JP2010235412A - Mesopore orientation material - Google Patents

Abstract

The present invention provides a mesopore orientation material comprising a plate-like particle, in which mesopores are oriented in the thickness direction of the plate-like particle and having a relatively large aspect ratio.
A mesopore alignment material having the following configuration. (1) The mesopore alignment material includes an inorganic skeleton containing a Si—O—Si bond and a divalent organic group having one or more carbon atoms, and different Si atoms constituting the inorganic skeleton are between It consists of an organic-inorganic hybrid connected by the organic group. (2) The mesopore alignment material includes a (—O) ₃ Si—CH ₂ —CH ₂ —Si (O—) ₃ structure. (3) The mesopore orientation material is composed of plate-like particles, and has mesopores oriented substantially perpendicular to the plate surface of the plate-like particles.
[Selection] Figure 4

Description

  The present invention relates to a mesopore alignment material, and more particularly to an organic-inorganic hybrid mesopore alignment material in which mesopores are regularly arranged.

The mesopore material is a material having mesopores (nanospaces), and can be used for catalysts, electrolytes, photoreactions, etc., using the nanospace as a reaction field. In particular, a material in which the orientation of mesopores is controlled is expected to be used for highly conductive materials, highly active catalysts, highly sensitive sensors, ultra-high density recording media, and the like.
A reported example in which mesopores are vertically aligned is centered on a silica thin film. Controlling the orientation of pores in mesoporous membranes is extremely important for application to functional molecules and cluster orientation fixation, separation membranes, nanowires, electronic devices, and the like.

As a method of controlling the pores,
(1) Controlling the orientation of micelles using the structure of the substrate surface, such as a rubbed polymer substrate (see Non-Patent Document 1), the Si substrate (110) surface (see Non-Patent Document 2),
(2) Direct orientation of micelles by light (see non-patent document 3), electric field (see non-patent document 4), magnetic field (see non-patent document 5 and patent document 1),
Is mentioned.
In addition, a mesoporous film in which a mesoporous material is synthesized in pores oriented in an anodized alumina film and oriented perpendicularly to the film surface has also been reported (see Non-Patent Document 6 and Patent Document 2).

Furthermore, there is also a report example of a mesoporous silica thin film vertically aligned on a substrate by a normal film forming method other than the above (see Patent Document 3). Here, “ordinary film forming method” refers to, for example, a method for preparing a mesoporous thin film by a dip coating method. When an organic silane is added to a solution obtained by adding a surfactant, a small amount of water and hydrochloric acid to ethanol and stirred, a sol solution composed of an oligomer of the organic silane is obtained. When the substrate is immersed in the sol solution and pulled up at a predetermined speed, the sol solution is uniformly applied to the substrate. In the process of evaporating the solvent of the sol solution on the substrate, the surfactant is concentrated to form a regular micelle structure.
However, raising the pores on the substrate is an obstacle for the substrate itself (it is not possible to use a reaction in which the reactants move from the pore inlet to the pore outlet), making it difficult for industrial use. Seem.

Therefore, a vertical alignment material that does not cause a dead end due to a substrate or the like is desired.
For example, in Non-Patent Document 7, surfactant (P123), tetraethoxysilane (TEOS), ZrOCl ₂ .8H ₂ O, HCl, and H ₂ O are mixed at a predetermined ratio and reacted at a predetermined temperature. A mesoporous material obtained by burning off a surfactant from precipitated particles is disclosed.
In the same document,
(1) A plate-like mesoporous material having an average width of 800 to 1100 nm and an average thickness of 150 to 300 nm can be obtained by such a method, and
(2) The obtained plate-like particles have the pores regularly arranged along the thickness direction,
Is described.

JP 2001-58812 A JP 2008-195580 A JP 2008-266049 A

Miyata H., Kuroda K .: Chem. Mater. 11, 1609 (1999) Miyata H., Kuroda K .: J. Am. Chem. Soc. 121, 7618 (1999) Kawashima Y., Nakagawa M., Seki T., Ichimura K .: Chem. Mater. 14, 2842 (2002) Taru M., Yao N., Kim E., Xia Y., Whitesides G.M., Aksay I.A .: Nature, 390, 674 (1997) Yamaguchi A., Sawada m., Noma T., Ito H., Furumi S., Sakka Y., Kuroda K .: J. Mater. Chem. 15, 1137 (2005) Yamaguchi A., Uejo F., Yoda T., Uchida T., Yanamura Y., Yamashita T., Teramae N .: Nature Mater. 3, 337 (2004) Chen S.Y. et al .: Chem. Mater. 20, 3906 (2008)

As disclosed in Non-Patent Document 7, when a cation (Zr ^IV ) is added to the raw material, the morphology of the primary particles can be controlled by the cation addition effect. As a result, plate-like mesoporous silica having an aspect ratio of about 2.6 to 7.3 is obtained. Moreover, the pores are oriented substantially perpendicular to the plate surface.
However, this method has a drawback that Zr ions added to the raw material remain on the pore surface. In consideration of moldability, a material having a higher aspect ratio is desired.

  The problem to be solved by the present invention is to provide a mesopore alignment material comprising plate-like particles, mesopores oriented in the thickness direction of the plate-like particles, and having a relatively large aspect ratio. There is.

In order to solve the above problems, the mesopore alignment material according to the present invention is summarized as having the following configuration.
(1) The mesopore alignment material includes an inorganic skeleton containing a Si—O—Si bond and a divalent organic group having one or more carbon atoms, and different Si atoms constituting the inorganic skeleton are between It consists of an organic-inorganic hybrid connected by the organic group.
(2) The mesopore alignment material includes a (—O) ₃ Si—CH ₂ —CH ₂ —Si (O—) ₃ structure.
(3) The mesopore orientation material is composed of plate-like particles, and has mesopores oriented substantially perpendicular to the plate surface of the plate-like particles.
The plate-like particle preferably has an aspect ratio of 8 or more.

When synthesizing a mesopore alignment material, at least Z ₃ Si—CH ₂ —CH ₂ —SiZ ₃ (Z is —OCH ₃ , —OC ₂ H ₅ ) as a precursor for forming an organic-inorganic hybrid skeleton. When the synthesis is performed under basic conditions, a mesopore orientation material having a relatively high aspect ratio and mesopores oriented in the thickness direction can be obtained.

It is the XRD pattern (left figure) and SEM image (right figure) of the mesopore orientation material (ethane bridge | crosslinking type organic-inorganic hybrid) obtained in Example 1. FIG. 2A and 2B are a nitrogen adsorption isotherm and a pore distribution curve of the mesopore orientation material obtained in Example 1, respectively. 2 is a SEM image (same lot, 2 fields of view) of the mesopore alignment material obtained in Example 1. FIG. 2 is a STEM image of a mesopore alignment material obtained in Example 1.

Hereinafter, an embodiment of the present invention will be described in detail.
[1. Mesopore orientation material]
The mesopore orientation material according to the present invention has the following configuration.
(1) The mesopore alignment material includes an inorganic skeleton containing a Si—O—Si bond and a divalent organic group having one or more carbon atoms, and different Si atoms constituting the inorganic skeleton are between It consists of an organic-inorganic hybrid connected by the organic group.
(2) The mesopore alignment material includes a (—O) ₃ Si—CH ₂ —CH ₂ —Si (O—) ₃ structure.
(3) The mesopore orientation material is composed of plate-like particles, and has mesopores oriented substantially perpendicular to the plate surface of the plate-like particles.

[1.1. Organic-inorganic hybrid]
The mesopore alignment material according to the present invention comprises an organic-inorganic hybrid. In the present invention, the “organic-inorganic hybrid” means an inorganic skeleton containing a Si—O—Si bond and a divalent organic group having one or more carbon atoms, and different Si atoms constituting the inorganic skeleton are organic. A material connected by a group.
The inorganic skeleton may include both Si atoms bonded only to oxygen atoms and Si atoms bonded to oxygen atoms and organic groups. Alternatively, the inorganic skeleton may include only an Si atom bonded to an oxygen atom and an organic group. In order to obtain plate-like particles having mesopores oriented substantially perpendicular to the plate surface, the inorganic skeleton preferably contains only Si atoms bonded to oxygen atoms and organic groups.
The organic-inorganic hybrid preferably contains only Si—O—Si bonds and Si—organic group—Si bonds, but may contain inevitable impurities.

[1.2. Organic group]
In the present invention, the “organic group” refers to a divalent group having one or more carbon atoms. Examples of such an organic group, _{specifically, - (CH 2) n -} (n is an integer of 1 to 4), - CH = CH -, - CH = CH-CH 2 - , and the like.
Moreover, the mesopore orientation material according to the present invention includes a (—O) ₃ Si—CH ₂ —CH ₂ —Si (O—) ₃ structure. That is, the mesopore alignment material according to the present invention includes at least one ethylene group (—CH ₂ —CH ₂ —) as an organic group, and Si (O—) ₃ is bonded to both ends of at least one ethylene group. It has a structure.
The mesopore orientation material may contain only ethylene groups or may contain organic groups other than ethylene groups.
When the mesopore alignment material contains an organic group other than an ethylene group and an ethylene group, the ratio can be arbitrarily selected according to the purpose. When all of the organic groups are ethylene groups, mesopores are easily arranged in the thickness direction.

[1.3. shape]
The mesopore orientation material according to the present invention comprises plate-like particles.
When the method described later is used, plate-like particles having an aspect ratio of 8 or more, 9 or more, or 10 or more can be obtained.
Moreover, when the method to be described later is used, plate-like particles having a width of 400 to 2000 nm are obtained.

[1.4. Mesopore]
The mesopore orientation material according to the present invention has mesopores oriented substantially perpendicular to the plate surface of the plate-like particles.
“Mesopore” refers to a nanospace (1.5 to 50 nm) larger than the space contained in zeolite. As will be described later, in the case of polycondensation of the precursor that becomes the skeleton of the mesopore alignment material, when a surfactant is allowed to coexist, the surfactant forms micelles and self-organizes. As a result, a composite comprising a mesopore orientation material in which mesopores are regularly arranged and a surfactant filled in the mesopores is obtained.
At this time, at least Z ₃ Si—CH ₂ —CH ₂ —SiZ ₃ (Z is —OCH ₃ , —OC ₂ H ₅ , or halogen) is used as a precursor for forming the skeleton of the mesopore alignment material. When used and synthesized under basic conditions, a mesopore orientation material having a relatively high aspect ratio and mesopores oriented substantially perpendicular to the plate surface is obtained. “Oriented almost perpendicularly to the plate surface” means that the mesopores are oriented in the thickness direction of the plate-like particles, and may be slightly deviated from the direction perpendicular to the plate surface. Means.

[2. Method for producing mesopore alignment material]
The method for producing a mesopore alignment material according to the present invention includes a composite production process and a surfactant removal process.

[2.1. Complex production process]
In the composite manufacturing process, the precursor for forming the skeleton of the mesopore alignment material is subjected to polycondensation under the coexistence of the surfactant and the basic condition, and the surface activity is brought into the mesopores of the mesopore alignment material. This is a step of obtaining a composite filled with an agent.

[2.1.1 Precursor]
“Precursor” refers to a raw material for forming a skeleton of a mesopore alignment material. In the present invention, a silane compound represented by the following formula (1) is used as the precursor.
Z ₃ Si—R—SiZ ₃ (1)
However, Z _{is, -OCH 3, -OC 2 H 5} , or halogen.
R is a divalent organic group having 1 or more carbon atoms.
(1) In formula, R may mutually be the same or may differ.
Specific examples of the divalent organic group R include — (CH ₂ ) _n — (n is an integer of 1 to 4), —CH═CH—, —CH═CH—CH ₂ —, and the like.

In order to obtain plate-like particles in which mesopores are oriented substantially perpendicular to the plate surface, the precursor has at least an organic group R that is an ethylene group, that is, the following (1a) It is necessary to use a silane compound.
Z ₃ Si—CH ₂ —CH ₂ —SiZ ₃ (1a)
However, Z _{is, -OCH 3, -OC 2 H 5} , or halogen.
Among the silane compounds represented by the formula (1a), (EtO) ₃ Si—CH ₂ —CH ₂ —Si (OEt) ₃ (bistriethoxysilylethane: BTEE) is particularly preferable.

  As the starting material, only the precursor represented by the formula (1a) may be used, or used in combination with the precursor represented by the formula (1a) and a precursor containing an organic group R other than an ethylene group. May be. When a precursor containing an ethylene group and a precursor containing an organic group other than an ethylene group are used in combination, the ratio can be arbitrarily selected depending on the purpose. When only a precursor containing an ethylene group is used, it is easy to arrange mesopores in the thickness direction.

  Further, only the silane compound represented by (1) may be used as the precursor, or a precursor having no divalent organic group in addition to the silane compound represented by the formula (1) ( A second precursor may be used.

Specifically, the following can be used as the second precursor.
(1) Tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, tetrabutoxysilane, and dimethoxydiethoxysilane.
(2) Trimethoxysilanol, triethoxysilanol, trimethoxymethylsilane, trimethoxyvinylsilane, triethoxyvinylsilane, triethoxy-3-glycidoxypropylsilane, 3-mercaptopropyltrimethoxysilane, 3-chloropropyltrimethoxysilane, 3- (2-aminoethyl) aminopropyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, γ- (methacryloxypropyl) trimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, etc. Trialkoxysilane.
(3) Dialkoxysilanes such as dimethoxydimethylsilane, diethoxydimethylsilane, diethoxy-3-glycidoxypropylmethylsilane, dimethoxydiphenylsilane, and dimethoxymethylphenylsilane.
(4) Sodium metasilicate (Na ₂ SiO ₃ ), sodium orthosilicate (Na ₄ SiO ₄ ), sodium disilicate (Na ₂ Si ₂ O ₅ ), sodium tetrasilicate (Na ₂ Si ₄ O ₉ ), water Sodium silicate such as glass (Na ₂ O · nSiO ₂ , n = 2 to 4).
(5) Kanemite (NaHSi ₂ O ₅ .3H ₂ O), sodium disilicate crystals (α, β, γ, δ-Na ₂ Si ₂ O ₅ ), macatite (Na ₂ Si ₄ O ₉ ), eyelite ( _{Na 2 Si 8 O 17 · xH} 2 O), magadiite _{(Na 2 Si 14 O 17 ·} xH 2 O), kenyaite _{(Na 2 Si 20 O 41 ·} xH 2 O) layered silicates, such as.
(6) Fumed silica such as precipitated silica such as Ultrasil (Ultrasil), Cab-O-Sil (Cabot), HiSil (Pittsburgh Plate Glass), colloidal silica, Aerosil (Degussa-Huls).
(7) Tetrakis (hydroxyhydroxy) silane, tetrakis (3-hydroxypropoxy) silane, tetrakis (2-hydroxyproxy) silane, tetrakis (2,3-dihydroxypropoxy) silane and the like.
(8) Methyltris (2-hydroxyethoxy) silane, ethyltris (2-hydroxyethoxy) silane, phenyltris (2-hydroxyethoxy) silane, 3-mercaptopropyltris (2-hydroxyethoxy) silane, 3-aminopropyltris ( Tris (hydroxyalkoxy) silanes such as 2-hydroxyethoxy) silane and 3-chloropropyltris (2-hydroxyethoxy) silane.

  Any one of these may be used for the second precursor, or two or more may be used in combination. When using a 2nd precursor as a starting material, the ratio of the precursor containing an organic group and a 2nd precursor can be arbitrarily selected according to the objective.

In addition, when using silane compounds, such as an alkoxysilane and a hydroxy alkoxysilane, as a 2nd precursor, this is used as a starting material as it is.
On the other hand, when a compound other than the silane compound is used as the second precursor, the second precursor is added to water (or an alcohol aqueous solution to which an alcohol is added if necessary) in advance, such as sodium hydroxide. Add basic material. The addition amount of the basic substance is preferably about equimolar to the silicon atom in the second precursor. When a basic substance is added to a solution containing a second precursor other than a silane compound, a part of the Si— (O—Si) ₄ bond already formed in the second precursor is cleaved, resulting in a uniform solution. can get. Since the amount of basic substance contained in the solution affects the yield and porosity of the complex, after a homogeneous solution is obtained, a dilute acid solution is added to the solution, and excess base present in the solution is added. Neutralize sex substances. The amount of the diluted acid solution added is preferably an amount corresponding to 1/2 to 3/4 times moles of silicon atoms in the second precursor.

[2.1.2 Surfactant]
The surfactant serves as a template for forming mesopores. In the present invention, as the surfactant, any of a cationic surfactant, an anionic surfactant, and a nonionic surfactant can be used.

Specific examples of the cationic surfactant include alkyl quaternary ammonium salts represented by the following formula (2).
CH ₃ — (CH ₂ ) _n —N ⁺ (R ₁ ) (R ₂ ) (R ₃ ) X ⁻ (2)
(2) wherein, R _1, R _2, R ₃ each represent an alkyl group having 1 to 3 carbon atoms. R ₁ , R ₂ and R ₃ may be the same as or different from each other. In order to facilitate aggregation (formation of micelles) between alkyl quaternary ammonium salts, it is preferable that R ₁ , R ₂ , and R ₃ are all the same. Further, at least one of R ₁ , R ₂ , and R ₃ is preferably a methyl group, and all are preferably methyl groups.
(2) In the formula, X represents a halogen atom. Although the kind of halogen atom is not particularly limited, X is preferably Cl or Br in view of availability.
(2) In formula, n represents the integer of 7-21.

Specific examples of the anionic surfactant include fatty acid salts, alkyl sulfonates, and alkyl phosphates.
Specific examples of nonionic surfactants include polyethylene oxide nonionic surfactants and primary alkylamines.

  When synthesizing the complex, one type of surfactant may be used, or two or more types may be used. However, since the surfactant serves as a template for forming mesopores in the composite, the type greatly affects the shape of the mesopores. In order to synthesize a complex having more uniform mesopores, it is preferable to use one type of surfactant.

[2.1.3 Solvent]
As the solvent for dissolving the raw material, an optimum solvent is selected according to the kind of the precursor. As the solvent, water, alcohol, a mixed solvent of water and alcohol, or the like is usually used. The alcohol may be any of monovalent alcohols such as methanol, ethanol, and propanol, divalent alcohols such as ethylene glycol, and trivalent alcohols such as glycerin.

[2.1.4 Catalyst]
In order to polycondensate a precursor and obtain a mesopore alignment material, a catalyst is generally added to a solution containing the precursor. In the present invention, a basic catalyst is used as the catalyst. In the case where a precursor containing a silane compound represented by the formula (1) is subjected to condensation polymerization in the presence of a surfactant, plate-like particles having mesopores oriented in the thickness direction can be obtained by using a basic catalyst. .
Examples of such basic catalysts include sodium hydroxide and aqueous ammonia.

[2.1.5 Solution composition]
Solution composition such as solvent type, precursor type and concentration, surfactant type and concentration, catalyst type and concentration, etc. is optimal depending on the type of starting material and the properties required for the mesopore orientation material It is preferable to select one.

  For example, the alcohol content in the solvent affects the particle size, particle size distribution, micelle structure and the like of the particles. In order to synthesize plate-like particles having mesopores oriented substantially perpendicular to the plate surface, it is preferable to use water as the solvent.

Further, for example, if the concentration of the precursor in the solution is too low, the yield of the particles decreases, or it becomes difficult to control the particle size and particle size distribution of the particles.
On the other hand, if the concentration of the precursor in the solution is too high, it becomes difficult to control the particle size and particle size distribution, and the uniformity of the particle size decreases.
In order to synthesize plate-like particles having mesopores oriented substantially perpendicular to the plate surface, the solvent is preferably 10 to 80 mol with respect to 0.1 mol of the precursor.

For example, if the amount of the surfactant is too small, the amount of the surfactant is insufficient and continuous micelles cannot be formed.
On the other hand, when the amount of the surfactant becomes excessive, a lamellar substance is generated, and when the surfactant is removed, only a laminate of sheets is obtained, and no mesoporous material is obtained. In order to synthesize plate-like particles that are oriented almost vertically, the surfactant is preferably 0.01 to 0.1 mol with respect to 0.1 mol of the precursor.

For example, if the concentration of the basic catalyst in the solution is too low, the yield of the particles is extremely reduced.
On the other hand, if the concentration of the basic catalyst in the solution is too high, synthesis of the mesopore alignment material may be difficult.
In order to synthesize plate-like particles having mesopores oriented substantially perpendicular to the plate surface, the basic catalyst is preferably 0.01 to 1.0 mol with respect to 0.1 mol of the precursor, More preferably, it is 0.05-0.5 mol.

[2.1.6 Production of Composite]
The plate-like composite is obtained by adding a precursor to a solution containing a surfactant and a basic catalyst and reacting at a predetermined temperature.
As the reaction conditions, optimum conditions are selected according to the type and concentration of the raw material. For example, when a mesopore alignment material is synthesized using only the silane compound represented by the formula (1a), first, the solution is stirred at room temperature, and then the solution is allowed to stand under heating (reflux). preferable. When the solution is stirred at room temperature, a solution in which the precursor and the surfactant are uniformly dispersed is obtained. Further, when such a solution is allowed to stand under heating, condensation of the mesopore skeleton can be advanced.
When the solution is stirred at room temperature, the number of rotations during stirring is preferably 300 to 500 rpm, and the stirring time is preferably 2 to 24 hours. When the solution is allowed to stand under heating, the heating temperature is preferably 80 to 97 ° C., and the standing time is preferably 24 to 48 hours.

  When a basic catalyst is added to the mixed solution containing the precursor, hydrolysis and partial polymerization of the precursor occur. When a surfactant is added to this solution, the surfactant forms micelles in the solution. This micelle becomes a supramolecular template, and a hydrolyzed or partially polymerized precursor is adsorbed around it. Since the partial polymer does not enter the interior of the micelle, the interior of the micelle eventually becomes a pore portion. Therefore, the pore diameter inside the mesopore alignment material can be controlled by controlling the molecular chain length of the surfactant.

  The micelles adsorbing the precursor will eventually be arranged in a stable direction. Moreover, when the silane compound represented by the formula (1) is used as a precursor and reacted under basic conditions, micelles having relatively short lengths are arranged almost in parallel. When this is further reacted in solution, the precursor undergoes condensation polymerization between the arranged micelles. As a result, a plate-like composite in which mesopores are arranged in the thickness direction and the surfactant is filled in the mesopores is obtained.

[2.2 Surfactant removal step]
The surfactant removal step is a step of removing the surfactant from the complex. The method for removing the surfactant is not particularly limited, and it is preferable to select an optimum method according to the type of the surfactant, the structure of the complex, and the like.
As a method for removing the surfactant, specifically,
(1) A firing method of firing the composite at 300 to 1000 ° C. (preferably 300 to 600 ° C.) for 30 minutes or more (preferably 1 hour or more) in the air or under an inert atmosphere,
(2) The composite is immersed in a surfactant good solvent (for example, methanol containing a small amount of hydrochloric acid) and stirred while heating at a predetermined temperature (eg, 50 to 70 ° C.), and the interface in the composite An ion exchange method to extract the active agent,
and so on.

[3. Action of mesopore alignment material]
Conventional methods for orienting mesopores in a specific direction required direct orientation of the surfactant under special conditions such as high magnetic field, photoelectric field, and light.
On the other hand, as a method for orienting mesopores under relatively mild conditions, a method is known in which ZrOCl ₂ .8H ₂ O is added to TEOS and polycondensation is performed under acidic conditions. However, this method has a drawback that Zr ions remain on the pore surface. Further, the aspect ratio of the synthesizable powder remains below 8.

On the other hand, when synthesizing a mesopore alignment material, at least Z ₃ Si—CH ₂ —CH ₂ —SiZ ₃ is used as a precursor for forming an organic-inorganic hybrid skeleton, When the synthesis is performed, a mesopore alignment material having a relatively high aspect ratio and having mesopores oriented in the thickness direction under stirring and standing at 100 ° C. or lower is obtained. When the production conditions are optimized, plate-like particles having an aspect ratio of 8 or more and pores opened perpendicular to the bottom surface can be obtained.

Example 1
[1. Sample synthesis]
Water (190.62 g), a surfactant (octadecyltrimethylammonium chloride: C ₁₈ TMA ⁺ Cl ⁻ ) (5.95 g), and NaOH (2.8 g) were mixed and stirred at room temperature until a clear solution was obtained. BTEE (10.63 g) serving as the skeleton of the mesopore alignment material was added to the mixed solution and stirred (500 rpm) at room temperature for 24 hours. Furthermore, it was allowed to stand under heating at 97 ° C. (under reflux) (24 hours). As a result, a cloudy solution was formed. The powder was filtered from the solution and washed (water and ethanol).
Next, 500 mL of 1 wt% HCl solution (ethanol diluted) was added to 1 g of the product, and the surfactant was extracted at 60 ° C. for 15 hours.

[2. Test method]
[2.1 X-ray diffraction]
The X-ray diffraction pattern of the obtained mesopore alignment material (ethane-crosslinked organic-inorganic hybrid) was measured.
[2.2 Pore structure]
The BET specific surface area, pore volume, and pore size of the obtained mesopore orientation material were measured. In addition, SEM images and STEM images of the mesopore alignment material were taken.

[3. result]
[3.1 X-ray diffraction pattern]
FIG. 1 shows an X-ray diffraction pattern (left figure) and an SEM image (right figure) of a mesopore alignment material (ethane-crosslinked organic-inorganic hybrid). FIG. 1 shows that plate-like particles are obtained. In the left figure of FIG. 1, diffraction peaks corresponding to 4.8 nm, 2.82 nm, and 2.46 nm are peaks attributed to d (10), d (11), and d (20), respectively. It shows that 2D-hexagonal structure was formed.

[3.2 Pore structure]
FIG. 2 (a) and FIG. 2 (b) show the nitrogen adsorption isotherm and pore distribution curve of the mesopore orientation material, respectively.
The BET specific surface area and the pore volume were 751 m ² / g and 0.88 cc / g, respectively. Moreover, the average pore diameter by BJH method was 3.2 nm.

FIG. 3 shows an SEM image (same lot, 2 fields of view) of the mesopore alignment material. FIG. 3 shows that a plate-like powder having a width of 1600 to 2000 nm, a thickness of 150 to 200 nm, and an aspect ratio of 10 to 11 is obtained.
FIG. 4 shows a STEM image of the mesopore alignment material. From FIG. 4, it can be seen that pores of about 3 nm are oriented substantially perpendicular to the plate surface of the plate-like particles.

  Although the embodiments of the present invention have been described in detail above, the present invention is not limited to the above embodiments, and various modifications can be made without departing from the scope of the present invention.

  The mesopore orientation material according to the present invention can be used for highly conductive materials, highly active catalysts, highly sensitive sensors, ultra-high density recording media, and the like.

Claims (2)

A mesopore orientation material having the following configuration.
(1) The mesopore alignment material includes an inorganic skeleton containing a Si—O—Si bond and a divalent organic group having one or more carbon atoms, and different Si atoms constituting the inorganic skeleton are between It consists of an organic-inorganic hybrid connected by the organic group.
(2) The mesopore alignment material includes a (—O) ₃ Si—CH ₂ —CH ₂ —Si (O—) ₃ structure.
(3) The mesopore orientation material is composed of plate-like particles, and has mesopores oriented substantially perpendicular to the plate surface of the plate-like particles. The aspect ratio of the plate-like particles is 8 or more,
The mesopore orientation material according to claim 1, wherein the plate-like particles have a width of 400 to 2000 nm.

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