TWI746806B - Medium hole contact medium, gas processing device and manufacturing method of medium hole contact medium - Google Patents

Abstract

The subject of the present invention is to provide a touch media that can maintain activity for a longer period of time.

The solution is a mesoporous contact medium, which has: a support body with a plurality of mesopores, and oxidation of at least one of the noble metal, its oxide, and an alloy of noble metal and transition metal is supported in the middle hole of the support body Catalyst particles; in the support, a middle hole is connected to at least one other middle hole.

Description

Medium hole contact medium, gas processing device and manufacturing method of medium hole contact medium

The present invention relates to a catalyst capable of decomposing organic components such as ethylene, carbon monoxide, ammonia, and the like in gas.

Exhaust gas produced by internal combustion engines in automobiles or factories contains small amounts of harmful components such as carbon monoxide, so it is removed by means of removal before being discharged into the atmosphere. In addition, a small amount of malodorous substances are generated in a closed storage, etc., and when ammonia odor occurs, various removal methods are applied.

In addition, plants emit a variety of trace organic gases, but crops in storage emit ethylene gas that has a maturation effect, and the maturation system is known. Therefore, keeping the temperature and humidity constant while reducing the ethylene gas concentration is effective for maintaining freshness over a long period of time.

As a method of removing the components contained in the gas, adsorption of activated carbon and the like to an adsorbent, free radicals based on plasma generators, or decomposition and removal methods based on active species such as ozone, etc. are widely used. However, according to the adsorption treatment of the adsorbent, the adsorption capacity of the adsorbent has its upper limit, and the adsorbent must be exchanged regularly. The treatment method using active species such as plasma must be of a certain size In addition, the generating device requires electricity for its operation, which is not a method that can be easily utilized. Furthermore, it cannot be used because of concerns about changes in appearance such as discoloration for the storage of crops.

In addition to the method of oxidizing and decomposing the components contained in the gas by oxidation and decomposition using a catalyst such as the aforementioned plasma method, a method of oxidizing and decomposing components contained in the gas is also widely used. As an oxidizing catalyst, in order to increase the contact area, a structure in which an active material (catalyst particle) is supported on a support of inorganic particles is used (Patent Document 1) to make the active material porous to the membrane to treat volatile organic compounds. The method of the compound has been disclosed (Patent Document 4). In addition, a catalyst that supports catalyst particles in the pores of an inorganic mesoporous support with cylinder-shaped mesopores has also been developed, and a catalyst that supports catalyst particles on the outer surface of inorganic particles may be activated. Compared with a porous membrane, a contact medium with a very wide specific surface area and high activity is obtained (Patent Documents 2 and 3).

[Prior Technical Literature] [Patent Literature]

[Patent Document 1] JP 2003-080077 A

[Patent Document 2] JP 2004-283770 A

[Patent Document 3] JP 2007-326094 A

[Patent Document 4] JP 2006-326530 A

However, the aforementioned cylinder-shaped hollow support body supports the catalyst of the oxidation catalyst particles, and there is a problem that the catalyst activity decreases with use. The reason is not clear, but the possible reason is that the moisture in the air in the pores or the moisture generated by the oxidation reaction prevents the contact between the catalyst particles and the gas to be treated, and the decomposition reaction of the components to be treated cannot be prevented. Or the pores are sealed by adsorbed water, hindering the flow of the gas to be processed into the pores, etc.

The purpose of the present invention is to provide a contact medium that can maintain its activity for a longer period of time and a gas processing device using it.

The gist of the present invention is as follows.

[1] A mesoporous contact medium, comprising: a support body having a plurality of mesopores, and at least a noble metal, an oxide thereof, and an alloy of the noble metal and the transition metal supported in the mesopores of the support A kind of oxidation catalyst particles; in the aforementioned support, a middle hole is connected to at least one other middle hole.

[2] A mesoporous contact medium by forming a hydrolyzable product containing alkoxysilane or alkoxide, and drying and firing polyoxyethylene alkyl ether, and polyepoxy A mesoporous support obtained from a polyalkylene oxide tri-block copolymer or a solution of a cationic surfactant, and an alloy corresponding to the noble metal, its oxide, and the aforementioned noble metal and transition metal to The solution or colloidal solution of at least one compound is contacted and fired and/or reduced to form an oxidation containing at least one of the noble metal, its oxide, and the alloy of the noble metal and the transition metal in the pores of the support. It is derived from catalyst particles.

[3] As described in [1] or [2], the above-mentioned supporting system is formed of metal oxide or SiO ₂ in the hole contact medium.

[4] As described in [3], in the hole contact medium, the aforementioned metal oxide is a compound of one or more selected from the group _{consisting of TiO 2} , Fe ₂ O ₃ , ZrO ₂ , and CeO _2.

[5] As in any of [1] to [4], the aforementioned noble metal is one or more selected from the group consisting of gold, platinum and palladium.

[6] As in any one of [1] to [5], the hole touches the medium, and the aforementioned support is powder.

[7] As in the pore contact medium in any one of [1] to [6], the average pore diameter of the aforementioned mesopores measured by the BET method is 2 nm or more and 10 nm or less.

[8] As described in any one of [1] to [7], in the porous catalyst medium, the average particle diameter of the oxidation catalyst particles is 1 nm or more and 10 nm or less.

[9] As in any of the descriptions in [1] to [8], in the porous contact medium, the supporting amount of the aforementioned oxidation catalyst particles is 0.1-30% by mass to the support containing the oxidation catalyst particles.

[10] As described in any one of [1] to [8], the above-mentioned mesoporous contact medium is a catalyst for gas oxidation reaction.

[11] A gas processing device characterized by: at least a first electrode, a second electrode, and is arranged between the first electrode and the second electrode The dielectric substance; comprising: a plasma generating portion that generates plasma by applying a voltage between the first electrode and the second electrode to generate a discharge, and is formed on the electricity generated by the plasma generating portion The flow channel through which the processed gas flows in the area where the slurry exists, and the hole contacting the medium arranged in any of the aforementioned flow channels [1] to [10].

[12] A method for manufacturing a mesoporous contact medium, including forming a hydrolyzable product containing alkoxysilane or alkoxide, drying and firing polyoxyethylene alkyl ether, and polyoxyethylene alkyl ether. Polyalkylene oxide tri-block copolymer (polyalkylene oxide tri-block copolymer) or cationic surfactant solution obtained with mesoporous support, and corresponding to the noble metal, its oxide, and the aforementioned noble metal and transition metal Contact with a solution or colloidal solution of at least one compound of the alloy, and perform sintering and/or reduction treatment to form at least one of the noble metal, its oxide, and the alloy of the noble metal and the transition metal in the hole in the support的oxidation catalyst particles.

According to the present invention, it is possible to provide a contact medium that can maintain its activity for a longer period of time and a gas processing device using it.

11: Apply electrode

12: Ground electrode

12a: Ground wire

13: Dielectric

14: power supply

100: Touch media film

200: Gas treatment device

300: Gas treatment device

400: Gas treatment device

Fig. 1 schematically shows a cross-section of the gas processing device 200 of the first embodiment A picture of a part of the surface.

FIG. 2 is a diagram schematically showing a part of the cross-section of the gas processing device 300 of the second embodiment.

FIG. 3 is a diagram schematically showing a part of the cross-section of the gas processing device 400 of the third embodiment.

FIG. 4 is a diagram schematically showing a part of a cross-section of a gas processing device 500 of the fourth embodiment.

Fig. 5 is a 3-dimensional tomographic image in which it can be understood that the touch media of Example 1 has a connected structure.

Fig. 6 is a 3-dimensional tomographic image in which it can be understood that the touch media of Example 1 has a connected structure.

Fig. 7 is a 3-dimensional tomographic image in which it can be understood that the touch media of Example 1 has a connected structure.

Hereinafter, the implementation mode of the present invention will be described in detail.

In this embodiment, the pore touch medium (hereinafter also referred to as the touch medium) is an air-permeable member, which is included in the surface of the support body and has a plurality of pores (middle pores) with gas-permeable apertures. A porous support, and an oxidation catalyst particle containing at least one of a noble metal, a noble metal oxide, and an alloy of noble metal and transition metal supported in the mesopores of the support (hereinafter also referred to as an oxidation catalyst particle). In the touch medium of this embodiment, the supporting body includes a middle hole that is connected to at least one other middle hole.

The touch media of this embodiment can decompose organic gas and other components to be processed into titanium dioxide or water by oxidation reaction, and then discharge them into the atmosphere. The gas that can be processed by the touch media of this embodiment is not particularly limited. Examples include carbon monoxide in the sidestream smoke of cigarettes, or compounds emitted by plants such as agricultural products or flowers, interior materials for automobiles, and building materials/interior materials for houses. , Substances volatilized from materials such as housings/components of home appliances, substances volatilized from organic solvents such as paints, adhesives, detergents, etc. Specifically, examples of hydrocarbons such as methane, ethane, propane, butane, ethylene, propylene, isopropylene, benzene, xylene, toluene, ethylbenzene, styrene, α-bacterene, β-bacterene, etc. Class, methanol, ethanol, 1-propanol, 1-butanol, 1-pentanol, 1-hexanol, 1-heptanol, 1-octanol, trans-2-hexenol, cis-2-hexene Alcohol, trans-3-hexenol, cis-3-hexenol, linalool, benzyl alcohol and other alcohols, formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, valeraldehyde, nonanal, benzaldehyde , Hexanal, trans-2-hexenal, cis-2-hexenal, trans-2-octenal, trans-2-nonenal, cis-2-nonenal, trans, cis-2, Aldehydes such as 6-nonadienal, trans, cis-2,4-decadienal, acetone, methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone, cyclohexanone, acetophenone and other ketones, methyl formate , Ethyl acetate, propyl acetate, isopropyl acetate, octyl acetate, hexyl acetate, benzyl acetate, methyl butyrate, ethyl butyrate, propyl butyrate, methyl salicylate, ethyl caproate Ester, propyl valerate, ethyl-2-methyl propyl, ethyl butyrate, methyl 2-methyl butyrate, ethyl 2-methyl butyrate, ethyl 3-methyl butyrate, 3 -Methyl hydroxybutyrate, methyl caproate, ethyl caproate, hexyl caproate, methyl 3-hydroxyhexanoate, octyl caproate, ethyl caprylate, methyl 3-hydroxyoctanoate, ethyl nicotinate, γ-caprolactone, γ-caprolactone, δ-caprolactone, γ-decanolide, δ-decanolide Esters, γ-laurolactone, δ-laurolactone and other esters, formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, heptanoic acid, caprylic acid, 2-methylpropionic acid, 2-methyl Butyric acid and other carboxylic acids, trans-nerolidol, cis-nerolidol, farnesol and other terpenes, or eugenol, vanillin and other phenols, ammonia Or amines such as trimethylamine and triethylamine, mercaptans such as methyl mercaptan, ethyl mercaptan, and propyl mercaptan, sulfur organic compounds such as methyl sulfide, dimethyl sulfide, dimethyl sulfide, etc.

Among them, in the decomposition of ethylene, carbon monoxide, etc., the catalyst activity is maintained for a longer period of time when the catalyst of this embodiment is used, so it is preferable. In addition, when ethylene is the decomposition target, SiO _{2 is used to} form a support, and the oxidation catalyst particles are composed of a group consisting of platinum, platinum oxide, platinum and transition metal alloy, palladium palladium oxide, and palladium and transition metal alloy. It is preferable to select one or two or more, and one or two or more selected from the group consisting of platinum, platinum oxide, and an alloy of platinum and transition metals are more preferable, and platinum oxide is more preferable . When carbon monoxide is used as a decomposition target, a metal oxide is used to form a support, and it is more preferable that the oxidation catalyst particles contain gold and/or an alloy of gold and transition metals.

In this specification, mesopores refer to pores with a diameter of 2 nm or more and 50 nm or less obtained by the BET method, and refer to pores where the opening on the surface of the touch medium communicates with other openings. The shape of the middle hole or the positional relationship of the openings thereof are not particularly limited.

In the touch medium of this embodiment, one middle hole is branched inside the support body and communicates with the other middle holes (hereinafter, also referred to as a connected structure). Also, whether the support has a connected structure can be penetrated by 3 dimensions Type electron microscope (TEM) to confirm.

The touch media of this embodiment can be in various forms such as powder, particle, and film. Among them, a film shape, particularly a film shape having a film thickness of 1000 nm or less, is less likely to cause a decrease in the catalyst efficiency, so it is preferable. In addition, if it is a powder, it can be used in various shapes and forms, so it is preferred. In the case of powder, the size is not particularly limited, and can be appropriately set by those skilled in the art.

By exposing the gas to be processed to the contact medium of this embodiment, the gas to be processed diffuses into the medium and comes into contact with the oxidation catalyst particles in the pores, and the organic gas and other components to be processed are oxidized and decomposed.

The former powdered medium-hole contact media, the medium-hole does not have a connecting structure, and a cylinder structure in which the upper opening of the support body with one middle hole communicates with the lower opening linearly. In this case, even if there is only one occluded part in the middle hole due to adsorption of water, the air permeability of the middle hole is lost, especially in the case of powder, the distance from the inside of the middle hole to the air flow is relatively long The part, in this part, will be in a state where it is difficult for the moisture adsorbed inside the powder to escape. Therefore, it is inferred that in the former mesoporous contact media, the occlusion of the mesopores due to adsorption of water is likely to occur, which reduces the catalyst activity.

On the other hand, the communication structure is connected with the holes in the support body, so even if moisture adheres inside the support body, it is not easy to damage the air permeability, and it is not easy to hinder the oxidation catalyst particles and the gas to be processed in the holes in the support body. Of contact. As a result, regardless of the shape of the catalyst medium such as powder, granule, film, etc., the catalyst activity can be maintained for a longer period of time.

In addition, in the touch medium of this embodiment, as long as it has a connecting structure, the purpose of the invention can be achieved, and a part of the middle hole may contain a part that is not connected to other middle holes.

In the catalyst of this embodiment, the diameter of the mesoporous hole is not particularly limited as long as it satisfies the aforementioned definition. However, the average diameter according to the BET method is 2 nm or more and 10 nm or less, and the particle diameter of the supported oxidation catalyst particles is also Within this range, a contact medium with higher activity can be obtained, so it is preferable.

In addition, the diameter of the pores of the support body related to this embodiment is a value calculated using an automatic specific surface area/pore distribution measuring device according to the BET method in accordance with the Japanese Industrial Standard JIS-Z-8831.

The oxidation catalyst particles are not particularly limited as long as they contain at least one of a precious metal, a precious metal oxide, and an alloy of a precious metal and a transition metal, which has a catalytic function that promotes the oxidation reaction.

In this specification, precious metals refer to ruthenium, rhodium, palladium, osmium, iridium and platinum of the gold, silver and platinum groups. Noble metal oxides are the aforementioned noble metal oxides and their hydrates, specifically Au ₂ O ₃ , Ag ₂ O, AgO, Ag ₂ O. Ag ₂ O ₃ , RuO ₂ , RuO ₄ , Rh ₂ O ₃ , PdO, OsO ₂ , OsO ₄ , IrO ₂ , Ir ₂ O ₃ . nH ₂ O, PtO ₂ , PtO ₂ . H ₂ O, platinum black, etc.

The transition metal of the alloy is not particularly limited as long as it can form an alloy with the noble metal. Examples include Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Tc , Ru, Rh, Pd, Ag, Cd, W, etc.

Preferably, one or two or more selected from the group consisting of gold, platinum, palladium, oxides of these, and alloys of at least any one of gold, platinum, and palladium, and transition metals with higher oxidation catalyst ability The way to form oxidation catalyst particles is better. In this case, suitable components of the oxidation catalyst particles include Au, Pt, Pd, PdO, Au ₂ O ₃ , PtO ₂ , and PtO ₂ . A particle composed of one or more selected from the group consisting of H _{2 O and platinum black.}

If the average particle size of the oxidation catalyst particles is 10nm or less (more preferably 1nm or more and 10nm or less, still more preferably 1nm or more and less than 10nm, and still more preferably 1nm or more and 6nm or less), the oxidation catalyst particles It is preferable that the specific surface area increases and the catalyst activity greatly increases the decomposition efficiency of the components of the treatment target in the gas to be treated, and therefore it is better.

In addition, the average particle size of the oxidation catalyst particles is calculated from the image photograph of a transmission electron microscope (TEM), and the average value can be obtained.

The oxidation catalyst particles preferably support 0.1-30 mass% (mass %) of the support containing the oxidation catalyst particles, 0.5-20 mass% is more preferable, and 0.5-10 mass% is even more preferable. If the support is more than 30% by mass, the oxidation catalyst particles will easily agglomerate with each other, and the catalyst activity will be reduced compared to when it is within the range. If it is less than 0.1% by mass, the catalyst activity cannot be sufficiently obtained compared with the case within the range, so it is not preferable.

In addition, in addition to the oxidation catalyst particles, the catalyst in this embodiment may also include auxiliary catalyst particles, various metal elements, and the like, and it is not particularly limited. Specifically, it may be a mixture of co-catalyst particles and oxidation catalyst particles, or a composite catalyst composed of composite particles composed of various metal elements and oxidation catalyst particles. When the oxidation catalyst particles exist alone or when the oxidation catalyst particles are mixed with a co-catalyst, the oxidation catalyst particles may be within the aforementioned size range. In addition, compounded its In the case of composite particles of other metal elements, as long as the size of the composite particles is within the aforementioned size range. Metal particles (nanoparticles) other than the catalyst particles used in the co-catalyst or composite catalyst include base metals and oxides of these. The particles of these noble metals and their oxides, base metals and their oxides can also be mixed with two or more types so as to be supported on the inner surface of the pores of the support.

Regarding the support body with mesopores in this embodiment, considering that it includes the steps of forming mesopores using a compound that becomes a mold, and heating to remove the compound, it should be made of a material that does not degrade above the heating temperature. The material is better.

The support body related to this embodiment can be formed of a metal oxide. The support composed of metal oxide acts on the catalyst particles to increase the catalyst activity of the catalyst.

Metal oxides are oxides of metals. The so-called metals refer to groups 1 (except for H), 2 to 12, 13 (except for B), 14 (except for C and Si), and 15 of the periodic table. N, P, and As are excluded), and 16 (except O, S, Se, and Te) elements, as well as lanthanoid and actinoid elements. Metal oxides, for example, γ-Al ₂ O ₃ , α-Al ₂ O ₃ , θ-Al ₂ O ₃ , η-Al ₂ O ₃ , amorphous Al ₂ O ₃ , TiO ₂ , ZrO ₂ , SnO ₂ , MgO, ZnO ₂ , Bi ₂ O ₃ , In ₂ O ₃ , MnO ₂ , Mn ₂ O ₃ , Nb ₂ O ₅ , FeO, Fe ₂ O ₃ , Fe ₃ O ₄ , Sb ₂ O ₃ , CuO, Cu ₂ O, NiO, Ni ₃ O ₄ , Ni ₂ O ₃ , CoO, Co ₃ O ₄ , Co ₂ O ₃ , WO ₃ , CeO ₂ , Pr ₆ O ₁₁ , Y ₂ O ₃ , In ₂ O ₃ , PbO , ThO ₂ and other metal oxides. In addition, the metal oxide may also be, for example, Al ₂ O ₃ -TiO ₂ , Al ₂ O ₃ -ZrO ₂ , Al ₂ O ₃ -CaO, Al ₂ O ₃ -CeO ₂ , Al ₂ O ₃ -Fe ₂ O ₃ , TiO ₂ -CeO ₂ , TiO2- _{ZrO 2} , TiO _{2 -WO 3} , ZrO ₂ -WO ₃ , SnO ₂ -WO ₃ , CeO ₂ -ZrO ₂ , Al ₂ O ₃ -TiO ₂ -ZrO ₂ , cerium/zirconium/ A composite oxide containing two or more metals such as bismuth composite oxide. In addition, the cerium/zirconium/bismuth composite oxide is _{a solid solution represented by the general formula Ce 1-XY} Zr _X Bi _Y O _2-δ , and the values of X, Y, and δ are 0.1≦X≦0.3, 0.1≦Y, respectively The range of ≦0.3, 0.05≦δ≦0.15.

In addition, the support may be formed of _{SiO 2.}

The material of these supports may be selected in accordance with the type of processing target gas, etc., equipment to which the touch media is applied, or various environmental conditions. SiO ₂ , TiO ₂ , Fe ₂ O ₃ , ZrO ₂ , and CeO ₂ can support the catalyst particles more firmly, and at the same time, it can be more strongly bonded to the substrate when the substrate is used, so it is better.

As described above, the shape of the support body of the touch medium of this embodiment is not particularly limited, and may be, for example, powder, granular, film, or the like. On the other hand, the shape of the support is preferably a film shape.

When the support is in the form of a film, the distance between the middle hole where the oxidation catalyst particles exist and the gas flow to be processed is relatively short compared with other shapes such as powdered catalysts. Therefore, when moisture in the gas is adsorbed in the mesopores of the film-like contact medium, a concentration gradient will occur in the gas flow to be processed, and the adsorbed water will be re-diffused into the gas flow. As a result, the adsorbed water will be suppressed to a certain amount. Thereby, when the support body has a film-like shape, it becomes a structure in which the occlusion of the mesopore is less likely to occur.

In addition, in this specification, the "film-like shape" refers to a shape such as a layer that partitions a space or covers at least a part of an object.

The touch media of this embodiment, for example, can be made on the substrate The top is formed into a film shape. At this time, whether or not the substrate has air permeability is not particularly limited. When the contact medium of this embodiment is arranged on a non-air-permeable base material, the surface of the contact medium may be embossed or the like to form irregularities. If the surface of the contact medium is formed with unevenness, the contact area with the gas flowing is increased, and the oxidation reaction of the gas to be processed can be further promoted.

If the substrate of the contact medium of this embodiment is formed into a film shape on its surface is a filter-like or mesh-like substrate that is permeable, the gas to be processed can also be used in the thickness direction of the contact medium of this embodiment Circulation. In addition, when the substrate has a shape such as a plate, the touch media of this embodiment can also be formed on both sides of the substrate. Which type to use may depend on the design of the device incorporating the touch media of this embodiment, etc. Decide.

When the touch medium of this embodiment has a film-like shape, the film thickness is preferably 50 nm or more and 1000 nm or less. If it is less than 50 nm, the absolute amount of the catalyst decreases, so it is more difficult to decompose the organic gas in the gas to be processed than when it is within the range. If it is larger than 1000 nm, the moisture adsorbed in the pores in the position away from the gas to be processed becomes difficult to release again, and the amount of moisture adsorbed in the pores increases, hindering the action of the oxidation catalyst particles. Compared with the occasions within the range, the catalyst efficiency of the catalyst medium is reduced.

In addition, the film thickness when the touch medium of this embodiment has a film-like shape can be measured by observing the cross-section of the film by TEM and measuring the size of the cross-sectional image.

The touch media of this embodiment can be formed on a substrate. When the touch medium of this embodiment is formed into a film on the base material, it is easier to make the film thickness of the touch medium thinner. The substrate, as mentioned before, It may be a structure without air permeability such as a plate shape, or a structure having air permeability. As a structure having air permeability, for example, a sheet-like, fiber-like, cloth-like, mesh-like fibrous structure (filtered fabric, mesh, non-woven fabric, etc.) in which many through holes are formed by press processing Vessel-like). Other shapes and sizes suitable for the purpose of use can also be appropriately used.

When the substrate on which the film-like contact medium is formed is heated when the support is formed into a film, it is preferable to use a material having heat resistance that can withstand the heating temperature. Specifically, it is preferable to use metal materials, ceramics, glass, carbon fibers, silicon carbide fibers, or heat-resistant organic polymer materials, and more preferably metals, metal oxides, and glass.

As the metal material used for the substrate, high melting point metals such as tungsten, molybdenum, tantalum, niobium, TZM (Titanium Zirconium Molybdenum), W-Re (Tungsten-rhenium), or precious metals such as silver and ruthenium, and alloys of these can be used Or special metals such as oxide, titanium, nickel, zirconium, chromium, Inconel, Hastelloy (acid-resistant and heat-resistant nickel-based super alloy), aluminum, copper, stainless steel, zinc, magnesium, iron, etc. The metal used is an alloy containing these general-purpose metals or oxides of these general-purpose metals. In addition, it is also possible to use various plating and vacuum vapor deposition, or CVD method, sputtering method, etc., to form the member on which the aforementioned metal, alloy, or oxide film is formed, as a metal material.

In addition, a natural oxide film is usually formed on the aforementioned metal surface and its alloy surface, and when the support is formed of a silane compound, the natural oxide film can be used to firmly fix the substrate and the support. here In this case, it is preferable to remove oil or dirt adhering to the surface of the oxide film by a conventional method, so that it can be fixed stably and firmly. In addition, instead of using a natural oxide film, an oxide film can be chemically formed on a metal surface or an alloy surface by a conventional method, or an oxide film can be formed by an electrochemical conventional method such as anodization.

Furthermore, ceramics used for the base material include ceramics such as earthenware, pottery, stoneware, and porcelain, and ceramics such as glass, cement, plaster, enamel, and fine ceramics. The composition of the constituted ceramics can include element series, oxide series, hydroxide series, carbide series, carbonate series, nitride series, halide series, and phosphate series. In addition, it can also be a composite of these Things.

In addition, as ceramics used for the substrate, there can be mentioned barium titanate, lead zirconate titanate, ferrite, alumina, forsterite, zirconia, zircon, and mullite. (mullite), steatite, cordierite, aluminum nitride, silicon nitride, silicon carbide, new carbon material, new glass, etc., or high-strength ceramics, functional ceramics, superconducting ceramics, nonlinear Ceramics such as optical ceramics, antibacterial ceramics, biodegradable ceramics, and biomedical ceramics.

In addition, the glass used for the substrate includes soda lime glass, alkali glass, crystal glass, quartz glass, chalcogenide glass, uranium glass, water glass, polarized glass, tempered glass, Laminated glass (laminated glass), heat-resistant glass, borosilicate glass, bulletproof glass, glass fiber, dichroic glass (dichroic glass), gold stone (tea lapis, aventurine, amethyst), glass Ceramics, low melting point glass, metallic glass, and sapphire glass (Saphiret) and other glass.

In addition, in addition to the base material, ordinary Portland cement, quick-drying Portland cement, ultra-fast-drying Portland cement, moderate thermal Portland cement, low-heat Portland cement, Sulfate-resistant Portland cement, and Portland cement mixed with blast furnace ash, fly ash, and silicic acid-based admixtures are cements such as blast furnace cement, portland cement, and fly ash cement.

In addition, titanium dioxide, zirconia, alumina, cerium oxide (Ceria), zeolite, apatite, silica, activated carbon, diatomaceous earth, etc. can be used in addition to the base material. Furthermore, as the base material, metal oxides such as chromium, manganese, iron, cobalt, nickel, copper, and tin can also be used.

Furthermore, polyimide, polyetheretherketone, polyphenylene sulfide, polyaramide, benzothiazole, polybenzoxazole, polybenzimidazole, polyquinoline (quinoline ), quinoxaline (quinoxaline), fluororesin, etc., or thermosetting resin such as phenol resin or epoxy resin, etc. heat-resistant organic polymer materials known to those skilled in the art.

Next, an example of a method of obtaining the touch media of this embodiment will be described.

The contact medium of this embodiment can be obtained by forming a hydrolyzable product containing alkoxysilane or alkoxide, and drying and firing a solution containing a surfactant. The support body of the hole, and make and correspond to the noble metal, its oxide, and noble metal and The solution of at least one compound of the transition metal alloy or the colloidal solution of the noble metal compound is contacted, and the sintering and/or reduction treatment is performed to form a noble metal, its oxide, and a noble metal and a transition metal in the pores in the support. It is obtained by oxidizing catalyst particles of at least one kind of alloy.

In this method, the support is first formed.

The support having mesopores, for example, can be obtained by forming a support precursor in which a substance that functions as a mold for the mesopore is contained in the inside, and then decomposing and removing the substance that functions as a mold to form a mesopore.

An example of this method is described. First, a solution (hereinafter referred to as a precursor solution) containing a water-decomposed product of a surfactant used as a mold and an alkoxide or metal alkoxide (alkoxide) is prepared. Specifically, for example, an alkoxide or alkoxide is added to a solution in which a surfactant is dissolved, and the pH is adjusted to hydrolyze the alkoxide or alkoxide. Thereby, a hydrolyzable product having a silanol group or a metal hydroxide is produced. Surfactants form micelles in the solution and become mesoporous molds. By heating the precursor solution to volatilize the solvent, the silanol group or the metal hydroxide is condensed and hardened at the same time to form the support precursor. Thereafter, by firing at a high temperature of 300° C. or higher, the surfactant of the mold in the precursor is decomposed and volatilized to be removed, and a support with mesopores is obtained.

In addition, the film-like support can be obtained, for example, by applying a precursor solution to the base material and heating to volatilize the solvent to perform condensation hardening or the like. In addition, if the precursor solution is formed into particles with a spray dryer or the like, and then the solvent is volatilized and condensation hardened, a powder support can be obtained. In addition, the support of powder The support body can also be obtained by crushing after obtaining a solid support body in the foregoing steps.

The precursor solution may include, for example, (1) hydrolyzed product of alkoxysilane or metal alkoxide, (2) solvent (solvent), and (3) surfactant. For alkoxysilanes or metal alkoxides (alkoxides) in the solution to undergo hydrolysis treatment to obtain hydrolysis products, water is necessary, so the solvent is water, or a mixed solvent of water and alcohols such as ethanol or methanol. For better. In addition, a catalyst used for the hydrolysis treatment of alkoxysilanes or metal alkoxides (alkoxide) may be further included in the solution, and it is preferable to use acids such as nitric acid and hydrochloric acid as the catalyst.

The ratio of the surfactant, alkoxysilane, or metal alkoxide (alkoxide) is not particularly limited, and can be set appropriately, and is not particularly limited. By changing the molar ratio of surfactant/alkoxysilane or alkoxide, the probability and porosity of the obtained support can be controlled.

In addition, when forming a film-like support, it is particularly preferable to form a film with a more uniform film thickness by generating precipitates in the middle of the precursor solution before coating the substrate. Alcohols with acidic pH can avoid precipitation of precursors. As other methods, you can adjust only the molar ratio of water and alkoxysilane or metal alkoxide, or adjust the molar ratio together with pH adjustment, or add alcohol, or perform both molar ratio adjustment and alcohol addition. Avoid precipitation.

As the surfactant, for example, a nonionic surfactant or a cationic surfactant can be used.

Nonionic surfactants, for example, polyvalent alcohol fatty acid esters, Polyoxyalkylene (polyoxyalkylene) fatty acid ester, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether or polyalkylene oxide block copolymer, etc.

Among them, when polyoxyethylene ether or polyalkylene oxide block copolymer is used as the nonionic surfactant, a catalyst that is less likely to decrease in catalyst activity can be obtained, so it is preferred. In addition, for the same reason, it is also better to use a cationic surfactant.

As the polyoxyethylene alkyl ether, C ₁₂ H ₂₅ (OCH ₂ CH ₂ ) _n OH (n is 2 to 100), C ₁₆ H ₃₃ (OCH ₂ CH ₂ ) _n OH (n is 2 to 100) can be used specifically , C ₁₈ H ₃₇ (OCH ₂ CH ₂ ) _n OH (n is 2~100), etc., can also be used alone or as a mixture. Commercially available polyoxyethylene ethers such as Brij (registered trademark) 56, Brij76, and Brij78 can also be used.

Examples of polyalkylene oxide block copolymers include polyalkylene oxide triblock copolymers of ethylene oxide and propylene oxide. More specifically, Pluronic (registered trademark) L121, P123 and other Pluronic interfacial actives can be exemplified. Agent.

Examples of cationic surfactants include dioctadecyldimethylammonium chloride, hydroxychloroaniline, cetylpyridinium chloride, cetyltrimethylammonium bromide, and didecyldimethylammonium chloride. Ammonium chloride, dequalinium chloride, etc.

The molecular chain length of the surfactant will affect the diameter of the mesopores. As long as the surfactant is selected according to the pore diameter of the target. In addition, hydrophobic compounds such as 1,3,5-trimethylbenzene, 1,3,5-triethylbenzene, 1,3,5-triisopropylbenzene, n-heptane, etc. are added to the precursor solution Alternatively, the hydrophobic compound increases the diameter of micelles in the precursor solution, so it is used to adjust the pore diameter of the mesopores.

Examples of alkoxysilanes include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, methyltrimethoxysilane, methyltriethoxysilane, n-propane Trimethoxysilane, n-propyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, octyltriethoxysilane, decyltrimethoxysilane, etc.

Metal alkoxides (alkoxides) include, for example, aluminum tetrapropoxide, tin tetrapropoxide, titanium tetrapropoxide, zirconium tetrapropoxide, and the like.

As described above, when a film-like support is formed on a substrate, a precursor solution is applied to the substrate to form a film-like support. The method of coating the precursor solution on the substrate is sufficient as long as it is a method that can uniformly apply the precursor solution thinly. Spin coating method or immersion blowing of the substrate after immersing the substrate in the precursor solution and blowing off the unnecessary solution may be used. The dip & blow method or the like may be selected in accordance with the shape of the substrate to be coated and the like.

In addition, the heating conditions for removing the mold molecules after forming the precursor are also not particularly limited. For example, the precursor may be heated at 300 to 600°C.

Secondly, the oxidized catalyst particles are supported in the holes in the support body to obtain the catalyst medium of this embodiment. First, contact with a solution or colloidal solution of a compound corresponding to at least one of the noble metal, its oxide, or the alloy of noble metal and transition metal contained in the support and the supported oxidation catalyst particles (hereinafter, also this (Referred to as precious metal compound solution for short), the precious metal compound solution is introduced into the hole in the support. When an alloy of a noble metal and a transition metal is contained in the oxidation catalyst particles, it is only necessary to use a solution in which a compound corresponding to the noble metal is dissolved, and a salt of the transition metal is dissolved as a noble metal compound solution. Afterwards, by Carrying out firing and/or reduction treatments to form oxidation catalyst particles in the mesopores to obtain the contact medium of this embodiment.

Specifically, for example, the support may be immersed in a precious metal compound solution, and then sintered and/or reduced.

More specifically, the precious metal compound solution is heated to 20 to 90°C, preferably to 50 to 70°C, and adjusted to pH 3 to 10, preferably to pH 5 to 8, with an alkali solution while stirring. Next, the support is immersed in the noble metal compound solution, and then a reduced-pressure degassing treatment is performed to impregnate the noble metal compound solution into the pores. Thereafter, by heating and firing at 200 to 600°C, oxidation catalyst particles containing precious metals and the like in the pores can be obtained.

In addition, after impregnating the noble metal compound solution into the pores as described above, the hydrogen reduction method of sintering at 200 to 600°C and exposure to hydrogen flow at 100 to 300°C, or immersion in sodium borohydride solution Known reduction operations such as the liquid phase reduction method can also form oxidation catalyst particles in the pores. In addition, depending on the type of compound contained in the noble metal compound solution, it is possible to obtain oxidation catalyst particles in the pores only by heating and sintering at 200 to 600° C. without performing the aforementioned known reduction operation. In addition, the reduction of the compound contained in the noble metal compound solution is only part, and the oxidation catalyst particles in the mesopores may be noble metal monomers and noble metal oxides coexisting.

Corresponding to the noble metal, its oxide, or the alloy of noble metal and transition metal constituting the oxidation catalyst particles, as a compound containing noble metal elements, for example, a gold compound may be HAuCl ₄ . 4H ₂ O, NH ₄ AuCl ₄ , KAuCl ₄ . nH ₂ O, KAu(CN) ₄ , Na ₂ AuCl ₄ , KAuBr ₄ . 2H ₂ O, NaAuBr _4, etc., platinum compounds include chloroplatinic acid, dinitrosodiamine platinum, dichlorotetraammine platinum, etc., and palladium compounds include dinitrosodiamine palladium and palladium chloride Acid ammonia and so on.

The concentration of the noble metal compound in the noble metal compound solution is not particularly limited, but it is better to prepare a solution of 1×10 ^-2 to 1×10 ^-5 mol/L because the generated oxidation catalyst particles are not easy to agglomerate.

The transition metal salt contained in the noble metal compound solution is not particularly limited as long as it is a compound that is soluble in the solution and does not cause precipitation when it coexists with the metal compound corresponding to the noble metal or noble metal oxide. It is not particularly limited and can be used as examples. Halides, nitrates, carbonates, bicarbonates, carboxylates, etc. of transition metals such as chlorides and bromides. The concentration of the transition metal salt is not particularly limited, but ^{it is preferably prepared as a solution of 1×10 -2} to 1×10 ^-5 mol/L, since the generated oxidation catalyst particles are not easy to agglomerate.

As mentioned above, the touch medium of this embodiment is provided with holes in the support having air permeability and connected structure to support the oxidation of one or more of precious metals, precious metal oxides, and alloys of precious metals and transition metals. Compared with the previous technology, the composition of the catalyst particles can maintain the activity for a longer period of time.

In addition, the contact medium of this embodiment can also decompose and remove ethylene and the like at a temperature lower than room temperature (23.4°C). Furthermore, it varies with the size of the contact medium, but it can be decomposed and removed even at a concentration of about 0.5 ppm.

The hole contact medium in this embodiment can be used to construct a member or device that can remove organic gas components and the like.

Examples of such components or devices include air purifiers, air conditioners, ice Filters such as boxes, or air purification filters, packaging components such as green fruits or flowers installed in warehouses or display cabinets, or exhaust gas purification devices such as internal combustion engines, or water vapor reformers for fuel cells, etc. Furthermore, for green fruits or flowers, articles that can be used for various purposes such as raw food, food processing, or viewing (freshness preserving agent) can also be provided with the hole contact medium in this embodiment. .

Next, the gas processing device using the touch medium of this embodiment will be explained. In addition, in the following, as an example of the touch medium of this embodiment, a case where a film-like touch medium (touch medium film) is used is exemplified.

FIG. 1 is a diagram schematically showing a part of a cross-section of a gas processing device 200 of the first embodiment. The gas processing device 200 of this embodiment uses the components to be processed in the gas to be processed that is supplied to the gas processing device 200 in the direction of arrow A. The plasma and the contact medium film 100 generated in the gas processing device 200 The function of oxidizing and decomposing device.

The gas processing device 200 has a plasma generating unit including an application electrode 11, a ground electrode 12, and a dielectric substance 13. The application electrode 11 is connected to a (high-voltage) power source 14 of the power supply unit. The ground electrode 12 and the application electrode 11 are arranged to face each other, and a dielectric 13 is arranged between the ground electrode 12 and the application electrode 11. The dielectric 13 is only in close contact with the ground electrode 12 and is isolated from the application electrode 11. In the gas processing device 200, the application electrode 11, the ground electrode 12 and the dielectric substance 13 are components/devices (plasma generation part) for generating plasma. The power supply 14 is used to connect the application electrode 11 and the ground electrode 12 Applying a voltage, by applying the electrode 11, the ground electrode 12 and the dielectric 13, a low-temperature plasma reaction layer caused by the discharge is formed between the applying electrode 11 and the dielectric 13 (Area where plasma exists). In addition, one of the application electrode 11 and the ground electrode 12 is the first electrode, and the other is the second electrode. In addition, in other embodiments, even when the application electrode 11 and the ground electrode 12 are respectively combined in plural, the plural electrodes of one type are the first electrodes, and the plural electrodes of the other type are the second electrodes. In addition, the dielectric 13 is only provided between the ground electrode 12 and the touch media film 100 but is not limited to this. For example, in addition to the ground electrode 12 and the touch media film 100, it is provided between the application electrode 11 and the touch media film 100. Between time is also possible.

The application electrode 11 is an electrode to which a voltage is applied by the power supply 14. The ground electrode 12 is grounded by a ground wire 12a. Next, the application electrode 11, the ground electrode 12, and the dielectric substance 13 have a structure in which the gas to be processed can pass through. Specifically, as the structure of the application electrode 11, the ground electrode 12, and the dielectric 13, a grid-like or curtain-like structure, a porous or expanded mesh-like structure, or a honeycomb-like structure (hereinafter It is abbreviated as honeycomb), and two or more of these structures can be combined. The application electrode 11 and the ground electrode 12 may have a needle-shaped structure. In addition, the application electrode 11, the ground electrode 12, and the dielectric 13 may have the same shape/structure among the aforementioned shapes/structures. In FIG. 1, the application electrode 11 has many small openings like a mesh, and the ground electrode 12 and the dielectric 13 have a few large openings like a porous shape caused by punching.

The gas to be processed supplied from the direction of arrow A to the plasma generating part passes through the opening formed in the application electrode 11 to reach the low-temperature plasma reaction layer formed between the application electrode 11 and the dielectric 13. The gas to be processed that reaches the low-temperature plasma reaction layer is directly discharged to the outside of the plasma generation part, or It passes through the opening formed in the dielectric 13 and the opening formed in the ground electrode 12 and is discharged to the outside of the plasma generating part. In short, the plasma generating part is formed by openings formed in the application electrode 11 and the ground electrode 12 and the dielectric 13 and a low-temperature plasma reaction layer formed between the application electrode 11 and the dielectric 13 Composition of the runner.

In the flow channel formed in the plasma generating part, in the low-temperature plasma reaction layer (between the application electrode 11 and the dielectric 13 ), a contact medium film 100 in close contact with the contact medium 13 and the application electrode 11 is arranged. Therefore, the gas to be processed flowing through the flow channel and reaching the low-temperature plasma reaction layer can pass through the contact medium film 100 through the middle hole. That is, the components to be processed in the gas to be processed are oxidized and decomposed by the function of the contact medium film 100 by the action of plasma.

The application electrode 11 and the ground electrode 12 used in the gas processing device 200 can use materials that function as electrodes. As the material of the application electrode 11 and the ground electrode 12, for example, metals such as Cu, Ag, Au, Ni, Cr, Fe, Al, Ti, W, Ta, Mo, Co, or alloys thereof can be used.

The dielectric 13 only needs to have the properties of an insulator. Examples of the material of the dielectric substance 13 include ZrO ₂ , γ-Al ₂ O ₃ , α-Al ₂ O ₃ , θ-Al ₂ O ₃ , η-Al ₂ O ₃ , and amorphous Al ₂ O ₃ , Aluminum nitride, mullite, talc, forsterite, cordierite, magnesium titanate, barium titanate, SiC, Si ₃ N ₄ , Si-SiC, mica, glass And other inorganic materials, or polyimide, liquid crystal polymer, PTFE (polytetrafluoroethylene), ETFE (ethylenetetrafluoroethylene), PVF (polyvinylfluoride), PVDF (polyvinylidene difluoride), polyether imide, poly imide, etc. Molecular materials. In consideration of plasma resistance and heat resistance, inorganic materials are preferred.

In addition, when the contact medium film 100 also has a function as a dielectric as described above (for example, when a part of the contact medium is an insulator), the contact medium film 100 can also be used as a dielectric, so it does not have a dielectric. Electricity quality 13 is also possible. In addition, in the gas processing device 200 of this embodiment, the usage conditions such as the amount or flow rate of the gas to be processed flowing through the flow channel are not particularly limited. For example, a blower is connected to the gas processing device 200 so that a specific amount of the gas to be processed can be sent to the flow channel at a specific flow rate. The gas processing device 200 can be placed in the gas to be processed and only the gas to be processed can flow into the flow naturally. The way is also possible.

The power source 14 is a power source that can apply a high voltage. As the power source 14, a high-voltage power source such as an alternating high voltage, a pulsed high voltage, a power source in which an alternating current or a pulse is superimposed on a DC bias, and the like can be used. As an example of AC high voltage, sine wave AC, rectangular wave AC, triangle wave AC, saw wave AC, etc. can be cited. With this power supply 14, a specific voltage can be applied between the application electrode 11 and the ground electrode 12 in such a manner that plasma is generated in the discharge space formed by the application electrode 11, the connection electrode 12 and the dielectric 13. Depending on the applied voltage of the power supply 14, it will vary with the concentration of the component to be processed in the gas to be processed, etc., and it can usually be 1-20 kV, preferably 2-10 kV. In addition, as the type of discharge generated by the power supplied from the power supply 14 for generating plasma, there is no special feature as long as it can generate plasma. It is not limited, and it may be, for example, silent discharge, creeping discharge, corona discharge, or pulse discharge. In addition, two or more types of these discharges may be combined to generate plasma.

In addition, the output frequency of the power supply 14 is preferably a high frequency, and specifically may be 0.5 kHz or more. Furthermore, it is preferably 0.5 kHz or more and 30 kHz or less, and more preferably 1 kHz or more and 20 kHz or less. If the frequency is lower than 0.5kHz, the amount of intermediate products or ozone generation may increase. If the frequency is greater than 30kHz, the decomposition of any component of the treatment object due to oxidation will be suppressed.

In addition, in this embodiment, the dielectric 13 is formed in close contact with the ground electrode 12, but it is not limited to this. As long as plasma can be generated, the dielectric 13 is in close contact with at least one of the application electrode 11 and the ground electrode 12. In addition, a configuration in which the dielectric substance 13 and the application electrode 11 and the ground electrode 12 are arranged in close contact with each other, and the contact medium film 100 is provided between the two dielectric substances 13 may be adopted. Furthermore, when the touch media film 100 is formed on the aforementioned substrate, the dielectric 13 can be used as the substrate.

Next, the gas processing device 300 of the second embodiment will be described. In this embodiment, for members having the same functions as those described in the first embodiment, the same symbols are used, and detailed descriptions are omitted. In the following, the differences from the first embodiment are mainly explained.

FIG. 2 is a diagram schematically showing a part of the cross-section of the gas processing device 300 of the second embodiment. The gas processing device 300 of this embodiment generates plasma by silent discharge. The gas processing device 300 of this embodiment is disposed between the application electrode 11 and the ground electrode 12 to face each other In the laminated structure of the two dielectrics 13, the respective dielectrics 13 are in close contact with the application electrode 11 and the ground electrode 12.

The gas processing device 300 uses a high-voltage power supply 14 to apply a voltage between the application electrode 11 and the ground electrode 12 to form a low-temperature plasma reaction layer generated by electric discharge between the two dielectric substances 13. In addition, in FIG. 2, the dielectric substance 13 is laminated in close contact with both the application electrode 11 and the ground electrode 12, but the dielectric substance 13 may be in close contact with one of them.

In the gas processing device 300 of this embodiment, the application electrode 11, the ground electrode 12, and the dielectric 13 have a non-permeable structure through which the processed gas cannot pass. Therefore, the gas to be processed supplied to the plasma generating part in the direction of arrow a in FIG. 2 passes through the low-temperature plasma reaction layer formed between the two dielectric substances 13 and is discharged to the outside of the plasma generating part (arrow b direction). In short, in the plasma generating part, a flow channel formed by a low-temperature plasma reaction layer (a region where plasma exists) formed between two dielectric substances 13 is formed. In the flow channel formed in the low-temperature plasma reaction layer, two opposing contact media 100 in close contact with different dielectrics 13 are arranged at a specific interval. Therefore, the gas to be processed flowing through the low-temperature plasma reaction layer can pass through the contact medium film 100 through the middle hole. That is, the components to be processed in the gas to be processed are oxidized and decomposed by the function of the contact medium film 100 by the action of the plasma similarly to the first embodiment. In addition, the contact medium film 100 may be in close contact with the dielectric 13 or not. Depending on the amount of the processed gas to be processed, when the pressure loss of the flow channel becomes high, it is preferable that the contact medium film 100 is not in close contact with the dielectric 13. In addition, in this embodiment, the touch media film 100 can also be used as the dielectric 13, and the dielectric 13 can also be used as the blanket. The base material of the touch media film 100 is formed and used.

The gas processing device 300 adopts a multilayer structure, making it easy to secure a flow path. Therefore, it is easy to increase the amount of gas to be processed, and it is possible to efficiently decompose a large amount of components to be processed. The gas processing device 300 is installed in such a way that the components can be oxidized and decomposed efficiently in accordance with usage conditions such as the amount of the component to be processed or the flow rate. The touch media film 100 can be a single layer or can be divided into multiple layers, and can be set arbitrarily.

Next, the gas processing device 400 of the third embodiment will be described. In this embodiment, for members having the same functions as those described in the first embodiment, the same symbols are used, and detailed descriptions are omitted. Hereinafter, the difference from the first embodiment will be mainly explained.

FIG. 3 is a diagram schematically showing a part of the cross-section of the gas processing device 400 of the third embodiment. In the gas processing device 400 of this embodiment, there are two ground electrodes 12 opposed to each other, two dielectric substances 13 arranged between the two ground electrodes 12, and two dielectric substances 13 arranged between them. Between the application electrode 11. The ground electrode 12 and the dielectric substance 13 are in close contact with each other, and the dielectric substance 13 and the application electrode 11 are arranged at a predetermined interval. The gas processing device 400 uses a high-voltage power supply 14 to apply a voltage between the application electrode 11 and the ground electrode 12, so that plasma can be generated between the two dielectric substances 13 and the application electrode 11, and the application electrode 11 can be formed. The 2 plasma reaction layers.

In the gas processing device 400 of this embodiment, the ground electrode 12 and the dielectric 13 have a non-permeable structure through which the processed gas cannot pass. On the other hand, the application electrode 11 has a plurality of openings and has a gas-permeable structure through which the gas to be processed can pass. Therefore, by the arrow a in Figure 2 The gas to be processed supplied to the plasma generation part moves to the two plasma reaction layers through the openings formed in the application electrode 11, and at the same time passes through the low-temperature plasma reaction layer, and is discharged to the outside of the plasma generation part. In short, in the plasma generating part, a flow channel formed by the opening formed in the application electrode 11 and two plasma reaction layers is formed.

In the flow channel formed in the plasma generating part, two low-temperature plasma reaction layers (between the two dielectric substances 13 and the application electrode 11) are respectively arranged with a contact medium film 100 in close contact with the application electrode 11 . Therefore, the gas to be processed flowing through the flow channel can pass through the contact medium film 100 through the middle hole. That is, the components to be processed in the processed body are oxidized and decomposed by the function of the contact media film 100 by the action of plasma.

The gas processing device 400, like the gas processing device 300 of the second embodiment, has a multi-layer structure, which makes it easy to secure a flow path. Therefore, it is easy to increase the amount of gas to be processed, and it is possible to efficiently decompose a large amount of components to be processed. The gas processing device 400 is installed in such a way that the components can be oxidized and decomposed efficiently in accordance with usage conditions such as the amount of the component to be processed or the flow rate. The touch media film 100 can be a single layer or can be divided into multiple layers, and can be set arbitrarily.

Next, the gas processing device 500 of the fourth embodiment will be described. In this embodiment, for members having the same functions as those described in the first embodiment, the same symbols are used, and detailed descriptions are omitted. In the following, the differences from the first embodiment are mainly explained.

FIG. 4 is a diagram schematically showing a part of a cross-section of a gas processing device 500 of the fourth embodiment. Gas processing device of this embodiment 500. The plasma is generated by silent discharge to decompose the components of the processing object. In the gas processing device 500 of this embodiment, the cylindrical applying electrode 11, the contact medium film 100, and the dielectric 13 are stacked radially outward in the shape of an annual ring with the cylindrical ground electrode 12 as the central axis And constitute a cylindrical structure.

In the gas processing device 500, two dielectric substances 13 are provided. The dielectric 13 on one side is arranged on the radially outer side of the ground electrode 12 and is in close contact with the ground electrode 12 at the same time. The other dielectric substance 13 is arranged on the radially inner side of the applying electrode 11 and is in close contact with the applying electrode 11 at the same time. The gas processing device 500 can apply a voltage between the application electrode 11 and the ground electrode 12 by using the high-voltage power supply 14 to form a low-temperature plasma reaction layer generated by discharge between the two dielectric substances 13. In addition, in FIG. 4, the application electrode 11 and the ground electrode 12 are respectively laminated with the dielectric substance 13 in close contact with each other, but the dielectric substance 13 may be in close contact with one of them.

In the gas processing device 500 of this embodiment, the application electrode 11, the ground electrode 12, and the dielectric 13 have an impermeable structure through which the processed gas cannot pass. Therefore, the gas to be processed supplied to the plasma generating part from one of the circular end faces (in the direction of arrow a in FIG. 3) passes through the low-temperature plasma reaction layer formed between the two dielectric substances 13, and Discharge from one end surface side (in the direction of arrow b in Figure 3). In short, in the plasma generating part, a flow channel formed by a low-temperature plasma reaction layer formed between two dielectric substances 13 is formed. In the flow channel formed in the low-temperature plasma reaction layer, a contact medium film 100 separated from the two dielectric substances 13 is arranged. Therefore, the gas to be processed flowing through the low-temperature plasma reaction layer can pass through the contact medium film 100 through the middle hole. That is, the components of the gas to be processed are the same as the first to third In the same implementation mode, the function of the contact medium film 100 acted by plasma is oxidized and decomposed. In addition, in FIG. 4, a space is formed between the touch media film 100 and the two dielectric substances 13. In addition, the touch media film 100 may be in close contact with the dielectric 13 on one side, or may not be in close contact.

As in the gas processing device 500 of this embodiment, it is also possible to adopt a multi-layer structure in the shape of tree rings. By adopting a multi-layer structure, it is easy to secure a flow path. Therefore, it is easy to increase the amount of gas to be processed, and it is possible to efficiently decompose a large amount of components to be processed. The gas processing device 500 arbitrarily sets the number of cylindrical growth rings of the contact medium film 100 in a manner that can efficiently oxidize and decompose the processing target gas in accordance with the use conditions such as the amount of the components to be processed or the flow rate. Multiple or one.

Here, when the gas processing apparatuses of the first to fourth embodiments process the components contained in the gas Supply to the runner. Thereby, the components in the gas to be processed flowing through the flow channel to the middle hole are oxidized and decomposed at room temperature by the contact medium film 100 not being heated. Furthermore, the components in the gas to be processed are also oxidized and decomposed by the plasma. In addition, if only the catalyst film 100 is used, the surface of the catalyst film 100 (gold catalyst particles) may be poisoned due to contact with the components, and the catalyst may be inactivated, resulting in reaction intermediates such as formaldehyde. The combined use of plasma cleans the surface of the catalyst film 100 and maintains the catalyst activity for a longer period of time. In addition, the yield of reaction intermediates is almost zero, and the decomposition of harmful components due to oxidation can be maintained for a long period of time.

In addition, in the gas processing device 200 of the first embodiment, It is described that the applying electrode 11 is arranged on the upstream side of the gas flow direction, but it is not limited to this, and the gas may be circulated from the ground electrode 12 side.

In the gas processing apparatuses of the first to fourth embodiments described above, the combination of the contact medium film 100 and the plasma can suppress the generation of reaction intermediates. At the same time, even the contact medium film 100 (gold touch The catalyst particles) are poisoned and the catalyst film 100 is also cleaned by the plasma, so the catalyst activity of the catalyst film 100 can be maintained for a long period of time. That is, according to the gas treatment devices of the first to fourth embodiments, it is possible to realize a gas treatment device that can oxidize and decompose the target compound for a longer period of time.

[Example]

Next, examples are given to explain the present invention more specifically. However, the present invention is not limited only to these examples.

[Example 1]

In the beaker, 5.2 g of tetraethoxysilane (TEOS) was added, and 6.0 g of ethanol was further added. Here, 2.7 g of 0.01 M hydrochloric acid was further added, and stirred at room temperature for 20 minutes (A liquid). In another beaker, 1.38 g of a nonionic surfactant (Pluronic P123) and 2.62 g of ethanol were added, and the mixture was stirred at room temperature for 30 minutes (liquid B). The solution A was added to solution B, mixed at room temperature, and then stirred for 3 hours to prepare a mesoporous silica precursor solution. The solvent of the precursor solution is distilled off, and the resulting solid is dried and then pulverized to obtain a powder-like support.

Put the aforementioned powder support into the solution containing dinitrodiammine platinum nitric acid Body, stir. After filtering the powder from the solution and drying it at 300°C for 3 hours, it is fired in a reduction gas of 10% hydrogen and 90% nitrogen at 250°C for 1 hour to obtain Pt/Pt/Mesoporous silica powder. For the mesoporous silica film, the Pt supporting capacity is 1 weight percent (wt%).

According to the BET method for Pt/medium-porous silica powder, the specific surface area, pore volume, and pore diameter of the mesoporous silica film are ^{377 m 2 /} g, 0.52 cm ^{3 /} g, and 7.0 nm, respectively. The size of the Pt particles observed by TEM was 3.2 nm.

In addition, the three-dimensional tomography (tomography) using electron microscope images from various angles of the touch media to form a three-dimensional image confirmed the existence of the Pt/Mesoporous silica powder interconnection structure. Part of the reconstructed 3D image is shown in Figure 5, Figure 6 and Figure 7 (tilt angle 60~-50°, shooting in 1° steps). The positions and shapes of the oxidation catalyst particles (bright white dots) and the middle holes (the dark parts around the oxidation catalyst particles) are different in each photo. The middle holes are not in the shape of a cylinder. It is confirmed that the holes in the catalyst have a plurality of holes inside the catalyst. Connected structure with holes in the middle.

In addition, the contact media of other examples were also manufactured by the same method as Example 1, and the test examples shown below also confirmed that the catalyst activity was maintained longer, so it can be understood that it has the same connection structure as Example 1. .

[Example 2]

Instead of dinitrodiammine platinum nitric acid and use palladium chloride other than Pd/Mesoporous silica powder was obtained in the same way as in Example 1. The Pd particle size was 3.0nm observed by TEM.

[Example 3]

Except for dissolving iron (III) chloride in a solution containing dinitrodiammine platinum nitric acid, the same method as in Example 1 was used to obtain a platinum iron alloy/mesoporous silica powder contact medium. The particle size of the Pt/Fe alloy observed by TEM was 3.6nm.

[Example 4]

In the beaker, 5.2 g of tetraethoxysilane (TEOS) was added, and 6.0 g of ethanol was further added. Here, 2.7 g of 0.01 M hydrochloric acid was further added, and stirred at room temperature for 20 minutes (A liquid). In another beaker, 1.38 g of a nonionic surfactant (Pluronic (registered trademark, the same hereinafter) P123) and 2.62 g of ethanol were added, and the mixture was stirred at room temperature for 30 minutes (liquid B). After that, add solution B to solution A, mix at room temperature, and stir for 3 hours to obtain a precursor solution of mesoporous silica. The ceramic honeycomb (manufactured by Iwatani Sangyo Co., Ltd.) was immersed in the mesoporous silica precursor solution, and the pressure was reduced for 15 minutes. After that, the ceramic honeycomb was pulled up to remove the excess solution with an air spray gun, then the temperature was raised at a rate of 1°C/min, and then fired at 450°C for 4 hours to obtain a ceramic honeycomb with the middle-hole silicon dioxide film immobilized.

After that, the ceramic honeycomb with the mesoporous silica film immobilized was immersed in a solution containing dinitrodiammine platinum nitric acid, and the excess solution was removed with an air spray gun. After drying at 300°C for 3 hours, the Firing in the original treatment gas at 250°C for 1 hour to obtain Pt/medium-porous silica film/honeycomb. For the mesoporous silica film (including particles (Pt particles in the case of Example 1, the same below)), the Pt supporting amount is 1 weight percent (wt%).

According to the measurement of Pt/medium-porous silica film/honeycomb, the specific surface area, pore volume, and pore diameter of the mesoporous silica film are ^{377 m 2 /} g, 0.52 cm ^{3 /} g, and 7.0 nm, respectively. In addition, the thickness of the mesoporous silicon dioxide film is 500 nm. In addition, the size of the Pt particles observed by TEM was 3.2 nm.

[Example 5]

To the liquid B, except for adding 1.3 g of mesitylene, the same method as in Example 4 was carried out to obtain Pt/middle-porous silica film/honeycomb. For the mesoporous silica film, the Pt supporting capacity is 1 weight percent (wt%).

According to the measurement of Pt/medium-porous silica film/honeycomb, the specific surface area, pore volume, and pore diameter of the mesoporous silica film are 401 m ² /g, 0.64 cm ³ /g, and 20 nm, respectively. In addition, the thickness of the mesoporous silicon dioxide film is 500 nm. In addition, the size of the Pt particles observed by TEM was 12 nm.

[Example 6]

In a beaker, 10.4 g of tetraethoxysilane (TEOS) was added, and 12.0 g of ethanol was further added. Here, 4.5 g of 0.01M hydrochloric acid was further added, and stirred at room temperature for 20 minutes (A liquid). Add non-ionic surfactants to other beakers (Brij (registered trademark) 56) 2.9 g and 8.0 g of ethanol were stirred at room temperature for 30 minutes (liquid B). After that, add solution B to solution A, mix at room temperature, and stir for 3 hours to obtain a precursor solution of mesoporous silica. The ceramic honeycomb (manufactured by Iwatani Sangyo Co., Ltd.) was immersed in the mesoporous silica precursor solution, and the pressure was reduced for 15 minutes. After pulling up the ceramic honeycomb and removing the excess solution with an air spray gun, it is heated at a rate of 1°C/min, and fired at 450°C for 4 hours to obtain a ceramic honeycomb with the middle-hole silicon dioxide film immobilized.

After that, the ceramic honeycomb with the mesoporous silica film immobilized was immersed in a solution containing dinitrodiammine platinum nitric acid solution, and the excess solution was removed with an air spray gun. After drying at 300°C for 3 hours, it was fired in a reducing gas of 10% hydrogen and 90% nitrogen at 250°C for 1 hour to obtain Pt/medium-porous silica film/honeycomb. For the mesoporous silica film, the Pt supporting capacity is 1 weight percent (wt%).

According to the measurement of Pt/medium-porous silica film/honeycomb, the specific surface area, pore volume, and pore diameter of the mesoporous silica film are 380 m ^{2 /} g, 0.38 cm ^{3 /} g, and 4.5 nm, respectively. In addition, the thickness of the mesoporous silicon dioxide film is 500 nm. In addition, the size of the Pt particles observed by TEM was 3.2 nm.

[Example 7]

To the liquid B, except for adding 1.3 g of mesitylene, the same method as in Example 6 was carried out to obtain Pt/mesoporous silica film/honeycomb. For the mesoporous silica film, the Pt supporting capacity is 1 weight percent (wt%).

According to the BET method for Pt/medium-porous silica film/honeycomb, the specific surface area, pore volume, and pore diameter of the mesoporous silica film are 365m ² /g, 0.44cm ³ /g, and 12nm, respectively. In addition, the thickness of the mesoporous silicon dioxide film is 500 nm. In addition, the size of the Pt particles observed by TEM was 3.2 nm.

[Example 8]

In a beaker, 6.2 g of tetraethoxysilane (TEOS) was added, and then 4.8 g of ethanol was added. Here, 2.2 g of 0.01 M hydrochloric acid was further added, and the mixture was stirred at room temperature for 20 minutes (liquid A). In another beaker, 1.53 g of a cationic surfactant (cetyltrimethylammonium bromide, CTAB) and 2.2 g of 0.01M hydrochloric acid were added, and the mixture was stirred at room temperature for 30 minutes (liquid B). After that, add solution B to solution A, mix at room temperature, and stir for 3 hours to obtain a precursor solution of mesoporous silica. The ceramic honeycomb (manufactured by Iwatani Sangyo Co., Ltd.) was immersed in the mesoporous silica precursor solution, and the pressure was reduced for 15 minutes. After that, the ceramic honeycomb was pulled up to remove the excess solution with an air spray gun, then the temperature was raised at a rate of 1°C/min, and then fired at 450°C for 4 hours to obtain a ceramic honeycomb with the middle-hole silicon dioxide film immobilized.

After that, the ceramic honeycomb with the mesoporous silica film immobilized was immersed in a solution containing dinitrodiammine platinum nitric acid, and the excess solution was removed with an air spray gun. After drying at 300°C for 3 hours, it was fired in a reducing gas of 10% hydrogen and 90% nitrogen at 250°C for 1 hour to obtain Pt/medium-porous silica film/honeycomb. For the mesoporous silica film, the Pt supporting capacity is 1 weight percent (wt%).

For Pt / pores in the silicon dioxide film / honeycomb embodiment according to the BET method, the pores in the silicon dioxide film surface area, pore volume, pore diameter, respectively 341m ² /g,0.50cm ³ /g,2.43nm. In addition, the thickness of the mesoporous silicon dioxide film is 500 nm. In addition, the Pt particle size was 2.0 nm as observed by TEM.

[Example 9]

Except for using palladium chloride instead of dinitrodiammine platinum nitric acid, a Pd/medium-porous silica film/honeycomb was obtained in the same manner as in Example 4. For the mesoporous silica film, the Pt supporting capacity is 1 weight percent (wt%).

For Pd / pores in the silicon dioxide film / honeycomb embodiment according to the BET method, the pores in the silicon dioxide film surface area, pore volume, pore diameter, respectively ^{377m 2 /g,0.52cm 3 / g, 7nm} . In addition, the thickness of the mesoporous silicon dioxide film is 500 nm. In addition, the Pd particle size was 3.0 nm as observed by TEM.

[Example 10]

Except for using palladium chloride instead of dinitrodiammine platinum nitric acid, a Pd/medium-porous silica film/honeycomb was obtained in the same manner as in Example 6. For the mesoporous silica film, the Pt supporting capacity is 1 weight percent (wt%).

According to the measurement of Pd/medium-porous silica film/honeycomb, the specific surface area, pore volume, and pore diameter of the mesoporous silica film are 380 m ^{2 /} g, 0.38 cm ^{3 /} g, and 4.5 nm, respectively. In addition, the thickness of the mesoporous silicon dioxide film is 500 nm. In addition, the Pd particle size was 3.0 nm as observed by TEM.

[Example 11]

Except for using palladium chloride instead of dinitrodiammine platinum nitric acid, a Pd/medium-porous silica film/honeycomb was obtained in the same manner as in Example 8. For the mesoporous silica film, the Pt supporting amount is 1wt%.

For Pd / pores in the silicon dioxide film / honeycomb embodiment according to the BET method, the pores in the silicon dioxide film surface area, pore volume, pore diameter, respectively 341m ² /g,0.5cm ³ /g,2.43nm. In addition, the thickness of the mesoporous silicon dioxide film is 500 nm. In addition, the Pd particle size was 2.0 nm as observed by TEM.

[Example 12]

Except for not performing the firing treatment in a reduction treatment gas of 10% hydrogen and 90% nitrogen, a platinum oxide/mesoporous silica film/honeycomb was obtained in the same manner as in Example 4. The supporting amount of platinum oxide for the mesoporous silica film is 1wt%.

For a platinum oxide / silicon dioxide film in the hole / honeycomb embodiment according to the BET method, the specific surface area of pores in the silicon dioxide film, pore volume, pore diameter, respectively 377m ² /g,0.52cm ³ / g, 7nm . In addition, the thickness of the mesoporous silicon dioxide film is 500 nm. In addition, the particle size of platinum oxide observed by TEM was 3.2 nm.

[Example 13]

Except for the replacement of dinitrodiamine platinum nitric acid and the use of palladium chloride, it is not carried out in the Except for the sintering treatment in a reduction treatment gas of 10% hydrogen and 90% nitrogen, the same method as in Example 4 was used to obtain a palladium oxide/mesoporous silica film/honeycomb. The supporting amount of palladium oxide for the mesoporous silica film is 1wt%.

For palladium oxide / silicon dioxide film in the hole / honeycomb embodiment according to the BET method, the specific surface area of pores in the silicon dioxide film, pore volume, pore diameter, respectively 377m ² /g,0.52cm ³ / g, 7nm . In addition, the thickness of the mesoporous silicon dioxide film is 500 nm. In addition, the particle size of the palladium oxide observed by TEM was 3.0 nm.

[Comparative Example 1]

For cylinder-shaped mesoporous silica (ALDRICH, MCM-41) with a nano-pore structure, 10g is mixed with a dinitrodiammine platinum nitric acid solution with a loading amount of Pt equivalent to 1wt%, and it is heated and evaporated to dry and solidify . Furthermore, the obtained solid content was dried under reduced pressure for 12 hours. After that, the obtained solid content was fired in a reduction treatment gas of 10% hydrogen and 90% nitrogen at 250°C for 1 hour to prepare Pt/medium-porous silica catalyst particles. After that, a binder was used for molding, and the Pt/medium-porous silica catalyst particles were made into granules.

When the BET measurement was performed, the specific surface area, pore volume, and pore diameter of mesoporous silica were 760 m ^{2 /} g, 0.84 cm ^{3 /} g, and 3.7 nm, respectively. In addition, the size of the Pt particles observed by TEM was 3.1 nm.

[Comparative Example 2]

Except for replacing the middle-hole silica (ALDRICH, MCM-41) with a cylinder-shaped nano-pore structure (ALDRICH, SBA-15), the same method as that of Comparative Example 1 was used to obtain Pt/ Silica catalyst particles with mesoporous holes are shaped into granules.

When the BET measurement was performed, the specific surface area, pore volume, and pore diameter of the mesoporous silica were ^{635 m 2 /} g, 1.07 cm ^{3 /} g, and 6.3 nm 7 nm, respectively. In addition, the Pt particle size was 6.0 nm as observed by TEM.

[Comparative Example 3]

Except for using palladium chloride instead of dinitrodiammine platinum nitric acid, the same method as in Comparative Example 1 was used to obtain a pelletized Pd/medium-porous silica catalyst particles. In addition, the Pd particle size was 3.0 nm as observed by TEM.

[Comparative Example 4]

Except for the use of palladium chloride instead of dinitrodiammine platinum nitric acid, the same method as in Comparative Example 2 was used to obtain a pelletized Pd/mesoporous silica catalyst particles. In addition, the particle size of Pd observed by TEM was 6.0 nm.

[Comparative Example 5]

Mix titanium isopropoxide (hereinafter referred to as "TTIP") with isopropanol (hereinafter referred to as "IPA") as a dispersion medium, and hydrochloric acid as a catalyst, and then add a specific amount of water at about 4°C 1 hour of hydrolysis. The composition ratio (molar ratio) of the starting solution is TTIP/IPA/water/hydrochloric acid=1/140/4/0.4. After hydrolysis, the titanium dioxide colloidal gel was prepared by leaving it at room temperature for 10 hours. Thereafter, a ceramic honeycomb (manufactured by Iwatani Sangyo Co., Ltd.) was immersed in the titanium dioxide colloidal gel, and the pressure was reduced for 15 minutes. After that, the ceramic honeycomb was pulled up with an air spray gun to remove the excess solution, then the temperature was raised at a rate of 1°C/min, and then fired at 450°C for 4 hours to obtain a ceramic honeycomb with the titanium dioxide film immobilized.

After that, the ceramic honeycomb with the titanium dioxide film immobilized was immersed in a solution containing dinitrodiammine platinum nitric acid solution, and the excess solution was removed with an air spray gun, and then subjected to a reduction treatment gas of 10% hydrogen and 90% nitrogen at 250°C After firing for 1 hour, Pt/titanium dioxide film/honeycomb is obtained. For the titanium dioxide film, the supporting amount of Pt is 1wt%.

For Pt/titanium dioxide film/honeycomb, the specific surface area, pore volume, and pore diameter of the mesoporous silica film are 100m ^{2 /} g, 0.10 cm ^{3 /} g, and 5.0 nm, respectively. In addition, the thickness of the mesoporous silicon dioxide film is 1000 nm. In addition, the Pt particle size was 3.0 nm as observed by TEM.

[Example 14]

To 0.2 g of the surfactant (Pluronic P123), 3.55 mL of ethanol was added, and the mixture was stirred for more than 20 minutes to dissolve to obtain a liquid A. 1.05 g of titanium isopropoxide (TTIP) was added to 0.63 mL of hydrochloric acid, and stirred for 5 minutes to obtain liquid B.

Add liquid A to liquid B, and then stir for 15 hours to obtain a precursor solution of mesoporous titanium oxide.

The solvent is distilled off from the precursor solution, and the resulting solid is fired in an electric furnace at 450°C for 4 hours and then pulverized to obtain a powder support.

Add a specific concentration of gold chloride aqueous solution to the beaker, and heat the water bath to 70°C. A 0.1M aqueous sodium hydroxide solution was slowly added to adjust the pH to 7. The gold chloride aqueous solution was cooled to normal temperature, the aforementioned powder support was added and heated to 70°C, and after reaching 70°C, it was stirred for 1 hour. Filter out the powder from the solution and wash it with pure water 5 times. It was fired in an electric furnace at 300°C for 2 hours to obtain a mesoporous titanium oxide powder supporting Au.

The Au supporting amount of the mesoporous titanium oxide powder supporting Au was measured by atomic absorption spectroscopy, and the Au supporting amount of the mesoporous titanium oxide powder was 20% by mass. The Au-supporting mesoporous titanium oxide powder was measured according to the BET method. The specific surface area, pore volume, and pore diameter of the mesoporous titanium oxide powder were 118 m ^{2 /} g, 0.54 g/ ^{cm 3, and 9.23 nm, respectively.} In addition, the Au particle size was 2.4 nm as observed by TEM.

[Example 15]

Except that to 16.7 g of 2.5% triisopropoxy iron (III)/isopropanol solution, 0.286 mL of acetic acid and 0.1 mL of pure water were added, and stirred for 10 minutes as the B solution, and the support was obtained in the same manner as in Example 14. Iron oxide powder of Au. The Au supporting amount of the iron oxide powder supporting Au was measured by atomic absorption spectroscopy, and the Au supporting amount of the middle-hole iron oxide powder was 20% by mass. The specific surface area, pore volume, and pore diameter of the mesoporous iron oxide component are 351 m ^{2 /} g, 0.48 g/ ^{cm 3, and 6.20 nm, respectively.} In addition, the Au particle diameter observed by TEM was 3.3 nm.

[Example 16]

Except for further dissolving iron (III) chloride in the gold chloride aqueous solution and using it, the same method as in Example 14 was used to obtain a gold-iron alloy/mesoporous titanium oxide powder activator. The particle size of Au/Fe alloy observed by TEM is 3.8nm.

[Example 17] (Immobilized Ti plate supporting titanium oxide film with holes in Au)

To 0.2 g of the surfactant (Pluronic P123), 3.55 mL of ethanol was added, and the mixture was stirred for more than 20 minutes to dissolve to obtain a liquid A. 1.05 g of titanium isopropoxide (TTIP) was added to 0.63 mL of hydrochloric acid, and stirred for 5 minutes to obtain liquid B.

Add liquid A to liquid B, and then stir for 15 hours to obtain a precursor solution of mesoporous titanium oxide. After that, using the mesoporous titanium oxide precursor solution, a spin coater was used to form a film on a titanium (also referred to as Ti hereinafter) plate at a rotation speed of 3000 rpm. Put the film-forming Ti plate into a petri dish, and let it stand for 2 hours at -20°C and 20%RH (freezer). Take it out from the freezer, open the petri dish cover after returning to room temperature, and take out the Ti plate. It was fired in an electric furnace at 450°C for 4 hours to obtain a Ti plate with an immobilized middle-hole titanium oxide film (membrane support). In the firing step, the rate of temperature increase and temperature decrease was 1°C per minute.

Add a specific concentration of gold chloride aqueous solution to the beaker, and heat the water bath to 70°C. A 0.1M aqueous sodium hydroxide solution was slowly added to adjust the pH to 7. Cool the gold chloride aqueous solution to room temperature, immerse the Ti plate with the mesoporous titanium oxide film immobilized, and degas under reduced pressure for about 15 minutes. It was heated to 70°C with a water bath again, and stirred for 1 hour after reaching 70°C. Take out the Ti plate with the fixed hole titanium oxide film, wash it with pure water 5 times, and remove the excess water with a rag. It was fired in an electric furnace at 300°C for 2 hours to obtain an immobilized Ti plate supporting a titanium oxide film with holes in Au.

The cross-section of the titanium oxide film supporting the holes in Au was observed by TEM, and the film thickness was 100 nm. In addition, the Au supporting amount was measured by atomic absorption spectroscopy, and the Au supporting amount to the mesoporous titanium oxide film was 20% by mass. When the Ti oxide film of the pores in the plate-immobilized Au bearing unit according to an embodiment of the BET method, the specific surface area of pores in the titanium oxide film, pore volume, pore diameter, respectively 118m ² /g,0.54g/cm ³ , 9.23nm. In addition, the Au particle size was 2.4 nm as observed by TEM.

[Example 18] (Immobilized Ti plate supporting titanium oxide film with holes in Au)

Except that the sintering temperature was set to 300° C. to fix the middle hole titanium oxide film on the Ti plate, the same method as in Example 17 was used to obtain a Ti plate supporting the hole titanium oxide film in Au.

In addition, the cross-section of the titanium oxide film supporting the holes in Au was observed by TEM, and the film thickness was 100 nm. In addition, when measured by atomic absorption spectroscopy, the amount of Au supporting the mesoporous titanium oxide film was 30% by mass. The specific surface area, pore volume, and pore diameter of the mesoporous titanium oxide film are ^{206m 2 /} g and 0.34g/cm ^{3 when the Ti plate of the mesoporous titanium oxide film that is immobilized and supports Au is measured according to the BET method.} , 3.71nm. In addition, the Au particle size was 2.4 nm as observed by TEM.

[Example 19] (Immobilized Ti plate supporting zirconia film with holes in Au)

Add 1 mL of ethanol to 0.2 g of surfactant (Pluronic P123), and stir for 20 minutes to obtain liquid A. To 0.58 g of tetrapropoxyzirconium (IV) (Zr(OPr) ₄ ), 0.286 mL of acetic acid and 0.1 mL of pure water were added, and the mixture was stirred for 10 minutes to obtain liquid B.

After adding solution A to solution B, add 0.093mL of hydrochloric acid and stir for 1 hour to get To the precursor solution of medium-porous zirconia oxide.

After that, using a precursor solution of mesoporous zirconia, a spin coater was used to form a film on the Ti plate at a rotation speed of 3000 rpm. Put the film-forming Ti plate into a petri dish, and let it stand for 2 hours under -20℃, 20%RH environment (freezer). Take it out from the freezer, open the petri dish cover after returning to room temperature, and take out the Ti plate. It was fired in an electric furnace at 450°C for 4 hours to obtain a Ti plate with an immobilized mesoporous zirconia film (membrane support). In the firing step, the rate of temperature increase and temperature decrease was 1°C per minute.

Add a specific concentration of gold chloride aqueous solution to the beaker, and heat the water bath to 70°C. A 0.1M aqueous sodium hydroxide solution was slowly added to adjust the pH to 7. Cool the gold chloride aqueous solution to room temperature, immerse the Ti plate with the mesoporous zirconia film immobilized, and degas under reduced pressure for about 15 minutes. It was heated to 70°C with a water bath again, and stirred for 1 hour after reaching 70°C. Take out the Ti plate with the immobilized zirconia film in the hole, wash it with pure water 5 times, and remove the excess water with a rag. It was fired in an electric furnace at 300°C for 2 hours to obtain an immobilized Ti plate supporting the porous zirconia film in Au.

The cross-section of the zirconia film supporting the holes in Au was observed by TEM, and the film thickness was 150 nm. In addition, when measured by atomic absorption spectroscopy, the amount of Au supporting the mesoporous zirconia film was 10.6% by mass. When the plate holes Ti film of a zirconium oxide-immobilized Au bearing unit according to an embodiment of the BET method, the specific surface area of pores in the zirconium oxide film, pore volume, pore diameter, respectively 85.2m ² /g,0.29g/cm ^3. 6.18nm. In addition, the Au particle size was 2.5 nm as observed by TEM.

[Example 20] (Immobilized Ti plate supporting zirconia film with holes in Au)

Except that the sintering temperature was set to 300° C. and the mesoporous zirconia film was immobilized on the Ti plate, the same method as in Example 19 was used to obtain a Ti plate that immobilized the Au mesoporous zirconia film.

The cross-section of the zirconia film supporting the holes in Au was observed by TEM, and the film thickness was 150 nm. In addition, when measured by atomic absorption spectroscopy, the amount of Au supporting the mesoporous zirconia film was 18.2% by mass. The specific surface area, pore volume, and pore diameter of the mesoporous zirconia film on a Ti plate with an immobilized Au-supporting mesoporous zirconia film were measured according to the BET method, respectively 94.3m ^{2 /} g and 0.42g/cm ^3. 4.19nm. In addition, the Au particle size was 2.5 nm as observed by TEM.

[Comparative Example 6]

Except that the surfactant solution was not used (Pluronic P123) and the precursor solution was prepared, the same method as in Example 17 was used to obtain a Ti plate immobilized with a titanium oxide film supporting Au.

The cross-section of the titanium oxide film supporting Au was observed by TEM, and the film thickness was 100 nm. In addition, when measured by atomic absorption spectroscopy, the amount of Au supported on the titanium oxide film was 6.6% by mass. When the Ti plate on which the titanium oxide film supporting Au was immobilized was measured according to the BET method, the specific surface area of the titanium oxide film was 10 m ² /g, which confirmed that the titanium oxide film did not have a mesoporous structure. In addition, the Au particle size was 5 nm as observed by TEM.

[Comparative Example 7]

In addition to making precursors without using surfactants (Pluronic P123) Except for the solution, the same method as in Example 19 was used to obtain a Ti plate on which a zirconia film supporting Au was immobilized.

The cross-section of the zirconia film supporting Au was observed by TEM, and the film thickness was 150 nm. In addition, when measured by atomic absorption spectroscopy, the amount of Au supported on the zirconia film was 5 mass%. ^{The specific surface area of the titanium oxide film was 7.9 m 2} /g when the Ti plate on which the Au-supporting zirconia film was immobilized was measured by the BET method, which confirmed that the titanium oxide film did not have a mesoporous structure. In addition, the Au particle size was 5 nm as observed by TEM.

[Comparative Example 8]

470 mg of Au(I)(TPP)Cl complex was added to 20 mL of ethanol and stirred for 30 minutes. Dissolve 35.9 mg of sodium borohydride in 7.5 mL of ethanol, add this to the above liquid all at once, and stir for 3 hours. To this, 500 mL of hexane was added and left to stand for 24 hours. It is further filtered, washed with hexane and dried several times to obtain gold protected with triphenylphosphine. The gold protected with triphenylphosphine was dissolved in 24 mL of dichloromethane, and 1 g of medium-hole silica (SBA-15) was added and stirred for 2 hours. After stirring, it is filtered and then fired at 200°C to obtain silica with holes in Au. The obtained silicon dioxide supporting the holes in the Au is suspended in water, and a spin coater is used to form a film on the Ti plate at a rotation speed of 3000 rpm, and the film is dried to obtain an immobilized Ti plate supporting the silicon dioxide in the holes of the Au .

The cross-section of the silicon dioxide supporting the holes in Au was observed by TEM, and the film thickness was 100 nm. In addition, when measured by atomic absorption spectroscopy, the Au supporting amount for the middle hole silica is 1% by mass. According to the measurement of the pore silicon dioxide in Au supporting the BET method, the specific surface area, pore volume, and pore diameter are 871 m ^{2 /} g, 1.13 cm ^{3 /} g, and 7.5 nm, respectively. In addition, the Au particle diameter observed by TEM was 0.8 nm.

[Ethylene Decomposition Test]

Using the contact media of Examples 1 to 13 and Comparative Examples 1 to 5, the decomposition reaction of ethylene was carried out. The reaction gas is prepared by mixing air containing 10 ppm ethylene with indoor air, and the respective gas flow rates are controlled by a thermal mass flow controller. The reaction gas was analyzed using an infrared spectrophotometer (FTIR-6000, manufactured by JASCO Corporation) filled with gas cells with a long optical path (20 m). The reaction conditions were ethylene concentration of 0.5 ppm, oxygen concentration of 20%, gas flow rate of 1 L/min, reaction temperature of 5°C, and relative humidity of 90%.

The removal rate of ethylene is calculated by the following equation.

Ethylene removal rate (%)={(initial ethylene concentration-ethylene concentration after reaction)/initial ethylene concentration}×100

The results obtained are shown in Table 1.

As can be understood from the above results, the chlorine removal of ethylene in Comparative Examples 1 and 2 after 1 day was 8.4%, and it decreased to 4.7% and 3.0% after 7 days. In addition, in Comparative Examples 3 to 5, the removal rate was zero after one day. In this regard, it was confirmed that the ethylene removal rates of Examples 1 to 13 did not extremely decrease after 1 day and 7 days later.

From the above, it is shown that the example can decompose and remove hydrocarbons such as ethylene at a low concentration of about 0.5 ppm at a temperature 5°C lower than the generally considered room temperature. In addition, the degradation of its decomposition activity is not easy to occur, and it can be Used across a long period of time.

(Using one of the low-temperature plasma reactor (gas processing device) oxygen Carbon removal test (test examples 1-14))

As the gas processing device, a gas processing device 300 of the second embodiment shown in FIG. 2 is prepared. The touch medium 100 used the Ti plates obtained in Examples 17 to 20 and Comparative Examples 6 to 8, respectively. Copper tape is used for the application electrode 11 and the installation electrode 12. The dielectric 13 used α-alumina.

For the generation of plasma, a power source for generating electricity is used to connect the application electrode 11 and the ground electrode 12 to the power source for generating plasma, and the plasma is generated by applying a voltage. The applied voltage is 8kVp-p, and the discharge output is 0.1W.

Using carbon monoxide (CO), the oxidation reaction of the gas treatment device 300 using the Ti plate of the embodiment and the comparative example was evaluated. Specifically, carbon monoxide (concentration 1,000 ppm) and air are mixed to modulate the gas to be processed, and the flow rate is controlled by a mass flow controller, while the gas to be processed is supplied to the flow channel (between the two dielectric substances 13).

According to the analysis of the gas to be processed before and after the processing of the gas processing device 300, an infrared spectrophotometer (FTIR-6000, manufactured by JASCO Corporation) filled with a gas cell with a long optical path (2.5m) is used. . The reaction conditions were 1,000 ppm carbon monoxide, 20% oxygen concentration, 50% relative humidity, gas flow rate 0.1 L/min, catalyst size 25 cm ² , and reaction temperature at room temperature.

The contact media used was changed, and the presence or absence of plasma was also changed. Test examples 1 to 14 were also performed.

Using the aforementioned infrared spectrophotometer, measure the CO concentration in the gas to be processed before being supplied to the gas processing device 300 (hereinafter also referred to as the "initial CO concentration") and in the gas to be processed after being processed by the gas processing device 300 The CO concentration (hereinafter also referred to as the "post-reaction CO concentration") is used to calculate the CO removal rate using the following formula. In addition, the time for processing the gas to be processed by the gas processing device 300 is shown in Table 3 and Table 4 described later.

CO removal rate (%)={(initial CO concentration-post-reaction CO concentration)/initial CO concentration}×100

(Test Example 1)

Using the Ti plate obtained in Example 17, a CO removal test was carried out without generating plasma.

(Test Example 2)

Except that the Ti plate obtained in Example 18 was used, a CO removal test was carried out in the same manner as in Test Example 1.

(Test Example 3)

Except that the Ti plate obtained in Example 19 was used, a CO removal test was carried out in the same manner as in Test Example 1.

(Test Example 4)

Except that the Ti plate obtained in Example 20 was used, a CO removal test was carried out in the same manner as in Test Example 1.

(Test Example 5)

Except that the Ti plate obtained in Comparative Example 6 is used, it is the same as Test Example 1 The same method implemented CO removal test.

(Test Example 6)

Except that the Ti plate obtained in Comparative Example 7 was used, a CO removal test was carried out in the same manner as in Test Example 1.

(Test Example 7)

Except for using the Ti plate obtained in Comparative Example 8, a CO removal test was carried out in the same manner as in Test Example 1.

(Test Example 8)

Using the Ti plate obtained in Example 17, a plasma generating discharge power of 0.1 W was subjected to a CO removal test.

(Test Example 9)

Except for using the Ti plate obtained in Example 18, a CO removal test was carried out in the same manner as in Test Example 8.

(Test Example 10)

Except for using the Ti plate obtained in Example 19, a CO removal test was carried out in the same manner as in Test Example 8.

(Test Example 11)

In addition to using the Ti plate obtained in Example 20, it was compared with Test Example 8. The CO removal test was carried out in the same way.

(Test Example 12)

Except for using the Ti plate obtained in Comparative Example 6, a CO removal test was carried out in the same manner as in Test Example 8.

(Test Example 13)

Except that the Ti plate obtained in Comparative Example 7 was used, a CO removal test was carried out in the same manner as in Test Example 8.

(Test Example 14)

Except for using the Ti plate obtained in Comparative Example 8, a CO removal test was performed in the same manner as in Test Example 8.

The CO removal rates of Test Examples 1-14 are shown in Table 2.

[Carbon Monoxide Removal Test (Test Examples 15-17)]

Using the powder contact media of Example 14 (Test Example 15), Example 15 (Test Example 16), and Example 16 (Test Example 17), the decomposition reaction of carbon monoxide in Test Examples 15-17 was performed.

A test gas with a carbon monoxide concentration of 1,000 ppm is prepared by mixing carbon monoxide and air, and the mass flow controller is used to control the flow rate and supply to the contact medium at the same time. An infrared spectrophotometer (FTIR-6000, manufactured by JASCO Corporation) was used for the analysis of the gas to be processed before the treatment and the gas to be processed 1 hour after the treatment. The reaction conditions were 1,000 ppm carbon monoxide, 20% oxygen, 60% relative humidity, gas flow rate 1.0 L/min, and reaction temperature at room temperature.

The CO removal rate was calculated using the following formula, and the results are shown in Table 3.

CO removal rate (%)={(initial CO concentration-post-reaction CO concentration)/initial CO concentration}×100

[Ammonia removal test using a low-temperature plasma reactor (gas treatment device) (Experimental Examples 18, 19)]

The same gas treatment device as the carbon oxide removal test (Experiment Examples 1 to 14) using a low-temperature plasma reactor (gas treatment device) was used. In addition, the touch medium 100 used the Ti plates obtained in Example 19 and Comparative Example 8, respectively.

Except for mixing nitrogen containing 10,000 ppm of ammonia and indoor air to prepare a reaction gas and using it, it was performed in the same manner as the carbon monoxide removal test (Test Examples 1 to 14) using a low-temperature plasma reactor (gas processing device). The reaction gas was analyzed using an infrared spectrophotometer (FTIR-6000, manufactured by JASCO Corporation) filled with gas cells with a long optical path (2.5 m). The reaction conditions are: ammonia concentration 5ppm, oxygen concentration 20%, relative humidity 50%, gas flow rate 0.1L/min, catalyst size 25cm ³ , reaction temperature is room temperature.

The ammonia removal rate was calculated using the following formula, and the results are shown in Table 4.

Ammonia removal rate (%)={(initial ammonia concentration-post-reaction ammonia concentration)/initial ammonia concentration}×100

(Test Example 18)

Using the Ti plate obtained in Example 19, a plasma generating discharge power of 0.1 W was subjected to an ammonia removal test.

(Test Example 19)

Except for using the Ti plate obtained in Comparative Example 8, an ammonia removal test was carried out in the same manner as in Test Example 18.

[Trimethylamine removal test using low-temperature plasma reactor (gas treatment device) (Experiment 20, 21)]

The same gas treatment device as the carbon oxide removal test (Experiment Examples 1 to 14) using a low-temperature plasma reactor (gas treatment device) was used. In addition, the touch medium 100 used the Ti plates obtained in Example 19 and Comparative Example 8, respectively.

Except that the reaction gas was mixed with nitrogen containing trimethylamine 10,000 ppm and room air to prepare the reaction gas and used, it was carried out in the same manner as the carbon monoxide removal test (Experimental Examples 1 to 14) using a low-temperature plasma reactor (gas processing device). The reaction gas was analyzed using an infrared spectrophotometer (FTIR-6000, manufactured by JASCO Corporation) filled with gas cells with a long optical path (2.5 m). The reaction conditions are: trimethylamine concentration of 10 ppm, oxygen concentration of 20%, relative humidity of 50%, gas flow rate of 0.1 L/min, catalyst size of 25 cm ³ , and reaction temperature of room temperature.

The trimethylamine removal rate was calculated using the following formula, and the results are shown in Table 5.

Trimethylamine removal rate (%)={(initial trimethylamine concentration-trimethylamine concentration after reaction)/initial trimethylamine concentration}×100

(Test Example 20)

Using the Ti plate obtained in Example 19, a plasma generating discharge power of 0.1 W was subjected to a trimethylamine removal test.

(Test Example 21)

Except for using the Ti plate obtained in Comparative Example 8, a trimethylamine removal test was performed in the same manner as in Test Example 20.

As shown in Table 2, the CO removal rate of Test Examples 1 to 4 is above 92%. In addition, as shown in Table 3, the CO removal rate of Test Examples 15 to 17 was also 92% or more. On the other hand, the CO removal rate of Test Examples 5 to 7 was 4% or less. From these results, it was confirmed that the gas treatment devices of Examples 14 to 20 were used The setting 300 has superior catalytic activity compared with the gas treatment device 300 of Comparative Examples 6-8.

As shown in Table 2, the CO removal rate after 1 hour in Test Examples 8 to 11 was 92% or more, and the CO removal rate after 24 hours was 90.1% or more. On the other hand, in Test Examples 12-14, the CO removal rate after 1 hour was 4% or less, and the CO removal rate after 24 hours was also 0%. From these results, it can be understood that the gas treatment device 300 used in Examples 17 to 20 has superior catalytic activity compared to the gas treatment device 300 used in Comparative Examples 6 to 8, and the catalyst activity can be sustained.

As shown in Table 4, the ammonia removal rate of Test Example 18 after 1 hour was 91.2%, and the ammonia removal rate after 24 hours was 90.8%. On the other hand, in Test Example 19, the ammonia rate after 1 hour was 1.8% or less, and the ammonia removal rate after 24 hours was 1.7%. From these results, it can be understood that the use of the gas processing device 300 of Example 19 has superior catalyst activity compared to the use of the gas processing device 300 of Comparative Example 8, and the catalyst activity can be maintained.

As shown in Table 5, the removal rate of trimethylamine after 1 hour in Test Example 20 was 94.2%, and the removal rate of trimethylamine after 24 hours was 93.8%. On the other hand, in Test Example 21, the removal rate of trimethylamine after 1 hour was 2.2%, and the removal rate of trimethylamine after 24 hours was also 2.2%. From these results, it can be understood that the use of the gas processing device 300 of Example 19 has superior catalyst activity compared to the use of the gas processing device 300 of Comparative Example 8, and the catalyst activity can be maintained.

From the above results, the effectiveness of the present invention is shown.

Claims (11)

A mesoporous contact medium, which is characterized by having: a support body with a plurality of mesopores, and at least a noble metal, an oxide of noble metal, and an alloy of noble metal and transition metal supported in the mesopore of the aforementioned support One of the oxidation catalyst particles; in the aforementioned support, one middle hole is connected to at least one other middle hole; the average particle size of the aforementioned oxidation catalyst particles is 1 nm or more and 10 nm or less. A mesoporous contact medium, which is characterized by contacting a support with mesopores with a solution or colloidal solution of at least one compound corresponding to noble metals, noble metal oxides, and alloys of noble metals and transition metals to perform burning Formation and/or reduction treatment to form oxidation catalyst particles containing at least one of precious metals, precious metal oxides, and alloys of precious metals and transition metals in the pores of the aforementioned support, and having an average particle diameter of 1 nm or more and 10 nm or less ; The aforementioned support with mesopores is obtained by drying and firing a precursor solution, the precursor solution containing: alkoxysilane or metal alkoxide (alkoxide) hydrolyzed product, and polyoxyethylene Alkyl ether, polyalkylene oxide tri-block copolymer or cationic surfactant. For example, the hole contact media in item 1 or 2 of the scope of patent application, wherein the aforementioned support system is formed of metal oxide or SiO ₂ . For example, the hole contact medium in item 3 of the scope of patent application, wherein the aforementioned metal oxide is one or more compounds selected from the group _{consisting of TiO 2} , Fe ₂ O ₃ , ZrO ₂ , and CeO _2. For example, the porous touch media in item 1 or 2 of the scope of patent application, wherein the aforementioned noble metal is one or more selected from the group consisting of gold, platinum and palladium. For example, the hole contact media in item 1 or 2 of the scope of patent application, wherein the aforementioned support is powder. For example, the pore touch media in item 1 or 2 of the scope of patent application, wherein the average pore diameter of the aforementioned mesopores measured by the BET method is 2nm or more and 10nm or less. For example, the porous contact media in item 1 or 2 of the scope of patent application, wherein the supporting amount of the aforementioned oxidation catalyst particles is 0.1-30 mass percent to the support containing the oxidation catalyst particles. For example, the hole contact medium in item 1 or 2 of the scope of patent application, wherein the aforementioned medium hole contact medium is a catalyst for the oxidation reaction of gas. A gas processing device is characterized by: at least a first electrode, a second electrode, and a dielectric material arranged between the first electrode and the second electrode; The plasma generating part that generates plasma by applying a voltage between the electrodes to generate a discharge, a flow channel through which the gas to be processed flows formed in the region where the plasma generated by the plasma generating part exists, and is arranged in The hole in any one of items 1 to 9 of the aforementioned flow channel’s patent application scope touches the medium. A method for manufacturing a mesoporous contact medium, which is characterized in that a support body with mesopores is brought into contact with a solution or colloidal solution of at least one compound corresponding to noble metals, noble metal oxides, and alloys of noble metals and transition metals. Sintering and/or reduction treatment to form oxidation catalyst particles containing at least one of noble metals, noble metal oxides, and alloys of noble metals and transition metals in the pores of the aforementioned support, with an average particle size of 1 nm to 10 nm; The aforementioned support with mesopores is obtained by drying and firing a precursor solution, which contains the hydrolyzed product of alkoxysilane or metal alkoxide, and polyoxyethylene Base ether, polyalkylene oxide tri-block copolymer or cationic surfactant.

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