composite structure. The method of claim 1, wherein the carbon-silica composite structure comprises: preparing spherical silica particles; Reacting the spherical silica particles, the silica precursor, and the surfactant in a solvent to grow a shell part composed of silica and a surfactant component on the spherical silica particles; Heat treating the grown silica particles to remove the surfactant component of the shell portion to obtain silica mold particles having pores formed in the shell portion; Injecting and polymerizing a polymer precursor into the silica template particles having the pores to form a polymer-silica composite structure; Method for producing a hollow porous carbon-aluminosilicate composite structure, characterized in that formed in the step of carbonizing the polymer component of the polymer-silica composite structure. The hollow porous carbon-aluminosilicate composite structure according to claim 2, wherein the silica precursor is any one selected from the group consisting of tetraethoxysilane, tetramethylorthosilicate, tetraethylorthosilicate and mixtures thereof. Manufacturing method. The method of claim 2, wherein the polymer precursor is any one selected from the group consisting of acrylonitrile, phenol-formaldehyde and divinylbenzene. The method of claim 1, wherein the carbon-silica composite structure has a particle diameter of 10 to 1,000 nm. (S1) preparing a carbon-silica composite structure comprising a carbon component and a silica component; (S2) reacting the carbon-silica composite structure with a surfactant in a solvent to form a carbon-aluminosilicate composite structure; And (S3) A method of manufacturing a hollow porous aluminosilicate structure, comprising the step of heat-treating the carbon-aluminosilicate composite structure to remove both a surfactant component and a carbon component. Porous carbon capsule formed with a hollow core portion Hollow porous carbon-aluminosilicate composite structure comprising a porous aluminosilicate coating layer formed on the surface of the carbon capsule. The hollow porous carbon-aluminosilicate composite structure according to claim 7, wherein the hollow core portion has a particle diameter of 10 to 1,000 nm and a carbon capsule having a thickness of 50 to 500 nm. 8. The hollow porous carbon-aluminosilicate composite structure according to claim 7, wherein the porous aluminosilicate coating layer is made of ZSM-5 type aluminosilicate. (a) a plurality of hollow porous carbon-aluminosilicate composite structures comprising a porous carbon capsule having a hollow core portion and a porous aluminosilicate coating layer formed on a surface of the carbon capsule; And (b) a porous structure composition comprising a plurality of ZSM-5 type porous aluminosilicate structures. (a) a plurality of hollow porous aluminosilicate structures formed with hollow core portions; And (b) a porous structure composition comprising a plurality of ZSM-5 type porous aluminosilicate structures. The porous structure composition of claim 10 or 11, wherein the hollow core part has a particle diameter of 10 to 1,000 nm.

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