JP2003238118A - Nonsilica oxide porous material and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an organic group containing nonsilica oxide material and a nonsilica oxide porous material with uniform mesopores, which have stability in structure and realizing shape control, and a method for producing the same. <P>SOLUTION: The method for producing the nonsilica oxide porous material comprises adding a silane compound that is connected with organic functional groups having short alkyl chains into a solution containing a surfactant and an inorganic raw material, producing a mesostructure material containing the organic functional groups of the silane compound in the skeleton of the nonsilica oxide, and thereafter removing a part or all of the organic components, and the nonsilica oxide porous material is characterized by having mesopores of from a few nm to several tens of nm and macropores of several hundreds of nm to a few μm, and the nonsilica oxide porous material has a hygroscopic and a water absorptive function. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a non-silica-based oxide porous body and a method for producing the same, and more specifically to an organic compound within a non-silica-based oxide skeleton prepared by using a surfactant. A non-silica-based oxide porous body produced by removing a surfactant, or a surfactant and an organic functional group from an organic-group-containing non-silica-based oxide containing a functional group, and a method for producing the same. is there. INDUSTRIAL APPLICABILITY The non-silica-based oxide porous body of the present invention is useful as a functional member having a hygroscopic / water-absorptive effect, and utilizes the intrinsic physicochemical properties of the mesoporous material to produce functional molecules or harmful It is used as a functional member for all applications utilizing those functions, such as a material selective adsorption material, a toxic chemical decomposition catalyst, and a column packing material.

[0002]

2. Description of the Related Art In general, an inorganic oxide material can control an ordered structure at the nanometer level by utilizing an organic molecular assembly. Such materials are called mesostructured materials. Among these, as a material having a three-dimensional inorganic skeleton structure having pores on the nanometer level, that is, mesopores, an organic molecular assembly having a size on the nanometer level is introduced into an inorganic oxide material in advance, and then, It is obtained by removing organic molecular aggregates by firing or extraction. The mesoporous material thus obtained is expected to be used in containers for selectively synthesizing fine chemical molecules, pharmaceuticals, metals and semiconductor nanoclusters by utilizing the existence of uniform mesopores.

Further, by modifying the mesopore surface of the mesoporous material with an organic functional group, it becomes possible to construct a selective reaction field utilizing the interaction between the organic functional group and the organic compound. Further, it is possible to selectively adsorb and remove metal ions and form a metal complex in the mesopores by utilizing the organic functional group itself existing on the surface of the mesopores. The organic modification method includes 1) a method of utilizing an esterification or silylation reaction for surface modification of a mesoporous material, and 2).
A method in which the organic functional group is left on the surface of the mesopores by removing the organic molecular group by extraction after controlling the structure using the organic molecular group during the hydrolysis and polycondensation reaction process of the silane compound having the organic functional group. , And.

Not only the above, but the application is further expanded by controlling the morphology of the inorganic oxide material. For example, it is possible to synthesize a high molecular polymer having almost no branching by using a fibrous material. On the other hand, since it can be developed into an electronic device material by making it thin, it has received a great deal of attention. For example, there is an example in which an organic dye molecule is introduced to cause laser emission. A great deal of research has been conducted on silica-based materials for morphological control such as thin film formation and fiber formation. In addition, attempts to control the particle morphology are being actively made with silica-based materials, and for example, application as a device material with controlled particle arrangement or a column packing is expected. Nowadays, it is possible to synthesize silica-based mesoporous materials having various particle morphologies such as shell-like morphology, sphere-like, rope-like, hexagonal columnar particles and icosahedral particles reflecting the crystal structure.

As described above, it is highly expected to construct a specific reaction field utilizing the presence of organic functional groups by modifying the surface of a mesoporous material. Until now, research and development relating to surface modification of mesoporous materials have been made only for silica-based materials. In addition, various applications are expected by controlling the morphology of the particles that make up the mesoporous material, and research and development are also being conducted centering on silica-based materials. However, silica-based materials have a problem that characteristics such as electrical conductivity and superconductivity in transition metal oxides and semiconductivity in transition metal sulfides cannot be expected.

On the other hand, when the morphology control in the non-silica-based oxide porous body is realized, the electrical conductivity, superconductivity,
It is possible to develop materials derived from various characteristics that cannot be exhibited by silica-based materials such as semiconductors, and by utilizing these characteristics, it can be expected to develop into, for example, electronic device materials and sensor materials. At this time, not only the surface characteristics of the non-silica-based oxide porous material itself, but also the organic modification technology,
For example, when used as a sensor material, it becomes possible to impart effective adsorption performance. However, regarding the non-silica-based oxide porous body, the synthesis of a mesoporous titanium oxide thin film is known, and there are few successful examples of controlling the particle morphology. Research on particle morphology control involves synthesis of aluminophosphate mesostructures similar to diatomaceous earth, but the mesostructured materials have low structural stability, and there is a problem that the structure collapses during firing.

In addition, there are no examples of synthesizing a surface modified body of a mesoporous material with a non-silica oxide material. Therefore,
The present inventor has found a technique for producing a non-silica mesostructure material in which an organic group is introduced on the surface of an inorganic skeleton by adding an organosilane compound or the like as a silane compound having an organic group to a nonsilica mesostructure material. (Japanese Patent Application No. 2001-352)
595). In this method, by introducing an organic group on the surface of the inorganic skeleton, the structural stability during firing was greatly improved,
In the process of removing the surfactant, the introduced organic group may possibly be removed at the same time, and the organic group has not been surely left in the resulting non-silica-based oxide porous body. In addition, the morphology of the particles produced at this time is not well controlled, so that, for example, it is possible that only aggregated particles are produced.

In the above method, in order to synthesize the surface-modified body of the non-silica-based oxide body, an organic group is added at the stage of the precursor mesostructured material in view of its low structural stability. It is preferred to introduce and then remove the surfactant. Further, in order to control the morphology of the non-silica-based oxide porous body, it is considered necessary and unavoidable to perform the morphology control at the stage of the mesostructured material that is the precursor thereof. However, one of the reasons why it is difficult to control the particle morphology of a non-silica mesostructured material is that the particle morphology reflects the crystal structure of the obtained mesostructured material and its generation mechanism.

[0009]

Under these circumstances, the present inventor has, in view of the above-mentioned prior art, a new non-silica-based oxide porous material capable of solving the problems of the above-mentioned prior art. As a result of intensive research aimed at developing body materials, organic functional groups are introduced inside the inorganic skeleton rather than on the surface of the inorganic skeleton when synthesizing the surface-modified non-silica oxide material. As a result, they have found that the intended purpose can be achieved, and have completed the present invention.
That is, the present invention is to synthesize a surface modified product of a non-silica-based mesostructure material having high structural stability and to develop a new method capable of realizing control of particle morphology. It is intended to produce a non-silica-based oxide porous body by removing the organic component of the body. Further, the present invention makes it possible to impart structural stability and control the particle morphology in the process of producing a novel organic group-containing non-silica oxide material in which an organic functional group is introduced into the inorganic skeleton. The purpose is to provide a new method. Furthermore, the present invention adds a silane compound linked with an organic functional group having a short alkyl chain length during preparation of a precursor solution containing a surfactant and an inorganic raw material for synthesizing a non-silica oxide mesostructure. By changing the structure, the mesostructure is changed, and the organic functional groups are present inside the non-silica-based oxide skeleton. To prepare a non-silica-based oxide porous body having various mesopores, and further to provide a new method capable of changing from, for example, a particle morphology having macropores of several hundred nm to several μm. It is intended. A further object of the present invention is to provide a functional member having a hygroscopic / water-absorbing effect, which contains the non-silica-based oxide porous body.

[0010]

The present invention for solving the above-mentioned problems comprises the following technical means. (1) By adding a silane compound linked by an organic functional group having a short alkyl chain length to a solution containing a surfactant and an inorganic raw material, the organic functional group in the silane compound is added to the non-silica-based oxide skeleton. A method for producing a non-silica-based oxide porous body, which comprises removing a part or all of an organic component after forming a contained mesostructure. (2) The surfactant is an alkylamine, an alkylammonium salt, an alkyltrimethylammonium salt, an alkyltriethylammonium salt, an alkylpyridinium salt, an alkylpolyoxyethylene or a polyoxyethylene-polyoxypropylene-polyoxyethylene block copolymer. The method for producing a non-silica-based oxide porous body according to (1) above, which is one or more selected from the above. (3) The inorganic raw material is selected from 1) one or more selected from an aluminum source, a titanium source, a zirconium source, and a vanadium source, or 2) selected from an aluminum source, a titanium source, a zirconium source, and a vanadium source. 1 type and a phosphorus source, the method for producing a non-silica-based oxide porous body according to (1) above. (4) The silane compound linked by an organic functional group having a short alkyl chain length has, as an organic functional group, one selected from a methylene group, ethylene group, propylene group, and vinylene group. A method for producing a non-silica-based oxide porous body. (5) The method for producing a non-silica-based oxide porous body according to (1), wherein the combustion temperature of the organic functional group in the silane compound is higher than the combustion temperature of the surfactant. (6) The method for producing a non-silica-based porous oxide body according to (1), wherein the organic component is removed by extraction. (7) The method for producing a non-silica-based oxide porous body according to (1), wherein the organic component is removed by firing. (8) A non-silica oxide porous body produced by removing a part or all of an organic component from a mesostructure containing an organic functional group in the silane compound in the non-silica oxide skeleton. And a non-silica-based oxide porous body, wherein the non-silica-based oxide has mesopores. (9) The non-silica-based oxide porous body according to (8), wherein the mesopores are several nm to several tens nm. (10) The non-silica oxide porous body according to the above (8), wherein an organic group is present inside the non-silica oxide skeleton. (11) The non-silica-based oxide porous body according to (8), wherein the non-silica-based oxide has pores of several hundred nm to several μm. (12) The non-silica oxide is 1) aluminum oxide,
The above (8), which is one selected from titanium oxide, zirconium oxide, vanadium oxide or a composite oxide thereof, or 2) aluminum phosphate, titanium phosphate, zirconium phosphate or vanadium phosphate. Non-silica-based oxide porous body. (13) A functional member having a hygroscopic / water-absorbing function, which is made of the non-silica-based oxide porous body according to (8).

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION Next, the present invention will be described in more detail. The present invention relates to a non-silica-based oxide porous body having a controlled morphology, a method for producing the same, and the like. In the present invention, the non-silica-based oxide is, for example, 1) aluminum oxide, titanium oxide, zirconium oxide, vanadium oxide or a composite oxide thereof, or 2) aluminum phosphate, titanium phosphate, zirconium phosphate or phosphoric acid. It is preferably applied when it is one selected from vanadium.

In the present invention, the surfactant is preferably an alkylamine, an alkylammonium salt, an alkyltrimethylammonium salt, an alkyltriethylammonium salt, an alkylpyridinium salt, an alkylpolyoxyethylene or a polyoxyethylene-polyoxypropylene. -One or more kinds selected from polyoxyethylene block copolymers are used. Among them, alkylammonium salt, alkyltrimethylammonium salt, alkyltriethylammonium salt, and alkylpyridinium salt exist as a cation in a solution, and therefore, they may be electrostatically interacted with a non-silica inorganic species and a silica species in a solution. Action is possible, alkyl polyoxyethylene,
The polyoxyethylene-polyoxypropylene-polyoxyethylene block copolymer is capable of hydrogen bonding interaction with a non-silica type inorganic species and a silica type in a solution, and the non-silica type is possible due to the self-assembly ability of the surfactant. It enables mesostructure control of oxide materials. The action is not impaired even if two or more of the above surfactants are mixed.

Further, since the repeating unit of the non-silica-based oxide material changes depending on the size of the surfactant used, the size of the surfactant is appropriately selected to select the repeating unit of the non-silica-based oxide. Can be controlled. For example,
When an alkyl ammonium-based surfactant is used,
The structural regularity is on the order of several nm. In addition, for example, when alkylpolyoxyethylene is used, its size is slightly increased, and when a polyethylene-polypropylene-polyethylene block copolymer is used, a non-silica-based oxide material having a repeating structure of several nm to several tens of nm. Is obtained.

Further, in the present invention, 1) as an inorganic raw material
One or more selected from an aluminum source, a titanium source, a zirconium source, or a vanadium source, or 2) one selected from an aluminum source, a titanium source, a zirconium source, or a vanadium source and a phosphorus source are used. In solution, aluminum species, titanium species, zirconium species, vanadium species, phosphoric acid species or composite species thereof, on the contrary, allow electrostatic or hydrogen-bonding interactions with the surfactant species. To do.

Further, in the present invention, a silane compound linked with an organic functional group having a short alkyl chain length is used, and preferably, the organic functional group is one selected from methylene, ethylene, propylene and vinylene groups. An example is a silane compound having These silane compounds do not self-assemble themselves, and do not prevent the formation of a meso structure utilizing self-assembly by the surfactant. However, a silane compound linked with an organic functional group having a long alkyl chain such as butylene, hexylene, or octylene is not preferable because it does not form a meso structure due to the self-assembly ability of the silane compounds linked with the organic functional group.

Since the organic functional group portion has no electric charge, the electric charge generated by the formation of the inorganic skeleton structure can be reduced by the presence of the organic functional group, thereby inducing the change of the meso structure. Is possible. This effect is not impaired even if one or more silane compounds are added. In addition, since the silane compound is linked by the organic functional group, the organic functional group is incorporated not in the surface of the non-silica-based oxide inorganic skeleton but inside the non-silica-based oxide inorganic skeleton, and thus the non-silica-based oxide Exists within.

The inorganic skeleton structure of the obtained organic group-containing non-silica type oxide does not have a crystal structure but becomes an amorphous body. Amorphous inorganic oxides excluding silica-based materials may have various compositions, but aluminum oxide, titanium oxide, zirconium oxide, vanadium oxide or their composite oxides easily take an amorphous structure, Since crystallization requires a high temperature, it is a material that is relatively difficult to crystallize. Further, aluminum phosphate, titanium phosphate, zirconium phosphate, or vanadium phosphate is known to have a crystalline layered compound, but at the same time, an amorphous substance is also present. It can be handled as a highly effective substance system.

The burning temperature of the organic functional group is preferably higher than the burning temperature of the surfactant. Thereby,
Even when the organic component is burned, the surface of the inorganic oxide material becomes hydrophobic, structural destruction due to water molecules can be suppressed, and higher structural regularity is maintained. Therefore, in addition to the above-mentioned methylene, ethylene, propylene or vinylene group, an acetylene or phenylene group can be used as an organic functional group having a high combustion temperature.

Among the above-mentioned non-silica type oxides, it is preferable to use aluminum isopropoxide as the aluminum source and phosphoric acid as the phosphorus source for the synthesis of the aluminum phosphate type mesostructured material. Next, as an example, explaining a method for producing an organic group-containing aluminum phosphate-based mesostructured material having macropores, for example, aluminum isopropoxide, to prepare a precursor solution containing phosphoric acid and a surfactant, A silane compound linked with an organic functional group is added to the solution, stirred for about 30 minutes, dispersed in distilled water, and repeatedly washed to obtain an organic group-containing aluminum phosphate mesostructured material having macropores. To be

The precursor solution for preparing the organic group-containing aluminum phosphate-based mesostructured material is basic and is prepared so that the molar ratio of Al: P is 1: 1.
It is preferable to adjust the pH to 9 or more by adding tetramethylammonium hydroxide, tetraethylammonium hydroxide or tetrapropylammonium hydroxide as a base source. By synthesizing at room temperature, the composition range of the precursor solution is greatly expanded. If the composition of the precursor solution is optimum, a similar product can be obtained even if the synthesis temperature is raised, but it is preferably 100 ° C or lower.

The introduction amount of the silane compound linked by the organic functional group is from several hundred nm to several μm when the molar ratio of Si / (Al + P) in the precursor solution is larger than 0.50.
Although a two-dimensional hexagonal organic group-containing aluminum phosphate-based mesostructure having macropores is formed, in order to prevent the formation of an impurity phase (lamella structure), Si / (A
It is preferred that the molar ratio of l + P) is greater than 0.75. When the amount introduced is 0.50, the lamella structure becomes the main component, and when the amount introduced is further reduced, the proportion of the lamella structure decreases and a material having a two-dimensional hexagonal structure is obtained again, but only aggregated particles are produced.

The molar ratio of Si / (Al + P) in the product is 1.0 in the precursor solution.
0 was 0.38 and the precursor solution had a Si / (Al + P) molar ratio of 0.75 and 0.24. This indicates that the Si atom directly bonded to the organic functional group exists in the aluminum phosphate-based mesostructure, but its existence was also confirmed by nuclear magnetic resonance analysis. Nuclear magnetic resonance analysis is also an analysis method that can clarify how many Si atoms have bonds through oxygen atoms. The analysis result shows that the molar ratio of Si / (Al + P) in the precursor solution is 1.00. The number of bonds in the material prepared as
3 means that the silane compound linked by the organic functional group that is not bonded to the aluminophosphoric acid species does not exist in the mesostructure. That is, all the silane compounds linked by the organic functional groups are said to be incorporated inside the aluminum phosphate skeleton. At this time, the Al / P molar ratio of the product is about 1.3 in any case, and the content of the organic component is in the range of 50 to 52% by weight.

In the method of the present invention, in the step of preparing a precursor solution containing a surfactant and an inorganic raw material for synthesizing a non-silica oxide mesostructure, the organic functional group having a short alkyl chain length is linked. By adding the silane compound
It becomes possible to obtain an organic group-containing aluminum phosphate mesostructure having a two-dimensional hexagonal structure and having macropores of several hundreds nm to several μm. Further, since the combustion temperature of the organic functional group in the silane compound is higher than that of the surfactant,
The surface of aluminum phosphate is made hydrophobic when the organic component is burned, and it is possible to impart an effect that the structural destruction due to water molecules can be suppressed.

Next, when removing the surfactant by extraction, it is possible to remove only the surfactant component by using an aqueous solution of hydrochloric acid, nitric acid, phosphoric acid, sulfuric acid, acetic acid or fluoroacetic acid. However, preferably, by using a mixed solvent of the acidic aqueous solution and methanol or ethanol, the solubility of the surfactant molecule is increased, and the surfactant can be efficiently removed. Since the alkyl polyoxyethylene and the polyethylene-polypropylene-polyethylene block copolymer have a weak interaction with the inorganic oxide by hydrogen bond, extraction using only methanol or ethanol is also possible. At this time, since the organic functional group in the silane compound is directly bonded to the silicon atom, it is not removed in the acid treatment process and is present inside the inorganic skeleton of the obtained non-silica-based oxide porous body. To do.

The firing condition for removing the organic component by firing may be a method of raising the temperature to a predetermined temperature of 700 ° C. or less in air, but preferably a predetermined temperature of 7 in a nitrogen stream.
By raising the temperature to 00 ° C. or less and then treating it under air circulation, it becomes possible to efficiently remove the organic components. At this time, the organic functional group in the silane compound is burned and removed together with the surfactant molecule, and the non-silica-based oxide porous body is composed of only the inorganic oxide component. The aluminum phosphate-based mesoporous material in which the organic component is completely removed by firing becomes a material having both macropores and mesopores. Both the specific surface area and the pore volume are large, and the pore size distribution is uniform. Further, it has excellent water vapor adsorption characteristics and can adsorb a very large amount of water.

The non-silica-based oxide porous material of the present invention is useful as a functional member having a hygroscopic / water-absorbing effect, and by utilizing these characteristics, a selective adsorption material for a functional molecule or a harmful substance, a harmful material It is used as a catalyst for decomposing chemical substances and as a column packing material. The functional member having a hygroscopic / water-absorbing effect of the present invention includes functional members intended for all uses utilizing the function based on the intrinsic physicochemical properties of the mesoporous material.

[0027]

EXAMPLES Next, the present invention will be specifically explained based on examples, but the present invention is not limited to the following examples. Example 1 To a 16% by weight aqueous solution of tetramethylammonium hydroxide, 4.74 g of hexadecyltrimethylammonium chloride as a surfactant was added, and the mixture was stirred until it was completely dissolved.
When 85% phosphoric acid was added to the basic surfactant aqueous solution, an exothermic reaction occurred, and this was left to stand until it reached room temperature.
Add aluminum isopropoxide to this solution,
A uniform precursor solution was prepared by stirring for 4 hours. As a silane compound linked to this precursor solution with an organic functional group, 1,2-
Bis (trimethoxysilyl) ethane was added to Si / (Al +
P) was added so that the molar ratio was 1.00 or 0.75, 0.50, and after stirring for 30 minutes, the obtained solution was dispersed in distilled water. At this time, a white solid formed.
After repeated washing, it was dried at 50 ° C.

In order to evaluate the structure of the obtained organic group-containing aluminum phosphate mesostructured material, powder X-ray diffraction measurement was performed. A product having a two-dimensional hexagonal structure having a lattice constant of about 4.6 nm (d ₁₀₀ = 4.0 nm) when the molar ratio of Si / (Al + P) in the precursor solution is 1.00 or 0.75. It was confirmed that
The presence of one-dimensional mesopores was also observed by transmission electron microscopy. The molar ratio of Si / (Al + P) in the precursor solution is 0.
In the case of 50, a large diffraction peak with a d value of 3.0 nm was observed, and its high-order diffraction was also observed, which confirmed that a product having a lamella structure was obtained.

Example 2 Si / (Al + P) in the precursor solution shown in Example 1 above
In order to observe the morphology of the organic group-containing aluminum phosphate-based mesostructured material synthesized with the molar ratio of 1.00 or 0.75, 0.50, scanning electron microscope observation was performed. Scanning electron microscope images of organic group-containing aluminum phosphate-based mesostructured materials synthesized with the molar ratio of Si / (Al + P) in the precursor solution being 1.00 or 0.75 show several hundred nm in each case. Particles having macropores of several μm were observed. Further, from the transmission electron microscope image of the organic group-containing aluminum phosphate-based mesostructured material synthesized by setting the molar ratio of Si / (Al + P) in the precursor solution to 1.0,
It was confirmed that macropores existed inside the sample.

On the other hand, in the scanning electron microscope image of the organic group-containing aluminum phosphate-based mesostructured material synthesized by setting the molar ratio of Si / (Al + P) in the precursor solution to 0.5, the plate-like shape reflecting the lamella structure is shown. It was observed that the crystals were aggregated. In addition, it was also observed that a substance having an indefinite shape was already present in the form of a binder in the aggregated particles, and that some macropores were formed. This change in particle morphology clearly indicates macropore formation. Add to precursor solution 1,
When the amount of 2-bis (trimethoxysilyl) ethane is increased, a mesostructure change from a lamellar structure to a two-dimensional hexagonal structure occurs, and the particle morphology also changes at the same time. Therefore, a two-dimensional hexagonal structure having macropores is formed. It is considered that the organic group-containing aluminum phosphate-based mesostructures of 1) were generated. That is, it is considered that when the voids of the aggregated particles were converted into macropores, they were converted into spherical macropores so that the surface energy was minimized.

Example 3 In order to evaluate the structural stability of an organic group-containing aluminum phosphate-based mesostructured material synthesized with the molar ratio of Si / (Al + P) in the precursor solution being 1.00, N ₂ flow was conducted. in changing the predetermined temperature (400 ° C. or 550 ° C.) until the temperature was increased and held for one hour, circulation gas O ₂ while the temperature 40
Baking treatment was performed at 0 ° C. for 5 hours or at 550 ° C. for 2 hours to completely remove the organic component.

Si / (Al + P) molar ratio in the precursor solution
Aluminium phosphate containing organic groups synthesized with 1.00
X-ray powder of a material obtained by firing a mesostructured material
Diffraction measurement was performed. The result is shown in FIG. Of pore structure
Although shrinkage was observed, the d value was 2.9 regardless of the firing temperature.
A nm diffraction peak was observed. At any firing temperature
Also, the specific surface area is 600m²/ G or more, pore volume is 0.3
5 cm³ / G or more, which is a large value. What is the pore size
Even the fired product has a uniform pore size distribution of around 1.8 nm.
did. For example, for an unmodified sample baked at 550 ° C.
Area is 488m² / G, pore volume is 0.27 cm³ / G
And introduce a silane compound linked by an organic functional group.
Thus, it was confirmed that the structural stability was improved.

FIG. 2 shows the result of the water vapor adsorption measurement of the organic group-containing aluminum phosphate mesostructure material synthesized at a Si / (Al + P) molar ratio of 1.00 in the precursor solution and calcined at 400 ° C. . Abrupt adsorption of water vapor was observed in the range of very low relative pressure (0.0 to 0.3), and the obtained mesoporous material had a very hydrophilic surface structure. confirmed. It was also found that it is possible to adsorb a very large amount of water of about 0.32 g per 1 g of the material, and it is useful as a functional member having a hygroscopic and water absorbing action.

Example 4 Instead of the aluminum phosphate-based material of Example 1,
An organic group-containing titanium oxide-based or zirconium oxide material was synthesized. Hexadecyltrimethylammonium chloride was used as a surfactant, and 1,2-bis (trimethoxysilyl) ethane was used as a silane compound linked by an organic functional group. As a result of using titanium tetraisopropoxide or titanium tetrabutoxide as the titanium source or zirconium oxychloride as the zirconium source, a mesostructured material having an organic functional group in the titanium oxide skeleton or the zirconium oxide skeleton was obtained. . These can be made into a mesoporous material by baking treatment in the same manner as in Example 3 above to remove organic components. As a result, it was clarified that not only the phosphate-based material but also the oxide-based material can synthesize the organic group-containing non-silica-based oxide material and the non-silica-based oxide porous body.

[0035]

INDUSTRIAL APPLICABILITY As described above in detail, the present invention relates to a non-silica-based oxide porous body and a method for producing the same. According to the present invention, 1) an organic group having a high combustion temperature is used. By introducing it into the silica-based mesostructured material, it becomes possible to improve its structural stability and control the particle morphology. 2) Part or all of the organic components of the above non-silica-based mesostructured material By removing it, a mesoporous material having a high specific surface area, a high pore volume, and a uniform pore size distribution can be obtained. 3) The mesoporous material of the present invention has extremely excellent moisture absorption and water absorption effects. And is useful as a functional member having a function of absorbing moisture and water. 4) The non-silica-based oxide porous body of the present invention utilizes the function based on the intrinsic physicochemical properties of the mesoporous material. Available as a functional member for all applications In it, special effects that can be attained.

[Brief description of drawings]

FIG. 1 shows a powder X-ray diffraction pattern of a mesoporous material obtained by firing an organic group-containing aluminum phosphate mesostructured material at 400 ° C. or 550 ° C.

FIG. 2 shows water vapor adsorption isotherms of a mesoporous material obtained by calcining an organic group-containing aluminum phosphate mesostructured material at 400 ° C.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) B01J 20/08 B01J 20/08 AC 20/28 20/28 Z C01F 7/02 C01F 7/02 EF Terms (reference) 4G042 DA01 DA02 DB03 DB08 DD06 DE07 DE12 4G066 AA20A AA20B AA23A AA23B AA24A AA24B AA50A AA50B AB18A AB18B AD20B BA23 CA43 DA01 DA07 EA01 EA20 AB05 AB11 DA39 BC02 AB04

Claims (13)

[Claims] 1. A non-silica oxide skeleton containing an organic functional group in a non-silica oxide skeleton by adding a silane compound linked with an organic functional group having a short alkyl chain length to a solution containing a surfactant and an inorganic raw material. A method for producing a non-silica-based porous oxide body, which comprises removing a part or all of an organic component after forming a mesostructure containing a group. 2. The surfactant is alkylamine, alkylammonium salt, alkyltrimethylammonium salt, alkyltriethylammonium salt, alkylpyridinium salt, alkylpolyoxyethylene or polyoxyethylene-polyoxypropylene-polyoxyethylene block copolymer. The method for producing a non-silica-based oxide porous body according to claim 1, wherein the method is one or more selected from polymers. 3. The inorganic raw material is 1) an aluminum source,
One or more selected from a titanium source, a zirconium source, or a vanadium source, or 2) one selected from an aluminum source, a titanium source, a zirconium source, or a vanadium source, and a phosphorus source. The method for producing a non-silica-based oxide porous body according to 1. 4. The silane compound linked by an organic functional group having a short alkyl chain length has, as an organic functional group, one selected from methylene, ethylene, propylene and vinylene groups. 1. A method for producing a non-silica-based oxide porous body. 5. The method for producing a non-silica-based oxide porous body according to claim 1, wherein the combustion temperature of the organic functional group in the silane compound is higher than the combustion temperature of the surfactant. 6. The method for producing a non-silica-based oxide porous body according to claim 1, wherein the organic component is removed by extraction. 7. The method for producing a non-silica-based oxide porous body according to claim 1, wherein the organic component is removed by firing. 8. A non-silica-based oxide porous body prepared by removing a part or all of an organic component from a mesostructure containing an organic functional group in the silane compound in a non-silica-based oxide skeleton. A non-silica-based oxide porous body, wherein the non-silica-based oxide has mesopores. 9. The non-silica-based oxide porous body according to claim 8, wherein the mesopores are several nm to several tens nm. 10. The non-silica oxide porous body according to claim 8, wherein an organic group is present inside the non-silica oxide skeleton. 11. The non-silica-based oxide porous body according to claim 8, wherein the non-silica-based oxide has pores of several hundred nm to several μm. 12. The non-silica-based oxide is 1) aluminum oxide, titanium oxide, zirconium oxide, vanadium oxide or a composite oxide thereof, or 2) aluminum phosphate, titanium phosphate, zirconium phosphate or vanadium phosphate. The non-silica-based oxide porous body according to claim 8, which is one kind selected from the above. 13. A functional member having a hygroscopic / water-absorbing function, comprising the non-silica-based oxide porous body according to claim 8.