JP4305128B2 - Gas purification material and method for producing the same - Google Patents

Description

  The present invention relates to a gas purification material and a method for producing the same, and more specifically, a gas purification material that supports a metal component on a carrier made of a metal oxide and functions as a decomposition catalyst and / or an adsorbent for harmful gases, and It relates to the manufacturing method.

  In recent years, the presence of harmful gases that can be present in the environment surrounding humans and can affect the human body has been regarded as a problem. For example, aldehydes emitted from the building materials into the air Development of technology that can more reliably remove NOx and CO, which are harmful components in exhaust gas, at low temperatures is desired.

  Under such a background, various gas purification materials for removing harmful gases have been developed. For example, JP-A-8-24653 (Patent Document 1) discloses γ-alumina, titania, zirconia, and the like. A first catalyst in which a white metal is supported on a porous inorganic oxide by an impregnation method, a precipitation method, a sol-gel method, and the like, and a second catalyst in which a silver compound is supported on the porous inorganic oxide. Exhaust gas purification catalysts are described.

  Japanese Patent Application Laid-Open No. 8-52351 (Patent Document 2) discloses a volatility in which a support mainly composed of titania is loaded with a platinum group metal as a main catalytic active metal component and boron oxide as a promoter component by an impregnation method. An organochlorine compound decomposition catalyst is disclosed.

However, even in the case of gas purification materials in which a metal component such as a white metal metal is supported on a carrier such as a metal oxide by an impregnation method or the like as in the past, there is a limit to the efficient improvement of the removal performance against harmful gases. In order to achieve the desired removal performance, it is necessary to carry a relatively large amount of such metal components, so there is a limit to the cost reduction of the gas purification material, and it is not sufficient from the viewpoint of securing resources. There wasn't. Further, when manufacturing the above conventional gas purification material, a metal salt such as a white metal is used, so that post-treatment such as calcination for removing the salt component is necessary, and the manufacturing process becomes complicated. From the viewpoint of green chemistry, wastewater containing salt is still not enough.
Japanese Patent Laid-Open No. 8-24653 JP-A-8-52351

  The present invention has been made in view of the above-described problems of the prior art, and has a smaller amount of metal component supported on a metal oxide support (hereinafter referred to as “metal oxide support”). However, it is possible to provide a gas purification material capable of efficiently and reliably removing harmful gases such as aldehydes in the air and NOx, CO, etc. in the exhaust gas, It aims at providing the manufacturing method of the gas purification material which can simplify a manufacturing process.

  As a result of intensive research to achieve the above object, the present inventors have made it possible to attach metal scattering particles generated by irradiating a target made of metal with a laser beam on a metal oxide carrier. Has been found to be achievable, and the present invention has been completed.

That is, the manufacturing method of the gas purification material of the present invention includes Rh, Nb, Re, Ag, Au, Cu, Co, Cr, Ni, Fe, Ir, Mo, Pt, Pd, Sn, Ti, V, W, Zn , Zr, Ru, Os, and a target made of a metal selected from the group consisting of alloys containing them as a main component, a pulse width of 100 picoseconds to 100 nanoseconds and an irradiation intensity of 10 ⁶ W / cm ² to 10 Irradiate pulsed laser light of ¹² W / cm ² to generate vacuum ultraviolet light having a wavelength of 50 nm to 100 nm and scattered particles of the metal, Ti, Al, Si, Ce, Zr, Fe, Mn, Ni, Zn and at least one metal alone oxide or the composite oxide in which are deposited causes the scattered particles the to the surface of the support comprising a metal oxide while irradiating vacuum ultraviolet light carrier is selected from the group consisting of Cu A method characterized in that allowed to form a supported metal component.

The gas purification material of the present invention is
A support made of a metal oxide that is a single oxide or composite oxide of at least one metal selected from the group consisting of Ti, Al, Si, Ce, Zr, Fe, Mn, Ni, Zn, and Cu ;
Rh, Nb, Re, Ag, Au, Cu, Co, Cr, Ni, Fe, Ir, Mo, Pt, Pd, Sn, Ti, V, W, Zn, Zr, Ru, Os, and their main components A target made of a metal selected from the group consisting of alloys is irradiated with a pulse laser beam having a pulse width of 100 picoseconds to 100 nanoseconds and an irradiation intensity of 10 ⁶ W / cm ² to 10 ¹² W / cm ^2. The metal scattering particles generated in this manner are attached to the surface of the carrier in the state of being irradiated with the vacuum ultraviolet light having a wavelength of 50 nm to 100 nm generated by the irradiation of the pulse laser beam, and are supported on the carrier. The metal component being
It is characterized by comprising.

  In the gas purification material of the present invention and the method for producing the same, the reason why the harmful gas can be efficiently and reliably removed even when the amount of the metal component supported on the metal oxide support is small. Although not necessarily certain, the present inventors infer as follows. In other words, when laser light is irradiated onto a target made of metal, high-temperature plasma is formed on the target surface, and atoms or clusters containing the metal scatter from the target surface with high energy. In the target surface, the neutral atoms and ions formed by the evaporation of the material constituting the target and the clusters formed by combining some of the neutral atoms and ions have high energy. Scatter. When such scattered particles reach the metal oxide carrier, the scattered particles have high energy, and thus adhere to the carrier and are reconfigured as fine particles of the metal component. When the scattered particles reach further, a thin film composed of such metal component fine particles is formed on the carrier. Therefore, according to the present invention, such metal component fine particles or a thin film made of such metal component are supported only on the surface of the metal oxide carrier that contributes to the decomposition reaction and adsorption of harmful gases, and the amount of the metal component supported is small. However, the present inventors presume that harmful gas can be efficiently and reliably removed.

In the gas purification material and the method for producing the same according to the present invention, the scattered particles adhere in a state in which the metal component is irradiated with vacuum ultraviolet light having a wavelength of 50 nm to 100 nm on the surface of the carrier made of the metal oxide. der those formed Te Ru. When such ultraviolet light is irradiated onto the metal oxide support, the surface of the metal oxide support is activated, so scattered particles that have reached the activated metal oxide support are firmly bonded to the support surface. and, it increases the adhesion of the metal component to the metal oxide support.

Furthermore, in the gas purification material and the method for producing the same according to the present invention, the laser beam has a pulse width of 100 picoseconds to 100 nanoseconds and an irradiation intensity of 10 ⁶ W / cm ² to 10 ¹² W / cm ^2. Ru laser beam der. In that case, the target made of the metal is irradiated with the pulsed laser light to generate vacuum ultraviolet light having a wavelength of 50 nm to 100 nm and scattered particles of the metal, and the surface of the metal oxide support is irradiated with the vacuum ultraviolet light. However, it becomes possible to form the metal component supported on the carrier by adhering the scattered particles. Since the surface of the metal oxide support is more activated when such a vacuum ultraviolet light is irradiated onto the metal oxide support (particularly preferably, a metal oxide support containing carbon such as silicon carbide), activation is performed. metal oxide scattered particles reaching the carrier is firmly bonded by a carrier surface, improved adhesion of the metal component to the metal oxide support.

The vacuum ultraviolet light having a wavelength of 50 nm to 100 nm here means vacuum ultraviolet light having at least a part of wavelengths in a wavelength region of 50 nm to 100 nm. At least one of the following conditions is satisfied: It is preferable to satisfy.
(i) having at least one peak of light intensity in a wavelength region of 50 nm to 100 nm;
(ii) the total energy of light in the wavelength region of 50 nm to 100 nm is higher than the total energy of light in the wavelength region of 100 nm to 150 nm;
(iii) The total energy of light in the wavelength region of 50 nm to 100 nm is higher than the total energy of light in the wavelength region of 50 nm or less.
(iv) The energy density of light in the wavelength region of 50 nm to 100 nm is 0.1 μJ / cm ^{2 to} 10 mJ / cm ² (more preferably 1 μJ / cm ^{2 to} 100 μJ / cm ² ) on the carrier. When the energy density on the carrier is lower than 0.1 μJ / cm ² , the time required for the treatment tends to be excessively long. On the other hand, when the energy density is higher than 10 mJ / cm ² , the carrier tends to be decomposed. is there.

  In the method for producing a gas purification material of the present invention, the gas purification material is selected from the group consisting of hydrogen gas, helium gas, neon gas, and argon gas under reduced pressure in the container and / or either inside or outside the container. It is preferable that the scattered particles adhere to the surface of the carrier in a shielding gas atmosphere containing at least one kind of gas. When a container having a reduced pressure inside is used, the ultraviolet light (or vacuum ultraviolet light) is irradiated onto the surface of the metal oxide support without being absorbed by an ultraviolet light absorbing material such as oxygen in the air. Therefore, the support surface is activated more efficiently and the oxidation of the metal component tends to be sufficiently prevented. Further, when the treatment is performed in a shielding gas atmosphere, the surface of the carrier is more efficient because the ultraviolet light (or vacuum ultraviolet light) is irradiated onto the surface of the metal oxide carrier without being absorbed by the ultraviolet light absorbing material without being in a reduced pressure state. It is well activated and tends to sufficiently prevent oxidation of the metal component. Furthermore, in the latter case, it is not necessary to use a vacuum pump or a pressure vessel as compared with the former case, so that it tends to be more preferable in terms of simplicity of the apparatus and low cost.

  According to the gas purification material of the present invention, harmful gases such as aldehydes in the air, NOx in the exhaust gas, CO, and the like are removed even if the amount of the metal component supported on the carrier made of the metal oxide is smaller than before. Efficient and reliable removal is possible. Therefore, according to the gas purification material of the present invention, it is possible to reduce the cost by reducing the amount of the metal component supported, which is also effective from the viewpoint of securing resources.

  Further, according to the method for producing a gas purification material of the present invention, a gas purification material carrying a metal component can be obtained without using a conventional metal salt. Waste liquid treatment is unnecessary, and from the viewpoint of green chemistry, it is possible to reduce the burden on the environment and to manufacture the gas purification material of the present invention in a simplified process.

  Hereinafter, the gas purification material of the present invention and the production method thereof will be described in detail in line with preferred embodiments thereof.

FIG. 1 is a schematic diagram showing a basic configuration of a preferred embodiment of a gas purification material manufacturing apparatus suitable for the present invention. The gas purification material manufacturing apparatus shown in FIG. 1 is configured as a so-called laser ablation apparatus 1. ing. That is, the laser ablation apparatus 1 shown in FIG. 1 includes a laser light source 2 and a processing container 3 into which the laser light L ₁ emitted from the laser light source 2 is introduced. A target 4 irradiated with L ₁ and a metal oxide support 6 on which a metal component 5 is to be supported are disposed.

The laser light source 2 can irradiate a laser beam (preferably a pulse laser beam having a wavelength of 150 nm to 11 μm, a pulse width of 1 ps to 1 μs, and an energy per pulse of 0.01 J to 100 J). Although it does not restrict | limit in particular, For example, it is comprised by a hemtosecond laser apparatus, an excimer laser apparatus, and a YAG laser apparatus, Especially YAG which can irradiate the pulse laser beam whose pulse width is 100 picoseconds-100 nanoseconds It is preferably constituted by a laser device. Then, the laser light source 2 is disposed at a position irradiated with laser light L ₁ towards the target 4 which is located inside the treatment container 3. Further, although not shown, the laser beam L ₁ as scattered from the surface particles a target 4 when irradiated to target 4 is produced efficiently, the lens in the optical path of the laser light L _1, mirror Etc. may be appropriately arranged to adjust the energy density and irradiation angle of the laser beam. In particular, a condenser lens (not shown) is disposed inside or outside the processing container 3, and the irradiation intensity of the laser light L ₁ applied to the target 4 is 10 ⁶ W / cm ² to 10 ¹² W / cm ^2. It is preferable to become such that 10 ⁸ W / cm ² to 10 ¹¹ W / cm ² is more preferable.

Treatment container 3, at least the target 4 and the carrier 6 is a container for housing therein (e.g., stainless steel vessel), for introduction into the surface of the target 4 placed a laser beam L ₁ into the container 3 Window 9 (for example, a quartz window). Further, a vacuum pump (not shown) is connected to the processing container 3 so that the inside of the container 3 can be maintained in a reduced pressure state of a predetermined pressure. Thus, when the container 3 whose inside is in a reduced pressure state is used, the surface of the carrier 6 is irradiated with ultraviolet light (or vacuum ultraviolet light) L ₂ without being absorbed by an ultraviolet light absorbing material such as oxygen in the air. Therefore, the surface of the carrier 6 is activated more efficiently and the oxidation of the metal component 5 is sufficiently prevented. In addition, as a pressure at the time of maintaining the inside of the container 3 in a pressure-reduced state, a pressure of 133.3 Pa ( 1 Torr ) or less is preferable, and a pressure of 0.133 Pa ( 1 × 10 ⁻³ Torr ) or less is more preferable. In addition, it is preferable that the oxygen partial pressure and / or the nitrogen partial pressure be 133.3 Pa ( 1 Torr ) or less.

The target 4 is made of a metal to be carried as the metal component 5 on the carrier 6 to be described later. Specifically, the target 4 is appropriately determined depending on the use of the obtained gas purification material, the type of metal oxide used as the carrier, and the like. Is done. Such metals, Rh, Nb, Re, Ag , Au, Cu, Co, Cr, Ni, Fe, Ir, Mo, Pt, Pd, Sn, Ti, V, W, Zn, Zr, Ru, Os In addition, a metal selected from the group consisting of alloys containing them as a main component is used , among which noble metal elements (Pt, Pd, Rh, Ru, Ir, Os, Au, Ag) are more preferable, and platinum group elements (Pt, Pd, Rh, Ru, Ir, Os) are particularly preferred. The shape of the target 4 is not particularly limited, and a bulk material made of the target material formed into a plate shape, a rod shape, or the like, a tape target formed by applying the target material on a tape, vapor deposition, or the like Can be used.

Carrier 6 is the carrier of the metal component 5 on the surface thereof a metal oxide to be supported, Ru is appropriately determined depending on the type of metal component applications and supporting of gas purification material is specifically obtained.

As such a metal oxide, a single oxide or composite oxide of at least one metal selected from the group consisting of Ti, Al, Si, Ce, Zr, Fe, Mn, Ni, Zn, and Cu is used. Titanium oxide, alumina, silicon oxide, cerium oxide, zeolite, zirconia, iron oxide, manganese oxide, nickel oxide, zinc oxide, and copper oxide are more preferable. The metal oxide according to the present invention may contain a plurality of metal elements such as zeolite, titanium oxide-zirconia, and cerium oxide-zirconia, and may further contain a non-metal element. The support 6 may be a composite of a plurality of metal oxides laminated or mixed, and the metal oxide is combined with other materials (for example, resin materials) by lamination, mixing, or the like. It may be a thing.

  The shape of the carrier 6 made of such a metal oxide is not particularly limited, depending on the use of the gas purification material that can obtain a plate shape, honeycomb shape, powder shape, pellet shape, monolith shape, fiber shape, or the like. You can choose. Further, the size of the carrier 6 made of a metal oxide is not particularly limited and is appropriately determined according to the use of the obtained gas purification material. For example, when the carrier 6 has a plate shape or a honeycomb shape, it is generally used. Preferably has a thickness of about 0.1 mm to 5 mm. When the carrier 6 is in powder form, a particle size of about 0.5 mm to 5 mm is generally preferred.

The positional relationship between the carrier 6 and the target 4 is not particularly limited, and the carrier 6 is appropriately arranged with respect to the target 4 so that the scattered particles a generated from the surface of the target 4 are efficiently attached to the surface of the carrier 6. In FIG. 1, the carrier 6 is disposed at a position where the angle Θ with respect to the normal of the target 4 is 45 °. In addition, a target driving device (for example, a target turntable, not shown) is connected to the target 4, and a fresh surface of the target (laser light non-irradiated surface) is sequentially fed out to the irradiation position of the laser light L _1. ing. Further, a carrier driving device (for example, a carrier turntable, not shown) may be connected to the carrier 6 so that the metal component 5 is uniformly supported by the surface of the carrier 6.

As mentioned above, although one Embodiment of the manufacturing apparatus of the gas purification material suitable for this invention was described, the apparatus suitable for this invention is not limited to the said embodiment. That is, for example, in the above embodiment, the processing vessel 3 is connected to a vacuum pump (not shown), but at least one type of shielding gas selected from the group consisting of hydrogen gas, helium gas, neon gas, and argon gas is introduced. In this case, the interior of the container 3 can be maintained in a predetermined shielding gas atmosphere. When the container 3 having the shielding gas atmosphere inside is used in this way, the ultraviolet light (or vacuum ultraviolet light) L ₂ is not absorbed by the ultraviolet light absorbing material without the inside of the container 3 being in a reduced pressure state. As a result, the surface of the carrier 6 is activated more efficiently and oxidation of the metal component 5 is sufficiently prevented. Further, it is preferable that both the vacuum pump (not shown) and the gas cylinder (not shown) are connected to the processing container 3 so that the inside of the container 3 has a predetermined shielding gas atmosphere and is maintained at a predetermined pressure condition. is there. As such a condition, for example, a pressure of atmospheric pressure or lower is preferable in a helium gas atmosphere, and a pressure of 6.67 × 10 ⁴ Pa ( 500 Torr ) or lower is more preferable. In addition, it is preferable that the oxygen partial pressure and / or the nitrogen partial pressure be 133.3 Pa ( 1 Torr ) or less.

In the above embodiment, the laser light source 2 is disposed outside the processing container 3. However, the laser light source 2 may be disposed inside the processing container 3, in which case the laser light L ₁ is introduced into the container 3. This window 9 becomes unnecessary.

  Further, in the above-described embodiment, the carrier 6 is disposed at a position where the angle Θ with respect to the normal line of the target 4 is 45 °. However, the carrier 6 is not limited to such a positional relationship, and the angle with respect to the normal line of the target 4 The carrier 6 may be arranged at a position where Θ is in the range of about 10 ° to 60 °.

In addition, a target that can transmit the laser beam L ₁ is used as the target 4, the target 4 is disposed between the laser light source 2 and the carrier 6, and the surface of the target 4 (from the transparent film side) to the surface (target material side). The scattered laser beam L ₁ generates scattered particles a (or scattered particles a and ultraviolet light (or vacuum ultraviolet light L ₂ )) from the surface (target material side) of the target 4, and these are supplied to the surface of the carrier 6. You may make it do. Such a configuration tends to facilitate the loading of the metal component on a relatively large carrier. Moreover, as a target used for such a structure, the tape-shaped target which laminated | stacked the above-mentioned target material on the film (for example, PET film) transparent with respect to a laser beam by vapor deposition, sticking, etc. is preferable.

Further, when a powder, pellet, monolith, fiber or the like is used as the carrier 6 made of a metal oxide, a processing table (for example, a stainless steel table, not shown) on which such a carrier 6 is placed. And a vibrating device (for example, an ultrasonic generator, not shown) for rotating the carrier 6 placed on the processing table by applying vibration and / or stirring to the processing table. You may connect to. With this configuration, when the scattered particles a (or scattered particles a and ultraviolet light (or vacuum ultraviolet light L ₂ )) are supplied to the surface of the carrier 6, vibration and / or stirring applied by the vibration device. Since the carrier 6 is rotated by this, the fresh surface to which the scattered particles a are not attached is exposed sequentially, and the scattered particles a are attached over the entire surface of the carrier 6 so that the metal component 5 is more uniformly supported. Become so.

  Next, a preferred embodiment of the method for producing a gas purification material of the present invention and a preferred embodiment of the gas purification material of the present invention obtained thereby will be described with reference to FIG.

In the method for producing a gas purification material of the present invention, laser light L ₁ ( pulse width is 100 picoseconds to 100 nanoseconds and irradiation intensity is 10 ⁶ W / cm ² to 10 ¹² W on the target 4 made of the above-described metal. / ^cm 2, preferably pulsed laser light wavelength energy per 150nm~11μ m, 1 pulse is 0.01J～100J) is irradiated from the laser light source 2. Then, a high-temperature plasma P is formed on the surface of the target 4, and atoms or clusters containing metal are scattered with high energy from the surface of the target 4 irradiated with the laser beam L _{1. In} addition, the inside of the plasma P or the plasma P From the surface of the target 4 heated by the above, neutral atoms and ions formed by evaporation of the material constituting the target, and some of the neutral atoms and ions were bonded and supported. Clusters fly with high energy.

Since various scattered particles (ablators) a generated from the surface of the target 4 by irradiation with the laser beam L ₁ have high energy in this way, when they reach the metal oxide support 6, they adhere to the surface of the support 6. Reconstituted as fine particles of metal component 5. Further, when the scattered particles a reach further, a thin film composed of such fine particles of the metal component 5 is formed on the surface of the carrier 6. In the gas purification material of the present invention in which the metal component 5 is supported in this manner, the fine particles of the metal component 5 or the fine particles of the metal component 5 are formed only on the surface of the metal oxide support 6 that contributes to the decomposition reaction and adsorption of harmful gases. Since the thin film is supported, the harmful gas can be efficiently and reliably removed even if the amount of the metal component 5 supported is small.

Incidentally, large absorption by the atmosphere at the wavelength of the laser light L ₁ is less than the lower limit, it becomes impossible to supply sufficient energy to the target, there is a tendency that the plasma is not formed, while the high temperature plasma exceeds the above upper limit is formed Since it becomes impossible, it exists in the tendency which cannot form ultraviolet light (or vacuum ultraviolet light) and a fine scattering particle. Further, the pulse width of the laser beam L ₁ is excessively large kinetic energy of the scattered particles a the energy of the laser is concentrated in very short time at the lower limit, the metal when the scattering particles a has reached on the metal oxide support 6 The oxide carrier 6 tends to be destroyed. On the other hand, when the above upper limit is exceeded, energy does not concentrate in time, so that scattered particles a having sufficiently large energy tend not to be generated. Further, there is a tendency energy per pulse of the laser beam L ₁ is no longer a high-temperature plasma is formed by lack of energy is less than the lower limit, on the other hand, target dosage amount of heat is too large to target exceeds the upper limit melt However, it tends to easily cause droplets and spatter.

Also, you to various scattering particles (ablator) a described above is irradiated as it is supplied to the surface of the metal oxide support 6, to the surface of the support 6 a vacuum ultraviolet light L ₂ having a wavelength of 50 nm to 100 nm. With such ultraviolet light L ₂ on the surface of the metal oxide support 6 is irradiated, the surface of the metal oxide support 6 is activated, the scattering particles a having reached on the metal oxide support 6 which is activated strongly bonded to the surface of the support 6, it increases the adhesion of the metal component 5 to the metal oxide support 6.

Further, the laser light _{L 1} irradiated to target 4, and the irradiation intensity at the pulse width of 100 picoseconds to 100 nanoseconds and the pulse laser light _{L 1} is ^{10 6 W / cm 2 ~10 12} W / cm 2 you. When the target 4 is irradiated with the pulsed laser light L ₁ that satisfies such conditions, vacuum ultraviolet light L ₂ having a wavelength of 50 nm to 100 nm is generated from the high-temperature plasma P formed on the surface of the target 4. Then, the surface of the 6 the metal oxide support 6 this vacuum ultraviolet light L ₂ on are irradiated metal oxide support (metal oxide support particularly preferably contains carbon such as silicon carbide) are more active Therefore, the scattered particles a that have reached the activated metal oxide support 6 are strongly bonded by atoms on the surface of the support 6, and the metal component 5 is supported with sufficient adhesion strength to the metal oxide support 6. The

The pulse width of the pulsed laser light L ₁ becomes such that light having a wavelength less than 50nm because the laser energy in a short time is less than 100 picoseconds is irradiated to the target to concentrate produced, while the 100 nanosecond If exceeded, the energy of the laser is not sufficiently concentrated in time, and the wavelength of the generated light exceeds 100 nm. Further, in both cases where the wavelength of the generated light L ₂ is less than 50 nm and more than 100 nm, the degree of activation of the surface of the metal oxide support is reduced and the adhesion of the metal component 5 to the metal oxide support 6 is reduced. Tends to decrease. Furthermore, when the irradiation intensity of the pulse laser beam L ₁ is less than 10 ⁶ W / cm ^2, there is a tendency that the vacuum ultraviolet light L ₂ having a wavelength of 50 nm to 100 nm is not sufficiently generated, while when it exceeds 10 ¹² W / cm ² , the target Since the main wavelength region of the electromagnetic wave generated when the light is irradiated is 50 nm or less, the amount of the vacuum ultraviolet light L _{2 having} a wavelength of 50 nm to 100 nm tends to decrease.

  The metal component 5 supported on the surface of the metal oxide support 6 in this way is a thin film composed of fine particles of metal components formed by adhering scattered particles a and / or fine particles of such metal components. is there. Such a metal component is basically the same metal as the metal used for the target 4 described above, but is a material used for the target 4 because it has been reconstituted by molecules that have once become the scattered particles a. Need not have the same composition. Further, when the metal component 5 is a fine particle, the particle size is not particularly limited, but generally the average particle size is preferably about 0.1 nm to 10 nm. If the average particle size is less than the above lower limit, sufficient gas purification performance tends not to be obtained. On the other hand, even if the upper limit is exceeded, no further gas purification performance can be expected, and on the contrary, the production cost and resource consumption increase. It tends to be. Moreover, when the metal component 5 is a thin film, the film thickness is not particularly limited, but generally the film thickness is preferably about 5 nm to 40 nm. If the film thickness is less than the above lower limit, sufficient gas purification performance tends not to be exhibited. On the other hand, if the upper limit is exceeded, the metal oxide support is covered, and the gas purification action expected for the metal oxide support itself can be brought out. It tends to disappear.

  In the gas purification material of the present invention, by using such metal component fine particles and / or thin films supported on a metal oxide support, the catalytic action of the metal component and the catalytic action of the metal oxide support and / or Because the synergistic effect with the adsorption action sufficiently achieves the purification of harmful gases, and such metal components are supported only on the surface of the metal oxide support that contributes to the decomposition reaction and adsorption of harmful gases, the metal components Even if the loading amount is small, harmful gas is efficiently and reliably removed.

  The content of the metal component in the gas purification material of the present invention is not particularly limited, but is preferably 0.01 to 1.0 part by weight with respect to 100 parts by weight of the metal oxide support, 0.05 to 0 More preferably, it is 65 parts by weight. If the content of the metal component is less than the lower limit, sufficient catalytic action by the metal component tends not to be obtained. On the other hand, if the content exceeds the upper limit, no further catalytic action can be obtained. There is a tendency to increase the amount.

  In the above-described method for producing the gas purification material of the present invention, it is not necessary to heat the carrier 6 to a high temperature when the scattered particles a are attached to the surface of the carrier 6, and the temperature is not particularly limited. The room temperature may be about room temperature to 50 ° C. Further, the time required for forming the metal component 5 by attaching the scattered particles a to the surface of the carrier 6 (laser light irradiation time) is not particularly limited, and the supported metal component 5 has a desired particle size and / or Although it is appropriately determined so as to obtain a desired film thickness, generally a particle diameter of about 0.1 nm to 10 nm or a film thickness of about 5 nm to 40 nm is preferable, and a particle diameter of about 2 nm to 5 nm or a film thickness of about 8 nm to 20 nm is preferable. Particularly preferred.

  In the method for producing a gas purification material of the present invention, before and / or after (preferably after) supporting the metal component 5 on the metal oxide support 6 as described above, hydrogen, Reduction treatment in an atmosphere containing carbon oxide or hydrocarbon (methane, acetaldehyde, etc.) and / or calcination treatment in nitrogen or air may be performed. Conditions for such reduction treatment and firing treatment are not particularly limited, but for example, a condition of heating at a temperature of 200 to 800 ° C. for 1 to 10 hours is employed.

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

(Examples 1-6)
[Production of metal oxide support]
A slurry was prepared by mixing 100 g of CeO ₂ —ZrO ₂ solid solution {Cataler Co., Ltd., Ce: Zr = 5: 1 (molar ratio)}, 35 g of alumina sol (Nissan Chemical) and 20 ml of distilled water. The obtained slurry was applied to the surface of a cordierite honeycomb plate (manufactured by NGK, molded into 40 mm × 100 mm × 3 mm), dried at 120 ° C. for 3 hours, and further fired at 450 ° C. for 2 hours in an air stream. . The coverage of the CeO ₂ —ZrO ₂ solid solution on the obtained metal oxide support (CeO ₂ —ZrO ₂ substrate) was 0.7 g.

[Manufacture of gas purification materials]
Using the CeO ₂ —ZrO ₂ substrate thus obtained, a gas purification material manufacturing apparatus shown in FIG. 1 was produced. That is, a YAG laser apparatus (trade name: PRO-290, manufactured by Spectra Physics Co., Ltd.) as the laser light source 2, a vacuum container with a quartz window (stainless steel, capacity 30 liters) as the processing container 3, and a platinum plate (diameter as the target 4) 50 mm, thickness 1 mm), and using the CeO ₂ —ZrO ₂ substrate as the carrier 6, the gas purification material manufacturing apparatus shown in FIG. The carrier 6 was disposed at a position where the angle Θ relative to the normal of the target 4 was 60 °, and the distance between the carrier 6 and the target 4 (distance between the centers) was 80 mm.

Next, using the manufactured apparatus, the inside of the container 3 is set to a vacuum degree of 1.33 Pa ( 1 × 10 ⁻² Torr ) , the target 4 is rotated at 12 rpm, and the carrier 6 is rotated at 200 rpm. A pulse laser beam L ₁ having a wavelength of 532 nm, a pulse width of 7 nanoseconds, an energy of 1 J / pulse, a frequency of 10 Hz, and an irradiation intensity of 4.8 × 10 ⁹ W / cm ² (4.8 GW / cm ² ) from the light source 2 is used as the target 4. Irradiated. Container 3 pulsed laser light L ₁ for internal vacuum state reaches the target 4 without attenuation, the surface of the target 4 hot plasma P is formed, the vacuum ultraviolet light having a wavelength in the range of 50nm~100nm L ₂ is generated, simultaneously, the neutral atom of platinum from the surface of the target 4, ions, and these neutral atoms, the scattered particles (ablator) a cluster such that some are formed by bonding of the ions Scattered with high energy. Then, the surface of the carrier (CeO ₂ —ZrO ₂ substrate) 6 is sufficiently activated by being irradiated with the vacuum ultraviolet light L ₂ generated from the plasma P, and the scattered particles a reach and adhere at high speed with high energy. Then, the platinum thin film 5 made of platinum fine particles was formed on the surface of the carrier 6.

  In Examples 1 to 6, the laser irradiation time was set to the time shown in Table 1, and the thickness of the platinum thin film 5 supported on the surface of the carrier 6 and the supported amount of platinum were as shown in Table 1. . The carrier temperature was about 25 ° C.

[Hydrogen reduction treatment]
The CeO ₂ —ZrO ₂ substrate carrying platinum was subjected to hydrogen reduction treatment at 500 ° C. for 2 hours in a mixed gas of hydrogen and nitrogen (hydrogen content: 5% by volume).

[Evaluation of formaldehyde removal performance]
Formaldehyde (Air atmosphere) with an initial concentration of 300 ppm was sealed in a gas impermeable bag with a capacity of 50 liters together with 9.8 g of a CeO ₂ —ZrO ₂ substrate that had been supported by platinum and then subjected to hydrogen reduction treatment. (0.16 hours later) The formaldehyde concentration in the bag after the lapse of 1 hour and after the lapse of 3 hours was measured with a Kitagawa type gas detector tube (manufactured by Gaskuro Kogyo Co., Ltd.). The obtained results are shown in Table 1.

(Comparative Example 1)
A CeO ₂ —ZrO ₂ solid solution similar to that used in Example 1 was impregnated as follows with platinum (the amount of platinum supported was 1.5 weight with respect to 100 parts by weight of CeO ₂ —ZrO ₂ solid solution). Part). That is, CeO ₂ —ZrO ₂ solid solution powder was impregnated with a predetermined amount of an aqueous solution of a predetermined concentration of Pt salt (manufactured by Tanaka Kikinzoku Co., Ltd., trade name: platinum P salt), then evaporated to dryness, and then at 500 ° C. in the atmosphere. It was calcined for 2 hours to carry platinum.

Next, a slurry was prepared by mixing 100 g of CeO ₂ —ZrO ₂ solid solution carrying platinum by impregnation method, 35 g of alumina sol (Nissan Chemical Co., Ltd.) and 20 ml of distilled water, and the obtained slurry was used in Example 1. After coating on the surface of a cordierite honeycomb plate similar to the above, it was dried at 120 ° C. for 3 hours, and further fired in an air stream at 450 ° C. for 2 hours. The coverage of the CeO ₂ —ZrO ₂ solid solution on the obtained metal oxide support (CeO ₂ —ZrO ₂ substrate) was 0.7 g.

Subsequently, hydrogen reduction treatment was performed on the CeO ₂ —ZrO ₂ substrate supporting platinum by the impregnation method in the same manner as in Example 1, and then the formaldehyde removal performance was evaluated in the same manner as in Example 1. did. The obtained results are shown in Table 1.

(Comparative Example 2)
A CeO ₂ —ZrO ₂ substrate carrying platinum was produced by the impregnation method in the same manner as in Comparative Example 1 except that the amount of platinum supported was 0.15 parts by weight with respect to 100 parts by weight of the CeO ₂ —ZrO ₂ solid solution. Then, after performing the hydrogen reduction treatment in the same manner as in Comparative Example 1, the performance for removing formaldehyde was evaluated in the same manner as in Comparative Example 1. The obtained results are shown in Table 1.

(Comparative Example 3)
As a blank, only formaldehyde (Air atmosphere) with an initial concentration of 300 ppm was sealed in a gas-impermeable bag with a capacity of 50 liters, immediately after sealing (after 0.16 hours), after 1 hour and after 3 hours. The formaldehyde concentration in the bag was measured later. The obtained results are shown in Table 1.

表１に示した結果から明らかな通り、レーザーアブレーション法で白金をＣｅＯ_２−ＺｒＯ_２基板に担持させた本発明のガス浄化材料（実施例１〜６）は、従来の含浸法により白金をＣｅＯ_２−ＺｒＯ_２基板に担持させたガス浄化材料（比較例１〜２）に比べてホルムアルデヒド除去性能が非常に優れており、白金担持量が少量であっても同等若しくはそれ以上の除去性能が達成されることが確認された。

As is clear from the results shown in Table 1, the gas purification materials (Examples 1 to 6) of the present invention in which platinum was supported on a CeO ₂ —ZrO ₂ substrate by a laser ablation method were obtained by converting platinum into CeO by the conventional impregnation method. Compared to gas purification materials (Comparative Examples 1 and 2) supported on a _2- ZrO ₂ substrate, formaldehyde removal performance is extremely superior, and equivalent or better removal performance is achieved even with a small amount of platinum supported. It was confirmed that

  As described above, according to the gas purification material of the present invention, even if the amount of the metal component supported on the carrier made of the metal oxide is smaller than the conventional amount, aldehydes in the air, NOx in the exhaust gas, It is possible to efficiently and reliably remove harmful gases such as CO. Therefore, according to the gas purification material of the present invention, it is possible to reduce the cost by reducing the amount of the metal component supported, which is also effective from the viewpoint of securing resources. Further, according to the method for producing a gas purification material of the present invention, a gas purification material carrying a metal component can be obtained without using a conventional metal salt. Waste liquid treatment is unnecessary, and from the viewpoint of green chemistry, it is possible to reduce the burden on the environment and to manufacture the gas purification material of the present invention in a simplified process. Accordingly, the present invention provides a “room temperature air purification catalyst” for purifying harmful gases such as aldehydes in the air at room temperature, and a “low temperature” for purifying harmful gases such as NOx and CO in exhaust gas at low temperatures. The present invention is very useful as a technique for providing a gas purification material that functions as a decomposition catalyst and / or an adsorbent for harmful gases, such as an “exhaust gas purification catalyst”.

It is a schematic diagram which shows the basic composition of suitable one Embodiment of the manufacturing apparatus of the gas purification material suitable for this invention.

Explanation of symbols

1 ... apparatus for producing gas purification material, 2 ... laser light source, 3 ... processing vessel 4 ... target, 5 ... metal component, 6 ... metal oxide support, 7 ... window, L 1 _... pulsed laser beam, L 2 _... vacuum Ultraviolet light, a ... scattered particles, P ... plasma.

Claims (7)

Rh, Nb, Re, Ag, Au, Cu, Co, Cr, Ni, Fe, Ir, Mo, Pt, Pd, Sn, Ti, V, W, Zn, Zr, Ru, Os, and their main components A target made of a metal selected from the group consisting of alloys is irradiated with a pulse laser beam having a pulse width of 100 picoseconds to 100 nanoseconds and an irradiation intensity of 10 ⁶ W / cm ² to 10 ¹² W / cm ^2. to generate vacuum ultraviolet light and the metal sputtered particles wavelength 50nm~100nm Te, Ti, Al, Si, Ce , Zr, Fe, Mn, Ni, at least one metal selected from the group consisting of Zn and Cu A metal component supported on the carrier is formed by attaching the scattered particles to the surface of the carrier made of a metal oxide that is a single oxide or a complex oxide while irradiating the vacuum ultraviolet light. A method for producing a gas purification material. The method for producing a gas purification material according to claim 1 , wherein the metal is a noble metal selected from the group consisting of Pt, Pd, Rh, Ru, Ir, Os, Au, and Ag . The metal oxide is at least one metal oxide selected from the group consisting of titanium oxide, alumina, silicon oxide, cerium oxide, zeolite, zirconia, iron oxide, manganese oxide, nickel oxide, zinc oxide and copper oxide. The method for producing a gas purification material according to claim 1 or 2.   The scattered particles are attached to the surface of the carrier in a reduced pressure state and / or in a shield gas atmosphere containing at least one gas selected from the group consisting of hydrogen gas, helium gas, neon gas, and argon gas. The manufacturing method of the gas purification material as described in any one of Claims 1-3. A support made of a metal oxide that is a single oxide or composite oxide of at least one metal selected from the group consisting of Ti, Al, Si, Ce, Zr, Fe, Mn, Ni, Zn, and Cu ;
Rh, Nb, Re, Ag, Au, Cu, Co, Cr, Ni, Fe, Ir, Mo, Pt, Pd, Sn, Ti, V, W, Zn, Zr, Ru, Os, and their main components A target made of a metal selected from the group consisting of alloys is irradiated with a pulse laser beam having a pulse width of 100 picoseconds to 100 nanoseconds and an irradiation intensity of 10 ⁶ W / cm ² to 10 ¹² W / cm ^2. The metal scattering particles generated in this manner are attached to the surface of the carrier in the state of being irradiated with the vacuum ultraviolet light having a wavelength of 50 nm to 100 nm generated by the irradiation of the pulse laser beam, and are supported on the carrier. The metal component being
A gas purification material comprising: 6. The gas purification material according to claim 5 , wherein the metal is a noble metal selected from the group consisting of Pt, Pd, Rh, Ru, Ir, Os, Au, and Ag . The metal oxide is at least one metal oxide selected from the group consisting of titanium oxide, alumina, silicon oxide, cerium oxide, zeolite, zirconia, iron oxide, manganese oxide, nickel oxide, zinc oxide and copper oxide. The gas purification material according to claim 5 or 6, characterized in that

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