CN115569648B - Photocatalyst composite material, method for producing photocatalyst composite material, and photocatalyst device - Google Patents
Photocatalyst composite material, method for producing photocatalyst composite material, and photocatalyst device Download PDFInfo
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- CN115569648B CN115569648B CN202211426631.0A CN202211426631A CN115569648B CN 115569648 B CN115569648 B CN 115569648B CN 202211426631 A CN202211426631 A CN 202211426631A CN 115569648 B CN115569648 B CN 115569648B
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- photocatalyst
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 297
- 239000002131 composite material Substances 0.000 title claims abstract description 83
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 18
- 239000002245 particle Substances 0.000 claims abstract description 192
- 239000000463 material Substances 0.000 claims abstract description 31
- 239000000758 substrate Substances 0.000 claims description 49
- 239000006185 dispersion Substances 0.000 claims description 37
- 239000000126 substance Substances 0.000 claims description 36
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 31
- 239000002042 Silver nanowire Substances 0.000 claims description 30
- 230000001699 photocatalysis Effects 0.000 claims description 30
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims description 23
- 229910001930 tungsten oxide Inorganic materials 0.000 claims description 23
- 239000007788 liquid Substances 0.000 claims description 21
- 238000000576 coating method Methods 0.000 claims description 17
- 230000003197 catalytic effect Effects 0.000 claims description 14
- 239000011248 coating agent Substances 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 10
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 238000009826 distribution Methods 0.000 claims description 6
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 6
- 229910044991 metal oxide Inorganic materials 0.000 claims description 5
- 150000004706 metal oxides Chemical class 0.000 claims description 5
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 4
- 229910001887 tin oxide Inorganic materials 0.000 claims description 4
- 229910000484 niobium oxide Inorganic materials 0.000 claims description 3
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 claims description 3
- 239000011787 zinc oxide Substances 0.000 claims description 3
- 230000000694 effects Effects 0.000 abstract description 16
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 17
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 12
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 2
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- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 2
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- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
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- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
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- 239000000123 paper Substances 0.000 description 1
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Classifications
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- B01J23/6527—Tungsten
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- B01J23/622—Platinum group metals with gallium, indium, thallium, germanium, tin or lead with germanium, tin or lead
- B01J23/626—Platinum group metals with gallium, indium, thallium, germanium, tin or lead with germanium, tin or lead with tin
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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- Condensed Matter Physics & Semiconductors (AREA)
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Abstract
The invention provides a photocatalyst composite material which has high activity, can be simply manufactured and is not easy to peel, a manufacturing method thereof and a photocatalyst device. A photocatalyst composite material comprising a base material and a photocatalyst layer formed of photocatalyst particles, wherein the photocatalyst layer in contact with the surface of the base material has an average particle diameter smaller than that of the surface of the photocatalyst layer.
Description
The present application is a divisional application of the invention patent application having the application date of 2019, 9, 12, 201910863185.1 and the invention name of "photocatalyst composite material, method for producing photocatalyst composite material, and photocatalyst device".
Technical Field
Embodiments of the present invention relate to a photocatalyst composite material, a method for producing the photocatalyst composite material, and a photocatalyst device.
Background
Photocatalysts are known to generate excited holes by light, promoting strong oxidation reactions. As a photocatalyst having such an action, various photocatalysts are known, and the promotion action is utilized for decomposition and removal of harmful organic molecules, sterilization, maintenance of hydrophilicity of a substrate, and the like.
When the photocatalyst is to be used for such a purpose, for example, the photocatalyst composite material having the photocatalyst supported on the substrate is brought into contact with a substance to be treated. In order to effectively perform the treatment by this method, the amount of the photocatalyst supported on the substrate is generally increased. However, the increase in the amount of the photocatalyst is directly related to the increase in cost, and there is a problem that the photocatalyst is easily peeled from the substrate. In addition, in order to increase the surface area, a fractal structure or other shape may be used, but the manufacturing method is easy to become complicated, and there is room for investigation.
Prior art literature
Patent literature
Patent document 1: japanese patent No. 4163374 specification
Patent document 2: japanese patent laid-open No. 2000-135755
Disclosure of Invention
Problems to be solved by the invention
In view of the above problems, it is desirable to provide a photocatalyst composite material having high activity and being less likely to be peeled off, a method for producing the photocatalyst composite material in a simple manner, and a photocatalyst device provided with the photocatalyst composite material.
Means for solving the problems
The photocatalyst composite material according to the embodiment includes a base material and a photocatalyst layer containing photocatalyst particles, and the interface on the substrate side of the photocatalyst layer is S b Let the opposite side interface be S t At the time, S is as described above b Average particle diameter r of the photocatalyst particles in the vicinity b Less than the S t Average particle diameter r of the photocatalyst particles in the vicinity t 。
The method for producing a photocatalyst composite material according to the embodiment includes the following steps: a step of coating a dispersion liquid containing the 1 st photocatalyst particles on a substrate; and a step of coating a dispersion liquid containing 2 nd photocatalyst particles having an average particle diameter larger than the 1 st photocatalyst particles.
The photocatalyst device according to the embodiment includes:
the photocatalyst composite material,
Light irradiation means for producing photocatalytic activity on the substrate, and
a supply member for supplying a substance to be treated to the above-mentioned photocatalyst composite material,
the photocatalyst composite material, which generates catalytic activity by the light, promotes chemical reactions for treating the above-mentioned substances.
Drawings
Fig. 1 is a schematic view of a photocatalyst composite material according to an embodiment.
Fig. 2 is a schematic diagram of a method for producing a photocatalyst composite material according to an embodiment.
Fig. 3 is a schematic view of a photocatalyst apparatus according to an embodiment.
Description of symbols
10 … photocatalyst composite, 11 … substrate, 12 … photocatalyst layer, 21 … 1 st photocatalyst particle, 22 … 2 nd photocatalyst particle, 30 … photocatalyst device, 31 … photocatalyst composite, 32 … light irradiation member, 33 … member for supplying substance for receiving photocatalytic action to substrate, 34 … reaction chamber
Detailed Description
Hereinafter, embodiments will be described with reference to the drawings.
Note that the same reference numerals are given to common components in the embodiments, and overlapping descriptions are omitted. The drawings are schematic views for explaining the embodiments and promoting understanding thereof, and the shapes, dimensions, proportions, and the like thereof are different from those of actual devices, and may be appropriately changed in design by referring to the following description and known techniques.
(embodiment 1)
As shown in fig. 1, a photocatalyst composite material 10 according to an example of an embodiment includes a base material 11 and a photocatalyst layer 12. The photocatalyst layer 12 has a substrate-side interface S b And opposite side interface S t . In the photocatalyst layer illustrated in fig. 1, the particles having a small particle diameter are S b Side part exists, and the particle with large particle diameter is in S t The sides are locally present. Thus, if it is to be at S b Average particle diameter r of nearby photocatalyst particles b And is at S t Average particle diameter r of nearby photocatalyst particles t Comparing r b Become smaller.
Wherein, is called S b Nearby or S t The vicinity may be generally set to divide the photocatalyst layer into two portions close to S b And approach S t Is defined in the specification.
In FIG. 1, as a schematic diagram, S is shown b Side is provided with 'small particles', at S t The side is provided with 2 structures of "macroparticles". When the particle diameter distribution of such photocatalyst particles is measured, the distribution curve has 2 peaks. However, the present invention is not limited thereto, and 2 or more kinds of particles having different sizes may be layered, or S may be formed b Orientation S t While the particle diameter is continuously changed. In the former case, the particle size distribution curve has 2 or more peaks, but in the latter case, there are cases where no clear peaks appear in the particle size distribution.
By disposing the photocatalyst particles in this manner, excellent effects can be obtained. First, if the photocatalyst particles are small, they tend to be easily peeled off in water or air by the action of water flow or air flow. However, particles existing in the vicinity of Sb and in contact with the surface of the substrate are easily strongly adsorbed by the substrate, and therefore are not easily peeled off even if the average particle diameter is small. In addition, if the photocatalyst particles in the vicinity of Sb are small, the surface area of the photocatalyst present in the vicinity of the substrate surface increases, so that it becomes easy to obtain high catalytic activity.
On the other hand, the photocatalyst particles existing in the vicinity of St have a larger average particle diameter, and become more difficult to be peeled off. Further, the larger the particle diameter, the larger the space between the particles becomes, so that the substances or decomposition products treated by the photocatalyst are easily diffused.
The particle diameter or average particle diameter of the photocatalyst particles can be measured by observing the surface and cross section of the photocatalyst layer photographed by a TEM (Transmission Electron Microscopy: transmission electron microscopy). Specifically, the cross section of the photocatalyst layer was observed 100 ten thousand times by TEM, and the diameter at the time of converting the projected area of particles into circles of the same area by image processing was set as the particle diameter. In addition, S b Average particle diameter r of nearby photocatalyst particles b Or S t Average particle diameter r of nearby photocatalyst particles t Is configured at S b Nearby or S t Nearby photocatalyst particles, e.g. of at least 100 particle sizesAnd (5) averaging.
In an embodiment, r b Preferably 2 to 50nm. If r b When the particle size is 2nm or more, the stability of the dispersion of the photocatalyst particles in the production process is high, and the possibility of dissolution or aggregation is low. On the other hand, if r b When the particle size is 50nm or less, the photocatalyst particles can be sufficiently adhered to the surface of the substrate, and the total surface area of the photocatalyst particles becomes large, so that a high catalytic activity can be obtained. In addition, r t Preferably 40 to 500nm. If r t When the particle size is 40nm or more, the space between particles is widened, so that the substance to be treated is sufficiently diffused into the photocatalyst layer to obtain high catalytic activity, and peeling of the photocatalyst layer due to air flow, water flow or the like is less likely to occur. On the other hand, if r t When the particle diameter is 500nm or less, the dispersion in the production process tends to have high dispersibility and high catalytic activity.
The average particle diameter of all the photocatalyst particles contained in the photocatalyst layer is preferably 2 to 500nm, more preferably 10 to 400nm, particularly preferably 20 to 200nm, from the viewpoints of stability of the dispersion, workability at the time of application to a substrate, and performance of a photocatalytic function.
As the photocatalyst particles, particles containing metal oxides such as tungsten oxide, titanium oxide, zinc oxide, niobium oxide, and tin oxide are used. These photocatalyst particles may be used in combination of 2 or more kinds. The photocatalyst containing tungsten oxide is preferable because of its visible light responsiveness. In particular, when the crystal of tungsten oxide contains a monoclinic or triclinic crystal structure, the activity of the catalyst tends to be high, which is preferable.
The photocatalyst particles having different chemical compositions may be used in combination. Thus, not only the photocatalysts having different functions can be combined, but also the fastness of the photocatalyst layer can be improved or the light energy irradiated to the catalyst can be more effectively utilized. For example, in the case where a material that is easily positively charged is used for the substrate, if at S b Tungsten oxide easily negatively charged is disposed in the vicinity of S t Nearby configured oxidationThe adhesion of the photocatalyst layer to the substrate is improved and the durability is improved. In this case, the average particle diameter of the tungsten oxide is smaller than that of the titanium oxide. In addition, by combining photocatalysts having large differences in light absorption spectra, each photocatalyst particle efficiently absorbs light, and catalytic activity can be exhibited. For example, by at S b A tungsten oxide having an absorption edge of 470nm and disposed in the vicinity of the light absorption, at S t Titanium oxide having an absorption end of light absorption of about 400nm is disposed nearby, so that tungsten oxide at a position distant from the light absorption surface becomes capable of efficiently absorbing light.
The photocatalyst layer preferably contains 20 to 100 mass% of photocatalyst particles based on the total mass of the photocatalyst layer to obtain high catalytic activity. The photocatalyst layer may be composed of only photocatalyst particles, but may contain a promoter, silver nanowires, a binder, and the like, which will be described later.
The photocatalyst layer of the present embodiment may further contain a cocatalyst. The cocatalyst is mostly contained in the form of nanoparticles. As the material of the cocatalyst, a metal element compound is preferable. For example, the promoter for the tungsten oxide photocatalyst may contain at least 1 metal element selected from Ti, sn, zr, mn, fe, ni, pd, pt, cu, ag, zn, al, ru and Ce. Among them, metal oxides of Cu, fe, ni or composite oxides thereof are preferable. The content of the metal element such as the transition metal element with respect to the total amount of the photocatalyst particles and the promoter particles may be set to be in the range of 0.01 to 50 mass%. If the content of the transition metal element exceeds 50 mass%, the light transmittance tends to decrease, and the activity of the catalyst tends to decrease. The content of the transition metal element is more preferably 10 mass% or less, and still more preferably 2 mass% or less. The lower limit of the content of the transition metal element is not particularly limited, but the content thereof is preferably set to 0.01 mass% or more in view of more effectively exhibiting the addition effect of the cocatalyst. The above-mentioned oxides of transition metals are easily positively charged. Noble metal promoter particles such as Pt and Pd are also preferable, since they can be easily positively charged by the protection of the organic polymer.
In an embodiment, zeta potential can be measured by an electrophoretic light scattering method. Specifically, the measurement can be performed by combining a capillary sample cell in a sample cell manufactured by Malvern corporation under the trade name Zetasizer Nano ZS. The pH of the dispersion is adjusted by adding dilute hydrochloric acid and dilute aqueous potassium hydroxide solution to pure water in which photocatalyst-containing material or promoter particles are dispersed.
The cocatalyst is a substance that further enhances the photocatalytic action of the photocatalyst particles. More specifically, for example, copper oxide or the like as a p-type semiconductor is preferably used as a promoter with respect to tungsten oxide as an n-type semiconductor. Since the energy level of the conduction band of tungsten oxide is slightly higher than the valence band of the promoter, electrons excited from the valence band to the conduction band by irradiation of light to tungsten oxide move to the valence band of the promoter, and so-called Z-Scheme excited to the conduction band of the promoter by further excitation by light, oxygen in the air can be reduced by the energy level of electrons by visible light to generate oxygen radicals or hydrogen peroxide. Holes are generated in the valence band of tungsten oxide, and organic molecules and the like are decomposed. Oxygen radicals or hydrogen peroxide also decompose organic molecules and the like.
The metal oxide promoter has a positive Zeta potential. In contrast, photocatalyst particles such as tungsten oxide have a negative Zeta potential. Therefore, the photocatalyst particles and the promoter particles become easily adsorbed and the catalytic activity is easily further enhanced.
The photocatalyst layer of the present embodiment may further include silver nanowires. Tungsten oxide and spherical silver particles which are easily negatively charged are not likely to form a uniform composite, but a uniform composite structure is easily formed by easily holding photocatalyst particles between mesh structures formed of silver nanowires.
In addition, although silver nanowires generally tend to aggregate easily, the photocatalyst dispersion liquid according to the embodiment has little aggregation. This is thought to be due to: the coexisting photocatalyst particles also have a function of a dispersant, and are less likely to cause aggregation.
In addition, the mesh structure of the photocatalyst layer formed by the silver nanowires is also mechanically stable, and the outflow of the silver nanowires is not easily caused. Further, the antibacterial property is generated by an extremely small amount of silver ions, and the antibacterial property is maintained for a long time. Further, the silver nanowire has a photoelectric field enhancement effect by plasmon resonance, and has an effect of improving the activity of photocatalyst particles around the silver nanowire.
The shape of the silver nanowire is not particularly limited, and is selected so as to be capable of optimizing a desired plasmon effect, a dispersion state in a dispersion liquid, and the like. For example, in an embodiment, silver nanowires preferably have an average diameter of 10 to 200nm, an average length of 1 to 50 μm, and an average aspect ratio of 100 to 1000. More preferably, the average diameter is 20 to 100nm, the average length is 4 to 30 μm, and the average aspect ratio is 200 to 500. The average diameter or average length of the silver nanowires was measured by observing the surface and cross section of the photocatalyst layer photographed at 20 ten thousand times by SEM (Scanning Electron Microscopy: scanning electron microscopy). The diameter of the silver nanowire corresponds to the length of the width of the planar image of the silver nanowire. The length of the silver nanowire corresponds to the length of the silver nanowire in the length direction of the planar image. In the case where the silver nanowire is bent, a length obtained by shaping the silver nanowire into a linear shape is used. In the case of one silver nanowire, when the width varies in the length direction, the width was measured at 3 different points, and the average was set as the width of the nanowire. The average of these values was obtained from the measured values of 50 nanowires randomly selected respectively.
Regarding the mixing ratio of the photocatalyst particles to the silver nanowires, in the case of combining the silver nanowires, the mass of the silver nanowires is preferably 1/100000 to 1/10 times, more preferably 1/1000 to 1/10 times, based on the mass of the photocatalyst particles. If the mixing ratio of the silver nanowires is large, the light excitation of the photocatalyst tends to be easily blocked by the light absorption of the silver nanowires, and if the mixing ratio of the silver nanowires is small, the effect of improving the catalytic activity by the silver nanowires tends to be small.
The photocatalyst layer of the present embodiment may further contain aluminaA hydrate. Alumina hydrate is prepared from Al 2 O 3 ·(H 2 O) x (0<x.ltoreq.3) a hydrate. Alumina hydrate particles (hereinafter, simply referred to as alumina particles) are excellent as a binder and prevent aggregation of catalyst particles, so that the photocatalyst dispersion liquid is stabilized. When applied to a substrate, a uniform and fast film is easily formed.
Alumina particles have various forms, but boehmite (x=1) or pseudoboehmite (1 < x < 2) is preferable. Boehmite or pseudoboehmite is stable in a polar solvent such as water, and can be easily formed into a coating film by coating and drying. In particular, alumina particles having a fibrous or plate-like shape have a great effect of preventing aggregation of catalyst particles with each other.
When alumina particles are used, the mixing ratio of the photocatalyst particles to the alumina particles is preferably 0.005 to 0.1 times, preferably 0.01 to 0.03 times, based on the mass of the photocatalyst particles. If the amount of the alumina hydrate is too large, the photocatalytic activity of the photocatalyst layer may be lowered, and if the amount of the alumina hydrate is too small, the stability of the photocatalyst layer may be lowered.
The shape of the alumina particles is not particularly limited, and may be, for example, fibrous. When the alumina particles are fibrous, the diameter is preferably 1 to 10nm and the length is preferably 500 to 10000nm. More preferably 2 to 8nm in diameter and 800 to 60000nm in length, still more preferably 3 to 6nm in diameter and 1000 to 3000nm in length.
The photocatalyst layer may further contain other oxides. For example, silicon oxide has a function of increasing the hydrophilicity of the photocatalyst layer. Further, tin oxide increases the conductivity of the photocatalyst layer to prevent electrification and to prevent dirt from adhering easily.
The photocatalyst layer may also contain graphene oxide or graphite oxide. This prevents the catalyst particles from agglomerating with each other, and can maintain stability and photocatalytic activity for a long period of time. Regarding the mixing ratio of graphene oxide or graphite oxide contained in the photocatalyst layer to the photocatalyst particles, the mass of graphene oxide or graphite oxide based on the mass of the photocatalyst particles is preferably 1/200,000 to 1/100 times, more preferably 1/100,000 to 1/1000 times, particularly preferably 1/50,000 to 1/10,000 times. If the blending ratio is small, the stability improvement effect tends to be small, and if the blending ratio is large, the photocatalytic activity improvement effect tends to be small.
In an embodiment, a base layer may be provided between the substrate and the photocatalyst layer. The layer containing an inorganic oxide is preferable as the underlayer because it can prevent deterioration of the substrate due to the photocatalyst and can prevent peeling from the photocatalyst layer. Examples of the inorganic oxide include silica, alumina, and zirconia. The inorganic oxide is further preferably aluminum oxide. Most substrates have negative Zeta potential, and aluminum oxides that easily have positive Zeta potential easily stably cover the substrate. In addition, photocatalyst particles and silver nanowires having a negative Zeta potential are easily and stably supported.
In the embodiment, the coverage of the surface area of the base layer with respect to the substrate is preferably 80% or more. The coverage is the ratio of the area covered by the base layer to the surface area of the base material. By setting the coverage within this range, the effects of catalyst fixation of the base layer and protection of the substrate can be obtained. The coverage was measured by SEM at 25 times, and the area of the substrate surface and the area of the portion covered with the substrate layer were measured from the ratio.
The Zeta potential of the substrate or underlayer can be measured by an electrophoretic light scattering method using Zetasizer Nano ZS manufactured by Malvern corporation and using polystyrene latex as a tracer particle in a flat plate Zeta potential measuring cuvette. The pH is adjusted by adding dilute hydrochloric acid and dilute aqueous potassium hydroxide solution to pure water.
The substrate may be selected from any materials such as organic materials and metallic materials, and examples thereof include metals, ceramics, papers, and polymer films. The substrate may be a smooth surface material or a porous body. In the case of the porous body, the surface area can be increased, and the photocatalyst loading can be easily increased, which is preferable. In addition, if the material of the base material is a material containing an organic substance, coloring or surface modification becomes easy, so that it is preferable.
The polymer film can be made into a flexible transparent film, so that the application range of the photocatalyst composite material can be expanded. As the polymer material, a material having high visible light transparency such as polyethylene terephthalate, polycarbonate, polyethylene naphthalate, and acrylic resin can be preferably used. It is also preferable to use a curable resin that forms a firm surface. In particular, polyethylene terephthalate is preferable because of its high flexibility and good adhesion to graphene oxide when used. It is also preferable to use a curable resin that forms a firm surface.
The substrate preferably has a negative Zeta potential in water at 20℃and pH 6. By using such a base material, association of catalyst particles can be suppressed, and a uniform film can be easily obtained.
The surface of the substrate may be smooth or may have irregularities. When the surface roughness of the substrate is increased, the surface area of the substrate surface is increased, and the photocatalyst particles of the photocatalyst layer on the substrate can be supported more.
For example, the absolute value of the arithmetic average roughness Ra of the surface of the substrate is preferably 0.2 μm to 20 μm. The arithmetic average roughness Ra may be measured in accordance with JIS standard. When the arithmetic average roughness Ra is less than 0.2 μm, the contact area between the photocatalyst and the substrate becomes small, and the photocatalyst tends to be easily peeled off. If the arithmetic average roughness Ra is larger than 20 μm, the photocatalyst particles accumulate only in the concave portion of the substrate, and the film thickness of the photocatalyst layer becomes too large, so that activation of the photocatalyst in the lower portion by light tends to be less likely to occur.
The term "photocatalytic effect" in the present embodiment means decomposition of harmful substances such as ammonia and aldehydes, decomposition and deodorization of unpleasant odors such as cigarette and pet odors, antibacterial action against staphylococcus aureus, escherichia coli and the like, antiviral action, and antifouling action with less adhesion of dirt.
(embodiment 2)
The photocatalyst composite material according to the embodiment may be produced by any method, but may be produced by, for example, the method described below.
Fig. 2 (a) to (C) schematically show an example of a method for producing the photocatalyst composite material according to embodiment 2.
First, the 1 st photocatalyst particle layer 21a is formed by coating the dispersion liquid 21 containing the 1 st photocatalyst particles on the surface of the substrate 11 (fig. 2 (a)). The 1 st photocatalyst particle may be selected from the above-mentioned photocatalyst particles. The average particle diameter of the 1 st photocatalyst particles is preferably 2 to 50nm. The dispersion may contain promoter particles, silver nanoparticles, and the like, as necessary. Water is generally used in the dispersion medium. However, alcohols may be mixed as needed. If the dispersion medium contains an alcohol, the surface tension of the dispersion liquid is reduced, and the coating on the substrate becomes easy. The alcohol is preferably ethanol, methanol, isopropanol, or the like, and ethanol is more preferable from the viewpoint of safety. The content of the alcohol is preferably 1 to 95% by mass, more preferably 5 to 93% by mass, and even more preferably 10 to 90% by mass, based on the total mass of the dispersion.
The content of the photocatalyst particles contained in the dispersion is preferably set to 0.1 to 20% by mass based on the total mass of the dispersion from the viewpoint of ease of application and the like.
As the coating method, any method such as spray coating, die coating, bar coating, spin coating, screen printing, and the like can be used. The coating may be performed continuously over a large area by a batch method or a roll-to-roll method.
After the application, a part or all of the dispersion medium contained in the layer 21a is dried and removed as necessary. As the drying method, there are methods such as warm air heating, infrared heating, hot plate heating, microwave heating, and the like. Among them, infrared heating or warm air heating is preferable because it can easily cope with the roll-to-roll method.
Thereafter, a dispersion liquid containing the 2 nd photocatalyst particles 22 is applied to form a 2 nd photocatalyst particle layer 22a (fig. 2 (B)). The dispersion used was prepared by using a 2 nd photocatalyst having an average particle diameter larger than that of the 1 st photocatalyst particlesThe photocatalyst particles may be selected from the materials described for the dispersion of the 1 st photocatalyst and the adjustment conditions. The average particle diameter of the 2 nd photocatalyst particles is preferably 40 to 500nm. The coating method and the drying conditions may be arbitrarily selected from the above-mentioned coating method and drying conditions. Wherein, in the case where the 1 st photocatalyst particle layer is not completely dried to form the 2 nd photocatalyst particle layer, some mixing is sometimes caused in their interface, but for the interface S b Interface S t Less influence, at S b The 1 st photocatalyst particles are locally present in the vicinity, S t The 2 nd photocatalyst particles are locally present in the vicinity.
Further, the dispersion medium is dried and removed as necessary, whereby the photocatalyst composite material 10 according to the embodiment can be obtained (fig. 2 (C)).
By this method, the photocatalyst composite material based on the embodiment can be obtained. The dispersion liquid containing the 2 nd photocatalyst particles may be applied, a part or all of the dispersion medium may be dried and removed, and then photocatalyst particles having a large average particle diameter may be further laminated.
Generally, when a mixed dispersion of large particles and small particles is applied, the influence of gravity causes the small particles to be concentrated in the vicinity of the interface opposite to the substrate-side interface, that is, S, due to the influence of the liquid flow generated in the dispersion during drying t Nearby. Therefore, the structure is different from the photocatalyst particles according to the embodiment. Therefore, the photocatalyst particles according to the embodiment can be obtained by stacking small particles in the first place and large particles in the second place.
The base layer may be formed in advance before the 1 st photocatalyst is applied. The underlayer may be formed by dispersing an inorganic oxide or the like as a material of the underlayer in a dispersion medium, and then coating and drying the dispersed material in the same manner as described above.
The total weight of the 1 st photocatalyst particles deposited on the substrate is preferably smaller than the total weight of the 2 nd photocatalyst particles deposited on the substrate. Since the surface area of the particles is inversely proportional to the particle diameter, a sufficient catalytic activity can be obtained even when the deposition amount of the 1 st photocatalyst particles is small. On the other hand, if the deposition amount of the 1 st photocatalyst particles is too large, the photocatalyst layer tends to be easily peeled off, the space between the particles becomes small, and diffusion of the substance to be treated tends to be hindered.
The 1 st photocatalyst particle, the 2 nd photocatalyst particle, and the underlayer material to be used are preferably selected from materials having appropriate Zeta potentials. The stability of the photocatalyst layer can be improved by selecting the 1 st photocatalyst particle and the 2 nd photocatalyst particle as particles having different signs of Zeta potential and selecting the base layer material and the 1 st photocatalyst particle as materials having different signs of Zeta potential.
(embodiment 3)
Fig. 3 is a schematic diagram showing an example of the configuration of the photocatalyst device according to embodiment 3.
As shown in the figure, the photocatalyst device 30 according to the embodiment includes a photocatalyst composite material 31 according to embodiment 1, a light irradiation means 32 for generating photocatalytic activity to a base material, and a supply means 33 for supplying a substance to the photocatalyst composite material. The present invention may further include a chamber 34 in which these members are incorporated. The apparatus may further include an introduction portion 35a for introducing a substance to be treated or a discharge port 35b for discharging the treated substance.
Among these, the substance to be treated is a substance which is intended to be changed by a chemical reaction promoted by the photocatalytic action of the photocatalyst composite material. Specifically, the gas containing a toxic component, which is desired to remove a harmful component, the gas containing an odor, which is desired to be deodorized, the waste liquid containing a pollutant, and the like can be cited.
The light irradiation means may be an optical system means for inducing light to the photocatalyst composite material by external light or indoor light, a light source such as a lamp or LED, or the like. In the case of using external light or indoor light, the photocatalyst composite material may be provided or moved to a position where light is easily received. In the case of using a light source, an LED is preferable from the viewpoint of low power consumption and downsizing.
As the means for supplying a substance to the photocatalyst composite material, for example, a fan or a pump may be mentioned if the substance is a gas. In addition, when a gas or a liquid is introduced into the chamber in which the photocatalyst composite material is incorporated, the chamber, a nozzle for introducing the gas or the liquid into the chamber, and the like are also supply means. Further, the gas or liquid may be naturally diffused in the chamber, but convection generated by a heater or the like may be used. In this case, the heater is also a supply member. Further, in the case of utilizing natural diffusion, the photocatalyst composite material may be provided or moved to a position where the photocatalyst composite material is likely to come into contact with a substance.
In the case where the photocatalyst composite material is in a flat plate shape, a substance to be treated can be caused to flow along the surface thereof. In addition, in the case where the photocatalyst composite material is a porous body and the substance is a substance that can pass through the porous body, the contact area between the substance and the catalyst increases, and therefore, the treatment efficiency increases, which is preferable. In addition, even when a substance to be treated flows along the surface of the photocatalyst composite material, the contact area increases if the substance is porous. Therefore, the photocatalyst composite material is preferably a porous body, and more preferably a cloth-like shape.
In this embodiment, the photocatalyst layer may further include an adsorbing material for adsorbing a substance. When such an adsorbent is contained in the photocatalyst, the efficiency of the catalytic action can be improved by increasing the concentration of the substance in the vicinity of the catalyst. As such an adsorbent, there are activated carbon, alumina, zeolite, silica gel, and the like.
Examples
Example 1
The surface of a glass plate (10 cm. Times.10 cm) having a thickness of 1mm was rubbed with #40 sandpaper, then washed with isopropyl alcohol, and then washed with pure water. The arithmetic average roughness of the surface was 4 μm. On this, 1g of a fibrous alumina hydrate dispersion having an average diameter of 4nm and an average length of 1 μm was added dropwise in an amount of 0.5 mass%, and after spreading over the whole surface, the resultant was dried at room temperature for 1 hour to form a base layer.
Next, 1g of a 10% aqueous dispersion of tungsten oxide fine particles having an average particle diameter of 20nm was added dropwise thereto, and the resulting mixture was spread over the whole surface and dried at 60℃for 1 hour. Next, 4g of a 10% aqueous dispersion of tungsten oxide fine particles having an average particle diameter of 100nm was added dropwise, and the resulting mixture was spread over the whole surface and dried at 60℃for 1 hour to obtain a photocatalyst composite material.
(photocatalytic Activity test)
In the acetaldehyde decomposition test, the concentration after the lapse of the same time was 10ppm in the case of using a light-shielded sample, which was 0ppm after the irradiation of a fluorescent lamp of 6000lux for 15 minutes, with respect to the initial concentration of 10ppm.
In the antibacterial test of Escherichia coli, the initial bacterial concentration was 1X 10 5 Per ml, the number of bacteria after 2 hours of light irradiation by a fluorescent lamp was 0. When a light-shielded sample is used, the number of bacteria after the same time is 1×10 3 /ml。
The photocatalytic activity described above hardly changed even after 300 hours of light irradiation.
(peel resistance test)
The above photocatalyst was left in water at 30℃for 1 day. No peeling was seen and the photocatalytic activity was hardly changed.
Example 2
A PET film (10 cm. Times.10 cm) having a thickness of 150 μm was subjected to UV ozone treatment, 1g of a fibrous alumina hydrate dispersion having an average diameter of 4nm and an average length of 1 μm was added dropwise in an amount of 0.5 mass%, and the resultant was spread over the whole surface, and then dried at room temperature for 1 hour to form a base layer.
Next, 1g of a 10% aqueous dispersion of tungsten oxide fine particles having an average particle diameter of 20nm was added dropwise thereto, and the resulting mixture was spread over the whole surface and dried at 60℃for 1 hour. Next, 4g of a 10% aqueous dispersion of fine particles of anatase-type titanium oxide having an average particle diameter of 100nm was added dropwise thereto, and the resulting mixture was spread over the whole surface and dried at 60℃for 1 hour to form a photocatalyst composite material.
(photocatalytic Activity test)
In the acetaldehyde decomposition test, the initial concentration was set to 0ppm by irradiation with light of an LED having a center wavelength of 395nm for 13 minutes. In the case of using a light-shielded sample, the concentration after the same time was 10ppm.
In the antibacterial test of Escherichia coli, the initial bacterial concentration was 1X 10 5 Per ml, the number of bacteria after 2 hours of light irradiation with LED was 0. When a light-shielded sample is used, the number of bacteria after the same time is 1×10 3 /ml。
The photocatalytic activity described above hardly changed even after 300 hours of light irradiation.
(peel resistance test)
The above photocatalyst was left in water at 30℃for 1 day. No peeling was seen and the photocatalytic activity was hardly changed.
Example 3
A photocatalyst composite material was formed in the same manner as in example 2, except that a melamine resin film (10 cm×10 cm) formed on an aluminum plate was used in place of the PET film, without treatment, and without formation of a base layer, with a photocatalyst-containing liquid.
(photocatalytic Activity test)
In the acetaldehyde decomposition test, the initial concentration was set to 0ppm after 20 minutes of LED light irradiation. In the case of using a light-shielded sample, the concentration after the same time was 10ppm.
In the antibacterial test of Escherichia coli, the initial bacterial concentration was 1X 10 5 Per ml, the number of bacteria after 2 hours of light irradiation with LED was 0. When a light-shielded sample is used, the number of bacteria after the same time is 2×10 3 /ml。
The photocatalytic activity described above hardly changed even after 300 hours of light irradiation.
(peel resistance test)
The above photocatalyst was left in water at 30℃for 1 day. No peeling was seen and the photocatalytic activity was hardly changed.
Example 4
A photocatalyst composite material was obtained in the same manner as in example 1, except that copper oxide nanoparticles having an average particle diameter of 20nm were added to the coating liquid as a cocatalyst at 0.05 mass%.
(photocatalytic Activity test)
In the acetaldehyde decomposition test, the initial concentration was set to 0ppm after 12 minutes of irradiation with fluorescent light. In the case of using a light-shielded sample, the concentration after the same time was 10ppm.
In the antibacterial test of Escherichia coli, the initial bacterial concentration was 1X 10 5 Per ml, the number of bacteria after 1.5 hours of light irradiation by a fluorescent lamp was 0. When a light-shielded sample is used, the number of bacteria after the same time is 1×10 3 /ml。
The photocatalytic activity described above hardly changed even after 300 hours of light irradiation.
(peel resistance test)
The above photocatalyst was left in water at 30℃for 1 day. No peeling was seen and the photocatalytic activity was hardly changed.
Example 5
The surface of an aluminum plate (10 cm. Times.10 cm) having a thickness of 1mm was rubbed with #100 sandpaper, then washed with isopropyl alcohol, and then washed with pure water. The arithmetic average roughness of the surface was 1 μm.
Next, 1g of a 10% aqueous dispersion of tungsten oxide fine particles having an average particle diameter of 20nm was added dropwise thereto, and the resulting mixture was spread over the whole surface and dried at 60℃for 1 hour. Next, 4g of a 10% aqueous dispersion of tungsten oxide fine particles having an average particle diameter of 100nm was added dropwise thereto, and the resulting mixture was spread over the whole surface and dried at 60℃for 1 hour. The photocatalyst composite was then obtained by heating at 600℃for 3 hours in the atmosphere.
(photocatalytic Activity test)
In the acetaldehyde decomposition test, the concentration was 0ppm after 12 minutes of irradiation with a 6000lux fluorescent lamp, and the concentration after the same time was 10ppm when a light-shielded sample was used.
In the antibacterial test of Escherichia coli, the initial bacterial concentration was 1X 10 5 Per ml, the number of bacteria after 1.5 hours of light irradiation by a fluorescent lamp was 0. When a light-shielded sample is used, the number of bacteria after the same time is 1×10 3 /ml。
The photocatalytic activity described above hardly changed even after 300 hours of light irradiation.
(peel resistance test)
The above photocatalyst was left in water at 30℃for 1 day. No peeling was seen and the photocatalytic activity was hardly changed.
Example 6
The photocatalyst apparatus having the photocatalyst composite material obtained in example 2, 395nm LED and a small fan was set in a refrigerator. The power supply and the control device are arranged outside the refrigerator.
(Activity test of photocatalyst apparatus)
The photocatalyst apparatus was driven while light was being irradiated with the LED, and the initial concentration of methyl mercaptan of 10ppm became 0 after 30 minutes.
The photocatalytic activity described above hardly changed even after 300 hours of light irradiation.
Comparative example 1
The surface of a glass plate (10 cm. Times.10 cm) having a thickness of 1mm was rubbed with #40 sandpaper, then washed with isopropyl alcohol, and then washed with pure water. The arithmetic average roughness of the surface was 4 μm. On this, 1g of a fibrous alumina hydrate dispersion having an average diameter of 4nm and an average length of 1 μm was added dropwise in an amount of 0.5 mass%, and after spreading over the whole surface, the resultant was dried at room temperature for 1 hour to form a base layer.
Then, 5g of a 10% aqueous dispersion of tungsten oxide fine particles having an average particle diameter of 20nm was added dropwise thereto, and the resulting mixture was spread over the whole surface and dried at 60℃for 1 hour to form a photocatalyst composite material.
(photocatalytic Activity test)
In the acetaldehyde decomposition test, the initial concentration was set to 0ppm after 20 minutes of irradiation with a fluorescent lamp of 6000 lux. In the case of using a light-shielded sample, the concentration after the same time was 10ppm.
(peel resistance test)
The above photocatalyst was left in water at 30℃for 1 day. The photocatalytic activity was also reduced due to the peeling of the photocatalyst particles.
As is apparent from the results of the examples, according to the embodiments, a photocatalyst composite material having excellent catalytic activity, a method for producing the same, and a photocatalyst device including the photocatalyst composite material can be provided.
[ solution 1]
A photocatalyst composite material comprising a base material and a photocatalyst layer containing photocatalyst particles, wherein S is defined as the substrate-side interface of the photocatalyst layer b Let the opposite side interface be S t At the time, S is as described above b Average particle diameter r of the photocatalyst particles in the vicinity b Less than the S t Average particle diameter r of the photocatalyst particles in the vicinity t 。
[ solution 2]
The photocatalyst composite material according to claim 1, wherein the particle size distribution curve of all the photocatalyst particles contained in the photocatalyst layer has two or more peaks.
[ solution 3]
The photocatalyst composite according to claim 1 or 2, wherein r is as defined above b 2-50 nm, r is as described above t 40-500 nm.
[ solution 4]
The photocatalyst composite material according to any one of claims 1 to 3, wherein the photocatalyst particles comprise a metal oxide selected from the group consisting of tungsten oxide, titanium oxide, zinc oxide, niobium oxide, and tin oxide.
[ solution 5]
The photocatalyst composite material according to any one of claims 1 to 4, wherein the photocatalyst layer contains 20 to 100% by mass of the photocatalyst particles based on the total mass of the photocatalyst layer.
[ solution 6]
The photocatalyst composite material according to any one of claims 1 to 5, wherein the photocatalyst layer further comprises a promoter containing a metal element compound, and the content of the metal element is 0.01 to 50% by mass relative to the total amount of the photocatalyst particles and the promoter particles.
[ solution 7]
The photocatalyst composite material according to any one of claims 1 to 6, wherein the photocatalyst layer further comprises 1/100000 to 1/10 times of silver nanowires based on the total mass of the photocatalyst particles.
[ solution 8]
The photocatalyst composite material according to any one of claims 1 to 7, further comprising a base layer between the base material and the photocatalyst layer.
[ solution 9]
The photocatalyst composite material according to any one of claims 1 to 8, wherein the base layer contains an inorganic oxide.
[ solution 10]
The photocatalyst composite material according to any one of claims 1 to 9, wherein the surface of the base material has an arithmetic average roughness of 0.2 to 20 μm.
[ solution 11]
The photocatalyst composite material according to any one of claims 1 to 10, wherein the photocatalyst layer contains photocatalyst particles having different chemical compositions.
[ solution 12]
A method for producing a photocatalyst composite material, comprising the steps of: a step of coating a dispersion liquid containing the 1 st photocatalyst particles on a substrate; and a step of coating a dispersion liquid containing 2 nd photocatalyst particles having a larger average particle diameter than the 1 st photocatalyst particles.
[ solution 13]
The method for producing a photocatalyst composite material according to claim 12, wherein the total weight of the 1 st photocatalyst particles deposited on the substrate is smaller than the total weight of the 2 nd photocatalyst particles deposited on the substrate.
[ solution 14]
The method for producing a photocatalyst composite material according to claim 12 or 13, wherein the Zeta potential of the 1 st photocatalyst particle measured in water having a pH of 6 and the Zeta potential of the 2 nd photocatalyst particle measured in the same manner have different signs.
[ solution 15]
The method for producing a photocatalyst composite material according to any one of claims 12 to 14, further comprising a step of forming a base layer on a substrate before applying the dispersion liquid containing the 1 st photocatalyst particles, wherein the Zeta potential of the material constituting the base layer measured in water having a pH of 6 has a sign different from the Zeta potential of the 1 st photocatalyst particles measured in the same manner.
[ solution 16]
A photocatalyst device is provided with:
the photocatalyst composite material according to any one of claims 1 to 11,
Light irradiation means for producing photocatalytic activity on the substrate, and
a supply member for supplying a substance to be treated to the above-mentioned photocatalyst composite material,
the photocatalyst composite material, which generates catalytic activity by the light, promotes chemical reactions for treating the above-mentioned substances.
[ solution 17]
The photocatalyst apparatus according to claim 16, wherein the light irradiation means is an LED.
[ solution 18]
The photocatalyst apparatus according to claim 16 or 17, wherein the supply member is a fan.
[ solution 19]
The photocatalyst device according to any one of claims 16 to 18, wherein the substance is supplied to the front surface of the photocatalyst composite material, and a product produced by the chemical reaction is discharged from the back surface of the photocatalyst composite material.
[ solution 20]
The photocatalyst device according to any one of claims 16 to 19, wherein the photocatalyst layer further comprises an adsorbent material that adsorbs the substance.
Although several embodiments of the present invention have been described, these embodiments are presented as examples and are not intended to limit the scope of the invention. These novel embodiments may be implemented in various other forms, and various omissions, substitutions, and changes may be made without departing from the spirit of the invention. These embodiments and modifications are included in the scope and gist of the invention, and are included in the invention described in the claims and their equivalents.
Claims (8)
1. A photocatalyst composite material comprising a base material and a photocatalyst layer comprising photocatalyst particles and silver nanowires,
the photocatalyst particles comprise tungsten oxide,
the substrate-side interface of the photocatalyst layer is S b Let the opposite side interface be S t When the S is b Average particle diameter r of the photocatalyst particles in the vicinity b Less than the S t Average particle diameter r of the photocatalyst particles in the vicinity t ，
The r is b 2-50 nm, r is as follows t Is within the range of 40 to 500nm,
the surface of the substrate has an arithmetic average roughness of 0.2-20 [ mu ] m.
2. The photocatalyst composite material according to claim 1, wherein a particle diameter distribution curve of all photocatalyst particles contained in the photocatalyst layer has two or more peaks.
3. The photocatalyst composite material according to claim 1 or 2, wherein the photocatalyst particles further comprise a metal oxide selected from the group consisting of titanium oxide, zinc oxide, niobium oxide, and tin oxide.
4. The photocatalyst composite material according to claim 1 or 2, wherein the photocatalyst layer contains 1/100000 to 1/10 times of silver nanowires based on the total mass of photocatalyst particles.
5. The photocatalyst composite material according to claim 1 or 2, wherein the photocatalyst layer contains photocatalyst particles having different chemical compositions.
6. A method for producing a photocatalyst composite material, comprising the following steps in this order: a step of coating a dispersion liquid containing the 1 st photocatalyst particles and silver nanowires on a substrate; a step of coating a dispersion liquid containing 2 nd photocatalyst particles having an average particle diameter larger than that of the 1 st photocatalyst particles,
the 1 st photocatalyst particles are tungsten oxide with an average particle diameter of 2-50 nm, the 2 nd photocatalyst particles have an average particle diameter of 40-500 nm,
the surface of the substrate has an arithmetic average roughness of 0.2-20 [ mu ] m.
7. A photocatalyst device is provided with:
the photocatalyst composite material according to any one of claims 1 to 5,
A light irradiation member for imparting photocatalytic activity to the substrate, and
a supply member that supplies a substance to be treated to the photocatalyst composite material,
the photocatalyst composite material, which generates catalytic activity by light, promotes chemical reactions for treating the substance.
8. The photocatalyst apparatus according to claim 7, wherein the photocatalyst layer further comprises an adsorbing material that adsorbs the substance.
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