KR100513603B1 - Novel Gemini Surfactants and Method for Preparing Mesoporous Materials Using the Same - Google Patents

Abstract

The present invention relates to a new gemini-type surfactant and a method for producing a mesoporous material using the same, and more particularly, to a method for producing a mesoporous material using the Gemini-type surfactant represented by the following formula (1) and a structural derivative thereof According to the present invention, it is possible to provide a mesoporous material in which pores of 10 nm or less are regularly arranged.

[Formula 1]

Wherein R ₁ and R ₂ are each independently a methyl or ethyl group, R ₃ is an alkyl group having 5 to 40 carbon atoms, X is a halogen atom, and r is each independently a hydrogen atom, a methyl group or alkoxy having 1 to 10 carbon atoms and n is an integer of 1-12, m is an integer of 0-10.

Description

Novel Gemini Surfactants and Method for Preparing Mesoporous Materials Using the Same

The present invention relates to a new surfactant and a method for producing a mesoporous material using the same, and more particularly, to a novel gemini surfactant containing a siloxane group and a structure-directing agent. It relates to a method for producing mesoporous (mesoporous) material in which sub-nm pores are regularly arranged.

In 1991, Mobil researchers created a new type of mesoporous molecular sieve material called the M41S family using ionic surfactants as structural derivatives. Since the publication of US Pat. Nos. 5,057,296 and 5,102,643 and the like, research on such mesoporous molecular sieve materials is now actively conducted worldwide. Mesoporous materials, unlike microporous materials whose pore size is 1.5 nm or less, like those of conventional zeolite or AlPO-based materials, extend the pore size to the mesopore range (2-50 nm). This enables the application of molecular sieve materials to adsorption and separation of molecules having a size larger than the pore size of microporous materials, catalytic conversion reactions, and the like, which have been limited in the application of molecular sieve materials. In the M41S family announced by Mobil, MCM, where the one-dimensional mesoporous pores form a hexagonal array like a honeycomb, the MCM-41 material and the mesoporous pores are connected by an array of cubic structures of 1a3d. There are -48 substances. U.S. Pat.Nos. 6,027,706, 6,054,111 and 1998, Volume 279, page 548, describe the preparation of mesoporous materials using amphiphilic block copolymers, which are nonionic surfactants. It is specified. The production of mesoporous materials using gemini surfactants was published in the 1995 Science, volume 8, page 1324 and 1996 Chemistry of Materials, volume 8, page 1147. The mesoporous material having such regular pores has a very large surface area and excellent adsorption characteristics of atoms or molecules, and the size of the pores is constant, so that the mesoporous material can be used as a sieve for filtering molecules, that is, a molecular sieve. Many applications are expected, including conductive materials, optical display materials, chemical sensors, fine chemical and bio-catalysis, and new mechanical and thermal insulators and packaging materials.

One of the most important factors in the design and synthesis of mesoporous materials is the design of structural derivatives. In the present invention, a new type of gemini-type surfactant containing siloxane groups is prepared and used. Conventionally, the surfactant mainly used to prepare mesoporous material was a general type of surfactant having one hydrophobic group and a hydrophilic group, whereas the surfactant to be pursued in the present invention has two or three ionic parts in the hydrophilic part. Gemini surfactants with several hydrophobic alkyl chains, especially those containing siloxane groups in the middle of the ionic moiety.

Because of their structural properties, Gemini type surfactants exhibit excellent interfacial properties such as very low critical micellar concentration, high surface tension lowering ability, good foaming and emulsifying power, good solubility and water resistance. It is a material recognized as a next-generation surfactant, and has a more innovative property than the conventional surfactant in the micelle formation due to the intramolecular hydrophobic action of the molecule. As mentioned above, Gemini-type surfactants were first reported in 1995 to be used as structural derivatives in the preparation of mesoporous materials to produce mesoporous materials of various structures. However, since then, research on this has not been actively carried out, because the preparation of Gemini surfactants is not easy compared to conventional surfactants, whereas the physical properties of mesoporous materials obtained when using them as structural derivatives are This is because the degree is similar to mesoporous material. Therefore, in order to impart the desired physical properties (especially hydrophobic surface properties and pore size) of the mesoporous material, it is necessary to design and manufacture the Gemini type surfactant.

In other words, it is an object of the present invention to provide a new gemini-type surfactant comprising a siloxane mioety as a structural derivative.

Another object of the present invention is to provide a method for producing mesoporous (mesoporous) material having a pore distribution of 10 nm or less by using the new gemini-type surfactant.

One aspect of the present invention for achieving the above object relates to a Gemini type surfactant represented by the following formula (1).

[Formula 1]

Wherein R ₁ and R ₂ are each independently a methyl or ethyl group, R ₃ is an alkyl group having 5 to 40 carbon atoms, X is a halogen atom, and r is each independently a hydrogen atom, a methyl group or alkoxy having 1 to 10 carbon atoms and n is an integer of 1-12, m is an integer of 0-10.

Another aspect of the present invention is a mixture of the material represented by the following formula (2) and the material represented by the following formula (3) in a molar ratio of 1: 1 to 5, using a reaction temperature of 30 ~ 120 ℃ using ethanol, acetonitrile or toluene as a solvent It relates to a method for producing a gemini-type surfactant by reacting for 1 to 100 hours.

[Formula 2]

In said formula, X is a halogen atom, r is respectively independently a hydrogen atom, a methyl group, or a C1-C10 alkoxy group, n is an integer of 1-12, m is an integer of 0-10.

[Formula 3]

R ₃ R ₂ R ₁ N

In the above formula, R ₁ and R ₂ are each independently a methyl group or an ethyl group, and R ₃ is an alkyl group having 5 to 40 carbon atoms.

Another aspect of the present invention relates to a method for preparing a mesoporous material using the surfactant as a structure-directing agent.

Hereinafter, the present invention will be described in more detail with reference to the following examples and accompanying drawings.

 The present invention provides a gemini-type surfactant represented by the following Chemical Formula 1 including a siloxane mioety as a structural derivative to prepare a mesoporous material.

Wherein R ₁ and R ₂ are each independently a methyl or ethyl group, R ₃ is an alkyl group having 5 to 40 carbon atoms, X is a halogen atom, and r is each independently a hydrogen atom, a methyl group or alkoxy having 1 to 10 carbon atoms and n is an integer of 1-12, m is an integer of 0-10.

The surfactant may be reacted with ethanol, acetonitrile, toluene, and the like represented by the following Chemical Formulas 2 and 3 using a solvent at a reaction temperature of 30 to 120 ° C., preferably at 60 to 90 ° C. for 1 to 100 hours, preferably Is prepared by reacting for 24 to 72 hours. At this time, the reaction molar ratio of the material represented by the formula (2) and the material represented by the formula (3) is 1: 1 to 5, preferably 1: 2 to 3.

In said formula, X is a halogen atom, r is respectively independently a hydrogen atom, a methyl group, or a C1-C10 alkoxy group, n is an integer of 1-12, m is an integer of 0-10.

R ₃ R ₂ R ₁ N

In the above formula, R ₁ and R ₂ are each independently a methyl group or an ethyl group, and R ₃ is an alkyl group having 5 to 40 carbon atoms.

The present invention provides a method for preparing a mesoporous material by using the gemini-type surfactant as a structure-directing agent.

The method for producing the mesoporous material is preferably carried out through the following steps:

(A) mixing an aqueous solution of the gemini surfactant represented by Formula 1 with a precursor;

(B) adjusting the pH of the mixture of step (A) using an acid or a base;

(C) hydrothermally reacting the mixture of step (B);

(D) filtering, washing and drying the material obtained in step (C); And

(E) calcining the material obtained in step (D).

[Formula 1]

Wherein R ₁ and R ₂ are each independently a methyl or ethyl group, R ₃ is an alkyl group having 5 to 40 carbon atoms, X is a halogen atom, and r is each independently a hydrogen atom, a methyl group or alkoxy having 1 to 10 carbon atoms and n is an integer of 1-12, m is an integer of 0-10.

Hereinafter, the steps will be described in more detail.

In step (A), the aqueous solution of gemini surfactant may be prepared either basic or acidic. The basic aqueous solution is prepared by containing 0.1 to 5.0% by weight of Gemini-type surfactant, preferably 0.5 to 3.0% by weight, and 0.5 to 2.0% by weight of a strong base such as sodium hydroxide, preferably 0.7 to 1.0% by weight. The acidic aqueous solution is prepared by containing 0.1 to 5.0% by weight of Gemini-type surfactant, preferably 0.5 to 3.0% by weight, and 0.5 to 10% by weight of strong acid, such as hydrochloric acid or sulfuric acid, preferably 1.0 to 5.0% by weight. .

It is preferable to use a material represented by the following formula (4) as a precursor in the step (A).

R ⁴ _j R ⁵ _k M ¹ Y _4-jk or M ² (Y) ₃

Wherein R ⁴ and R ⁵ are each independently an alkyl group having 1 to 10 carbon atoms, Y is alkoxy having 1 to 5 carbon atoms, M ¹ is a Si or Ti atom, M ² is an Al atom, and j + k is 0 An integer greater than or equal to and less than or equal to 3.

The precursor is preferably added slowly while vigorously stirring the aqueous surfactant solution at room temperature using a stirring device. Representatively used precursor in the present invention is tetraethylorthosilicate (TEOS). At this time, the amount of the added precursor is suitably 1 to 100 moles based on 1 mole of the gemini-type surfactant, and preferably 10 to 50 moles. After the precursor is added to the aqueous surfactant solution, the reaction mixture is preferably stirred at room temperature for 1 to 2 hours.

In step (B), the pH of the aqueous solution prepared in step (A) is adjusted to 9 to 13, preferably 11 to 12, using an acid or a base.

In step (C), a mesoporous material having pores of 10 nm or less is prepared through hydrothermal reaction. At this time, the hydrothermal reaction temperature is suitable 60 ~ 150 ℃, the reaction time is 1 hour to 144 hours, preferably 12 hours to 48 hours.

In step (D), the prepared precipitate is filtered through a filtration apparatus, washed with distilled water 2 to 5 times, and dried at 50 to 200 ° C. for 3 to 30 hours.

In step (E), the firing conditions are preferably calcined at 400 to 600 ° C. for 0.5 to 30 hours in an air or nitrogen atmosphere.

Through the method of the present invention as described above it is possible to prepare a powder of mesoporous (mesoporous) material in which pores of less than 10 nm is regularly distributed.

In addition to the above method, it is possible to produce a mesoporous material by a method known in the art within a range that does not impair the object of the present invention. For example, aromatic hydrocarbons such as anisole and xylene, ketone solvents such as methyl isobutyl ketone and acetone, tetrahydrofuran and isopropyl ether Gemini-type precursors are dissolved in a solvent such as an ether solvent such as isopropyl ether, an alcohol such as ethanol, isopropylalcohol, butanol, or a mixture thereof, and the precursor aqueous solution is added thereto. After mixing, it is also possible to coat and dry it to form a mesoporous thin film.

Next, the present invention will be described in more detail with reference to Examples, but the following Examples are provided for the purpose of explanation and are not intended to limit the present invention.

Example 1 Surfactant Synthesis

(C _n H _{2n + 1} N (CH ₃ ) ₂ ClCH ₂ Si (CH ₃ ) ₂ OSi (CH ₃ ) ₂ CH ₂ ClN (CH ₃ ) ₂ C _n H _{2n + 1} , n = 6, 8, 10, 12, 14, 16, 18, 22)

A solution was prepared by mixing 100 ml of acetonitrile and 10.0 g of bis (chloromethyl) tetramethyldisiloxane ( A ) and then 21.4 g of tetradecyldimethylamine (n = 14, B ) was added to this solution. The molar ratio of A and B in the reaction was 1: 2.05. The resulting solution was heated to 82 ° C. for 24 h under reflex conditions. The solvent acetonitrile was removed using a rotary evaporator to obtain a solid product. After dissolving by adding 2 ml of chloroform to the solid product, 500 ml of ethyl acetate was added, followed by recrystallization by standing at 0 ° C. for 12 hours. The recrystallized material was filtered, washed three times with ethyl acetate, and then recrystallized, filtered and washed twice more. The obtained material was dried at 50 ° C. for 12 hours using a vacuum oven to completely remove the solvent, thereby removing C ₁₄ H ₂₉ N (CH ₃ ) ₂ ClCH ₂ Si (CH ₃ ) ₂ OSi (CH ₃ ) ₂ CH ₂ ClN (CH ₃ ) ₂ C ₁₄ H ₂₉ was prepared.

Next, except that alkyldimethylamine (C _n H _{2n + 1} N (CH ₃ ) ₂ , n = 6, 8, 10, 12, 16, 18, 22) having different alkyl chain lengths is used. Gemini-type surfactant was prepared by adjusting the size of n to 6, 8, 10, 12, 16, 18, 22.

Example 2 Preparation of Powdered Mesoporous Material (1)

C ₁₄ H ₂₉ N (CH ₃ ) ₂ ClCH ₂ Si (CH ₃ ) ₂ OSi (CH ₃ ) ₂ CH ₂ ClN (CH ₃ ) having an alkyl chain length of 14 in the gemini surfactant prepared in Example 1 ₂ C ₁₄ H ₂₉ the 0.84 g and 1.21 g of sodium hydroxide to prepare an aqueous solution was dissolved into double distilled water to 158 g. 12 g of TEOS was added while stirring this aqueous solution vigorously using a magnetic stirring device. At this time, the molar ratio of the reactants in the reaction mixture was 0.4: TEOS 1: NaOH 0.5: H ₂ O 150. Since the pH of the obtained mixture was in the range of 9-13, it did not go through the process of adjusting pH specifically. The mixture was stirred at room temperature for 1 hour and then reacted in an oven at 100 ° C. for 24 hours. The precipitate was then filtered, washed clean with secondary distilled water and dried at 100 ° C. It was calcined at 550 ° C. for 10 hours in air to remove the surfactant contained in the dried sample.

1 is an X-ray diffraction spectrum of the prepared mesoporous material. In FIG. 1, A shows the spectrum after baking and B shows the baking. 1, there is only about 10% contraction of the structure before and after the firing treatment, regardless of the before and after firing treatment, the X-ray diffraction patterns (100) and (110), which can be expressed in a two-dimensional hexagonal arrangement, Peaks 200 and 210 are shown in the low angle region. Thus, the nanoporous silica material produced by the production method of the present invention can be confirmed in the X-ray diffraction spectrum of FIG.

2 is a nitrogen adsorption-desorption isotherm obtained at a liquid nitrogen temperature for a fired sample. The Brunauer-Emmett-Teller surface area obtained from FIG. 2 was 840 m ² / g per g. In general, the BET surface area of the mesoporous silica materials prepared by the present invention was found to have a value of 800 ~ 1000 m ² / g, although slightly different depending on the preparation method. The adsorption-desorption isotherm of nitrogen as shown in Figure 2 is characteristic of mesoporous material as an isotherm in the form according to the International Union of Pure and Applied Chemistry (IUPAC) definition. 2 shows a sudden increase in the adsorption amount of nitrogen at p / p ₀ near 0.2. The pore size distribution curve obtained by the Barrett-Joyner-Halenda (BJH) method from the adsorption isotherm of FIG. 2 is shown in FIG. 3. 3 shows the peak form (the line width is 0.5 nm or less at the middle height) in which the pore size is concentrated at 2.00 nm.

4 is a transmission electron microscopy (TEM) photograph of the prepared material. As shown in the picture, the pores of the prepared material are mesoporous materials arranged regularly.

Example 3 Preparation of Powdered Mesoporous Material (2)

C ₁₄ H ₂₉ N (CH ₃ ) ₂ ClCH ₂ Si (CH ₃ ) ₂ OSi (CH ₃ ) ₂ CH ₂ ClN (CH ₃ ) having an alkyl chain length of 14 in the gemini surfactant prepared in Example 1 0.91 g of ₂ C ₁₄ H ₂₉ and 2.02 g of sodium hydroxide were dissolved in 264 g of secondary distilled water to prepare an aqueous solution. 20 g of TEOS was added while stirring this solution strongly using a magnetic stirring device. The molar ratio of reactants in the reaction mixture was surfactant 0.12: TEOS 1: NaOH 0.5: H ₂ O 150. Since the pH of the obtained mixture was in the range of 9-13, it did not go through the process of adjusting pH specifically. The mixture was stirred at room temperature for 1 hour and then reacted in an oven at 100 ° C. for 24 hours. The precipitate was then filtered, washed clean with secondary distilled water and dried at 100 ° C. It was calcined at 550 ° C. for 10 hours in air to remove the surfactant contained in the dried sample.

For comparison, 1.0 g of the sample immediately after the hydrothermal reaction was washed twice with a solution containing 100 g of ethanol and 5 g of 35% HCl to completely remove the surfactant, and then calcined at 550 ° C. for 10 hours in air.

5 is an X-ray diffraction spectrum of the prepared mesoporous material. In FIG. 5, A is a spectrum before firing, B is a spectrum when the prepared sample is calcined at 550 ° C. to remove surfactant, and C is a surfactant obtained by solvent extraction using a mixture of hydrochloric acid and ethanol. It is the spectrum when it removes previously and heat-processes at 550 degreeC after that. The lattice constant values obtained from the X-ray diffraction spectra B and C of FIG. 5 were very similar at 4.04 nm and 4.09 nm, respectively.

FIG. 6 shows nitrogen adsorption-desorption isotherms of samples that have been calcined as it is and samples which have been washed with a solvent extraction method to remove surfactants. The BET surface area and pore size were determined from FIG. 6. The BET surface area was 827 m ² per 1 g, the pore size was 2.13 nm, and the BET surface area was 853 m ² per 1 g, and the pore size was 2.37 nm. 7 is a pore size distribution diagram obtained by the BJH method from FIG. It can be seen that when the surfactant is not removed or removed, the pore size is 2.13 nm and 2.37 nm. The difference between the lattice constant and the pore size means the wall thickness of the mesoporous material, which in this case has a wall thickness of 1.91 nm and 1.72 nm, respectively, and thus the wall thickness of the mesoporous material depending on the method of removing the surfactant. It can be seen that there is. This means that when the calcination treatment is performed in the presence of the surfactant, the siloxane portion existing in the surfactant is deposited on the wall surface of the mesoporous material as it is, and the wall is thicker than the state removed by the solvent extraction method, which is the siloxane prepared in the present invention. It can be an advantage with gemini-type surfactants that include portions.

Example 4 Preparation of Powdered Mesoporous Material (3)

Mesoporous material was synthesized using surfactants having different alkyl chain lengths among the gemini-type surfactants prepared in Example 1. Gemini surfactants having alkyl chain lengths of 12, 14, and 16, respectively, were dissolved in 158 g of secondary distilled water at 0.78 g, 0.84 g, and 0.90 g, respectively, and then aqueous solution was prepared by adding 1.21 g of sodium hydroxide. 12 g of TEOS was added while stirring this aqueous solution vigorously using a magnetic stirring device. Since the pH of the obtained mixture was in the range of 9-13, it did not go through the process of adjusting pH specifically. The reaction mixture was stirred at room temperature for 1 hour and then reacted in an oven at 100 ° C. for 24 hours. The precipitate was then filtered, washed clean with secondary distilled water and dried at 100 ° C. to prepare a mesoporous material.

 8 is an X-ray diffraction spectrum of the prepared mesoporous materials. All materials in FIG. 8 show peaks of (100), (110), (200), and (210) in the low angle region, which means that the structural uniformity and pores are two-dimensional hexagonal arrangement. The lattice constant values obtained from each of the X-ray diffraction forms are 3.52 nm, 4.35 nm and 4.96 nm, and can be seen to increase in proportion to the carbon number of the alkyl chain. FIG. 9 is a spectrum in which the value of the lattice constant a obtained from the X-ray diffraction pattern of FIG. 7 corresponds to the carbon number n in the long chain of the gemini-type surfactant. It can be seen that as the length of the alkyl chain of the surfactant increases, the lattice constant of the prepared mesoporous material increases linearly from 3.5 nm to 5.0 nm. This means that the pore size of the silica material produced can be controlled by changing the surfactant structure according to the invention. As a result, it can be seen that the gemini-type surfactant provided by the present invention is not only excellent in structural uniformity of the mesoporous material prepared, but also a new type of structural derivative whose pore size can be easily controlled.

Example 5 Preparation of Thin Film Mesoporous Material

To prepare the thin film, 1-propanol and 2-butanol were used in a 1: 1 mass ratio as a solvent. Solution (a) was prepared by dissolving 3 g of the Gemini-type surfactant (n = 12, 14, 16, 18) prepared in Example 1 in 6 g of a mixed solvent. Solution (b) was prepared by mixing 6 g of TEOS and 2.2 g of 1 M HCl aqueous solution and 12.8 g of the mixed solvent, and then heating at reflux for 1 hour. The solution (b) was cooled to room temperature and then mixed with the solution (a), followed by stirring for 1 hour. The resulting solution was sprayed onto a silicon wafer rotating at 3000 rpm and then dried at room temperature for 24 hours to obtain a mesoporous thin film material. .

Fig. 10 shows the X-ray diffraction spectrum of this thin film. Figure 10 shows that the mesoporous pores of the thin film prepared in Example 5 has a structure arranged parallel to the surface. 10 shows that the Gemini-type surfactant prepared in the present invention can be used not only as a structural derivative for the powdery mesoporous material as in Examples 2, 3 and 4, but also as a pore structural derivative of the thin film material. Show that there is.

The present invention can provide a mesoporous material in which pores having a size of 10 nm or less are regularly arranged.

1 is an X-ray diffraction spectrum of a mesoporous material prepared in Example 2;

2 is an adsorption-desorption isotherm of nitrogen obtained at liquid nitrogen temperature for the mesoporous material prepared in Example 2;

Figure 3 is a pore size distribution curve (pore size distribution curve) obtained by the Barrett-Joyner-Halenda (BJH) method from the adsorption isotherm of nitrogen shown in Figure 2;

4 is a transmission electron microscopy (TEM) photograph of the mesoporous material prepared in Example 2;

5 is an X-ray diffraction spectrum of the mesoporous material prepared in Example 3;

6 is an adsorption-desorption isotherm of nitrogen obtained at liquid nitrogen temperature for the mesoporous material prepared in Example 3;

7 is a pore size distribution curve obtained by the BJH method from the adsorption isotherm of nitrogen shown in FIG. 6;

8 is an X-ray diffraction spectrum of a mesoporous material prepared in Example 4;

FIG. 9 is a spectrum of lattice constant a for each mesoporous silica material obtained from the X-ray diffraction spectrum of FIG. 8 expressed as carbon number n in the long chain of the surfactant; FIG. And

10 is an X-ray diffraction spectrum of the nanoporous thin film samples prepared in Example 5.

Claims (11)

Gemini type surfactant represented by the following formula (1). [Formula 1] Wherein R ₁ and R ₂ are each independently a methyl or ethyl group, R ₃ is an alkyl group having 5 to 40 carbon atoms, X is a halogen atom, and r is each independently a hydrogen atom, a methyl group or alkoxy having 1 to 10 carbon atoms and n is an integer of 1-12, m is an integer of 0-10. After mixing the material represented by the formula (2) and the material represented by the formula (3) in a molar ratio of 1: 1 to 5, using a ethanol, acetonitrile or toluene as a solvent for 1 to 100 hours at a reaction temperature of 30 ~ 120 ℃ To prepare the gemini surfactant according to claim 1. [Formula 2] In said formula, X is a halogen atom, r is respectively independently a hydrogen atom, a methyl group, or a C1-C10 alkoxy group, n is an integer of 1-12, m is an integer of 0-10. [Formula 3] R ₃ R ₂ R ₁ N In the above formula, R ₁ and R ₂ are each independently a methyl group or an ethyl group, and R ₃ is an alkyl group having 5 to 40 carbon atoms. A method for preparing a mesoporous material using the gemini-type surfactant of claim 1 as a structure-directing agent. The method of claim 3, wherein the mesoporous material is prepared through the following steps: (A) mixing an aqueous solution of the gemini surfactant with a precursor; (B) adjusting the pH of the mixture of step (A) using an acid or a base; (C) hydrothermally reacting the mixture of step (B); (D) filtering, washing and drying the material obtained in step (C); And (E) calcining the material obtained in step (D). According to claim 4, wherein the aqueous solution of step (A) is a basic aqueous solution prepared by containing 0.1 to 5.0% by weight of the Gemini-type surfactant, 0.5 to 2.0% by weight of the strong base, or 0.1 to 5.0 of the Gemini-type surfactant Wt%, strong acid is a method characterized in that the acidic aqueous solution prepared containing 0.5 to 10% by weight. The method of claim 4, wherein in the step (A), the precursor is represented by the following formula (4). [Formula 4] R ⁴ _j R ⁵ _k M ¹ Y _4-jk or M ² (Y) ₃ In the above formula, R ⁴ and R ⁵ are each independently an alkyl group having 1 to 10 carbon atoms, Y is alkoxy having 1 to 5 carbon atoms, M ¹ is a Si or Ti atom, M ² is an Al atom, and j + k is 0 An integer greater than or equal to and less than or equal to 3. 7. The method of claim 6, wherein the precursors are mixed to be from 1 to 100 moles based on 1 mole of gemini surfactant. The method of claim 4, wherein in the step (C), the hydrothermal reaction is carried out at 60 to 150 ℃ for 1 hour to 144 hours. The method of claim 4, wherein the precipitate prepared in step (D) is filtered through a filtration apparatus, washed 2 to 5 times with distilled water, and dried at 50 to 200 ° C. for 3 to 30 hours. Way. 5. The method according to claim 4, wherein the firing in the step (E) is performed for 0.5 to 30 hours at an air or nitrogen atmosphere at a temperature of 400 to 600 ° C. The method of claim 3, wherein the gemini-type precursor is dissolved in an aromatic hydrocarbon solvent, a ketone solvent, an ether solvent, alcohols, or a mixture thereof, an aqueous solution of the precursor is mixed therein, and then coated and dried to form a thin film. A method of forming a mesoporous material in the form.