JP4596233B2 - Mesoporous material, air purification material, and method for producing mesoporous material - Google Patents

Description

  The present invention relates to a mesoporous material, an air purification material using the mesoporous material, and a method for producing the mesoporous material.

Conventionally, research on mesoporous materials for adsorption and storage of various substances has been conducted, and application to applications such as adsorbents, separation materials, and catalyst carriers has been studied. As such a mesoporous material, for example, silica mesoporous material MCM-41 obtained by polymerizing silica in a concentrated solution of a surfactant (CT Kresge et al., J. Am. Chem. Soc.,
114, 10834 (1992): Non-Patent Document 1) and silica mesoporous material FSM-16 obtained by allowing a surfactant to act on Kanemite, which is a kind of layered clay mineral (Japanese Patent Laid-Open No. 10-68719): Patent Document 1 However, these mesoporous materials have pores having a one-dimensional channel structure arranged in a hexagonal structure. The mesoporous material having such a one-dimensional channel structure is difficult to diffuse the adsorbing substance and the reaction substrate into the pores due to the pore structure, and the obtained adsorption performance and catalytic performance are not yet sufficient.

  In addition, US Pat. No. 5,098,684 (Patent Document 2) discloses MCM-48, which is a silica mesoporous material having a three-dimensional channel structure together with MCM-41. However, although MCM-48 has a three-dimensional channel structure, it has a 3D-Cubic Ia3d structure in which the pores of the tunnel structure are not connected to each other. It was not always enough.

Furthermore, Japanese Patent Application Laid-Open No. 2003-221209 (Patent Document 3) discloses a mesoporous material made of a metal oxide having a 3D-Cubic Fm3m structure which is a three-dimensional channel structure. However, even a mesoporous material made of a metal oxide having an Fm3m structure has a limit to the enlargement of the pore diameter, and in particular, aldehydes, benzene, toluene, The diffusion rate of adsorbed substances and the like in the pores is not always sufficient for harmful substances such as vinyl and other VOCs.
Japanese Patent Laid-Open No. 10-68719 US Pat. No. 5,098,684 JP 2003-221209 A CTKresge et al., J. Am. Chem. Soc., 114, 10834 (1992)

  The present invention has been made in view of the above-described problems of the prior art, and can quickly diffuse an adsorbed substance and a reaction substrate into pores, and is useful as an adsorbent, a separating material, a catalyst carrier, and the like. In particular, an object of the present invention is to provide a mesoporous material excellent as an air purification material for removing harmful substances such as VOC in the air, a method for producing the same, and an air purification material using the mesoporous material.

  As a result of intensive studies to achieve the above object, the present inventors have added a specific block copolymer type polyalkylene oxide surfactant and a specific metal salt in a non-aqueous solvent having a low water content. By generating a porous precursor, pores having a central pore diameter of 2 to 10 nm, which could not be obtained conventionally, are interconnected to form a 3D channel having a 3D-Cubic Im3m structure. A mesoporous material made of a metal oxide has been obtained, and it has been found that the object can be achieved by such a mesoporous material, and the present invention has been completed.

That is, the mesoporous material of the present invention is a mesoporous material made of a metal oxide, and pores having a central pore diameter of 2 to 10 nm are interconnected to form a 3D channel having a 3D-Cubic Im3m structure. And
Wherein the metal oxide, cobalt, copper, characterized in that an oxide of at least one metal selected from the group consisting of chromium and cerium.

  The air purification material of the present invention is characterized by comprising the mesoporous material of the present invention.

  The mesoporous material of the present invention exhibits excellent performance as an adsorbent, separation material, catalyst carrier, etc., and the air purification material of the present invention is excellent in removal performance against harmful substances such as VOC in the air. The reason for this is not necessarily clear, but the present inventors speculate as follows. That is, in the mesoporous material of the present invention, a 3D channel having a 3D-Cubic Im3m structure is formed by connecting pores having a central pore diameter of 2 to 10 nm, and the pore structure is relatively simple and fine. Since the pore size can be expanded, the adsorbent and reaction substrate can diffuse quickly into the pore without being restricted by the pore structure, and the pore structure has a cage structure. Therefore, the present inventors infer that the adsorbed substance and the reaction substrate are hardly re-released.

The method for producing a mesoporous material of the present invention includes:
In a non-aqueous solvent having a water content of 1% by weight or less, the following general formula (1):
HO (CH ₂ CH ₂ O) _a (CH ₂ CH (CH ₃ ) O) _b (CH ₂ CH ₂ O) _c H (1)
[In Formula (1), a represents an integer of 20 to 150, b represents 20 to 100, and c represents an integer of 20 to 150, respectively]
And / or the following general formula (2):
_{HO (CH 2 CH 2 O)} x (CH 2 CHCH (CH 3) O) y H (2)
[In Formula (2), x represents an integer of 30 to 60, and y represents an integer of 50 to 150, respectively]
And at least one selected from the group consisting of nitrates, sulfates, halides and acetates of at least one metal selected from the group consisting of cobalt, copper, chromium and cerium A first step of adding a seed metal salt to produce a porous precursor;
A second step of obtaining the mesoporous material by removing the surfactant from the porous material precursor;
It is the manufacturing method of the mesoporous material of the said invention characterized by including this .

  According to the method for producing a mesoporous material of the present invention, the mesoporous material of the present invention that could not be obtained conventionally, that is, a pore having a central pore diameter of 2 to 10 nm is interconnected to form a 3D-Cubic Im3m structure. Thus, a mesoporous material made of a metal oxide forming the three-dimensional channel can be obtained. The reason why a mesoporous material that forms a three-dimensional channel having a 3D-Cubic Im3m structure can be obtained by the method for producing a mesoporous material of the present invention is not clear, but a specific block copolymer that is a surfactant. The inventors speculate that the joint organization of a type of polyalkylene oxide and a metal oxide precursor derived from a specific metal salt is important.

  The “3D-Cubic Im3m” in the present invention is determined based on the space group notation and represents the symmetry of the pore structure. And the three-dimensional channel of such 3D-Cubic Im3m structure can be confirmed by measuring the X-ray diffraction pattern by the X-ray diffraction analysis method. In the mesoporous material of the present invention, 2Θ = 0.5-3 It is preferable that five diffraction peaks indexed by (110), (200), (211), (310), (222) are observed in the region of °. That is, since these five diffraction peaks indicate that the d-space ratio is √2: √4: √6: √10: √12, it is confirmed that the structure has a 3D-Cubic Im3m structure. Become.

  According to the present invention, a mesoporous material that can quickly diffuse an adsorbent and a reaction substrate into pores and exhibits excellent performance as an adsorbent, a separation material, a catalyst carrier, etc., and a VOC in the air Thus, it is possible to provide an air purification material having excellent removal performance against harmful substances such as the above.

  In addition, according to the method for producing a mesoporous material of the present invention, the mesoporous material of the present invention that could not be obtained conventionally, that is, a pore having a central pore diameter of 2 to 10 nm is connected to each other to form a 3D- It becomes possible to obtain a mesoporous material made of a metal oxide forming a three-dimensional channel having a cubic Im3m structure. Furthermore, in the method for producing a mesoporous material of the present invention, since a specific block copolymer type polyalkylene oxide which is a nonionic surfactant that is safe for the environment is used as the surfactant, Emission is sufficiently prevented.

  Hereinafter, the mesoporous material, the production method thereof, and the air purification material using the mesoporous material of the present invention will be described in detail according to preferred embodiments thereof.

(Mesoporous material)
The mesoporous material of the present invention is a mesoporous material made of a metal oxide, and pores having a central pore diameter of 2 to 10 nm are connected to each other to form a three-dimensional channel having a 3D-Cubic Im3m structure. Is. Since the mesoporous material of the present invention has such a pore structure, the diffusion resistance when the adsorbed substance and the reaction substrate are diffused into the pores is extremely small, and the channels cross each other. The diffusion rate of the adsorbed substance and the reaction substrate is remarkably improved as compared with MCM-48 that is not used and a mesoporous material having a conventional three-dimensional channel in which the pore diameter of the channel is actually small.

Examples of the metal element contained in the metal oxide according to the present invention include cobalt, copper, chromium and cerium .

Moreover, the use of transition metals as the metal element, mesoporous skeleton (framework) specificity by is composed of an oxide of a metal having a catalytic capability adsorption properties and catalytic activity of the present invention It is preferable because it tends to be played, and among these, it is more preferable to use cobalt, copper, chromium and cerium . In addition, the metal oxide concerning this invention may contain only 1 type of said metal element, and may be complex oxide containing 2 or more types of metal elements.

  The mesoporous material of the present invention comprises the above-mentioned metal oxide and has so-called mesosize pores (mesopores), and the central pore diameter is 2 to 10 nm, more preferably 4 to 10 nm. is there. In the mesoporous material of the present invention, when the central pore diameter is less than 2 nm, the adsorbed substance and the reaction substrate do not diffuse at a sufficient rate in the pores, and sufficient adsorption characteristics and catalytic activity are not exhibited. On the other hand, when the center pore diameter exceeds 10 nm, the specific surface area decreases, and the adsorption characteristics and catalytic activity decrease.

  The central pore diameter is a curve (pore diameter distribution curve) in which a value (dV / dD) obtained by differentiating the pore volume (V) with respect to the pore diameter (D) is plotted against the pore diameter (D). It is the pore diameter at the maximum peak. The pore size distribution curve can be obtained by the method described below. That is, the mesoporous material is cooled to a liquid nitrogen temperature (−196 ° C.), nitrogen gas is introduced, the adsorption amount is determined by a constant volume method or a gravimetric method, and then the pressure of the introduced nitrogen gas is gradually increased. Then, the adsorption amount of nitrogen gas with respect to each equilibrium pressure is plotted to obtain an adsorption isotherm. Using this adsorption isotherm, a pore size distribution curve can be obtained by a calculation method such as Cranston-Inklay method, Pollimore-Heal method, BJH method or the like.

  In such a mesoporous material of the present invention, it is preferable that 60% or more of the total pore volume is included in the range of ± 40% of the central pore diameter in the pore size distribution curve. Here, “60% or more of the total pore volume is included in the range of ± 40% of the pore diameter showing the maximum peak in the pore diameter distribution curve” means that the central pore diameter is 3.00 nm, for example. In this case, it means that the total volume of pores in the range of ± 40% of 3.00 nm, that is, 1.80 to 4.20 nm occupies 60% or more of the total pore volume. A mesoporous material satisfying this condition means that the pore diameter is very uniform.

The specific surface area of the mesoporous material of the present invention is not particularly limited, but is preferably 50 m ² / g or more. The specific surface area can be calculated as a BET specific surface area from the adsorption isotherm using the BET isotherm adsorption equation.

  Furthermore, the mesoporous material 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. The X-ray diffraction peak means that a periodic structure having a d value corresponding to the peak angle is present in the sample. Therefore, having one or more peaks at a diffraction angle corresponding to a d value of 1 nm or more means that the pores are regularly arranged at intervals of 1 nm or more.

  Further, the pores of the mesoporous material of the present invention are formed not only on the surface of the porous material but also on the inside. In the mesoporous material of the present invention, the pores are interconnected to form a three-dimensional channel having a 3D-Cubic Im3m structure. As described above, the three-dimensional channel having such a 3D-Cubic Im3m structure can be confirmed by measuring an X-ray diffraction pattern by an X-ray diffraction analysis method, and in a region of 2Θ = 0.5 to 3 ° (110 ), (200), (211), (310), and (222), if five diffraction peaks indexed, such five diffraction peaks have a d-space ratio of √2: √4: √. 6: √10: √12 indicates that it is a 3D-Cubic Im3m structure.

  In addition, it is not necessary for all the pores in the mesoporous material of the present invention to have a 3D-Cubic Im3m structure, and 70% or more of all the pores preferably have a 3D-Cubic Im3m structure.

  The shape of the mesoporous material of the present invention is not particularly limited, but powders, granules, support films, free-standing films, transparent films, alignment films, spheres, fibers, burning on a substrate, particles having a clear form of μm size, etc. Can be mentioned. Moreover, you may shape | mold and use as needed. Any molding means may be used, but extrusion molding, tablet molding, rolling granulation, compression molding, CIP and the like are preferable. The shape can be determined according to the place of use and method, and examples thereof include a columnar shape, a crushed shape, a spherical shape, a honeycomb shape, an uneven shape, and a corrugated plate shape.

(Method for producing mesoporous material)
In the method for producing a mesoporous material of the present invention, first, in a nonaqueous solvent having a water content of 1% by weight or less, the following general formula (1):
HO (CH ₂ CH ₂ O) _a (CH ₂ CH (CH ₃ ) O) _b (CH ₂ CH ₂ O) _c H (1)
[In Formula (1), a represents an integer of 20 to 150, b represents 20 to 100, and c represents an integer of 20 to 150, respectively]
And / or the following general formula (2):
_{HO (CH 2 CH 2 O)} x (CH 2 CHCH (CH 3) O) y H (2)
[In Formula (2), x represents an integer of 30 to 60, and y represents an integer of 50 to 150, respectively]
And at least one selected from the group consisting of nitrates, sulfates, halides and acetates of at least one metal selected from the group consisting of cobalt, copper, chromium and cerium A seed metal salt is added to produce a porous precursor (first step).

  The non-aqueous solvent used in the present invention is not particularly limited as long as it is a non-aqueous solvent having a water content of 1% by weight or less, but alcohols such as propanol, ethylene glycol, and ethanol, and ketones such as acetone and methyl ethyl ketone. Among them, propanol, ethylene glycol, and ethanol are preferable from the viewpoint of easy handling, safety, and cost. In addition, although the said non-aqueous solvent can also be used independently, it can also be used in combination of 2 or more types.

  Further, the water content in the non-aqueous solvent used in the present invention is required to be 1% by weight or less, and particularly preferably 0.5% by weight or less. When the water content in the non-aqueous solvent exceeds 1% by weight, the co-organization of the surfactant and the metal oxide precursor becomes unstable, and a 3D channel having a 3D-Cubic Im3m structure is formed. Not formed.

The metal salt used in the present invention is selected from the above-mentioned metal nitrates, sulfates, halides (fluorides, chlorides, etc.), and acetates, which are the types of metal oxides constituting the target mesoporous material. is selected depending on, inter alia cobalt from the viewpoint of the anion is easily thermally decomposed during baking, copper, at least one metal nitrate salt is selected from the group consisting of chromium and cerium are particularly preferable. In addition, although the said metal salt can also be used independently, it can also be used in combination of 2 or more types.

Furthermore, the block copolymer type surfactant used as a template in the present invention is represented by the following general formula (1):
HO (CH ₂ CH ₂ O) _a (CH ₂ CH (CH ₃ ) O) _b (CH ₂ CH ₂ O) _c H (1)
[In Formula (1), a represents an integer of 20 to 150, b represents 20 to 100, and c represents an integer of 20 to 150, respectively]
An ethylene oxide / propylene oxide / ethylene oxide (EO-PO-EO) triblock copolymer represented by: and / or the following general formula (2):
_{HO (CH 2 CH 2 O)} x (CH 2 CHCH (CH 3) O) y H (2)
[In Formula (2), x represents an integer of 30 to 60, and y represents an integer of 50 to 150, respectively]
An ethylene oxide / butylene oxide (EO-BO) diblock copolymer represented by:

  In addition, even when a surfactant other than these block copolymer type polyalkylene oxide surfactants is used as a template, the regularity of the crystal structure of the obtained mesoporous material is lowered, resulting in a 3D channel having a 3D-Cubic Im3m structure. Is not formed. Moreover, even if it uses as a template the surfactant whose a, b, c in the said General formula (1) or x, y in the said General formula (2) is less than the said minimum, the crystal | crystallization of the mesoporous body obtained The regularity of the structure is lowered, and a 3D channel having a 3D-Cubic Im3m structure is not formed. Furthermore, it is difficult to obtain a surfactant in which a, b and c in the general formula (1) or x and y in the general formula (2) exceed the upper limit.

  In the method for producing a mesoporous material of the present invention, the metal salt as a starting material and the block copolymer type surfactant as a template coexist in the non-aqueous solvent to produce a porous precursor, In this case, a method is generally used in which an organic / inorganic composite gel is first formed, and then the organic / inorganic composite is aged to obtain a porous precursor.

  That is, first, the block copolymer type surfactant as a template is dissolved in the non-aqueous solvent to form micelles. Such surfactant micelles are regularly arranged, and an organic / inorganic composite gel is formed by aggregation of metal salts around the surfactant. The temperature of the surfactant solution at this time is preferably 10 to 80 ° C., more preferably about room temperature.

  Next, the metal salt which is a metal precursor is added to the surfactant solution and stirred. By doing so, the hydrolysis of the organic / inorganic composite is promoted and ripened, and the metal oxide forms a three-dimensional channel having a 3D-Cubic Im3m structure around the three-dimensionally arranged surfactant. A body precursor is obtained.

  The temperature in such an aging process is preferably 15 ° C to 200 ° C, more preferably 30 ° C to 80 ° C. If this temperature is less than the above lower limit, hydrolysis tends not to be promoted sufficiently. On the other hand, if it exceeds the above upper limit, a reaction vessel having excellent pressure resistance is required and the cost tends to increase. The time in the aging process is preferably 1 minute to 14 days, more preferably 1 hour to 14 days, and particularly preferably 3 days to 7 days. If this time is less than the above lower limit, hydrolysis tends not to be promoted sufficiently. On the other hand, if the upper limit is exceeded, the hydrolysis reaches saturation, meaningless time is spent. Further, the pH of the solution in the aging process is preferably 1 to 14, and more preferably 3 to 8. If this pH is less than the above lower limit, the dissolution of the metal in the solvent tends to progress and the yield of the target porous body tends to deteriorate. On the other hand, if the upper limit is exceeded, the proportion of the metal precipitated as a hydroxide increases. The yield of the porous body tends to deteriorate. The pH of the solution in the aging process is further selected within a suitable range depending on the metal oxide constituting the target mesoporous material. For example, when obtaining a mesoporous material composed of copper oxide, 4 to 7 is preferable.

  In the first step of the method for producing a mesoporous material of the present invention, the ratio (molar ratio) of the metal salt, the non-aqueous solvent, and the block copolymer type surfactant is the mole of the block copolymer type surfactant. When the number is 1, it is preferable that the metal salt: nonaqueous solvent: block copolymer type surface activity = 50 to 150: 1000 to 2500: 1 (molar ratio). When the ratio of the metal salt is less than the lower limit, the amount of the surfactant with respect to the metal salt is excessively increased, and the unreacted surfactant tends to increase and the uniformity of the pores tends to decrease. When the upper limit is exceeded, the amount of the surfactant with respect to the metal salt becomes excessively small, and the pore formation tends to be incomplete. In addition, when the ratio of the non-aqueous solvent is less than the lower limit, the amount of the surfactant introduced into the metal salt is saturated, the amount of the unreacted surfactant remaining in the non-aqueous solvent is increased, and the pores are reduced. On the other hand, when the upper limit is exceeded, the surfactant is not sufficiently introduced into the metal salt and the formation of pores tends to be incomplete.

  Furthermore, in the first step of the method for producing a mesoporous material of the present invention, a further metal salt may be added in order to accelerate the aging of the organic / inorganic composite. As such further metal salts, metal salts of group 1 elements (alkali metal salts) and metal salts of group 2 elements (alkaline earth metal salts) in the long-period periodic table proposed by IUPAC are suitable. Among them, alkali metal halides (for example, potassium chloride) are particularly preferable. The addition amount of such a metal salt is preferably about 0.1 to 20.0 equivalents relative to the metal salt that is a precursor of the metal oxide constituting the mesoporous material. More preferably, it is about 5 to 2.0 equivalents.

  Next, in the method for producing a mesoporous material of the present invention, the block copolymer type surfactant is removed from the porous material precursor obtained in the second step to obtain a mesoporous material (second step). ).

  As a method for removing the surfactant in this way, for example, (i) the porous body precursor is immersed in a solvent having a high solubility in the surfactant (for example, methanol, ethanol, acetone, water), and the surfactant is And (ii) a method of removing the surfactant by firing the porous precursor in air or in an inert gas at 400 to 700 ° C. for 4 to 6 hours. According to the second step, the mesoporous material of the present invention comprising a metal oxide in which pores having a central pore diameter of 2 to 10 nm are interconnected to form a three-dimensional channel having a 3D-Cubic Im3m structure. Is obtained.

  In the production method of the present invention, the main components of decomposition products generated when the block copolymer type surfactant is removed by baking are water and carbon dioxide, and other cationic or anionic surfactants are removed by baking. The impact on the environment is small compared to the decomposition products that are produced. Thus, the method for producing a mesoporous material of the present invention is advantageous in that the discharge of environmentally hazardous substances is sufficiently prevented.

(Air purification material)
The air purification material of the present invention only needs to have the mesoporous material of the present invention. Even if the mesoporous material of the present invention itself constitutes the air purification material of the present invention, or the mesoporous material of the present invention. The air purification material of the present invention may be configured by supporting the body on another substrate. In the air purification material of the present invention, a material in which catalyst fine particles such as noble metals are supported on the mesoporous material of the present invention may be used.

  The shape of the air purification material of the present invention is not particularly limited, either powder, granule, support film, self-supporting film, transparent film, alignment film, spherical shape, fibrous shape, burning on the substrate, particles having a clear form of μm size, etc. Can be mentioned. Further, it may be formed into a columnar shape, a crushed shape, a spherical shape, a honeycomb shape, an uneven shape, a corrugated plate shape, or the like.

  EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example and a comparative example, this invention is not limited to a following example.

The F-127 block copolymer and the P-123 block copolymer used as the organic template in the examples and comparative examples are both block copolymer type surfactants manufactured by Aldrich, each having the following chemical formula:
(F-127)
HO (CH ₂ CH ₂ O) ₁₀₆ (CH ₂ CH (CH ₃ ) O) ₇₀ (CH ₂ CH ₂ O) ₁₀₆ H
(P-123)
HO (CH ₂ CH ₂ O) ₂₀ (CH ₂ CH (CH ₃ ) O) ₇₀ (CH ₂ CH ₂ O) ₂₀ H
It is represented by

Example 1
1 g of F-127 block copolymer was added to 10 g of propanol and stirred to dissolve. To the resulting solution, Cu (NO ₃ ) ₂ .3H ₂ O (0.01 mol) was added and stirred vigorously for 30 minutes. The gel composition at this time was 134 (Cu): 2230 (propanol): 1 (F-127) in molar ratio. Thereafter, the obtained sol was aged at 40 ° C. for 7 days, and then heated to 200 ° C. at a temperature rising rate of 1 ° C. per minute. Finally, an organic template, that is, an F-127 block copolymer was extracted with ethanol to obtain a mesoporous material made of copper oxide.

  When the X-ray diffraction pattern was measured, it was confirmed that a 3D channel having a 3D-Cubic Im3m structure was formed in the mesoporous material obtained in this example. Further, the d value, central pore diameter and specific surface area of the obtained mesoporous material were determined, and the obtained results are shown in Table 1.

(Example 2)
The same as Example 1 except that the addition amount of Cu (NO ₃ ) ₂ .3H ₂ O was 0.005 mol and the gel composition was 67 (Cu): 2230 (propanol): 1 (F-127) in molar ratio. Thus, a mesoporous material made of copper oxide was obtained.

  When the X-ray diffraction pattern was measured, it was confirmed that a 3D channel having a 3D-Cubic Im3m structure was formed in the mesoporous material obtained in this example.

(Example 3)
A mixed solvent of 5 g of ethylene glycol and 5 g of propanol was used in place of 10 g of propanol, and the gel composition was 134 (Cu): 1115 (propanol): 1080 (ethylene glycol): 1 (F-127) in molar ratio. A mesoporous material made of copper oxide was obtained in the same manner as in Example 1.

  When the X-ray diffraction pattern was measured, as shown in FIG. 1, the mesoporous material obtained in this example had (110), (200), (211) in the region of 2Θ = 0.5-3 °. , (310), and (222) are recognized as five diffraction peaks, and these five diffraction peaks have a d-space ratio of √2: √4: √6: √10: √12. As shown, it was confirmed that a three-dimensional channel having a 3D-Cubic Im3m structure was formed. Further, the d value, central pore diameter and specific surface area of the obtained mesoporous material were determined, and the obtained results are shown in Table 1.

Example 4
A mesoporous material made of copper oxide was obtained in the same manner as in Example 3 except that the aging temperature of the sol was 60 ° C.

When the X-ray diffraction pattern was measured, it was confirmed that a 3D channel having a 3D-Cubic Im3m structure was formed in the mesoporous material obtained in this example. Further, when the obtained mesoporous material was photographed with a transmission electron microscope, as shown in FIG. 2, a regular arrangement of bright spots and an orderly large channel were observed, and this mesoporous material had a three-dimensional cage structure. It was confirmed to have. In addition, FIG. 3 shows an N ₂ adsorption isotherm obtained for the mesoporous material obtained in this example, and FIG. 4 shows a pore distribution curve obtained by the SJK method.

(Example 5)
A mesoporous material made of copper oxide was obtained in the same manner as in Example 3 except that the aging time of the sol was 3 days.

  When the X-ray diffraction pattern was measured, it was confirmed that a 3D channel having a 3D-Cubic Im3m structure was formed in the mesoporous material obtained in this example. Further, the d value, central pore diameter and specific surface area of the obtained mesoporous material were determined, and the obtained results are shown in Table 1.

(Example 6)
1 g of F-127 block copolymer was added to 10 g of propanol and stirred to dissolve. To the resulting solution, Co (NO ₃ ) ₂ .3H ₂ O (0.01 mol) was added and stirred vigorously for 30 minutes. The gel composition at this time was 134 (Co): 2230 (propanol): 1 (F-127) in molar ratio. Thereafter, the obtained sol was aged at 40 ° C. for 7 days, and then heated to 200 ° C. at a temperature rising rate of 1 ° C. per minute. Finally, an organic template, that is, an F-127 block copolymer was extracted with ethanol to obtain a mesoporous material made of cobalt oxide.

  When the X-ray diffraction pattern was measured, it was confirmed that a 3D channel having a 3D-Cubic Im3m structure was formed in the mesoporous material obtained in this example. Further, the d value, central pore diameter and specific surface area of the obtained mesoporous material were determined, and the obtained results are shown in Table 1.

(Example 7)
The same as Example 6 except that the addition amount of Co (NO ₃ ) ₂ .3H ₂ O was 0.005 mol, and the gel composition was 67 (Co): 2230 (propanol): 1 (F-127) in molar ratio. Thus, a mesoporous material composed of cobalt oxide was obtained.

  When the X-ray diffraction pattern was measured, it was confirmed that a 3D channel having a 3D-Cubic Im3m structure was formed in the mesoporous material obtained in this example.

(Example 8)
A mixed solvent of 5 g of ethylene glycol and 5 g of propanol was used in place of 10 g of propanol, and the gel composition was 134 (Co): 1115 (propanol): 1080 (ethylene glycol): 1 (F-127) in molar ratio. A mesoporous material made of cobalt oxide was obtained in the same manner as in Example 6.

  When the X-ray diffraction pattern was measured, as shown in FIG. 5, the mesoporous material obtained in this example had (110), (200), (211) in the region of 2Θ = 0.5-3 °. , (310), and (222) are recognized as five diffraction peaks, and these five diffraction peaks have a d-space ratio of √2: √4: √6: √10: √12. As shown, it was confirmed that a three-dimensional channel having a 3D-Cubic Im3m structure was formed. Further, the d value, central pore diameter and specific surface area of the obtained mesoporous material were determined, and the obtained results are shown in Table 1.

Example 9
A mesoporous material made of cobalt oxide was obtained in the same manner as in Example 8 except that the sol aging temperature was 60 ° C. When the X-ray diffraction pattern was measured, it was confirmed that a 3D channel having a 3D-Cubic Im3m structure was formed in the mesoporous material obtained in this example.

(Example 10)
A mesoporous material made of cobalt oxide was obtained in the same manner as in Example 8 except that the aging time of the sol was 3 days. When the X-ray diffraction pattern was measured, it was confirmed that a 3D channel having a 3D-Cubic Im3m structure was formed in the mesoporous material obtained in this example.

(Example 11)
A mesoporous material made of cobalt oxide was obtained in the same manner as in Example 6 except that after the sol was aged, it was heated to 400 ° C. at a rate of 1 ° C. per minute.

  When the X-ray diffraction pattern was measured, it was confirmed that a 3D channel having a 3D-Cubic Im3m structure was formed in the mesoporous material obtained in this example. Further, the d value, central pore diameter and specific surface area of the obtained mesoporous material were determined, and the obtained results are shown in Table 1.

(Example 12)
1 g of F-127 block copolymer was added to 10 g of propanol and stirred to dissolve. Ce (NO ₃ ) ₂ .3H ₂ O (0.01 mol) was added to the resulting solution and stirred vigorously for 30 minutes. The gel composition at this time was 134 (Ce): 2230 (propanol): 1 (F-127) in molar ratio. Thereafter, the obtained sol was aged at 40 ° C. for 7 days, and then heated to 200 ° C. at a temperature rising rate of 1 ° C. per minute. Finally, an organic template, that is, an F-127 block copolymer was extracted with ethanol to obtain a mesoporous material composed of cerium oxide.

  When the X-ray diffraction pattern was measured, it was confirmed that a 3D channel having a 3D-Cubic Im3m structure was formed in the mesoporous material obtained in this example. Further, the d value, central pore diameter and specific surface area of the obtained mesoporous material were determined, and the obtained results are shown in Table 1.

(Example 13)
Example 12 except that the addition amount of Ce (NO ₃ ) ₂ .3H ₂ O was 0.005 mol and the gel composition was 67 (Ce): 2230 (propanol): 1 (F-127) in molar ratio. Thus, a mesoporous material composed of cerium oxide was obtained.

  When the X-ray diffraction pattern was measured, it was confirmed that a 3D channel having a 3D-Cubic Im3m structure was formed in the mesoporous material obtained in this example.

(Example 14)
A mesoporous material made of cerium oxide was obtained in the same manner as in Example 12 except that after the sol was aged, it was heated to 400 ° C. at a rate of 1 ° C. per minute.

  When the X-ray diffraction pattern was measured, it was confirmed that a 3D channel having a 3D-Cubic Im3m structure was formed in the mesoporous material obtained in this example. Further, the d value, central pore diameter and specific surface area of the obtained mesoporous material were determined, and the obtained results are shown in Table 1.

(Example 15)
A mixed solvent of 5 g of ethylene glycol and 5 g of propanol was used in place of 10 g of propanol, and the gel composition was 134 (Ce): 1115 (propanol): 1080 (ethylene glycol): 1 (F-127) in molar ratio. A mesoporous material composed of cerium oxide was obtained in the same manner as in Example 12.

  When the X-ray diffraction pattern was measured, it was confirmed that a 3D channel having a 3D-Cubic Im3m structure was formed in the mesoporous material obtained in this example.

(Example 16)
A mesoporous material composed of cerium oxide was obtained in the same manner as in Example 15 except that the aging temperature of the sol was 60 ° C. When the X-ray diffraction pattern was measured, it was confirmed that a 3D channel having a 3D-Cubic Im3m structure was formed in the mesoporous material obtained in this example.

(Example 17)
A mesoporous material composed of cerium oxide was obtained in the same manner as in Example 15 except that the aging time of the sol was 3 days.

  When the X-ray diffraction pattern was measured, as shown in FIG. 6, the mesoporous material obtained in this example had (110), (200), (211) in the region of 2Θ = 0.5-3 °. , (310), and (222) are recognized as five diffraction peaks, and these five diffraction peaks have a d-space ratio of √2: √4: √6: √10: √12. As shown, it was confirmed that a three-dimensional channel having a 3D-Cubic Im3m structure was formed. Further, the d value, central pore diameter and specific surface area of the obtained mesoporous material were determined, and the obtained results are shown in Table 1.

(Example 18)
1 g of F-127 block copolymer was added to 10 g of propanol and stirred to dissolve. Cr (NO ₃ ) ₂ · 9H ₂ O (0.01 mol) was added to the resulting solution and vigorously stirred for 30 minutes. The gel composition at this time was 134 (Cr): 2230 (propanol): 1 (F-127) by molar ratio. Thereafter, the obtained sol was aged at 40 ° C. for 7 days, and then heated to 200 ° C. at a temperature rising rate of 1 ° C. per minute. Finally, an organic template, that is, an F-127 block copolymer was extracted with ethanol to obtain a mesoporous material made of chromium oxide.

  When the X-ray diffraction pattern was measured, it was confirmed that a 3D channel having a 3D-Cubic Im3m structure was formed in the mesoporous material obtained in this example. Further, the d value, central pore diameter and specific surface area of the obtained mesoporous material were determined, and the obtained results are shown in Table 1.

(Comparative Example 1)
A silica mesoporous material having a 3D-Cubic Ia3d structure was prepared by the following procedure and used as a comparative sample. That is, first, 1.92 g of P-123 block copolymer and 11.24 g of sodium iodide were placed in a Teflon container, and further 45 g of water and 30 g of 4M HCl were added and dissolved. When the temperature of the obtained solution was maintained at 55 ° C. and then 4 g of tetraethyl orthosilicate (TEOS) was added as a silica precursor and stirred, crystals began to precipitate immediately after the addition of TEOS. After further stirring for 24 hours, the mixture was transferred to a constant temperature bath at 80 ° C. and further aged for 24 hours. The organic / inorganic composite thus obtained is filtered, washed with ion-exchanged water, and then fired in air at 500 ° C. for 6 hours, whereby the organic template in the organic / inorganic composite, ie, P− By removing the 123 block copolymer, a silica mesoporous material was obtained. The d value, central pore diameter and specific surface area of the obtained silica mesoporous material were determined, and the results obtained are shown in Table 1.

(Adsorption performance evaluation)
The adsorption performance of the mesoporous material obtained in Example 18 and Comparative Example 1 was evaluated according to the following procedure. That is, first, 1.0 g of the mesoporous material obtained in Example 18 and 1.0 g of the mesoporous material obtained in Comparative Example 1 were each gas-impermeable and sealed with 5 liters of air containing 80 ppm of toluene. Each bag was sealed and placed in a thermostatic bath maintained at 25 ° C. Thereafter, the toluene concentration in each bag was measured every predetermined time, and the mesoporous material obtained in Example 18 and the comparison were compared based on the difference from the blank concentration measured similarly without putting the mesoporous material in the bag. The toluene removal rate by the mesoporous material obtained in Example 1 was determined.

  The result of plotting the obtained toluene removal rate against the elapsed time is shown in FIG. As is clear from the results shown in FIG. 7, it was confirmed that the mesoporous material obtained in Example 18 was very excellent in toluene removal performance as compared with the mesoporous material obtained in Comparative Example 1.

(Comparative Example 2)
As an organic template, a block represented by HO (CH ₂ CH ₂ O) ₁₃ (CH ₂ CH (CH ₃ ) O) ₁₃ (CH ₂ CH ₂ O) ₁₃ H (hereinafter abbreviated as EO ₁₃ PO ₁₃ EO ₁₃ ). A mesoporous material composed of chromium oxide was obtained using the copolymer.

That is, 1 g of EO ₁₃ PO ₁₃ EO ₁₃ was added to 10 g of propanol and stirred to dissolve. Cr (NO ₃ ) ₂ · 9H ₂ O (0.01 mol) was added to the resulting solution and vigorously stirred for 30 minutes. The gel composition at this time was 134 (Cr): 2230 (propanol): 1 (EO ₁₃ PO ₁₃ EO ₁₃ ) in molar ratio. Thereafter, the obtained sol was aged at 40 ° C. for 7 days, and then heated to 200 ° C. at a temperature rising rate of 1 ° C. per minute. Finally, an organic template, that is, EO ₁₃ PO ₁₃ EO ₁₃ was extracted with ethanol to obtain a mesoporous material made of chromium oxide.

  When the X-ray diffraction pattern was measured, the mesoporous material obtained in this comparative example showed only a broad peak in the low angle region of 2Θ = 0.5 to 2 °, and the mesoporous material having no regular structure. It was confirmed to be a body.

(Comparative Example 3)
A mesoporous material made of chromium oxide was obtained using a surfactant represented by cetyltrimethylammonium bromide (hereinafter abbreviated as CTAB) as an organic template.

That is, 1 g of CTAB was added to 10 g of propanol and stirred to dissolve. Cr (NO ₃ ) ₂ · 9H ₂ O (0.01 mol) was added to the resulting solution and vigorously stirred for 30 minutes. The gel composition at this time was 134 (Cr): 2230 (propanol): 10 (CTAB) in molar ratio. Thereafter, the obtained sol was aged at 40 ° C. for 7 days, and then heated to 200 ° C. at a temperature rising rate of 1 ° C. per minute. Finally, an organic template, ie, CTAB, was extracted with ethanol to obtain a mesoporous material made of chromium oxide.

  When the X-ray diffraction pattern was measured, the mesoporous material obtained in this comparative example showed only a broad peak in the low angle region of 2Θ = 1 to 2 °, and the mesoporous material without regular structure. It was confirmed that there was.

  As described above, the mesoporous material of the present invention can quickly diffuse the adsorbed substance and the reaction substrate into the pores, and exhibits excellent adsorption characteristics and catalytic activity. It is useful as a catalyst carrier. Moreover, since the air purification material of the present invention using such a mesoporous material of the present invention is excellent in the removal performance against harmful substances such as VOC in the air, the air for removing harmful substances in the air Very useful as a purification material.

  In addition, according to the method for producing a mesoporous material of the present invention, the mesoporous material of the present invention that could not be obtained conventionally, that is, a pore having a central pore diameter of 2 to 10 nm is connected to each other to form a 3D- Since it is possible to obtain a mesoporous material made of a metal oxide forming a three-dimensional channel having a cubic Im3m structure, the method for producing a mesoporous material according to the present invention produces an adsorbent, a separating material, a catalyst carrier and the like. It is a useful way to do.

4 is a graph showing an X-ray diffraction pattern of a mesoporous material obtained in Example 3. 4 is a transmission electron micrograph of the mesoporous material obtained in Example 4. 6 is a graph showing an N2 adsorption isotherm of a mesoporous material obtained in Example 4. 6 is a graph showing a pore distribution curve of a mesoporous material obtained in Example 4. 6 is a graph showing an X-ray diffraction pattern of a mesoporous material obtained in Example 8. 6 is a graph showing an X-ray diffraction pattern of a mesoporous material obtained in Example 17. It is a graph which shows the test result of the toluene removal rate by the mesoporous material obtained in Example 18 and the mesoporous material obtained in Comparative Example 1.

Claims (4)

It is a mesoporous material made of a metal oxide, and pores having a central pore diameter of 2 to 10 nm are interconnected to form a 3D channel having a 3D-Cubic Im3m structure,
Mesoporous said metal oxide is cobalt, copper, characterized in that an oxide of at least one metal selected from the group consisting of chromium and cerium.   In the X-ray diffraction analysis method, five diffraction peaks indexed by (110), (200), (211), (310), (222) are observed in the region of 2Θ = 0.5-3 °. The mesoporous material according to claim 1, wherein:   An air purification material comprising the mesoporous material according to claim 1 or 2. In a non-aqueous solvent having a water content of 1% by weight or less, the following general formula (1):
HO (CH ₂ CH ₂ O) _a (CH ₂ CH (CH ₃ ) O) _b (CH ₂ CH ₂ O) _c H (1)
[In Formula (1), a represents an integer of 20 to 150, b represents 20 to 100, and c represents an integer of 20 to 150, respectively]
And / or the following general formula (2):
_{HO (CH 2 CH 2 O)} x (CH 2 CHCH (CH 3) O) y H (2)
[In Formula (2), x represents an integer of 30 to 60, and y represents an integer of 50 to 150, respectively]
And at least one selected from the group consisting of nitrates, sulfates, halides and acetates of at least one metal selected from the group consisting of cobalt, copper, chromium and cerium A first step of adding a seed metal salt to produce a porous precursor;
A second step of obtaining the mesoporous material by removing the surfactant from the porous material precursor;
The method for producing a mesoporous material according to claim 1, comprising: