KR101589581B1 - Process for preparing of Metal oxide with mesopore - Google Patents

Abstract

More particularly, the present invention relates to a method for producing a metal oxide having mesopores by using a polymer having a functional group and a metal oxide prepared therefrom.

Description

Technical Field [0001] The present invention relates to a metal oxide having mesopores and a process for preparing the same,

More particularly, the present invention relates to a method for producing a metal oxide having mesopores by using a polymer having a functional group and a metal oxide prepared therefrom.

The metal present in the metal oxide may have various oxidation states. Therefore, it is necessary to maximize the amount of the metal exposed on the surface of the particle, which plays a role of giving or receiving electrons to the reactant in various oxidation-reduction reactions, so that the metal and the reactant are in much contact with each other. However, it is difficult to actually synthesize these metal oxide materials. As is the case with conventional nanomaterials, the smaller the size, the more thermodynamically unstable it has because of its higher surface energy. Such a metal oxide can be solved by introducing mesopores into the skeleton to synthesize a mesoporous metal oxide. For this reason, attempts have been made to improve the specific surface area by synthesizing a mesoporous metal oxide having mesopores (2 <diameter <50 nm) introduced into the metal oxide framework.

A commonly used method for synthesizing a mesoporous metal oxide is to use a micelle formed by self-assembly of an organic surfactant or a block copolymer as a mesoporous derivative (P. Yang, et al. Nature 1998, 396, 152). However, it is not uncommon for a microshell formed on the basis of a weak van der walls force to effectively limit the crystal growth of metal oxides. In addition, since it has to be designed to have a special functional group, the material cost required for synthesizing an organic surfactant or a block copolymer is very expensive.

In order to overcome the disadvantages described above, a variety of organic surfactants have been used to synthesize metal oxides regularly or irregularly connected (F. Schuth et al., Chem. 2001, 13, 3184). In particular, various types of mesoporous metal oxides were synthesized by functionalizing various groups at the head of organic surfactants. However, since the tail portion of the hydrocarbon is excellent in chemical stability, it can not increase the hydrocarbon indefinitely, and it has a limit in that it is expensive and time consuming to synthesize a specially designed surfactant.

KR 10-2000-7006287 KR No. 10-2008-0035621

The present invention maximizes the diffusion of molecules into the metal oxide by maximizing the molecular diffusion into the metal oxide, and using the polymer random copolymer to synthesize catalysts, adsorbents and separating agents with long life and high efficiency.

Accordingly, the present inventors made attempts to prepare a mesoporous metal oxide by using a macromolecular compound containing a functional group as a mesoporous derivative. More specifically, a polymer having various types of functional groups was used as a mesoporous derivative to prepare a material having a mesopore and a skeleton of crystalline metal oxide.

The present invention relates to a method for preparing an organic-inorganic hybrid gel, comprising the steps of: a) mixing a polymer compound having a functional group with a metal oxide precursor to form an organic-inorganic hybrid gel;

b) crystallizing the organic-inorganic hybrid gel to prepare a crystalline organic-inorganic hybrid gel; And

c) selectively removing the organic material from the crystalline organic-inorganic hybrid gel obtained in the step b); Wherein the mesoporous metal oxide is a mesoporous metal oxide.

The functional group contained in the polymer compound having a functional group in the production process according to the present invention may be a (C1-C10) alkyl group, a (C5-C10) aryl group, a (C5- A mesoporous metal oxide comprising at least one organic functional group selected from the group consisting of a carboxyl group, a hydroxyl group, a (C1-C10) alkyl ester, (C1-C10) alkyl ether, and sulfide Of the present invention.

The polymer compound having the functional group may be selected from polyacrylic, polyacrylic ester, polyacrylamide, polyphenylene, polystyrene, or polyvinyl.

The present invention is characterized in that the polymer compound comprising the functional group is a random polymer in which units are randomly formed, wherein the random polymer is a block-type polymer in which units are randomly formed in one block region of the polymer chains of the polymer compound In the case of the block-type polymer, the random polymer includes a polymer in which units are randomly formed in one block region of the block-type polymer chain.

 The metal element of the metal oxide precursor may be selected from the group consisting of Group 4 to Group 12 elements, and specifically, it may be a metal element selected from Group 4, Group 5, Group 8, and Group 12 elements.

The metal oxide precursor may be a metal halide, a metal alkoxide, a metal acetylacetate, a metal acetyltate, or a metal salt, but is not limited thereto.

The organic solvent used in the present invention is preferably an aprotic solvent other than water or alcohol. Specific examples thereof include dimethylformamide (DMF), tetrahydrofuran (THF), or tetrahydrofuran it is preferable to use n-methyl-2-pyrrolidone (NMP), but not limited thereto.

More specifically, since it is preferable that the crystallization step is performed at 80 ° C or higher, particularly 100 ° C or higher, the boiling point of the solvent is preferably 100 ° C or higher, but it is preferably 100 ° C such as tetrahydrofuran (THF) In the case of a solvent having a BP of not more than 100 DEG C in the crystallization step, the range of the BP of the solvent is not particularly affected.

The mesoporous metal oxide produced according to the production method of the present invention is characterized in that it comprises a single unit cell lattice having a crystalline skeleton having a thickness of 1 to 10 and a mesopore of 2 nm or more formed by assembling the crystalline lattice, And has a BET specific surface area of 100 to 800 m ² / g and a mesopore volume of 0.1 to 2.0 ml / g.

The present invention uses a polymer compound having a functional group capable of strongly bonding with a metal oxide precursor to induce an extremely thin crystalline structure and to form a mesoporous structure having a uniform size due to intramolecular interactions and intermolecular interactions of the polymer And a method for producing the metal oxide.

The mesoporous metal oxide prepared by the method of the present invention is a novel material containing a crystalline skeleton having a thickness of several nm or less and at least one mesopore or micropored formed by organic bonds thereof.

1 is a transmission electron microscope (TEM) photograph of a titanium oxide nanosheet made according to Example 2 of the present invention.
2 is a high-angle X-ray diffraction result of a titanium oxide nanosheet made according to Example 2 of the present invention.
3 is a nitrogen adsorption isotherm (a) and pore distribution diagram (b) of a titanium oxide nanosheet made according to Example 2 of the present invention.
4 is a transmission electron microscope (TEM) photograph of the mesoporous titanium oxide prepared according to Example 4 of the present invention.
5 is a low angle and elevation angle X-ray diffraction result of the mesoporous titanium oxide prepared according to Example 4 of the present invention.
6 is a nitrogen adsorption isotherm (left) and a pore distribution diagram (right) of the mesoporous titanium oxide prepared according to Example 4 of the present invention.
7 is a transmission electron microscope (TEM) photograph of a mesoporous tin oxide made according to Example 5 of the present invention.
FIG. 8 is a high-angle X-ray diffraction result of mesoporous tin oxide made according to Example 5 of the present invention.
9 is a nitrogen adsorption isotherm (left) and pore distribution diagram (right) of the mesoporous tin oxide produced according to Example 5 of the present invention.
10 is a transmission electron microscope (TEM) photograph of mesoporous zirconia prepared according to Example 6 of the present invention.
11 is a high-angle X-ray diffraction result of mesoporous zirconia prepared according to Example 6 of the present invention.

Hereinafter, the present invention will be described in detail. In the following description of the present invention, a detailed description of known configurations and functions will be omitted. Also, the terms and words used should not be construed as being limited to ordinary or dictionary meanings and should be construed in accordance with the technical meanings and concepts of the present invention.

Hereinafter, the process for producing the mesoporous meso-porous metal oxide of the present invention will be described in more detail by dividing it into stages.

Step 1 : A polymer compound containing a functional group having strong binding force to the metal element and the metal oxide precursor is mixed and reacted to form an organic-inorganic hybrid gel.

At this time, the hydrophobic organic region is formed by self-assembling between inorganic regions by non-covalent bonding between organic materials, that is, van der Waals force, dipole-dipole interaction, ion interaction, At this time, depending on the structure and concentration of the polymer, each gel region has a regular or irregular arrangement.

Step 2 : Thereafter, the organic-inorganic hybrid gel formed and stabilized by the polymer compound is converted into a crystalline organic-inorganic hybrid gel-type metal oxide through crystallization. The polymer compound comprising the functional group of the present invention is characterized in that the units are random polymers composed randomly. In the case of the block-type polymer, the random polymers are randomly formed within one block region of the block- Polymer. The mesoporous structure derivative of the polymer compound may form a broader range of metal oxide skeletons by changing the types of functional groups and arranging the kind of crystal skeleton and arrangement of mesopores. Specifically, at this time, a metal oxide skeleton having a thickness of 5 to 10 or less of a single unit cell is formed according to the structure of the polymer and the composition of the gel, and they are organically assembled to form macropores having an irregular structure.

Step 3 : After the crystallization process, the metal oxide may be obtained through filtration or centrifugation. The obtained crystalline metal oxide can selectively remove only organic substances through firing or other chemical reaction.

The functional group contained in the polymer compound having a functional group in the production process according to the present invention may be a (C1-C10) alkyl group, a (C5-C10) aryl group, a (C5- A mesoporous metal oxide comprising at least one organic functional group selected from the group consisting of a carboxyl group, a hydroxyl group, a (C1-C10) alkyl ester, (C1-C10) alkyl ether, and sulfide Of the present invention.

The polymer compound having the functional group may be selected from polyacrylic, polyacrylic ester, polyacrylamide, polyphenylene, polystyrene, or polyvinyl.

The functional group may be a (C1-C10) alkyl group, a (C5-C10) aryl group, a (C5-C10) aralkyl group, a nitrile group, a carboxyl acid group, (C1-C10) alkyl ester, (C1-C10) alkyl ether group, and sulfide, but the present invention is not limited thereto.

More specifically, the functional group preferably includes a carboxylic acid, a hydroxyl group, or a phenol group, but is not limited thereto. The polymer compound containing the carboxylic acid as a functional group includes at least one carboxylic acid functional group.

Examples of the monomer having at least one carboxylic acid functional group include acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, anhydrides thereof, or a mixture of two or more thereof. And any substance can be used as long as it can impart a carboxylic acid functional group to the finally obtained polymer compound.

In the present invention, the polymer compound having a functional group is a random polymer in which units are randomly formed. In the case of the block polymer, the random polymer is a polymer in which units are randomly formed in one block region of a block- .

The polymer compound can vary the physical and chemical specificity of the polymer in a wide range by using various types of monomers alone or in combination. Unlike small organic surfactant molecules, polymers have the advantage that they can easily control the properties of nanomaterials by combining with polymer nanomaterials. In addition, since the size of the polymer can be easily controlled according to the synthesis method of the polymer, the size of the mesopores and the meso structure can be varied.

The polymer compound is characterized by being selected from polyacrylic, polyacrylic ester, polyacrylamide, polyphenylene, polystyrene, or polyvinyl. However, the present invention is not limited thereto.

More specifically, it is preferable to use polyacrylic acid (PAA) or poly (4-vinylphenol- co- methylmethacrylate), but not limited thereto .

The molecular weight of the polymer compound may be 1000 < Mw < 1000000, but the present invention is not limited thereto. More important in the polymer compound is the kind and molar ratio of the functional group in the polymer.

 The polymer compound comprising the functional group of the present invention is characterized in that the units are random polymers composed randomly. In the case of the block-type polymer, the random polymers are randomly formed within one block region of the block- Polymer. Random-type polymer compounds can be classified into organic molecular types of mesoporous derivatives by presenting a crystalline skeleton derivative having mesopores of random copolymer type, apart from the existing organic surfactants or structural derivatives of block interpolymer type Can be further expanded. In addition, the mesoporous structure derivatives of the polymer compounds of the random or cluster type units can easily modify the types of the crystalline skeletons and the arrangement of mesopores in a wider range by diversifying the types of functional groups. In addition, since the inherent specificity of the polymer is reflected in the metal oxide as it is before the removal of the organic material, the application range of the mesoporous crystalline metal oxide can be broadened by utilizing this point.

The metal oxide precursor may be a metal halide, a metal alkoxide, a metal acetylacetate, a metal acetyltate, or a metal salt, but is not limited thereto.

  The metal element of the metal oxide precursor may be a method of producing a mesoporous metal oxide consisting of a metal element selected from the group consisting of Group 4 to Group 12 and Group 14 alone or a mixture thereof. However, the present invention is not limited thereto.

Specifically, it may be a metal element selected from Group 4, Group 5, Group 8, Group 12 and Group 14.

Preferably, at least one element selected from the group consisting of Ti, Zr, Hf, Ce, Th in Group 4, V, Nb, Ta, Pr in Group 5, Fe, Ru, Os, Sm, Pu in Group 8, Zn, Hg, and Group 14 of C, Si, Ge, Sn, and Pb, but are not limited thereto.

More preferably, it may be a Group 4 element of Ti, Zr, Ce, V of Group V and Fe of Group 8, a transition metal element of Group 12, and a Group 14 element of Sn.

The organic solvent used in the present invention is preferably an aprotic solvent. More preferably, an aprotic solvent other than a solvent which releases hydrogen ions such as water or alcohol can be employed. This is because a solvent capable of generating hydrogen ions can interfere with the interaction between a polymer compound containing a functional group and a metal element and a metal oxide precursor due to the OH group first attached to the functional group.

 Specifically, it is preferable to use dimethylformamide (DMF), tetrahydrofuran (THF) or n-methyl-2-pyrrolidone (NMP) I do not.

More specifically, since the crystallization step is preferably performed at 80 to 200 ° C, particularly 100 ° C or more, the solvent preferably has a boiling point (BP) of 100 ° C or more, but it is preferable to use a solvent such as tetrahydrofuran It is possible to maintain the solvent at 100 DEG C or higher by using an autoclave in the crystallization step, so that the range of the boiling point (BP) of the solvent is not particularly affected.

The present invention can further accelerate the reaction by acting as a catalyst in the process of mixing the metal element, the metal oxide precursor and the polymer compound by further adding a reaction promoter, and examples of the reaction promoter include triethylamine, trialkylamine, tributyl Amines, tripropylamines, tripropylethylamines, trihexylamines, and the like.

The crystallization process is preferably performed at a temperature of 80 to 200 ° C, but is not limited thereto.

The crystallization may be performed by conventional methods such as solvothermal synthesis, dry-gel synthesis and microwavesynthesis, but the present invention is not limited thereto. The solvent thermal synthesis method is preferably carried out at 80 ° C to 200 ° C, and it is more preferable to maintain the high pressure state at 1 to 10 atmospheres at 100 ° C or higher, but it is not limited thereto. Further, when the solvent used in the solvent thermal synthesis method is 100 ° C or lower, it may be carried out at a high pressure of 1 to 5 atm.

The crystalline organic-inorganic hybrid gel may be subjected to filtration or washing with filtration or centrifugal separation, and then the organic material may be selectively or wholly or partially removed through calcination to produce a crystalline mesoporous mesoporous metal oxide having mesopores. have.

The filtration method or the centrifugal separation method can be carried out in any conventional manner.

In the production process according to the present invention, the organic-inorganic hybrid gel formed and stabilized by the polymer compound is converted into a crystalline organic-inorganic hybrid gel-like metal oxide through crystallization. At this time, a mesoporous metal oxide is formed by forming a metal oxide skeleton having a thickness of 5 to 10 or less in a single unit lattice according to the structure of the polymer and the gel, organically assembled to form large pores having an irregular structure can do.

The mesopores produced by the mesoporous metal oxide production method can be controlled according to the synthesis environment and the composition ratio of the reactants. Also, by controlling the molar ratio of functional groups of the metal oxide and the polymer unit used in the reaction, mesoporous metal oxides characterized by a plurality of hierarchical metal oxides can be synthesized.

An important parameter in the production of the mesoporous metal oxide by the method of the present invention is the composition of the reactant, in particular, the metal oxide precursor, the number of moles of the polymer functional group, and the amount of water.

As a first embodiment to be produced according to the present invention, it is preferable that the composition of the reactant in the production of the mesoporous metal oxide is such that the molar ratio of the metal element: polymeric monomer functional group: water in the metal precursor is 1: 0.1 to 0.8: 1 to 40 And the molar ratio of the metal element: polymeric monomer functional group: water of the metal precursor is more preferably 1: 0.1 to 0.5: 1 to 20. When the molar ratio of the functional group of the polymer unit based on the metal element of the metal precursor is less than 0.1, meso structure metal oxide is not formed. When the mole ratio is larger than 0.8, all the polymers are not dissolved. When the molecular weight is less than 1, the polymer can not be completely dissolved. When the molecular weight is more than 40, the amount of the meso-porous metal oxide per unit volume is small.

The amount of the organic solvent in the crystallization is not more important than the amount of the polymeric monomer functional group and water, but it is preferable to add a solvent amount of 100 to 1000 molar ratio based on the metal element of the metal precursor, have.

More specifically, when the metal is titanium, the molar composition ratio of the reactants for producing the mesoporous titanium oxide is Ti: [-CH (COOH) CH ₂ -]: H ₂ O: DMF = 1: 0.1 to 0.5: 20: 100-300.

As another embodiment of the present invention, the mesoporous metal oxide may be prepared in the form of a nanosheet.

The metal oxide produced by the process for preparing a mesoporous metal oxide according to the present invention may be a metal oxide having 1 to 2 mesopores and 1 to 2 micropores (50 nm <diameter <1000 nm), but the present invention is not limited thereto .

Specifically, it is a mesoporous metal oxide containing a single unit lattice and a crystalline skeleton having a thickness of 1 to 10 and a mesopores of 2 nm to 20 nm formed by assembling the crystalline skeleton. A specific surface area of 100 to 800 m ² / g, and a mesopore volume of 0.1 to 2.0 ml / g.

The nanosheet formed using the metal oxide may be controlled according to the molar composition ratio of the organic-inorganic synthetic gel.

 Specifically, the molar composition of the organic-inorganic synthetic gel may be in the form of a metal oxide nanosheet having another mesoporous skeleton depending on the ratio of water, a polymer compound and a solvent.

The metal oxide nanosheet prepared by the production method of the present invention is a structure that is the first to be produced in the present invention as a novel structure compound which is not present in the prior art.

The metal oxide nanosheet produced by the production method of the present invention may have a composition ratio of the reactants in the production step of the organic-inorganic synthetic gel is in the range of 1: 0.3 to 0.8: The molar ratio of the metal element: polymeric monomer functional group: water of the metal precursor is preferably in the range of 1: 0.3 to 0.5: 10 to 20. When the mole ratio of the functional group of the polymer unit is less than 0.3 on the basis of the metal element of the metal precursor, there is a problem that a metal oxide having a meso structure other than the nanosheet may be formed. When the mole ratio is larger than 0.8, When the amount of water is less than 10, crystallization does not occur. When the amount of water is larger than 30, there is a problem that a metal oxide having a meso structure other than the nanosheet is formed.

The amount of the organic solvent in the nanosheet crystallization according to the present invention is not more important than the amount of the polymeric monomer functional group and water, but it is preferable to add a solvent amount of 200 to 1000 molar ratio based on the metal element of the metal precursor. There is a problem that does not exist.

Specifically, the molar composition ratio of the reactants in the crystallization of the titanium oxide nanosheets obtained using titanium is Ti: [-CH (COOH) CH ₂ -]: H ₂ O: DMF = 1: 0.3 to 0.8: Lt; / RTI &gt;

As shown in the X-ray diffraction results of FIG. 2, the titanium oxide nanosheets prepared according to the above-described manufacturing method have 20 °?? 2? 30 °, 45 °? 2? 55, 60 °? 2? The diffraction peak appears. It was also confirmed that FWHM (full width at half maximum) had a diffraction peak of 25 ° ≤ FWHM ≤ 30 °, 45 ° ≤ FWHM ≤ 50 °, and 60 ° ≤ FWHM ≤ 65 °. Each of the diffraction peaks corresponds to the diffraction angles of (101), (200), and (204) shown in the titania of the anatase structure. In addition, the titanium oxide nanosheets having a thickness of 1 nm or less are irregularly assembled and have a specific surface area of 300 to 800 m ² / g.

Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. These embodiments are provided for illustrative purposes only and are not intended to limit the present invention.

[Example]

The BET of the mesoporous metal oxide prepared according to the present invention is a measurement method for measuring the specific surface area having powdery or massive form regardless of the material of the sample using physical adsorption and chemisorption phenomenon. The specific surface area of the mesoporous metal oxide was measured. The measurement principle of BET is that when a gas is adsorbed and desorbed on the inner surface of a container or other solid due to a change in temperature without changing other conditions in the closed container, some of the molecules in a given amount of gas are adsorbed or desorbed , The specific surface area of the sample can be measured by calculating the volume of the adsorbed gas by measuring the pressure. The mesopore size was calculated by the Kelvin equation-based BJH method (Barrett-Joyner-Halenda). In order to measure the mesopore volume, the amount of adsorbed nitrogen was analyzed at a relative pressure of 0.95 or less.

 [Example 1]. Synthesis of Titanium Oxide Nanosheet

For the synthesis of titanium oxide, the polymer is a homopolymer and the unit is acrylic acid. 0.051 g of polyacrylic acid (PAA) and 0.1 g of titanium isopropoxide, a titanium oxide precursor, were mixed with 10 ml of dimethylformamide (DMF) in a glove box. 0.075 ml of water is added to the mixture, and the mixture is stirred at room temperature for 9 hours. The molar composition of the synthetic gel is as follows.

1 TiO ₂ : 0.5 [-CH (COOH) CH ₂ -]: ₂ O H ₂ O: 600 DMF

The resulting mixture is placed in a stainless steel autoclave and stored at 100 ° C for 2 days. Thereafter, it was centrifuged at 4000 rpm for 10 minutes, and washed with acetone. The obtained final product was dried in a room-temperature vacuum oven, and then the organic polymer was removed by sintering at 350 ° C for 4 hours while flowing air, thereby synthesizing a titanium oxide nanosheet. The BET specific surface area of the synthesized titanium oxide nanosheets was measured, and the mesopore size was measured by the BJH method (Barrett-Joyner-Halenda) based on the Kelvin equation.

[Example 2] Synthesis of titanium oxide nanosheet

0.72 g of poly (4-vinylphenol-co-methylmethacrylate) and 0.67 ml of titanium chloride were mixed in 25 ml of DMF. To the mixed mixture After adding 0.33 ml of water, triethylamine was added as a reaction accelerator of 3.4 ml, and the mixture was placed in a stainless autoclave and stored at 150 ° C. for 3.5 days. The obtained product was dried in a vacuum oven at room temperature, and then the organic polymer was removed by sintering at 350 DEG C for 4 hours while flowing air, thereby synthesizing a titanium oxide nanosheet. The BET specific surface area of the titanium oxide nanosheets was measured and the mesopore size was measured by the BJH method based on Kelvin equation (Barrett-Joyner-Halenda).

FIG. 1 is a transmission electron microscope (TEM) image of a titanium oxide nanosheet prepared according to Example 2, showing that titanium oxide is composed of a mesoporous structure in nanosheet form.

In addition, FIG. 2 shows that the material has a crystalline antarase nanosheet skeleton structure through the high-angle X-ray diffraction pattern of the titanium oxide nanosheet prepared according to Example 2. The nitrogen adsorption analysis results of FIG. 3 also show that the material has a BET surface area of 350 m ² / g and a total pore volume of 0.6 ml / g.

[Example 3] Synthesis of mesoporous titanium oxide.

 Polyacrylic acid (PAA) having 0.025 g of carboxylic acid functional groups and 0.3 g of titanium isopropoxide, a titanium oxide precursor, were mixed with 10 ml of DMF in a glove box. 0.075 ml of water was added to the mixture, and the mixture was stirred at room temperature for 9 hours. The molar composition of the synthesized gel is as follows.

3 TiO ₂ : 1 [-CH (COOH) CH _{2 -} ]: 20 H ₂ O: 600 dimethylforamide

The mixture was placed in a stainless steel autoclave, stored at 100 ° C for 14 hours, centrifuged at 4000rpm for 10 minutes, and washed with acetone. The resulting final product was dried in a room-temperature vacuum oven, and then the organic polymer was removed through calcination at 350 ° C for 4 hours while flowing air to synthesize the final mesoporous titanium oxide. The BET specific surface area of the synthesized mesoporous titanium oxide was measured and the mesopore size was measured by the BJH method (Barrett-Joyner-Halenda) based on the Kelvin equation.

[Example 4] Synthesis of mesoporous titanium oxide

0.72 g of poly (4-vinylphenol) and 1.98 ml of titanium chloride were mixed in 15 ml of DMF, and 6.48 ml of water was added to the mixture. Placed in a stainless steel autoclave, and stored at 100 DEG C for 30 hours. Thereafter, the mixture was centrifuged at 13,000 rpm for 15 minutes and washed with acetone. The resulting product was dried in a room-temperature vacuum oven, and then the organic polymer was removed through calcination at 350 ° C. for 4 hours while flowing air to synthesize the final mesoporous titanium oxide. The BET specific surface area of the synthesized mesoporous titanium oxide was measured and the mesopore size was measured by the BJH method (Barrett-Joyner-Halenda) based on the Kelvin equation.

As a result, FIG. 4 is a transmission electron microscope (TEM) photograph of the titanium oxide nanocrystals prepared according to Example 4, confirming that the mesoporous titania is composed of a mesoporous structure in the form of nano sponge.

FIG. 5 also shows that the material has a crystalline anti-nano-sponge skeleton structure through the low angle of the titanium oxide prepared according to Example 4 and the high angle X-ray diffraction pattern.

Figure 6 also shows that the titanium oxide prepared according to Example 4 had a homogeneous mesopore of 4 nm and a BET surface area of 270 m ² / g and a total pore volume of 0.3 ml / g.

[Example 5] Synthesis of mesoporous tin oxide (Tin Oxide)

0.72 g of poly (4-vinylphenol-co-methyl methacrylate) and 0.22 ml of Tin chloride were mixed and reacted in 13 ml of DMF. 0.099 ml of water was added to the mixture and then 1.02 ml of triethylamine was added to accelerate the reaction.The final mixture was placed in a stainless steel autoclave and then stored at 150 ° C. for 1 day, The resulting final product was dried in a room-temperature vacuum oven, and the organic polymer was removed by sintering at 350 DEG C for 4 hours while flowing air to remove the final mesoporous tin oxide The BET specific surface area of the synthesized mesoporous tin oxides was measured and meso pore size was measured using the Kelvin equation based BJH method (Barrett-Joyner-Halenda).

As a result, FIG. 7 shows transmission electron microscope (TEM) photographs of the tin oxide nanocrystals prepared in Example 5, confirming that the mesoporous tin oxide was composed of a mesoporous structure in the form of nano sponge. In addition, it was confirmed through the high-angle X-ray diffraction pattern of FIG. 8 that the material had a nano-sponge skeleton structure consisting of crystalline crystalline cassiterite. The nitrogen adsorption analysis of FIG. 9 and the resulting distribution curve of the mesopores shows that the material has a homogeneous mesopore of 4 nm and a BET surface area of 220 m ² / g and a total pore volume of 0.2 ml / g Respectively.

 [Example 6] Synthesis of mesoporous zirconium oxide

0.72 g of poly (4-vinylphenol-co-methyl methacrylate) and 0.71 g of zirconium chloride were mixed and reacted in 13 ml of DMF. To the mixture was added 0.164 ml of water and then 1.7 ml of triethylamine was added to accelerate the reaction. The final mixture was placed in a stainless steel autoclave and then stored at 150 ° C for 2 days. The resulting final product was dried in a room-temperature vacuum oven, and the organic polymer was removed by sintering at 350 ° C. for 4 hours while air was being flowed to obtain a final mesoporous zirconium oxide Were synthesized.

10 is a transmission electron microscope (TEM) image of zirconium oxide nanocrystals prepared according to Example 6, confirming that the mesoporous zirconium oxide has a mesoporous structure in the form of nano sponge. Also, it was confirmed through the high-angle X-ray diffraction pattern of FIG. 11 that the material had a mesoporous structure in the form of a nano sponge composed of a crystalline monoclinic structure.

Claims (15)

a) forming an organic-inorganic hybrid gel by mixing a polymer compound having a functional group of a carboxylic acid group, a hydroxyl group, or a phenol group and a metal oxide precursor;
b) crystallizing the organic-inorganic hybrid gel to prepare a crystalline organic-inorganic hybrid gel; And
c) selectively removing the organic material from the crystalline organic-inorganic hybrid gel;
&Lt; / RTI &gt; delete The method according to claim 1,
The polymer compound may be a polyacrylic, polyacrylic ester, polyacrylic
An amide-based, polyphenylene-based, polystyrene-based, or polyvinyl-based one. The method according to claim 1,
Wherein the polymer compound having a functional group is a random polymer in which units are randomly formed, wherein the random polymer comprises a block-type polymer in which units are randomly formed in one block region of the polymer chains of the polymer compound &Lt; / RTI &gt; wherein the mesoporous metal oxide is a metal oxide. The method according to claim 1,
Wherein the metal element of the metal oxide precursor is at least one selected from Group 4 to Group 12 elements and Group 14 element. The method according to claim 1,
The metal oxide precursor is at least one selected from the group consisting of metal halide, metal alkoxide, metal acetylacetate, metal acetyltate, and metal salt. (Method for producing mesoporous metal oxide). The method according to claim 1,
Wherein the step (a) further comprises a non-protonic solvent. The method according to claim 1,
Wherein the organic-inorganic hybrid gel comprises a metal oxide precursor: polymer unit: water in a molar ratio of 1: 0.3 to 0.8: 10 to 30. 9. The method of claim 8,
Wherein the organic-inorganic hybrid gel is further doped with a metal oxide precursor: non-protic solvent in a molar ratio of 1: 200 to 1000 based on the content of the metal oxide precursor. The method according to claim 1,
Wherein the crystallization of the organic-inorganic hybrid gel is selected from solvent thermo-synthesis, dry-gel synthesis, or microwave synthesis. . The method according to claim 1,
Wherein the crystallization is performed at 80 to 200 ° C in the step b). A method of manufacturing a semiconductor device according to any one of claims 1 to 11, characterized in that it comprises the steps of: forming a single unit cell lattice with a thickness of 1 to 10 and a crystal skeleton mesoporous metal oxide comprising mesopores of nm. The mesoporous metal oxide according to claim 12, wherein the mesoporous metal oxide has a BET specific surface area of 100 to 800 m ² / g and a mesopore volume of 0.1 to 2.0 ml / g. delete delete

Images