JP2000281331A - Mesoporous body and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a porous body with porous pore walls, which has a peak at the diffraction angle corresponding to a specified d-value in a X-ray diffraction pattern by condensing and polymerizing an inorg. skeleton component and/or an inorg./org. composite skeleton component in the reaction system having less than a specified concn. of a nonionic surfactant. SOLUTION: The concn. of a nonionic surfactant is preferably <29.67 g/l. The mesoporous material shows one or more peaks at the diffraction angles corresponding to the d-value over 1 nm in a X-ray diffraction pattern. An inorg. skeleton component such as an alkoxysilane which forms a silicate skeleton and a polyethylene oxide-based nonionic surfactant as a template are mixed in a solvent such as water with the pH controlled to <=0.5 to condensate and polymerize them at 35 to 80 deg.C. The molar ratio of the skeleton component: surfactant:hydrochloric acid:solvent is preferably (0.042 to 0.175):(0.00073 to 0.030):1:27.79. The obtd. mesoporous body has >=2 nm center pore diameter and has >=60% of the whole pore volume in the pores of diameters within ±40% of the center pore diameter.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a technique relating to a mesoporous material which can be used as an adsorption / catalyst material useful for adsorption separation or selective catalytic reaction.

[0002]

2. Description of the Related Art Mesoporous molecular materials such as inorganic oxides having a pore diameter of 1.5 to 30 nm, which is larger than the pores of zeolite, and having a uniform and regularly arranged pore diameter. There is a sieve (hereinafter, referred to as a mesoporous body).

The mesoporous material is produced by heating a layered silicate mineral (kanemite) in an aqueous solution of alkyltrimethylammonium to form a three-dimensional silicate skeleton, and then removing the surfactant. There is FSM-16 (T. Yanagisawae)
t al. Bull. Chem. Soc. , Jp
n. , 63, 988 (1990); Inagaki
et al. , J. et al. Chem. Soc. Chem.
Commun. , 680 (1993)). Another example is that sodium silicate, silica, or Si alkoxide is heated in an aqueous solution of a surfactant to form a skeleton by condensing silicate around micelles formed by the surfactant or in gaps. Manufactured by removing a surfactant, for example, M41S (MCM-41, MC
M-48) (CT Kresge et a)
l. , Nature, 359, 710 (1992),
J. S. Beck et al. , J. et al. Am. Che
m. Soc. , 114, 10834 (1992)). Initially, a mesoporous material having a structure of SiO ₂ or SiO ₂ —Al ₂ O ₃ was synthesized, and thereafter, a metallosilicate ( ^{Mn +} , where n represents a charge of the metal) containing metal in a silicate skeleton ( A composition having the composition of SiO ₂ -MO _{n / 2} ) was synthesized. More recently, it contains no _{Si A1 2 O 3, TiO 2} , Nb 2 O 5, SnO 2, Zr
A mesoporous body of a transition metal oxide such as O ₂ has been synthesized. These mesoporous material, since it has to having pores enough to be structurally captures molecules larger enough, the very thin pore wall structure of about 1 nm, about 1000 m ² / G large specific surface area and about 1c
It has the feature of having a large pore volume of c / g. For this reason, even with a reaction catalyst or an adsorbent for a functional organic compound or a molecule of a normal size, such as a molecule having a molecular diameter that is too large to enter the pores of the zeolite, the pores can be quickly dispersed. Can be diffused. Therefore,
Such mesoporous materials are expected to be used as a high-speed catalytic reaction that requires a high-speed reaction or as a large-capacity adsorbent capable of adsorbing a large amount of adsorbate.

Attempts have also been made to introduce an organic group into the surface of the inorganic skeleton of these mesoporous materials, that is, the inner surfaces of the pores, to give the mesoporous substance a selective adsorption ability or a specific catalytic function. In addition to the surface treatment of the mesoporous body, attempts have been made to introduce an organic substance at the stage of synthesizing the mesoporous body. These modified mesoporous materials were intended to impart new catalytic properties and adsorption properties by organically modifying the pore skeleton and pore walls.

In recent years, as a nonionic surfactant, a mesoporous material using a triblock copolymer as a mesopore template has been obtained. This nonionic activator is (E
O) x (PO) y (EO) x [EO = ethylene oxide, PO = propylene oxide].
In particular, such a mesoporous material has a very thick pore wall structure of about 3 to 6 nm.

[0006]

As described above, various attempts have been made to modify the pore wall of the mesoporous material compositionally to modify the adsorption characteristics and the catalytic characteristics. No attempt has been made to modify the pore wall structurally by distributing pores (micropores) on the pore wall itself.

[0007]

Means for Solving the Problems The present inventors have focused on a new form of a mesoporous body, in which a pore wall is made porous separately from regularly arranged pores. The present invention has been completed. That is, the present invention relates to a mesoporous material having one or more peaks at a diffraction angle corresponding to a d value of 1 nm or more in an X-ray diffraction pattern, wherein the pore walls of the porous material are porous. I will provide a. In this mesoporous material, a mesoporous material having a center pore diameter of 2 nm or more in a pore diameter distribution curve is also provided. In the present invention, the central pore diameter in the pore diameter distribution curve is 2 nm or more,
Within a range of ± 40% of this central pore diameter, 60
% Or more, and a mesoporous body is provided, wherein pore walls between pores are porous. Furthermore, the present invention also provides a mesoporous body in which the composition of the pore walls is an oxide containing silicon. According to these inventions, since the pore walls are porous, adsorption / catalytic properties and the like are exhibited not only in the pores but also in the pores (micropores) of the pore walls.

[0008] The present invention also provides a mesoporous method for condensation-polymerizing an inorganic skeleton component and / or an inorganic / organic composite skeleton component in a reaction system in which the concentration of a nonionic surfactant is less than 29.67 g / l. A method for producing a body is provided. In the method for producing a mesoporous material, a production method in which the skeleton component is 0.012 mol or more per 1 g of the surfactant is also provided. According to this manufacturing method, the pore walls separating the pores can be formed porous. As a result, a porous body having adsorption / separation characteristics in the pores and the pores (micropores) of the pore wall is obtained.

[0009]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, embodiments of the present invention will be described in detail. (Mesoporous Body) (X-ray Diffraction Pattern) The mesoporous body of the present invention preferably has one or more peaks at a diffraction angle corresponding to a d value of 1 nm or more in the X-ray diffraction pattern. This is because, by having a regular pore structure, various properties are further provided by the porous pore walls while sufficiently exhibiting the catalytic properties and adsorption properties of the mesoporous body. The X-ray diffraction peak means that a periodic structure having a d value corresponding to the peak angle is present in the sample. The X-ray diffraction pattern reflects a structure in which pores having a diameter of 1 to 30 nm are regularly arranged at intervals of 1 nm or more. That is, it can be said that the mesoporous body having such a diffraction pattern has uniform pore structure and pore diameter from the regularity of the structure indicated by the diffraction pattern. More preferably, it is preferable to have one or more peaks at a diffraction angle corresponding to a d value of 5 nm or more.

(Pore Size Distribution) In the mesoporous material of the present invention, it is preferable that 60% or more of the total pore volume is included in a pore range of ± 40% of the central pore diameter in the pore diameter distribution curve. The pore size distribution curve is determined as follows. The pore diameter distribution curve is, for example, a curve obtained by plotting a value (dV / dD) obtained by differentiating the pore volume (V) with the pore diameter (D) with respect to the pore diameter (D). D of the pore distribution curve
The pore diameter at which the V / dD value is the largest (indicating the maximum peak) is called the center pore diameter. The pore size distribution curve is derived from various adsorption formulas based on, for example, an adsorption isotherm obtained by measuring the adsorption amount of nitrogen gas. The method for measuring the adsorption isotherm is illustrated below. The most commonly used gas in this method is nitrogen.

First, the mesoporous material is heated to liquid nitrogen temperature (-1
(96 ° C.), nitrogen gas is introduced, and the adsorption amount is determined by a constant volume method or a gravimetric method. The pressure of the introduced nitrogen gas is gradually increased, and the adsorption isotherm is created by plotting the adsorption amount of the nitrogen gas with respect to each equilibrium pressure.
From this adsorption isotherm, Cranston-Inklay
The pore size distribution curve can be obtained by a calculation formula such as the Pollmore-Heal method, the BJH method, or the like. Then, for example, when the maximum peak in the pore diameter distribution curve is at 3.00 nm, the central pore diameter is 3.00 nm.
Becomes At this time, "the pore range of ± 40% of the central pore diameter in the pore diameter distribution curve includes 60% or more of the total pore volume" means that the pore diameter is in the range of 1.80 to 4.20 nm. Occupies 60% or more of the total pore volume (the total volume of pores having a pore diameter of 50 nm or less, which is the upper limit measured by a gas adsorption method). Specifically, the pore diameter in the pore distribution curve is 1.8.
This means that the integral value of the pore volume of the pores at 0 nm to 4.20 nm accounts for 60% or more of the total integral value of the curve. Such a “pore volume of 60% of the total pore volume falls within a range of ± 40% of the pore diameter showing the maximum peak in the pore distribution curve.
% Or more "means that the pore size is substantially sufficiently uniform. Therefore, the mesoporous body of the present invention exhibits a function as a molecular sieve based on the pores, and invents a high selectivity to a reaction product or a product of the catalytic reaction. This effect is extremely effective, for example, when performing a multi-component selective catalytic reaction.

[0012] The mesoporous material of the present invention preferably has a central pore diameter of 2 nm or more, preferably 30 nm or less. When the central pore diameter is in the range of 2 to 30 nm, a functional organic compound having a large molecular diameter can easily enter the pores, and the diffusion of the molecules in the pores can be performed quickly. Therefore, a high-speed catalytic reaction and adsorption can be performed. More preferably, it is 5 nm to 30 nm, and further preferably, it is 5 nm to 15 nm.

The pore shape of the mesoporous material of the present invention may be one that extends one-dimensionally in a tunnel shape or one in which three-dimensional box-like or spherical pores are combined.
The pore structure of the porous material of the present invention may be a two-dimensional hexagonal structure, a three-dimensional hexagonal structure (p6 mm,
p63 / mmc), cubic structure (Ia3d, Pm
3n), lamellar, irregular structures, etc., but are not limited thereto, and include porous materials of various structures.

(Skeleton Composition of Pore Wall) Such a porous body having mesopores has a pore wall of an inorganic skeleton or an inorganic / skeleton.
It has pore walls of an organic hybrid skeleton. That is, the pore walls in the mesoporous body of the present invention have an inorganic skeleton or an inorganic / organic hybrid skeleton.
The inorganic skeleton is composed of a polymer main chain of an inorganic oxide such as silicate. The atoms replacing the silicon atoms in the basic silicate skeleton, or the atoms added to the silicate skeleton are aluminum, titanium, magnesium, zirconium, tantalum, niobium, molybdenum, cobalt, nickel, gallium, beryllium, yttrium, lanthanum, hafnium, tin , Lead, vanadium, boron and the like. Other inorganic skeletons include inorganic oxides such as non-Si zirconia, titania, niobium oxide, tantalum oxide, tungsten oxide, tin oxide, hafnium oxide, and alumina, or the basic skeleton of these inorganic oxides. And a composite oxide in which an atom to be added to the silicate skeleton is incorporated.

Various organic groups and the like may be added to the side chain of such an inorganic basic skeleton. Examples of such a side chain include a thiol group or an organic group containing a thiol group, a lower alkyl group such as a methyl group and an ethyl group, a phenyl group, a carboxyl group, an amino group, and a vinyl group.

In the inorganic / organic hybrid skeleton, an organic group containing one or more carbon atoms is directly or directly attached to a metal atom constituting the main chain at the carbon atom. Linked through an oxygen atom.
The bond between the organic group and the polymer main chain may be at one point or at two or more points. In addition, the form of the main chain is not particularly limited, and various forms such as linear, network, and branched can be adopted.

The metal atoms in the main chain are not particularly limited, but include silicon, aluminum, zirconium, tantalum, niobium, tin, hafnium, magnesium, molybdenum, cobalt, nickel, gallium, beryllium, yttrium, lanthanum, lead, Vanadium, titanium and the like can be mentioned. Preferred are silicon, titanium, zirconium and aluminum. Among them, silicon is preferable. In the present invention, various metal atoms can be used alone or in combination of two or more.

In such a main chain, the carbon atom is 1
Alternatively, it is contained in the form of an organic group having two or more carbon atoms. One or more carbon atoms in this organic group are bonded to the metal atoms constituting the main chain at one or more points. The bonding site with the metal atom may be at the terminal of the organic group or at a site other than the terminal. The organic group is not particularly limited. In addition to various hydrocarbon groups such as hydrocarbons including alkyl chains, alkenyl chains, vinyl chains, alkynyl chains, cycloalkyl chains, benzene rings, and benzene rings, various organic functional groups such as hydroxyl groups, amino groups, carboxyl groups, and thiol groups And various organic compounds derived from compounds having one or more carbon atoms. The organic group can be used alone or in combination of two or more. The organic group bonded to the polymer main chain at two or more points is preferably a hydrocarbon group derived from an alkyl chain, and more preferably a hydrocarbon group derived from a linear alkyl chain having 1 to 5 carbon atoms. is there. Specific examples include an alkyl chain such as a methylene group (—CH ₂ CH ₂ —). Further, as a preferable organic group, a phenylene group (—C ₆ H ₄ —) can be exemplified.

As the atoms constituting the inorganic / organic hybrid main chain, in addition to metal atoms and carbon atoms,
Other atoms can be included. The other atom is not particularly limited, but is preferably an oxygen atom located between metal atoms. Specifically, Si
-O, Al-O, Ti-O, Nb-O, Sn-O, Z
r-O, and the like. These bonds correspond to the bonds between metal atoms and oxygen atoms contained in polymetalloxane of various transition metals such as polysiloxane and polyalloxane. These bonds may be used alone or in combination of two or more. Also,
It may contain atoms such as nitrogen, sulfur and various halogens.

Although the main chain structure of such an inorganic / organic hybrid system has been described, various kinds of metal atoms, organic functional groups, and inorganic functional groups are included in the side chain portion bonded to the atoms constituting the main chain. It may be added. For example, those having a thiol group, a carboxyl group, a lower alkyl group such as a methyl group or an ethyl group, a phenyl group, an amino group, a vinyl group and the like are preferable.

(Pore Wall Structure) In the present porous body, the pore walls having such a skeleton are porous. The pore wall being porous means that the pore wall has a large number of pores. Hereinafter, such pores existing in the pore wall are referred to as micropores. The pore size of the micropores is preferably 0.2 nm
Or more and 2 nm or less, more preferably 0.5 nm or more and 1.5 nm or less. Further, in order to provide a property different from the property derived from the pore structure of the porous body, it is preferable that the pore diameter of the micropore is smaller than the center pore diameter of the pores of the porous body. Preferably, it has micropores having a pore diameter of 0.2 nm or more and 2 nm or less with respect to a central pore diameter of 3 nm or more and 30 nm or less. More preferably, the micropores have a pore diameter of 0.5 nm or more and 1.5 nm or less with respect to a center pore diameter of 5 nm or more and 30 nm or less.

Detecting the presence of micropores in the mesoporous material,
Further, the t-plot method can be used to determine the pore volume and pore size distribution. The t-plot is a curve in which the adsorption amount (v) is plotted against the average film thickness (t) of the adsorption film (the x-axis is the average film thickness, and the y-axis is the adsorption amount).
Say. The t-plot is the adsorption isotherm of the mesoporous material (the amount of adsorption is plotted against the relative pressure of the adsorbed gas)
Can be obtained from To detect the presence of micropores, first, an adsorption isotherm of the mesoporous material is obtained. Then, an approximate curve for converting the relative pressure (P / Po) into the film thickness (t) of the adsorption layer is obtained from an appropriate standard isotherm, and the approximate curve is used to calculate the relative pressure in the adsorption isotherm of the mesoporous material. The pressure is converted to the thickness of the adsorption layer. Here, the standard isotherm is created using a material having a C value of the same BET specific surface area as the mesoporous material as a standard material. Specifically, a non-porous material having a similar composition is used. For example, if the mesoporous material sample is a silica material, a standard isotherm created using non-porous silica is used. In addition, about a t-plot method,
M. R. Bhambaniet al. , J. et al. Col
loid and Interface Sci. , 3
8, 109 (1972).

When there are no micropores in the mesoporous material,
The adsorption isotherm of the mesoporous sample coincides with the standard isotherm, and t
The plot is a straight line passing through the origin. On the other hand, when a micropore exists, the t-plotted straight line does not pass through the origin, and the intersection of the vertical axis (y-axis) and this intersection, that is, the y-intercept, is positive. The value of this y-intercept indicates the volume of the micropore.

Further, the pore diameter of the micropores can be determined by the MP method (R. SH. Mikhaiet a).
l. , J. et al. Colloid and Interfac
eSci. , 26, 45 (1968)). In this t-plot, for example, 4 ° from the origin, 4 to 4.5 °,
For each t value section of 4.5-5Å, the first, second,
Third: n linear slopes are created. One example is shown in FIG. In this linear slope, the average thickness (t) of the adsorption layer is obtained by the following equation. t (Å) = 10 ⁴ × (adsorption amount (V) / surface area (BE)
T)) From the above equation, the surface area at each linear slope can be determined. For example, the pore surface area having a thickness in the range of 4 to 4.5 ° is a difference between the surface area value obtained from the first slope and the surface area value obtained from the second slope. Until the inclination of the straight line of the linear slope does not decrease (indicating a state in which all the micropores are filled), the micropore volume V is calculated according to the following equation. Micropore volume V (cc / g) = 10 ⁻⁴ × (S ₁ −
S ₂ ) (t ₁ + t ₂ ) / 2

For each t-value interval, the obtained difference in pore volume ΔV = V _n −V _n−1 is calculated as the average pore diameter r (= (t _n +
The divided by t _n-1) / 2 _{difference) Δr (= r n -r n} -1), by plotting against mean pore diameter r, it is possible to obtain a distribution of the micropore. Figure 2 for an example
Shown in

In the present mesoporous material, the micropore volume is preferably 0.01 (ml / g) or more and 0.3 (ml / g) or less. This is because the characteristics of the micropores are easily developed. Further, more preferably, 0.05 (ml /
g) or more and 0.3 (ml / g) or less, more preferably 0.1 (ml / g) or more and 0.3 (ml / g) or less. The micropore volume is preferably 10% or more of the total pore volume. This is because having such a pore volume ratio makes it easy to exhibit the characteristics of the micropores. Further, it is more preferably 20% or more and 50% or less, and further preferably 30% or more and 50% or less.

(Thickness of Pore Wall) In the present mesoporous body, the thickness of the pore wall is preferably 2 nm or more. This is because it is necessary to ensure the strength, heat resistance and hydrothermal resistance of the pore wall, and it is possible to secure the volume of the micropore. The presence of a certain degree of strength and micropore volume allows the micropores to exhibit good adsorption / separation properties and catalytic properties. More preferably, it is 3 nm or more, further preferably, 4 nm or more, and most preferably 5 nm or more.
nm or more. The pore wall thickness is determined by the lattice constant a ₀ (a ₀ = d ₁₀₀ × 2 / 1.73) determined by X-ray diffraction.
It can be determined by subtracting the center pore diameter from 2).

Examples of the form of the porous body of the present invention include powders, granules, support membranes, free-standing membranes, transparent membranes, alignment membranes, spherical, fibrous,
Burning on the substrate, particles having a clear morphology of μm size, and the like can be given. The preferred form is a powder.

(Method for Producing Porous Body) The porous body of the present invention
Preferably, it can be obtained by the following production method. Basically, the porous body of the present invention is obtained by subjecting a skeletal component constituting the mesoporous body to polycondensation using a surfactant as a template (template) for obtaining a pore structure. Are obtained.

(Skeleton component) As the inorganic skeleton component forming the inorganic polymer main chain by condensation polymerization, alkoxysilane, sodium silicate or silica can be used. As the alkoxysilane, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane can be used. These skeletal components form a silicate skeleton. Further, an alkylalkoxysilane having a lower alkyl group such as methyltrimethoxysilane and ethyltrimethoxysilane, an alkoxysilane having another organic group or a functional group, or the like can also be used. Other examples of the organic group include a phenyl group.
Examples of the functional group include an amino group, a carboxyl group, and a thiol group. When these organic groups or functional group-containing alkoxysilanes are used, the organic groups or functional groups are introduced into the silicate basic skeleton. These alkoxysilanes and the like can be used alone or in combination of two or more.

In addition to sodium silicate, silica or alkoxysilane, compounds containing other elements can be used as the inorganic skeleton component. For example, by adding pseudoboehmite, sodium aluminate, aluminum sulfate, or dialkoxyaluminotrialkoxysilane as an Al source, a mesoporous body having a basic skeleton composed of SiO ₂ —Al ₂ O ₃ can be synthesized. Further, Si is replaced with Ti, Zr,
Oxidized compounds replaced with metals such as Ta, Nb, Sn, Hf can also be used. Thus, a metallosilicate-based mesoporous material (SiO ₂ -M) containing various metals (M ^{n +} ; n is a charge of the metal) in the silicate skeleton.
On _{/ 2} ) can be obtained. For example, Ti (OC ₂
H ₅₎ titanate compounds such as _4, vanadyl sulfate (VOS
O ₄ ), boric acid (H ₃ BO ₃ ) or manganese chloride (M
By adding nCl ₂ ) to the alkoxysilane and performing a co-condensation reaction, a metallosilicate-based mesoporous material into which Ti, V, B or Mn has been introduced can be obtained.

Further, the following organometallic compounds can be used as the skeleton component of the inorganic / organic composite system which forms the inorganic / organic composite system skeleton by condensation polymerization. The organic group contained in the organometallic compound can introduce an organic group into the basic skeleton of the mesoporous body. The metal compound has an organic group bonded to two or more metal atoms, and an organic metal compound having one or more alkoxyl groups or halogen groups for each of the two or more metal atoms bonded to the organic group is used. That is, in this organometallic compound, the organic group has one or more carbon atoms, and the carbon atom is
It is bonded to two or more metal atoms.

Examples of the metal atom include, but are not limited to, silicon, aluminum, zirconium, tantalum, niobium, tin, hafnium, magnesium, molybdenum, cobalt, nickel, gallium, beryllium, yttrium, lanthanum, lead, and vanadium. Can be. As the organometallic compound used in the present invention, various kinds of metal atoms can be used alone or in combination of two or more kinds.

The organic group in this organometallic compound is 1
Or it has two or more carbon atoms, and has two or more bonding sites with a metal atom in the carbon atom. 1 in organic group
One carbon atom may have two or more bonding sites with a metal atom. In two or more different carbon atoms,
Each may have a bonding site with a metal atom. The organic group is not particularly limited except that it is bonded to two or more metal atoms. In addition to various hydrocarbons such as alkyl chains, alkenyl chains, vinyl chains, alkynyl chains, cycloalkyl chains, benzene rings, and hydrocarbons containing benzene rings,
Various kinds of organic groups such as a hydroxyl group, a carboxyl group, and a thiol group, and an organic group derived from a compound having one or more carbon atoms can be used. In particular,
Methylene group _(-CH 2 CH ₂ -) alkyl chain or a phenylene group such as _(-C 6 _{H 4} -) is.

Further, the present organometallic compound has one or more alkoxyl groups or halogen groups at each metal atom to which the organic group is bonded. The hydrocarbon group constituting the alkoxyl group is a chain, cyclic or alicyclic hydrocarbon group. Preferably, it is an alkyl group, and more preferably, it is a chain alkyl group having 1 to 5 carbon atoms. As the halogen group, various halogen atoms, chlorine, bromine, fluorine, iodine and the like can be used. An alkoxyl group or a halogen group is attached to each metal atom to which an organic group is bonded.
It may have at least one, and may have more alkoxyl groups or halogen groups. Specific examples of such an organometallic compound include an organometallic compound having a metal alkoxyl group or a metal halogen group at both ends of an organic group. For example, (CH ₃ O) ₃ S
_{i-CH 2 -CH 2 -Si (} OCH 3) 3 is. -C
(CH ₃ O) ₃ Si—C ₆ H ₄ —Si (OC (H ₂ —CH ₂ ) was replaced by another organic group such as —C ₆ H ₄ —.
H ₃ ) ₃ can also be used. In addition, Si is Al,
Compounds replaced with other metals such as Ti, Zr, Ta, Nb, Sn, and Hf can also be used. Further, a compound in which the methoxyl group is replaced with a halogen group can also be used. Here, the alkoxyl group and the halogen group are hydrolyzable groups in the condensation polymerization reaction.

The organometallic compound may contain, in addition to metal atoms and organic groups, other atoms and organic or inorganic functional groups. The other atoms and functional groups are not particularly limited. An atom such as nitrogen, sulfur, various halogens, or a functional group containing these atoms may be contained. Thus, as the organometallic compound, various combinations of the above-described various organic groups and various metal atoms can be obtained. The organometallic compound is
One type or a combination of two or more types can be used. Further, only this organic metal compound may be used as a skeleton component, or another skeleton component such as alkoxysilane and this organic metal compound may be used as a skeleton component.

(Template) As a surfactant serving as a template, a nonionic surfactant can be used. It is not particularly limited as long as it is a nonionic surfactant.For example, it is possible to use a polyethylene oxide nonionic surfactant having a hydrocarbon chain as a hydrophobic portion and polyethylene oxide as a hydrophilic portion. it can. As such a surfactant, C ₁₆ H
₃₃ (OCH ₂ CH ₂ ) OH (hereinafter, such a structure is abbreviated as C ₁₆ EO ₂ ), C ₁₂ EO ₄ , C
₁₆ EO ₁₀ , C ₁₆ EO ₂₀ , C ₁₈ EO ₁₀ , C
₁₆ EO ₂₀ , C ₁₈ H ₃₅ EO ₁₀ , C ₁₂ E
O ₂₃ and C ₁₆ EO ₁₀ can be exemplified.

As the hydrophobic portion, there are various sorbitan fatty acid esters having a fatty acid such as oleic acid, lauric acid, stearic acid and palmitic acid. Specifically, CH ₃ C (CH ₃ ) CH ₂ C (CH ₃ ) ₂ C ₆ H ₄
(OCH ₂ CH ₂ ) xOH (x is an average of 10) Tr
itonX-100 (Aldrich), polyethylene oxide (20) sorbitan monolaurate (Twe
en20, Aldrich) and polyethylene oxide (20) sorbitan monopalmitate (Tween4
0), polyethylene oxide (20) sorbitan monostearate, polyethylene oxide (20) sorbitan monooliate (Tween 60), sorbitan monopalmitate (Span 40) and the like. Polyethylene oxide-based nonionic surfactants can be 2
A combination of more than one type can also be used.

Further, a triblock copolymer having three polyalkylene oxide chains can also be used. In particular, a triblock copolymer having a polyethylene oxide chain-polypropylene oxide chain-polyethylene oxide chain can be used. This surfactant has a polypropylene oxide chain in the center,
It has a structure having polyethylene oxide chains on both sides and hydroxyl groups on both ends. The basic structure of this triblock copolymer is represented by (EO) x (PO) y (EO) x
Expressed as x and y are not particularly limited. For example, x = 5
To 110, y = 15 to 70. Preferably, x
= 15-20, y = 50-60. Note that (EO) x () is obtained by combining any X value selected from 15, 19, 18, 19, and 20 and a y value that is any integer included in y = 50 to 60. PO) y (EO) x is the preferred triblock copolymer. Further, a triblock copolymer ((PO) x (EO) y (PO) x) having a polypropylene oxide chain-polyethylene oxide chain-polypropylene oxide chain in which blocks are reversely arranged can also be used. Also for this copolymer, x and y are not particularly limited, but x = 5-110, y = 15
~ 70, more preferably x = 15 ~
20, y = 50-60.

As the triblock copolymer, specifically, EO ₅ PO ₇₀ EO ₅ , EO ₁₃ PO ₃₀ EO
_{13, EO 20 PO 30 EO 20} , EO 26 PO 39 E
O ₂₆ , EO ₁₇ PO ₅₆ EO ₁₇ , EO ₁₇ PO ₅₈
EO ₁₇ , EO ₂₀ PO ₇₀ EO ₂₀ , EO ₈₀ PO
₃₀ EO ₈₀ , EO ₁₀₆ PO ₇₀ EO ₁₀₆ , EO
₁₀₀ PO ₃₉ EO ₁₀₀ , EO ₁₉ PO ₃₃ E
O ₁₉ , EO ₂₆ PO ₃₉ EO _{26 and the} like can be used. Preferably, EO ₁₇ PO ₅₆ EO ₁₇ , EO ₁₇ PO
₅₈ EO _{17 and the} like. These triblock copolymers are commercially available from BASF and others, and
Triblock copolymers with the desired x and y values can be obtained on a small scale production level. The triblock copolymer can be used alone or in combination of two or more.

Further, a star diblock copolymer in which two polyethylene oxide chains-polypropylene oxide chains are respectively bonded to two nitrogen atoms of ethylenediamine can also be used. For example, (EO ₁₁₃ PO
₂₂ ) ₂ NCH ₂ CH ₂ N (PO ₂₂ EO ₁₁₃ ) ₂ ,
(EO ₃ PO ₁₈ ) ₂ NCH ₂ CH ₂ N (PO ₁₈ EO
₃ ) ₂ , (PO ₁₉ EO ₁₆ ) ₂ NCH ₂ CH ₂ N (E
O ₁₆ PO ₁₉ ) _{2 and the} like. The star diblock copolymer can be used alone or in combination of two or more.

Also, primary alkylamines and the like can be used as the nonionic surfactant. The pore size obtained can be controlled by the type of the surfactant used, specifically, by the length of the hydrophobic portion such as the alkyl chain of the surfactant.

(Polycondensation) Next, a mesoporous material is obtained from a reaction system (liquid) containing these skeleton components and a surfactant.
As the solvent in the polycondensation reaction, water, an organic solvent, a mixed solvent of water and an organic solvent, or the like can be used, but water is preferably used. The reaction system of the polycondensation reaction is not particularly limited to alkaline, neutral or acidic, but is preferably acidic. Specifically, the pH is preferably 1 or less. For example, hydrochloric acid, boric acid, bromic acid, fluoric acid, iodic acid, nitric acid, sulfuric acid, phosphoric acid, and the like can be used.
In the present invention, the acid can be used alone or in combination of two or more. The acid used in the present invention is preferably hydrochloric acid or sulfuric acid. It is particularly preferable to use hydrochloric acid to adjust the pH to 0.5 or less.

In order to obtain the porous body of the present invention, it is preferable that the concentration of the surfactant is low. Preferably, it is less than 29.67 g / l based on the total amount of the solvent used in the reaction system. This is because micropores are not formed at 29.67 g / l or more. Further, it is preferably at least 7 g / l. If the amount is less than 7 g / l, it is difficult to form micelles, and the upper limit concentration is preferably 29 g / l or less, more preferably 25 g / l or less, and even more preferably 20 g / l or less. The lower limit concentration is
10 g / l or more is preferable, and 12 g / l is more preferable.
That is all. In addition, about 15 g / l is preferable. Further, the skeleton component is preferably at least 0.012 mol per 1 g of the surfactant.

The mixing of each reaction system component is not particularly limited, but a surfactant is mixed with a solvent, and simultaneously or subsequently, an acid is added to form a preferable acidic atmosphere.
It is preferred to add a skeletal component. The temperature and time of the mixed system in which the surfactant and the acid are added are not particularly limited as long as a solution in which the surfactant is uniformly dissolved can be obtained.
It is preferable that the temperature is not lower than 100 ° C and not higher than 100 ° C.

If the surfactant and the skeletal component can be polycondensed, for example, if they are present in an acidic atmosphere, the polycondensation reaction starts. The skeleton component may be added all at once, or may be added little by little while stirring. The temperature at which the skeletal component is added is not particularly limited, but is preferably 35 ° C or more and 80 ° C or less, and more preferably 40 ° C or more and 45 ° C or less. The time required for addition is not particularly limited, but is preferably 1 minute or more.

In the reaction system, the molar ratio of each component,
That is, the molar ratio of the skeleton component: the surfactant: the hydrochloric acid: the solvent is 0.042 to 0.175: 0.00073 to 0.0.
030: 1: 27.79. In this case, the solvent is more preferably water. The molar ratio of the skeleton component: surfactant (skeleton component / surfactant) is
It is preferably 60 or more. It is more preferably 90 or more, and further preferably 120 or more. By increasing the molar ratio, the pore diameter can be reduced, and the pore wall thickness can be increased. At the same time, the pore volume can be reduced. Also, by increasing the molar ratio (by increasing the pore wall thickness), the micropore volume can be increased. Furthermore, since the pore volume decreases and the micropore volume increases with an increase in the molar ratio, the ratio (%) of the micropore volume to the pore volume can be increased. When the molar ratio is increased, the amount of the surfactant is reduced and / or the amount of the skeleton component is increased. When the concentration of the surfactant is not more than a certain concentration, specifically, less than 29.67 g / l, more preferably 15 g / l
If it is / l or less, an effect such as effectively increasing the micropore volume can be obtained by increasing the use amount of the skeleton component. The amount of the skeleton component used is preferably 0.012 mol or more per 1 g of the surfactant.

The polycondensation reaction temperature varies depending on the type and concentration of the surfactant and the skeletal component to be used.
It is performed in a range of not less than 100 ° C. and not more than 100 ° C. Preferably, 3
5 ° C. or more and 80 ° C. or less. In particular, when a triblock copolymer is used as a surfactant, the temperature is 40 ° C. or higher.
5 ° C. or lower is preferred. The lower the temperature, the higher the regularity of the product structure tends to be. Also, the lower the temperature, the smaller the pore diameter tends to be and the larger the pore wall thickness tends to be. The condensation polymerization time varies depending on the components of the reaction system, but is usually in the range of 8 hours to 24 hours. Further, the reaction may be performed in a standing state or a stirring state, or a combination of the stirring state and the standing state. Further, the temperature condition can be changed depending on the reaction state.

The pore diameter of the porous body can be controlled by adding a hydrophobic compound such as trimethylbenzene or triisopropylbenzene in addition to the surfactant.

(Hydrothermal treatment) After the polycondensation reaction, if necessary, a hydrothermal treatment is carried out. Before performing the treatment for removing the surfactant from the porous precursor (that is, the one in which the surfactant is still filled in the pores), a hydrothermal treatment is performed as follows. That is, the porous precursor is dispersed in an aqueous solution containing the same surfactant as used in the polycondensation reaction (typically, a surfactant concentration equal to or lower than that in the polycondensation reaction), The precursor is subjected to hydrothermal treatment within a range of 50 ° C. or more and 200 ° C. or less. Specifically, the reaction solution is heated as it is or after dilution. The heating temperature is preferably 60 ° C. or higher and 1
The temperature is not higher than 00 ° C, more preferably not lower than 70 ° C and not higher than 80 ° C. The pH at this time is slightly alkaline, and is preferably 8 or more and 8.5 or less. It may be adjusted appropriately with hydrochloric acid or sodium hydroxide. The processing time is not particularly limited, but is preferably 1 hour or more, and more preferably 3 hours to 8 hours. Further, the treatment may be continued for a long time, but if the treatment is carried out for a too long time, a remarkable difference in the effect is not observed. Note that the hydrothermal treatment is preferably performed while stirring the treatment liquid. After this hydrothermal treatment, the precursor is filtered and dried, and an excess treatment liquid is removed. After the precursor is dispersed in the aqueous solution, a stirring treatment may be performed at room temperature for several hours before starting the hydrothermal treatment. Thereby, the following effects based on the hydrothermal treatment can be further enhanced.

As a result of the hydrothermal treatment as described above, the strength and structural regularity of the porous body after the removal of the surfactant can be improved. For this reason, a mesoporous body having excellent pore stability and structural regularity, that is, excellent uniformity of pore distribution, can be provided as compared with those not subjected to the hydrothermal treatment. Therefore, for example, by subjecting a porous precursor having a hexagonal structure to the present hydrothermal treatment, the size of the pores in the mesoporous body (final product) can be determined by the ± It can be easily uniformized to the extent that 60% or more of the total pore volume is included in the range of 40%.

(Removal of Surfactant) After the polycondensation reaction or after the hydrothermal treatment, the formed precipitate or gel is filtered,
If necessary, a solid product is obtained by washing and drying. The surfactant is then removed from the solid product. The removal of the surfactant from these solidified products includes a method of baking and a method of treating with a solvent such as water or alcohol. 300 ° C in the firing method
To 1000 ° C., preferably 400 to 700
Heat to below ℃. The heating time may be 30 minutes or more, but it is preferable to heat for 1 hour or more to completely remove the organic components. The atmosphere may be air, but a large amount of combustion gas is generated, so that an inert gas such as nitrogen may be circulated at the beginning of combustion.

The method of treating with a solvent or the like is performed by dispersing a solid product in a solvent having a high solubility for a surfactant and recovering the solid after stirring. As the solvent, those having a high solubility in a surfactant, for example,
Water, ethanol, methanol, acetone and the like can be used. In the case of treating with water, it is preferable to carry out the treatment in a range of 25 ° C. or more and 80 ° C. or less. To obtain sufficient solubility, a small amount of a cation component may be added. Substances containing a cation component to be added include hydrochloric acid, acetic acid, sodium chloride, potassium chloride and the like. The concentration of the cation is preferably 0.1 to 10 mol / l. The amount of the solid product dispersed in the ethanol solution is 100
The solid product is preferably 0.5 to 50 g per cc. The dispersion is preferably stirred at a temperature in the range of 25C to 100C. In particular, in the case of a nonionic surfactant, it may be extracted only with a solvent. In addition, by using water to which hydrochloric acid is added or water as a solvent, extraction of the surfactant may be facilitated in some cases. The pulverization, sieving, or molding may be performed before or after removing the surfactant.

As a preferred polycondensation method, as a skeleton component, a lower alkoxysilane having 1 to 5 carbon atoms such as tetramethoxysilane or tetraethoxysilane, or (CH ₃ O) ₃ Si—CH ₂ —CH ₂ — Si (OC
_{H 3) 3, (CH 3} O) 3 Si-C 6 H 4 -Si (OC
H ₃ ) _{3 and the} like, and (EO) x (P
O) The triblock copolymer represented as y (EO) x (provided that x = 5-110, y = 15-70, preferably x = 15-20, y = 50-60) is 29.67.
The polycondensation is carried out at a concentration of g / l, preferably 15 g / l or less, using hydrochloric acid under acidic conditions with water.

According to such a reaction system, in the X-ray diffraction pattern, a diffraction angle corresponding to a d value of 1 nm or more corresponds to 1
More than 60 peaks, and / or 60% or more of the total pore volume is included in the range of ± 40% of the central pore diameter, and the pore walls between the pores are porous. A mesoporous body is easily obtained. Further, in this porous body, a mesoporous body having a center pore diameter of 4 nm to 7 nm is easily obtained. In addition, the micropore volume is 0.05 g / l or more and 0.3
g / l or less (preferably, about 0.2 g / l),
Micropore diameters of 0.2 nm or more and 2 nm or less (preferably about 1.6 nm) are easily obtained.

As described above, the present invention can employ the following embodiments. (1) A porous body having one or more peaks at a diffraction angle corresponding to a d value of 1 nm or more in an X-ray diffraction pattern, wherein the center pore diameter in a pore diameter distribution curve is 2 nm or more, A mesoporous material, wherein 60% or more of the total pore volume is included in a range of ± 40% of the pore diameter, and pore walls between the pores are porous. (2) The mesoporous body according to (1), which has one or more peaks at a diffraction angle corresponding to a d value of 5 nm or more in an X-ray diffraction pattern. (3) The pore volume of the pore wall is 0.01 ml / g or more and 0.3 or more.
The mesoporous body according to the above (1) or (2), wherein the content is not more than ml / g. (4) The pore diameter of the pore portion of the pore wall is 0.2 nm or more and 2n.
m. The mesoporous body according to any one of (1) to (3) above, (5) The mesoporous body according to any one of (1) to (3), wherein the pore volume of the pore wall is 10% or more of the total pore volume. (6) The mesoporous body according to any one of (1) to (3), wherein the thickness of the pore wall is 3 nm or more. (7) Triblock copolymer represented by (EO) x (PO) y (EO) x (where x = 15 to 20, y
= 50-60) in a reaction system having a concentration of less than 29.67 g / l, a method for producing a mesoporous body, comprising condensation-polymerizing an inorganic skeleton component and / or an inorganic / organic composite skeleton component. (8) When the concentration of the triblock copolymer is 15 g /
1 or less. (9) The method according to (7) or (8), wherein the skeleton component is at least 0.012 mol per 1 g of the triblock copolymer.

[0057]

According to the present invention, a mesoporous material having separation / adsorption characteristics based on the porous structure of the pore wall can be provided.

[0058]

Embodiments of the present invention will be described below. Note that the present invention is not limited to the following embodiments. (Example 1) (Synthesis of mesoporous material) As a nonionic surfactant,
A triblock copolymer represented by the composition formula (EO) ₁₇ (PO) ₅₈ (EO) ₁₇ (hereinafter, simply referred to as P104; manufactured by BASF) was used, and tetraethyl silicate (TEOS) was used as a skeleton component. In the presence of P104, TEOS was hydrolyzed and condensed using hydrochloric acid as a catalyst. 1.76 g of P104 (0.00035 mol)
It was dissolved in 105 ml of ion-exchanged water, and 20 ml (0.24 mol) of 12N hydrochloric acid was added to the surfactant solution (total water amount: 6.67 mol, surfactant concentration: 14.67 g).
/ L). 3. In a water bath at 45 ° C., for this mixture,
73 g of TEOS (0.021 mol) are added at once,
Stir for 8 hours. Furthermore, it was left still in an 80 ° C. oil bath for 8 hours. The generated white precipitate was collected by suction filtration, sufficiently washed with a large amount of ion-exchanged water, and left overnight in a dryer at 45 ° C. The surfactant is removed from room temperature to 550 ° C. while flowing air (flow rate: 0.5 ml / min).
The temperature was raised over 2 hours until calcination was performed at 550 ° C. for 6 hours. As a result, a porous body (powder) of Sample 1 was obtained.

(Structural Analysis of Product) X
The RD pattern is shown in FIG. For sample 1, d =
A strong peak was found at 1.96 and a weak peak was found on the high angle side. The diffraction patterns are (100) and (1) from the low angle side.
The sample 1 is attributed to the diffraction planes of 10) and (120).
Was confirmed to have a hexagonal structure. FIG. 4A shows the nitrogen adsorption isotherm of sample 1, and FIG.
3 shows a pore distribution curve obtained by the JH method. From the pore distribution curve, the central pore diameter is 6.0 nm and the specific surface area is 717.
5 m ² / g, total pore volume (relative pressure P / P0 = 0.98
) Showed 1.11 ml / g. Lattice constant a ₀ (a ₀ = d ₁₀₀ × 2 / 1.73) determined by powder X-ray diffraction
From 2) and the difference in pore diameter determined by nitrogen adsorption measurement,
The pore wall thickness was 5.08 nm.

Using the nitrogen adsorption isotherm of the nonporous silica having a specific surface area of 38.7 m ² / g as a standard isotherm, the nitrogen adsorption isotherm of the obtained sample 1 was t-plotted to calculate the micropore volume. did. The data of the standard isotherm is shown in FIG. 5, and the approximate curves applied in each range of the relative pressure at the time of t-plot conversion are shown in FIG. FIG. 7 shows a graph obtained by t-plotting the nitrogen adsorption isotherm of Sample 1 using this approximate curve.
Shown in From this graph, it was found that Sample 1 had micropores and the total micropore volume was 0.057 ml / g. FIG. 8 shows a pore size distribution curve of micropores obtained by the MP method using the t-plot. According to this distribution curve, the pore size of the micropores is 1.71 nm.
Met. The results of these analyzes are shown in FIG.

(Examples 2 to 4)
56 g (0.0315 mol), 8.75 g (0.042
(Mol), and the same blending and operation as in Example 1 except that the amount was 11.04 g (0.053 mol), thereby obtaining porous bodies (powder) of Samples 2, 3 and 4. The nitrogen adsorption isotherms of these samples are shown in FIGS. FIG. 9 shows the results of analysis based on powder X-ray diffraction and nitrogen adsorption isotherm.
When combined with the results of Sample 1, the pore diameter was 6.0-4.8 as the molar ratio of the skeletal component / surfactant was increased.
It decreased to 6 nm. The specific surface area is 717.1 to 87
Increased to 4.8 m ² / g. The thickness of the pore wall increased from 4.36 to 6.46 nm as the charging ratio increased. The pore volume decreased to 1.11 to 0.44 ml / g.

Similarly to Example 1, the nitrogen adsorption isotherm of each of Samples 2 to 4 was t-plotted using the standard isotherm to calculate the micropore volume. Further, a micropore distribution curve was obtained by the MP method. FIG. 9 shows the results of the total micropore volume and micropore diameter for each charging ratio. When combined with the results of Sample 1, the total micropore volume was 0.057-0.2
In the range of 08 ml / g and the micropore size was 1.71.
１．５1.54 nm. From these results, when the surfactant concentration is equal to or lower than a certain concentration, the molar ratio of the skeleton component / the surfactant is increased, specifically, 60%.
By increasing in the range of １５０150, the micropore volume could be controlled. At the same time, the pore diameter and pore volume could be controlled. In addition, as the molar ratio was increased, the pore volume was reduced and the micropore volume was increased, so that the ratio (%) of the micropore volume to the pore volume was increased to 5.4 to 39.0%.

(Comparative Example) In order to examine that the micropore formation was closely related to the surfactant concentration, 3.56 g of P104 was used (the surfactant concentration was 29.67 g /
l) A comparative sample was obtained in the same manner as in Example 1 except for the amount of P104 used. This sample was obtained by powder X-ray diffraction.
Hexagonal structure was shown. The nitrogen adsorption isotherm is shown in FIG. From the obtained pore distribution curve, the central pore diameter is
The specific surface area was 850 m ² / g, and the pore wall thickness was 3.1 nm. FIG. 14 shows a graph obtained by t-plotting the adsorption isotherm using the standard isotherm.
The adsorption isotherm was consistent with the standard curve, with no microporosity present. The analysis results are shown in FIG.

Example 5 0.44 g of P104 (0.
(0.0009 mol) was dissolved in 26.5 ml of ion-exchanged water, and 5 ml (0.061 mol) of a 12N hydrochloric acid aqueous solution was added thereto (total water amount: 1.67 mol). This mixture is
While stirring vigorously at 5 ° C., the skeleton component (CH
₃ O) ₃ SiCH ₂ CH ₂ Si (OCH ₃ ) ₃ (BEM
e) 1.42 g (0.00525 mol) was slowly added and the mixture was stirred as it was for 10 hours. Within minutes of the addition of BEMe, a white precipitate precursor formed. Further, the mixture was stirred in a 70 ° C. water bath for 10 hours, and the precursor was filtered. The precursor was washed twice with 300 ml of ion-exchanged water, and then left in a dryer at 45 ° C. overnight. This was designated as precursor sample 5 (powder).

Example 6 In addition, 0.3 of precursor sample 5
5 g was dispersed in 100 ml of ethanol, exposed to an ultrasonic cleaner for about 15 minutes, and the precipitate was collected by filtration. After performing this operation twice, it was left in a dryer at 45 ° C. overnight to obtain a sample 6 (powder).

Example 7 0.44 g of P104 (0.
(0.0009 mol) in 26.5 ml of ion-exchanged water, and 5 ml of a 12N hydrochloric acid aqueous solution (HCl: 0.0
61 mol) (total water amount 1.67 mol). While stirring vigorously in a 45 ° C. water bath, 1.42 g of BEMe
(0.00525 mol) slowly and add 10
Stirred for hours. A white precipitate formed within minutes of the addition of the monomer. The mixture was further stirred in a 70 ° C. water bath for 10 hours.
Next, in a 70 ° C. water bath, 12 ml of a 3N aqueous sodium hydroxide solution (NaOH: 0.036 mol) was added to the reaction solution, and the mixture was stirred for 3 hours, and a white precipitate was filtered. Precipitation is 30
After washing twice with 0 ml of ion-exchanged water, it was left in a dryer at 45 ° C. overnight to obtain a precursor sample 7 (powder).

(Structural Analysis of Product) The structure of the product was analyzed by powder X-ray diffraction. FIG. 15 shows precursor sample 5
3 shows an XRD pattern in a low angle region of FIG. For this precursor, a strong peak at d = 92.91 ° (2θ = 0.945) was found in the low-angle region and a weak shoulder peak was found on the high-angle side.

FIG. 16 shows an XRD pattern of Sample 6.
Even after removal of the surfactant by the ethanol solvent, the skeletal structure was retained. d = 95.54 ° (2θ = 0.92
0). FIG. 17 shows an XRD pattern of the precursor sample 7. For this precursor, d = 94.91 ° (20
= 0.930) and a weak shoulder peak on the high angle side. By comparing with the precursor sample 5, the degree of polycondensation in the skeleton is improved and the regularity of the structure is improved by changing the pH of the reaction system from acidic to basic after the white precipitate is formed. Was.

Sample 6 was subjected to a nitrogen adsorption measurement. FIG. 18 shows a nitrogen adsorption isotherm. Relative pressure P / P0 = 0.
At around 5, a sharp rise in the amount of adsorption due to capillary condensation was observed, indicating that it had pores. FIG. 19 shows a pore distribution curve analyzed using the BJH method. From this, it was found that this porous body had a pore diameter of 4.55 nm. The BET specific surface area was 878.1 m ² / g. In addition, it was confirmed that the pore wall thickness was as large as 6.53 nm.

From the adsorption isotherm of Sample 6, micropore analysis was performed using the t-plot method and the MP method. FIG. 20 shows the result of t-plot conversion of the nitrogen adsorption isotherm of Sample 6. In the t-plot, the specific surface area shown in FIG.
The nitrogen adsorption isotherm of 7 m ² / g non-porous silica was used as the standard isotherm. The micropore volume was determined from the y-intercept of the t-plot, which indicated that it had a micropore volume of 0.208 ml / g. FIG. 21 shows a distribution curve of micropores by the MP method. The micropore diameter as determined by the MP method was 1.52 nm.

[Brief description of the drawings]

BRIEF DESCRIPTION OF DRAWINGS FIG. 1 is a diagram showing slopes representing the slope of each t value section in a plot of pore volume (V) and thickness (t).

FIG. 2 shows a distribution curve of micropores created based on FIG.

FIG. 3 is a view showing an XRD pattern of Sample 1.

FIG. 4 is a diagram showing a nitrogen adsorption isotherm (a) of sample 1 and a pore distribution curve (b) obtained by a BJH method.

FIG. 5 is a diagram showing data of a standard isotherm.

FIG. 6 is a diagram showing an approximate curve obtained based on a standard isotherm.

FIG. 7 is a graph showing a t-plot of a nitrogen adsorption isotherm of Sample 1;

8 is a diagram showing a pore size distribution curve of micropores obtained by the MP method using the t-plot of FIG. 7;

FIG. 9 is a diagram showing analysis results of samples 1 to 4 and a comparative example.

FIG. 10 is a diagram showing a nitrogen adsorption isotherm of Sample 2.

FIG. 11 is a diagram showing a nitrogen adsorption isotherm of Sample 3.

FIG. 12 is a diagram showing a nitrogen adsorption isotherm of Sample 4.

FIG. 13 is a diagram showing a nitrogen adsorption isotherm of a comparative sample.

FIG. 14 shows a diagram obtained by t-plotting a nitrogen adsorption isotherm of a comparative sample.

FIG. 15 is a view showing an XRD pattern of a precursor sample 5.

FIG. 16 is a view showing an XRD pattern of Sample 6.

FIG. 17 is a view showing an XRD pattern of a precursor sample 7.

18 is a diagram showing a nitrogen adsorption isotherm of Sample 6. FIG.

FIG. 19 is a diagram showing a pore distribution curve of Sample 6 by the BJH method.

FIG. 20 shows a diagram obtained by t-plotting a nitrogen adsorption isotherm of Sample 6.

21 shows a pore size distribution curve of micropores of Sample 6. FIG.

Continued on the front page F-term (reference) 4G066 AA18A AA22B AA61B AC22D AE20D BA24 BA25 BA26 BA31 FA05 FA07 FA21 FA37 4G069 AA08 AA12 AA14 BA07A BA07B BA21A BA21B BA23A BA23B BC16B BC50B BC51B01 EC06 ECB ECA ZA42B ZB03 ZB05 ZC02 ZC04 ZC05 ZC07 ZC09 ZD03 4G073 BA20 BA21 BA63 BB02 BB04 BB13 BB57 BB58 BB71 BC02 CZ01 CZ52 DZ04 FA15 FB41 FB42 FC13 FC18 GA03 GA11 GA12 GA13 GA14 GA19 UA01 UA06

Claims (6)

[Claims] 1. An X-ray diffraction pattern having a d of 1 nm or more.
A mesoporous body having one or more peaks at a diffraction angle corresponding to a value, wherein the pore walls of the porous body are porous. 2. The method according to claim 1, wherein the central pore diameter in the pore diameter distribution curve is 2
The mesoporous body according to claim 1, which has a diameter of at least nm. 3. The method according to claim 1, wherein the central pore diameter in the pore diameter distribution curve is 2
A mesoporous material having a diameter of not less than nm, and a range of ± 40% of the center pore diameter includes 60% or more of the total pore volume, and pore walls between the pores are porous. 4. The mesoporous body according to claim 1, wherein the composition of the pore wall is an oxide containing silicon. 5. The method according to claim 5, wherein the concentration of the nonionic surfactant is 29.67.
A method for producing a mesoporous body, comprising condensation-polymerizing an inorganic skeleton component and / or an inorganic / organic composite skeleton component in a reaction system of less than g / l. 6. The method for producing a mesoporous material according to claim 5, wherein a skeleton component per 1 g of the surfactant is 0.012 mol or more.