KR101723999B1 - Manufacturing method attached fluorine silane functional group for hexagonal and cubic mesoporous silica materials at room temperature - Google Patents

Abstract

The present invention relates to a process for preparing a mesoporous silica material, comprising the steps of: (a) mixing H ₂ O and EtOH at a constant ratio; (b) adding a surfactant to the solution in which H ₂ O and EtOH are mixed at a predetermined ratio; (c) adding a compound selected from a precursor of the mesoporous silica material and a fluorosilane functional group to the solution formed in step (b), and stirring the mixture at room temperature for a predetermined time; (d) adding ammonia water to the solution stirred in step (c) and stirring for a predetermined time; (e) washing and drying the material synthesized in the step (d) after filtration; And (f) firing after the step (e).
In the present invention as described above, the carbon dioxide is chemically bonded by the fluorine group on the surface of the mesoporous silica adsorbent, so that the adsorption amount can be greatly increased.

Description

[0001] The present invention relates to a fluorine-containing mesoporous silica material,

The present invention relates to a method for producing a mesoporous silica material, and more particularly, to a method for producing a mesoporous silica material having a fluorine functional group with a pore structure of a hexagonal structure and a cubic structure at a room temperature manufacturing process.

The mesoporous material refers to a porous material having a nanometer size according to the definition of IUPAC (International Union of Pure and Applied Chemistry), and when the pore size is 2 nm or less depending on the pore size, microporous, (Mesoporous), and when they have pores of 50 nm or more, they are called macroporous. Porous materials with nanometer-sized pores can be used as a host or chromatographic separation of organic polymers when forming organic / inorganic composites, adsorption of toxic substances in air and water, and morphological selective catalysts of large organic polymers Much research has been done because of potential applicability.

The mesoporous material started in 1990 by T. Yanagisawa and his colleagues synthesized materials with uniform size pores ranging from 1.8 nm to 3.2 nm using the surfactant as a template. Subsequently, in 1992, J. S. Beck and others of Mobil synthesized hexagonal mesoporous materials and successfully synthesized mesoporous materials of cubic and lamellar structures.

The sol-gel method, which has been studied so far, reacts by heating at a high temperature during the condensation reaction, which complicates the process due to heating and increases the cost. Therefore, studies for conducting a condensation reaction at room temperature have been actively conducted. By adjusting the pH during the condensation reaction, the process can be simplified and the cost can be reduced.

To synthesize mesoporous materials, nonionic surfactants and cationic surfactants are used as supports. Synthesis of mesoporous material with the cationic surfactant of is no direct way of S ⁺ + I ^- → S ⁺ I ^- S ⁺ + X using the methods and media of synthesizing such as ^- + I ⁺ = S ⁺ X ^- I ^+. & Lt ^; / RTI > Where S ⁺ is a cationic surfactant, I ⁺ and I ^- are inorganic ions, and X ^- is a mediating ion.

The cationic surfactant, which is mainly used in the synthesis of mesoporous materials, is the alkali ammonium halide (C _n H _{2n +1} N ⁺ X ^- ). When this surfactant is dissolved in a certain concentration in a solution, it forms a structure, which is called a critical micelle concentration. Depending on the surfactant concentration, hexagonal, cubic, and lamellar structures lamellar. FIG. 1 is a schematic diagram of the structure formation according to the critical micelle concentration and the synthesis of the mesoporous material. FIG.

Silane with amine groups at the carbon chain end was used to attach the amine group to the mesoporous silica material thus regulated. A simple schematic diagram of gas adsorption is shown in FIG.

When carbon dioxide or toxic gas, which is a greenhouse gas, passes through a silica material having a functional group in the atmosphere, the gases are chemically bonded selectively to a functional group on the surface of the silica material.

The adsorption of carbon dioxide on the amine group is shown in Fig. When the two amine groups on the surface of the mesoporous silica adsorbent meet with carbon dioxide, they are converted into carbamate and ammonium ions by oxidation-reduction reaction, and eventually converted into ion-bonded forms in which carbonate and ammonium ions are bonded. do.

The sol-gel method, which has been studied so far, reacts by heating at a high temperature during the condensation reaction, which complicates the process due to heating and increases the cost. In addition, the mesoporous silica material used as the adsorbent A method for producing a mesoporous silica material which can broaden the specific surface area by an efficient and simple process is needed in order to improve the adsorption performance.

Korea Public No. 10-2011-0033575 (public date: March 31, 2011) Korea Public Release No. 10-2011-0085363 (public date: July 27, 2011)

The object of the present invention to solve the above problems is to synthesize a mesoporous silica material through a condensation reaction at room temperature, and to simplify the process and reduce the cost by synthesizing the mesoporous silica material by adjusting the pH during the condensation reaction.

The present invention also provides a method for increasing the adsorption capacity depending on the structure by enlarging the specific surface area, and the mesoporous silica capable of increasing the amount of adsorption due to the chemical bonding of carbon dioxide by the fluorine group on the surface of the mesoporous silica adsorbent, And to provide a method for producing a substance.

According to an aspect of the present invention, there is provided a method of manufacturing a semiconductor device, comprising: (a) mixing H ₂ O and EtOH at a predetermined ratio; (b) adding a surfactant to the solution in which H ₂ O and EtOH are mixed at a predetermined ratio; (c) adding a compound selected from a precursor of the mesoporous silica material and a fluorosilane functional group to the solution formed in step (b), and stirring the mixture at room temperature for a predetermined time; (d) adding ammonia water to the solution stirred in step (c) and stirring for a predetermined time; (e) washing and drying the material synthesized in the step (d) after filtration; And (f) firing after the step (e).

Here, in any of the compounds N6330 fluorinated silane is preferably, and the step (b) is selected from the fluorine silane functional group (functional group), it is preferable to add a CTACl as the surfactant, SiO ₂ and CTACl Is preferably in the range of 1 to 0.1 to 0.2.

Preferably, the pore structure of the silica material may have a hexagonal structure when the concentration ratio of SiO ₂ to CTACl is in the range of 0.1 to less than 0.15, and the concentration ratio of SiO ₂ to CTACl may be 0.15 to 0.15, 0.2 or less, the pore structure of the silica material may have a cubic structure.

In addition, it is preferable to add TEOS as the precursor in the step (c), and the molar ratio of the TEOS to the fluorosilane is adjusted to 1: 1 to 3, and the molar concentration of the synthesized TEOS and fluorosilane compound Is preferably in the range of 0.1 to 0.4 M, and it is preferable to increase the specific surface area of the silica material by increasing the molar concentration within the above range. In the step (d), ammonia water is added to adjust the pH of the solution in the range of 9 to 11 Is set.

In a second aspect of the present invention, there is provided a method for producing a mesoporous silica material, comprising the steps of: synthesizing a mesoporous silica material having a fluorine group attached thereto through a condensation reaction at room temperature by the above- The pH of the solution is adjusted to be in the range of 9 to 11 by adding the base solution at the room temperature to synthesize the mesoporous silica material.

Here, it is preferable that the cationic surfactant is a CTACl in the course of the synthesis of the silica material, to which a silane-based functional group is attached.

The present invention is advantageous in that a mesoporous silica material having a large specific surface area can be synthesized by controlling the structure of the hexagonal structure and the cubic structure by using the ratio of the additive materials at room temperature.

In addition, the present invention can synthesize a mesoporous silica material through a condensation reaction at room temperature without heating process for supplying heat, and at this time, by adjusting the pH during the condensation reaction, the process can be simplified and cost can be reduced.

Then, the fluorine group on the surface of the mesoporous silica adsorbent causes the carbon dioxide to chemically bond, which can greatly increase the amount of adsorbed.

FIG. 1 is a schematic diagram of the structure formation according to the critical micelle concentration and the synthesis of the mesoporous material,
Fig. 2 is a simple schematic diagram for gas adsorption,
3 is a schematic view showing adsorption of carbon dioxide on an amine group,
FIG. 4 is a view showing a flow of a process for producing a mesoporous silica material with a fluorine group according to an embodiment of the present invention,
FIG. 5 is a view illustrating the structure of N6330 fluorosilane used in a method for producing a mesoporous silica material according to an embodiment of the present invention,
FIG. 6 shows the XRD results of the mesoporous silica material with a fluorine group having a hexagonal pore structure,
7 is an XRD result of a mesoporous silica material with a fluorine group having a cube pore structure,
8 is a TEM photograph of a hexagonal mesoporous silica material with a fluorine group attached thereto,
9 is a TEM photograph of a fluorine-attached, cubic mesoporous silica material,
10 is a graph of FT-IR results of mesoporous silica having a fluorine group attached thereto as a hexagonal pore structure functional group.

BRIEF DESCRIPTION OF THE DRAWINGS The advantages and features of the present invention, and how to accomplish it, will be described with reference to the embodiments described in detail below with reference to the accompanying drawings. However, the present invention is not limited to the embodiments described herein but may be embodied in other forms. The embodiments are provided so that those skilled in the art can easily carry out the technical idea of the present invention to those skilled in the art.

In the drawings, embodiments of the present invention are not limited to the specific forms shown and are exaggerated for clarity. Also, the same reference numerals denote the same components throughout the specification.

The singular forms herein include plural forms unless the context clearly dictates otherwise. Also, components, steps, operations and elements referred to in the specification as " comprises "or" comprising " refer to the presence or addition of one or more other components, steps, operations, elements, and / or devices.

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the drawings.

FIG. 4 is a flow chart of a method for producing a fluorine-group-containing mesoporous silica material according to an embodiment of the present invention, and FIG. 5 is a graph showing the relationship between N6330 fluorine Lt; RTI ID = 0.0 > silane. ≪ / RTI >

As shown in FIG. 4, the method for producing a mesoporous silica material includes the steps of: (a) mixing H ₂ O and EtOH at a constant ratio; (b) adding a surfactant to the solution in which H ₂ O and EtOH are mixed at a predetermined ratio; (c) adding a compound selected from a precursor of the mesoporous silica material and a fluorosilane functional group to the solution formed in step (b), and stirring the mixture at room temperature for a predetermined time; (e) washing and drying the material synthesized in the step (d) after filtration; And (f) firing after the step (e).

In addition, the steps S110 to S160 except for the firing step (S170) are all performed at room temperature, and the pH is adjusted during the condensation reaction through the addition of the aqueous ammonia of S140.

In order to control the pores of the synthesized mesoporous silica material, the concentration ratio of SiO ₂ and CTACl was adjusted to 1: 0.1-0.2. In order to synthesize a mesoporous silica material having a high specific surface area, TEOS And fluorine silane (hereinafter, referred to as 'fluorosilane') was adjusted to 1: 1 to 3, and the molar concentration of the synthesized TEOS and fluorosilane compound was adjusted to 0.1 to 0.4 M to obtain SiO ₂ .

The pore structure of the mesoporous silica material can be selected to be a hexagonal structure and a cubic structure by controlling the concentration ratio of SiO ₂ and CTACl to 1: 0.1 to 0.2, and preferably, the concentration ratio of SiO ₂ to CTACl is 1: When it is set to 0.1 or more and less than 0.15, it can be selected as a hexagonal structure. When the concentration ratio of SiO ₂ and CTACl is set to 1: 0.15 or more to 0.2 or less, a cubic structure can be selected. Further, TEOS and fluorosilane can be adjusted to a molar ratio of 1: 1 to 3, respectively, and the molar concentration of the TEOS and fluorosilane compounds in the range of 0.1 to 0.4 M, The specific surface area of the material can be increased. For example, when the molar concentration of the compound is increased, the specific surface area of the cubic silica having a fluorine group is in the range of 237 to 450 m 2 / g, and in the case of the hexagonal structure silica, the specific surface area is in the range of 298 to 407 m 2 / g. < / RTI > It is also preferable to add ammonia water so that the pH of the solution is set in the range of 9 to 11.

Referring to FIG. 4, the process of the process for producing a fluorine-bonded mesoporous silica material according to an embodiment of the present invention will be described in more detail as follows.

As shown in FIG. 4, synthesis of a fluorine-bonded mesoporous silica material is performed based on optimal conditions among the synthesis of a hexagonal mesoporous silica material (HMS) and a cubic mesoporous silica (CMS).

As shown in Fig. 4, the process of the synthesis of the mesoporous silica material with functional groups is carried out by first mixing (S110) H ₂ O and EtOH at a certain ratio (S110), and adding the surfactant CTACl to the mixed solution (S120) Then, fluorosilane, which is a compound selected from the functional group, is added to TEOS, which is a precursor of the mesoporous silica material, and the mixture is stirred for 10 minutes (S130). 5. Aqueous ammonia was added dropwise a solution (NH ₄ OH) was added and (S140), at least about 15 hours, and reacted for one day. (S150) that after the composite material was filtered by washing and drying (S160), sintering (S170) meso Thereby synthesizing a porous silica material.

Results analysis

FIGS. 6 and 7 are graphs showing XRD results of a fluorophor-attached mesoporous silica material according to an embodiment of the present invention. FIG. FIG. 6 shows the XRD results of a fluorophorous mesoporous silica material with a hexagonal pore structure, and FIG. 7 shows the XRD results of a fluorophorous mesoporous silica material with a cubic pore structure.

Mesoporous silica was synthesized based on mesoporous mesoporous silica (HMS4) and cubic mesoporous silica (CMS3), which had the largest specific surface area among the mesoporous silica materials with controlled pore structure. 6 and 7 are mesoporous silica with a fluorine group. In the case of FIG. 6, the homogeneity of the pores was lowered due to the functional group, but the hexagonal mesoporous silica can be confirmed by confirming the d ₍₁₀₀₎ peak as the main peak. Here, in the fluorosilane used in the synthesis, the fluorine group affects the pH of the solution, and as the condensation reaction speeds up, the pores decrease and the specific surface area decreases. In the case of FIG. 7, it can be seen that the mesoporous silica is a cubic structure by confirming the d ₍₂₁₁₎ peak as the main peak. As shown in Fig. 6, which has a hexagonal structure, the size of the peak is reduced and the uniformity of pores is lowered.

N ₂ -sorption was used to measure the specific surface area and pore size and volume of the mesoporous silica material with fluorine groups. The specific surface area was determined from the BET relationship using the isothermal adsorption / desorption information of the measured sample, Size and volume can be obtained from the BJH relationship.

[Table 1] and [Table 2] describe the specific surface area, the pore size and the pore volume for a mesoporous silica material having a fluorine group. As the amount of the fluorosilane added increases, the specific surface area and pore size , Respectively. However, there is a difference in the volume of the pores, because the pore size distribution of the BJH method results in a difference in the pore volume because the micropore, that is, pores having a pore size of 2 nm or less, is ignored .

Sample name Si concentration
(M) Specific surface area
(BET) (m < 2 > / g) Pore size
(nm) Pore volume
(cc / g)   HMS4 0 1180 4.3 0.662 HMS4 (A1) One 407 3.8 0.332 HMS4 (A2) 2 347 3.8 0.292 HMS4 (A3) 3 298 3.7 0.256

Sample name Si concentration
(M) Specific surface area
(BET) (m < 2 > / g) Pore size
(nm) Pore volume
(cc / g)   CMS3 0 1620 3.4 0.110 CMS3 (A1) One 450 3.4 0.117 CMS3 (A2) 2 249 3.4 0.039 CMS3 (A3) 3 237 3.3 0.028

As shown in [Table 1] and [Table 2], the morphology, size and distribution of the pores of the mesoporous silica having a fluorine group were analyzed based on HMS4 and CMS3, and analyzed by TEM. Figs. 8 and 9 The results are shown in Fig.

8 is a TEM photograph of a hexagonal mesoporous silica material with a fluorine group attached thereto. As shown in FIG. 8, it is difficult to regulate the pH due to the fluorine group at the terminal, which makes it difficult to form pores. However, it can be seen that highly developed pores are uniformly arranged.

9 is a TEM photograph of a cubic mesoporous silica material with a fluorine group attached thereto. As shown in FIG. 9, although the pore size is slightly reduced due to the fluorine group, it can be seen that highly uniform pores in the upper, lower, left, and right sides are well developed in the form of cubic structure.

The mesoporous silica sample thus synthesized was analyzed by FT-IR (Fourier transform infrared analyzer) to confirm the presence of a functional group fluorine group, and the results are shown in FIG. 10 is a graph of FT-IR results of mesoporous silica having a fluorine group attached thereto as a hexagonal pore structure functional group.

As shown in Figure 10, in the case of FT-IR peaks of the fluorine group, 1050cm ^- is displayed on the ^1-1 of the Si-O peak is near 1000cm. As a result of the data confirmation, it can be seen that the fluorine group is attached to the mesoporous silica.

Thus, the present invention can improve the adsorption ability according to a wide specific surface area and various pore structures by providing a method for producing a mesoporous silica material with a fluorine group attached thereto. In particular, the fluorine group It can be confirmed that the adsorbed ability of the attached mesoporous silica adsorbent is excellent. That is, the fluorine group on the surface of the mesoporous silica adsorbent has a partial charge of δ ^-, the carbon in the carbon dioxide has a partial charge of δ ⁺ , and the fluorine group and the carbon dioxide are bound by the electrostatic attracting force, Can be greatly increased.

In addition, the conventional mesoporous silica material can be synthesized by sol-gel method, followed by heating to synthesize gel. However, the present invention is not limited to the method of synthesizing sol at room temperature, But the pH is adjusted to form a gel. Accordingly, since heat is not applied, it is possible to perform at room temperature, thereby simplifying the process and reducing the cost.

While the invention has been shown and described with respect to the specific embodiments thereof, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention as defined by the appended claims. Anyone with it will know easily.

Claims (11)

In a method for producing a mesoporous silica material,
(a) mixing H ₂ O and EtOH at a constant ratio;
(b) adding CTACl to a solution in which the H ₂ O and EtOH are mixed at a predetermined ratio;
(c) adding a compound selected from the group consisting of a precursor of the mesoporous silica material and a fluorosilane functional group to the solution formed in step (b), and stirring the mixture at room temperature for 10 minutes or more;
(d) adding ammonia water to the solution stirred in step (c) and stirring for not less than 15 hours but not longer than 24 hours;
(e) washing and drying the material synthesized in the step (d) after filtration; And
(f) firing after the step (e);
The concentration ratio of SiO ₂ , which is a silica material converted from the precursor of the silica material added in the step (c), and the CTACl is 0.1-0.2,
When the concentration ratio of SiO ₂ to CTACl is 1: 0.1 or more and less than 0.15, the pore structure of the silica material has a hexagonal structure,
Wherein the pore structure of the silica material has a cubic structure when the concentration ratio of SiO ₂ to CTACl is 0.15 or more to 0.2 or less.
The method according to claim 1,
Wherein one of the compounds selected from the fluorosilane functional group is N6330 fluorosilane.
The method according to claim 1,
Wherein TEOS is added to the precursor in step (c).
The method of claim 3,
The molar ratio of the TEOS to the fluorosilane is adjusted to 1: 1 to 3, and the molar concentration of the synthesized TEOS and fluorosilane compound is in the range of 0.1 to 0.4 M, Wherein the specific surface area of the mesoporous silica material is increased.
The method according to claim 1,
Wherein the pH of the solution is set in the range of 9 to 11 by adding ammonia water in the step (d). delete delete delete delete delete delete

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