KR100925746B1 - Mesoporous inorganic composite powder containing metallic oxides and the preparation method thereof - Google Patents

Abstract

The present invention has a wide range of ultraviolet (UV-A, B) blocking ability by supporting a metal oxide such as cerium and iron in the pores of the medium-porous silica molecular sieve substituted with metal elements such as titanium and zinc in the skeleton, The present invention relates to a medium-porous inorganic composite powder having improved usability and safety, and a method of manufacturing the same.

Metal Oxide, UV Protection, Medium Pore Inorganic Composite Powder, Inorganic Sunscreen

Description

Mesoporous inorganic composite powder containing metallic oxides and the preparation method

1 is a schematic view of the medium-porous inorganic composite powder prepared in Examples 4 and 5.

2 is an X-ray diffraction graph of the mesoporous inorganic composite powder prepared in Examples 1 and 4.

FIG. 3 is a graph showing the adsorption-desorption isotherm of nitrogen obtained at liquid nitrogen temperature for the mesoporous inorganic composite powder prepared in Example 4. FIG.

FIG. 4 is an energy dispersive x-ray (EDX) graph of the mesoporous inorganic composite powder prepared in Example 4. FIG.

5 is a UV-spectrum of the mesoporous inorganic composite powder loaded with cerium and iron in the mesoporous silica and titanium substituted mesoporous silica pores in which titanium prepared in Examples 1 and 4 is substituted into the skeleton.

The present invention has a wide range of ultraviolet (UV-A, B) blocking ability by supporting a metal oxide such as cerium and iron in the pores of the medium-porous silica molecular sieve substituted with metal elements such as titanium and zinc in the skeleton, The present invention relates to a medium-porous inorganic composite powder having improved usability and safety, and a method of manufacturing the same.

Mesoporous porous silica is one of mesoporous molecular sieves. It is a medium pore molecular sieve with uniformly arranged mesopores of uniform size. In 1991 a new type of mesoporous molecular sieve materials, named M41S family, manufactured by Mobil's team using ionic surfactants as structural derivatives, was described in US Pat. No. 5,057,296. Since published in US Pat. No. 5,102,643 and the like, research on such medium-porous molecular sieve material is now actively conducted worldwide. Unlike the synthesis of conventional molecular sieves, these mesoporous molecular sieves are synthesized through a liquid crystal templating mechanism, by controlling the type of surfactant used as a template material or the conditions for synthesis. Pore size can be adjusted up to 16 ~ 100Å.

U.S. Pat.Nos. 6,027,706, 6,054,111 and 1998, Volume 279, page 548, discloses mesoporous materials prepared using amphiphilic block copolymers, which are nonionic surfactants. Is disclosed. In the case of zeolites, one inorganic or organic molecule generally acts as a template material for inducing pore structure, while a medium-sized porous material induces pores with a micelle structure in which a plurality of surfactant molecules are collected instead of a single molecule. do. Surfactants are generally known to consist of hydrophilic heads and hydrophobic tails to form self-assembled micelles and liquid crystal structures of various structures under aqueous solutions. When the hydrophilic portion located on the surface of the micelle or liquid crystal structure and the precursor of the inorganic material interact with each other to form an organic / inorganic nanocomposite and remove the surfactant, a mesoporous material may be obtained. Medium porosity materials, unlike microporous materials with pore sizes of 1.5 nm or less, like those of conventional zeolites or AIPO-based materials, extend the size of the pores to the mesopore range (2-50 nm). This enables the application of molecular sieve materials to adsorption and separation of molecules having a size larger than the pore size of microporous materials, catalytic conversion reactions, and the like, which have been limited in the application of molecular sieve materials. The medium porosity material having such regular pores has a very large surface area (> 700m ² / g), which is excellent in adsorption characteristics of elements or molecules, and the size of the pores is constant, so that catalytic active agents such as transition metal compounds and amine oxides It is applied as a carrier. There are also many applications and applications for conductive materials, optical display materials, chemical sensors, fine chemicals and biopowders, new mechanical and thermal insulators and packaging materials.

On the other hand, skin aging is closely related to wrinkles, sagging, and relaxation. Aging caused by environmental factors such as physiological natural aging and UV exposure has been mentioned as a cause of this phenomenon. In particular, most of the causes of skin aging associated with cosmetics are continuous exposure to ultraviolet rays, which causes deep wrinkles, sagging skin, and uneven spots that damage the appearance of the skin. Histologically, this phenomenon shows that the skin's constant UV exposure causes thinning of the epidermis, decreasing the thickness of the dermis, and severe deformation of elastin, a major component of the elastic fibers present in the skin, forming large molecules in the upper and middle layers of the dermis. Elastotic 'accumulates, which leads to a loss of collagen due to the activity of matrix metalloproteinases (MMPs) and a wrinkled skin type that lacks elasticity by inhibiting the normal function of elastic fibers.

Therefore, many studies on cosmetics for reducing or retarding the skin aging phenomenon have been progressed for a long time. First, there is a method of reducing skin penetration of ultraviolet rays by using a sunscreen. In addition, much research has been conducted on sunscreen compounds for protecting the skin from ultraviolet rays (particularly UV-A, B). However, organic sunscreens have problems with light stability when used in cosmetics, and they are absorbed by the skin and cause serious problems in safety due to irritation or photoreaction products. There are many restrictions.

On the other hand, using an inorganic sunscreen can provide a sunscreen without irritation to the skin while blocking a wide range of ultraviolet spectroscopy. However, inorganic sunscreens can cause skin irritation and skin damage due to defects from the aesthetic point of view that appear white when applied to the skin and the ability of sunscreen to be weaker than organic sunscreens. However, there is a disadvantage in the functional aspect that the particle size is increased by the secondary agglomeration of the particles and the UV blocking ability is lowered over time.

The ideal sunscreen should be non-toxic to skin tissues, not irritating to the skin, resistant to chemical or photolysis when applied to the product and not absorbed by the skin. Therefore, there is a need for the development of inorganic sunscreens having high efficiency in the broad wavelength range and excellent skin safety.

In order to solve the above problems, it is an object of the present invention to provide a novel medium-porous inorganic composite powder having a UV protection ability and improved safety and safety.

In order to achieve the above object, the present invention provides a medium-porous inorganic composite powder characterized in that the metal oxide is supported in the pores of the medium-porous silica molecular sieve substituted with the metal element in the skeleton.

The metal element substituted in the skeleton is characterized in that at least one selected from titanium (Ti), zinc (Zn), the metal oxide supported in the pores from the group consisting of cerium oxide, iron oxide, titanium oxide and zinc oxide It is characterized in that at least one selected.

In addition, the present invention

(A) dissolving the surfactant in distilled water, dissolving the metal precursor in an acid and mixing them;

(B) adding a silica precursor to the mixture obtained in (A) and adjusting the pH to be neutral, followed by hydrothermal reaction;

(C) filtering, washing and drying the material obtained in step (B);

(D) calcining the material obtained in the step (C) to remove the surfactant;

(E) dissolving and mixing the metal precursor in distilled water or alcohol;

(F) mixing the metal precursor mixture obtained in step (D) with the mixed solution obtained in step (E); And

(G) It provides a method for producing a medium-porous inorganic composite powder comprising the step of drying the material obtained in the step (F), and then calcining.

Hereinafter, the steps will be described in more detail.

In step (A) of the present invention, the surfactant is dissolved in distilled water, and the metal precursor is dissolved in an acid solution, and then mixed. At this time, when the surfactant is mixed with distilled water, the surfactant acts as a template material to form a self-assembled molecular structure at an appropriate concentration. At this time, the amount of the surfactant to be added is preferably from 0.005 to 0.02 mol based on 1 mol of silica, more preferably 0.01 to 0.02 mol.

Preferred examples of the surfactant used in the step (A) is cetyltrimethylammonium chloride, cetyltrimethylammonium bromide, polyethylene glycol dodecyl ether, polyoxyethylene (23) Lauryl ether (polyoxyethylene (23) lauryl ether), polyoxyethylene (2) cetyl ether, polyoxyyethylene (10) cetyl ether, polyethylene glycol hexadecyl Polyethylene glycol hexadecyl ether, polyoxyethylene (10) stearyl ether, polyethylene glycol octadecyl ether and polyethylene glycol block (polypropylene glycol) block polyethylene glycol (poly ethylene glycol) -block-poly (propylene glycol) -block-poly (ethylene glycol), and the like. Preferably, polyethylene oxide block (polypropylene oxide) polyethylene oxide is used.

The metal precursor used in the step (A) is preferably a compound that can be dissolved in an acid such as acetic acid, hydrochloric acid, sulfuric acid, and the like. As a specific example, titanium isopropoxide and titanium butoxide Metal alkoxides such as titanium sulfate, titanium tetrachloride (TiCl ₄ ), zinc tetrachloride (ZnCl ₄ ), zinc acetate and the like.

In step (B) of the present invention, the mixture obtained in (A) is adjusted to have a neutral pH using a silica precursor, followed by hydrothermal reaction.

Preferred examples of the silica precursor used in step (B) are tetraethylorthosilicate (TEOS), tetramethylorthosilicate (TMOS), methyltrimethoxysilane, dimethyldimethoxysilane Trimethylmethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, trimethylethoxysilane, methyltrichlorosilane, dimethyldichlorosilane, trimethyl Trimethylchlorosilane, bis (trichlorosilyl) methane, 1,2-bis (trichlorosilyl) ethane (1,2-bis (trichlorosilyl) ethane), bis (trimethoxysilyl Methane (trimethoxysilyl) methane, 1,2-bis (triethoxysilyl) ethane, sodium metasilica And the like (Sodium metasilicate), more preferably, the colloidal silica (Ludox HS-40, Dupont Company).

The silica precursor is preferably added slowly to the mixed solution obtained in step (A) using vigorous stirring at room temperature. At this time, the amount of the silica precursor to be added is preferably 1 to 100 mol based on 1 mol of the surfactant, more preferably 10 to 50 mol. Subsequently, the mixture is subjected to hydrothermal reaction at 30 to 50 ° C. to synthesize a mesoporous molecular sieve material in which metal elements are substituted. In the step (A), the surfactant forms an micelle structure through self-combining phenomenon in the aqueous solution in the aqueous solution, and the silica precursor reacts on the surface of the micelle thus formed to form an oligomer and polymerize it. The reaction time takes 1 hour to 144 hours, preferably 12 hours to 48 hours.

In the step (C) of the present invention, the material formed above is dried by filtration and washing, followed by washing 2 to 5 times with ethanol and drying at 50 to 200 ° C. for 3 to 30 hours.

In step (D) of the present invention, the material after step (C) is calcined, and the medium-porous silica in which the metal element is substituted by removing the surfactant, which is a template material, is calcined at 400 to 600 ° C. for 0.3 to 30 hours. Prepare molecular sieves. The ratio of the silica and the substituted metal in the skeleton of the medium-porous silica molecular sieve substituted with the metal element is preferably 5: 1 to 20: 1.

In the step (E) of the present invention, the metal precursor is dissolved in distilled water or alcohol and mixed in order to support the metal oxide in the pores of the prepared medium-sized porous silica molecular sieve. At this time, the amount of the metal precursor to be mixed is preferably from 0.001 to 0.01 mol, based on 1 mol of silica, more preferably 0.001 to 0.005 mol.

The metal precursor used in step (E) is preferably a compound that can be dissolved in a solvent such as distilled water, alcohol, acetonitrile, and specific examples of cerium chloride, cerium nitrate, and iron. chloride (iron chloride), iron nitrate (iron nitrate), titanium isopropoxide (titanium isopropoxide), titanium butoxide (titanium butoxide), such as alkoxide and titanium sulfate (titanium sulfate), titanium tetrachloride (TiCl _4), Zinc tetrachloride (ZnCl ₄ ), zinc acetate (zinc acetate) and the like.

In step (F) of the present invention, the mixed metal precursor mixture solution obtained in step (E) is mixed with the medium-porous molecular sieve obtained in step (D) by using an incipient wetness method at room temperature. At this time, the mixing ratio of the medium-porous molecular sieve and the metal precursor mixed solution is preferably 1: 1 to 1.3 by weight ratio, more preferably 1: 1 is suitable.

Subsequently, in step (G) of the present invention, the material obtained in step (F) is dried at 50 to 200 ° C. for 3 to 30 hours, and then calcined at 400 to 600 ° C. for 0.3 to 30 hours to carry metal supported in the pores. The precursor is oxidized to prepare a mesoporous inorganic composite powder having UV blocking ability.

In addition to the above method, it is possible to manufacture by a method known in the art within a range that does not impair the object of the present invention.

In addition, such a medium-porous inorganic composite powder can be formulated in various ways, in particular, it can be utilized as a cosmetic.

Hereinafter, the present invention will be described in more detail with reference to Examples. However, these examples are intended to illustrate the invention, it is apparent to those skilled in the art that the scope of the present invention is not limited to these examples.

Example 1 Preparation of Medium-Scale Porous Silica Substituted with Metal Elements (1)

Solution A was mixed with 24.98 g of acetic acid (99.5%) and 17.70 g of titanium isopropoxide. Solution B was dissolved in 58.36 g of distilled water in 16.4 g (98%) of NaOH. At this time, it was sufficiently dissolved at about 80 ℃ in a water bath. To the solution was added 25 g of colloidal silica (Ludox HS-40, Dupont). The water bath was kept at 80 ° C and stopped heating when the solution changed from white to a clear color. Solution C was dissolved in 16.41 g of polyethylene oxide block (polypropylene oxide) block polyethylene oxide in distilled water, and then solution A was added while vigorously stirring at room temperature using a magnetic stirring device. The reaction mixture was stirred at room temperature for 5 minutes, then titrated to pH neutral with solution B and stirred at room temperature for 1 hour. After the solution was stirred at 40 ° C. for 20 hours, the precipitate was filtered, washed twice with distilled water, and dried at room temperature. In order to remove the surfactant contained in the dried sample was washed clean with ethanol and calcined for 10 hours at 650 ℃ in air.

Example 2 Preparation of Medium-Porosity Silica Substituted with Metal Elements (2)

Solution A was mixed with 24.98 g of acetic acid (99.5%) and 14.78 g of titanium butoxide. Solution B was dissolved in 58.36 g of distilled water in 16.4 g (98%) of NaOH. At this time, it was sufficiently dissolved at about 80 ℃ in a water bath. To the solution was added 25 g of colloidal silica (Ludox HS-40, Dupont). The water bath was kept at 80 ° C and stopped heating when the solution changed from white to a clear color. Solution C was dissolved in 16.41 g of polyethylene oxide block (polypropylene oxide) block polyethylene oxide in distilled water, and then solution A was added while vigorously stirring at room temperature using a magnetic stirring device. The reaction mixture was stirred at room temperature for 5 minutes, then titrated to pH neutral with solution B and stirred at room temperature for 1 hour. After the solution was stirred at 40 ° C. for 20 hours, the precipitate was filtered, washed twice with distilled water, and dried at room temperature. In order to remove the surfactant contained in the dried sample was washed clean with ethanol and calcined for 10 hours at 650 ℃ in air.

Example 3 Preparation of Medium-Scale Porous Silica Substituted with Metal Elements (2006.01)

Solution A was mixed with 21.76 g of acetic acid (99.5%) and 8.318 g of titanium sulfate. Solution B was dissolved in 58.36 g of distilled water in 16.4 g (98%) of NaOH. At this time, it was sufficiently dissolved at about 80 ℃ in a water bath. To the solution was added 25 g of colloidal silica (Ludox HS-40, Dupont). The water bath was kept at 80 ° C and stopped heating when the solution changed from white to a clear color. Solution C was dissolved in 16.41 g of polyethylene oxide block (polypropylene oxide) block polyethylene oxide in distilled water, and then solution A was added while vigorously stirring at room temperature using a magnetic stirring device. The reaction mixture was stirred at room temperature for 5 minutes, then titrated to pH neutral with solution B and stirred at room temperature for 1 hour. After the solution was stirred at 40 ° C. for 20 hours, the precipitate was filtered, washed twice with distilled water, and dried at room temperature. In order to remove the surfactant contained in the dried sample was washed clean with ethanol and calcined for 10 hours at 650 ℃ in air.

Example 4 Preparation of Medium Pore Composite Inorganic Sunscreen Impregnated with Metal Oxide (1)

After completely dissolving 15 g of cerium chloride in 10 g of distilled water, 10 g of the medium-porous silica prepared in Example 1 was mixed, mixed with the cerium precursor solution at room temperature, stirred for 1 to 3 hours, and then filtered and room temperature. Vacuum drying at 30 ° C. and firing were carried out to obtain 16 g of a medium-porous composite powder loaded with cerium oxide (A). After completely dissolving 5.8 g of iron chloride in 5 g of distilled water, the cerium oxide obtained in (A) was mixed with the porous precursor solution mixed with the iron precursor solution at room temperature and stirred for 1 to 3 hours. Next, the resultant was filtered, dried in vacuo at room temperature, and calcined to obtain 17.5 g of a medium-porous composite inorganic UV blocker having a final cerium oxide and iron oxide.

Example 5 Preparation of Medium Porosity Composite Inorganic Sunscreen Impregnated with Metal Oxide (2)

After fully dissolving 18.6 g of cerium nitrate in 10 g of distilled water, 10 g of the medium-porous silica prepared in Example 1 was mixed, mixed with the cerium precursor solution at room temperature, stirred for 1 to 3 hours, and then filtered. Vacuum drying at room temperature and baking to obtain 16 g of a medium-porous composite powder loaded with cerium oxide (A). After completely dissolving 7.2 g of iron nitrate in 5 g of distilled water, the cerium oxide obtained in (A) was mixed with the porous precursor solution and the iron precursor solution at room temperature and stirred for 1 to 3 hours. The mixture was then filtered and dried in vacuo at room temperature and calcined to obtain 17.5 g of a medium porosity composite inorganic UV blocker having a final cerium oxide and iron oxide.

Experimental Example 1 Safety of Medium Pore Composite Inorganic UV Blocker

Since raw materials for cosmetics are used in the human body, safety for the human body is important above all. Therefore, the presence or absence of toxicity and irritation to the human body of the compound obtained in Examples 4 and 5, which is a sunscreen compound, was examined through the following experiment. At this time, the safety experiment used a solution made by dispersing the medium-pore composite inorganic UV blocker compound in a concentration of 30% in PEG-400 oil.

1-1. Primary skin irritation test

For the first skin irritation test, the hairs of 12 rabbits (NZ White Rabbit, Hallim experimental animal) were removed 24 hours before application of the test substance, and the medium size of Examples 4 and 5 was 2.5 cm × 2.5 cm wide. The porous composite UV-blocking compound was applied by 0.1 ml each for 24 hours.

As a result, it was determined that there was no stimulus.

1-2. Skin sensitization test

For the skin sensitization experiment, Magnusson and the article were prepared using each of three medium and high pore composite inorganic sunscreen compounds of Examples 4 and 5 for each male and female guinea pig. The experiment was conducted according to the test method of Kligman.

As a result, skin abnormalities such as erythema, edema, and crust formation were not observed.

1-3. Human patch test

CTFA guidelines (Guideline) (The Cosmetic Toiletry and Fragrance Association, INC, Ltd.) for 30 healthy people aged 20 to 28 years with the human patch test for each of the medium-porous composite inorganic UV blocker compounds of Examples 4 and 5 Washington, DC20036, 1991).

As a result, there was no skin primary irritation response.

In the above toxicity and safety test for the skin, the medium porosity complex inorganic UV blocker according to the present invention was confirmed to be a safe material as a raw material without toxicity and irritation as a cosmetic, that is, a skin external preparation.

Meanwhile, X-ray diffraction graphs (X-ray diffraction, Rigaku, Inc.) of the mesoporous silica and the mesoporous inorganic composite powder prepared in Examples 1 and 4 are shown in FIG. 2. As can be seen in Figure 2, compared to the X-ray diffraction graph of the medium-porous silica molecular sieve substituted with the metal element obtained in Example 1, the medium-porous inorganic with the metal oxide in the pores obtained in Example 4 The composite powder retained its structural uniformity and its clarity was lowered, but this is believed to be due to the large amount of metal oxide supported in the pores.

Figure 3 is a graph showing the adsorption-desorption isotherm (quantachrome, Inc.) of nitrogen obtained at the liquid nitrogen temperature for the medium-porous inorganic composite powder prepared in Example 4. It can be seen that the overall pore volume and surface area are reduced by supporting the metal oxide in the pores of the molecular sieve substituted with the metal element.

Figure 4 shows the EDX (Energy Dispersive X-ray, oxford, Inc.) graph for the medium-porous inorganic composite powder material prepared in Example 4, titanium (Ti), cerium (Ce), iron (Fe) on the graph It was confirmed that the silica (Si) is detected, and through this, it can be seen that cerium (Ce), iron (Fe), and titanium (Ti) are contained in the silica molecular sieve according to the present invention.

FIG. 5 shows the support of cerium and iron in mesoporous silica and titanium-substituted mesoporous silica pores in which titanium prepared in Examples 1 (TiSiO _{2 of the} graph) and Example 4 (CeFe / TiSiO ₂ of the graph) is substituted into the skeleton. It shows the UV-spectrum (Jasco) of the medium-sized porous inorganic composite powder. One of the characteristics for the application of medium-sized pore molecular sieves substituted with metal oxides carrying metal oxides to cosmetics is the ability to block UV rays, so the medium-sized pores substituted with pure silica and metal elements carrying metal oxides according to the present invention. The UV blocking ability was compared with respect to the polymeric silica material. As a result of the measurement, in the case of Example 1 in which titanium is substituted as compared to pure silica, the absorption spectrum is shifted in the UV-A direction, and it is confirmed that the absorption is also slightly increased. In addition, in Example 4, in which the metal element supporting the metal oxide is substituted with a medium-porous silica material, the absorption spectrum is shifted in the UV-A and UV-B directions to simultaneously block UV-A and UV-B. I could confirm the ability. Therefore, it can be seen that the medium-porous silica substituted with the metal element carrying the metal oxide according to the present invention can be used for UV blocking purposes. Therefore, the medium-porous silica substituted with the metal element carrying the metal oxide of the present invention is used. In the case of a cosmetic containing, it is possible to further expect the sunscreen and scattering effect.

As described above, the medium-porous inorganic composite powder material in which the metal oxides such as cerium and iron are supported in the pores of the medium-porous silica molecular sieve in which metal elements such as titanium and zinc are substituted in the skeleton according to the present invention. Silver has a wide range of ultraviolet (UV-A, B) blocking ability, the use and safety is improved cosmetic composition containing it can be usefully used for UV protection.

Claims (11)

In the medium porous inorganic composite powder, wherein the metal oxide is supported in the pores of the medium porous silica molecular sieve material in which the metal element is substituted in the skeleton. The metal element substituted in the skeleton is titanium (Ti) or zinc (Zn), The metal oxide supported in the pores is a medium-porous inorganic composite powder, characterized in that at least one selected from the group consisting of cerium oxide, iron oxide, titanium oxide and zinc oxide. delete delete The medium-porous inorganic composite powder according to claim 1, wherein the powder is for cosmetics. The medium-porous inorganic composite powder according to claim 1, wherein the powder is for blocking ultraviolet rays. (A) dissolving the surfactant in distilled water, dissolving the metal precursor in an acid and mixing them; (B) adding a silica precursor to the mixture obtained in (A) and adjusting the pH to be neutral, followed by hydrothermal reaction; (C) filtering, washing and drying the material obtained in step (B); (D) calcining the material obtained in the step (C) to remove the surfactant; (E) dissolving and mixing the metal precursor in distilled water or alcohol; (F) mixing the metal precursor mixture obtained in step (D) with the mixed solution obtained in step (E); And (G) step of firing the material obtained in step (F) after drying In the manufacturing method of the medium-porous inorganic composite powder comprising a, The metal precursor used in the step (A) is a metal alkoxides, titanium sulfate, titanium tetrachloride (TiCl ₄ ), zinc tetrachloride (titanium isopropoxide) or titanium butoxide (titanium butoxide) ZnCl ₄ ), zinc acetate (zinc acetate) A method for producing a medium-porous inorganic composite powder, characterized in that at least one member selected from the group consisting of. delete delete The silica precursor used in step (B) is tetraethylorthosilicate, tetramethylorthosilicate, methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, methyltriethoxysilane, dimethyl Diethoxysilane, trimethylethoxysilane, methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, bis (trichlorosilyl) methane, 1,2-bis (trichlorosilyl) ethane, bis (trimethoxysilyl) methane And 1,2-bis (triethoxysilyl) ethane and sodium metasilicate. The method for producing a medium-porous inorganic composite powder, characterized in that at least one member selected from the group consisting of. The metal precursor used in step (E) is cerium chloride (cerium chloride), cerium nitrate (cerium nitrate), iron chloride (iron chloride), iron nitrate (iron nitrate), titanium isopro At least one selected from the group consisting of titanium isopropoxide, titanium butoxide, titanium sulfate, titanium tetrachloride (TiCl ₄ ), zinc tetrachloride (ZnCl ₄ ) and zinc acetate (zinc acetate) Method for producing a medium-porous inorganic composite powder characterized in that. The medium ratio of claim 6, wherein the mixing ratio of the medium-porous molecular sieve of step (D) and the metal precursor mixture of step (E) is 1: 1 to 1.3 by weight ratio. Method for producing a porous inorganic composite powder.

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