CN114308050B - Base material with photocatalyst and photocatalytic device - Google Patents

Base material with photocatalyst and photocatalytic device Download PDF

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CN114308050B
CN114308050B CN202210049033.XA CN202210049033A CN114308050B CN 114308050 B CN114308050 B CN 114308050B CN 202210049033 A CN202210049033 A CN 202210049033A CN 114308050 B CN114308050 B CN 114308050B
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photocatalyst
substrate
photocatalytic
zeta potential
layer
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CN114308050A (en
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内藤胜之
信田直美
千草尚
大川猛
荻原孝德
横田昌广
太田英男
猪又宏贵
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Toshiba Corp
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    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L9/00—Disinfection, sterilisation or deodorisation of air
    • A61L9/01—Deodorant compositions
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
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    • A62D3/10—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by subjecting to electric or wave energy or particle or ionizing radiation
    • A62D3/17—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by subjecting to electric or wave energy or particle or ionizing radiation to electromagnetic radiation, e.g. emitted by a laser
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    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/24—Chromium, molybdenum or tungsten
    • B01J23/30—Tungsten
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/39—Photocatalytic properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
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Abstract

Embodiments of the present invention relate to a photocatalyst-bearing substrate, a method for producing the same, and a photocatalytic device. The invention provides a photocatalyst-carrying base material which can be easily produced and is difficult to peel. The photocatalyst-bearing substrate of an embodiment comprises: a substrate; a base layer disposed on the substrate, the base layer having a positive Zeta potential in water at pH 6; and a photocatalyst layer provided on the base layer, the photocatalyst layer containing a photocatalyst material having a negative Zeta potential.

Description

Base material with photocatalyst and photocatalytic device
The present application is a divisional application of an invention patent application having a filing date of 2018, 12, 14, 201811532251.9 and a name of "base material with photocatalyst, method for producing the same, and photocatalytic device".
The present application is based on Japanese patent application publication No. 2017-239740 (application date: 12/14/2017), from which priority benefits are enjoyed. This application is incorporated by reference into this application in its entirety.
Technical Field
Embodiments of the present invention relate to a photocatalyst-bearing substrate, a method for producing the same, and a photocatalytic device.
Background
The photocatalyst generates holes excited by light and has strong oxidizing ability. The oxidizing ability is used for decomposition and removal of harmful organic molecules, sterilization, maintenance of hydrophilicity of a substrate, and the like. As a substrate carrying such a photocatalyst, there is a method of forming a film containing titanium oxide by applying a liquid obtained by dispersing titanium oxide particles and a thermoplastic resin in an organic solvent to a substrate, and drying the applied liquid. In addition, there is a method for producing a photocatalyst-treated body in which a photocatalyst is fixed to a base material by a binder resin, which comprises: by coating the binder resin, the photocatalyst powder is dispersed during the period in which the coated resin has adhesiveness, thereby fixing the photocatalyst on the substrate.
However, in these base materials, the coating film containing titanium oxide is likely to contain the photocatalyst particles by the binder resin, and the photocatalyst particles cannot come into contact with the external environment, and thus the photocatalytic activity is likely to be inhibited. In addition, in the binder resin in which the photocatalyst powder is dispersed, the photocatalyst particles are easily detached.
Disclosure of Invention
The purpose of the present invention is to provide a photocatalyst-carrying substrate which has sufficient photocatalytic activity and is difficult to peel.
The photocatalyst-bearing substrate of an embodiment comprises: a substrate; a base layer disposed on the substrate, the base layer having a positive Zeta potential in water at pH 6; and a photocatalyst layer provided on the base layer, the photocatalyst layer containing a photocatalyst material having a negative Zeta potential.
According to the above constitution, a photocatalyst-carrying base material which can be easily produced and hardly peeled can be obtained.
Drawings
Fig. 1 is a cross-sectional view showing the structure of the photocatalyst-containing substrate according to embodiment 1.
Fig. 2 is a flowchart showing a method for producing a photocatalyst-bearing substrate according to embodiment 2.
Fig. 3 is a schematic diagram showing an example of the structure of the photocatalytic device according to embodiment 3.
Fig. 4 is a schematic diagram showing another example of the structure of the photocatalytic device according to embodiment 3.
Fig. 5 is a schematic diagram showing another example of the structure of the photocatalytic device according to embodiment 3.
Symbol description
10. 20 … photocatalyst-bearing substrate, 11, 21, 31, 41, 51 … substrate, 12, 23, 32, 42, 52 … base layer, 13, 25, 33, 43, 53 … photocatalyst layer, 20 … photocatalyst-bearing substrate, 21 … substrate, 22 … base layer coating liquid, 24 … photocatalyst layer coating liquid, 30, 40, 50 … photocatalyst device, 38, 48, 58 … photocatalyst-bearing substrate, 34, 44, 54 … light irradiation mechanism, 35, 45, 55 … supply part, 57 … activated carbon
Detailed description of the preferred embodiments
Hereinafter, embodiments will be described with reference to the drawings.
In the embodiment, common structures are denoted by the same reference numerals, and repetitive description thereof will be omitted. The drawings are schematic views for explaining the embodiments and promoting understanding thereof, and the shapes, dimensions, ratios, and the like thereof are different from those of actual devices, but these may be appropriately changed in design by referring to the following description and known techniques.
The embodiments are divided into the following 3.
(first embodiment)
Fig. 1 is a cross-sectional view showing the structure of the photocatalyst-containing substrate according to embodiment 1.
As shown in the figure, the photocatalyst-coated substrate 10 of embodiment 1 has a substrate 11, a base layer 12 provided on the substrate 11, and a photocatalyst layer 13 provided on the base layer 12.
The substrate layer 12 has a positive Zeta potential in water at pH 6.
The photocatalyst layer 13 contains a photocatalyst material having a negative Zeta potential.
The Zeta potential of the substrate or underlayer can be measured by electrophoresis light scattering using Zetasizer Nano ZS manufactured by Malvern corporation, using a sample cell (cell) for measuring flat Zeta potential, and using polystyrene latex as a tracer particle.
The pH at the time of measuring the Zeta potential of the substrate or underlayer can be adjusted by adding a dilute hydrochloric acid and a dilute potassium hydroxide aqueous solution to pure water.
The photocatalyst layer may also contain a promoter material.
The promoter material may have a positive Zeta potential.
The Zeta potential of the photocatalytic material and the co-catalyst material can be measured by a capillary cell (capillary cell) by electrophoresis light scattering method using Zetasizer Nano ZS manufactured by Malvern corporation.
The pH at the time of measuring the Zeta potential of the photocatalytic material and the co-catalyst material can be adjusted by adding a dilute hydrochloric acid and a dilute potassium hydroxide aqueous solution to pure water for dispersing the photocatalytic material and the co-catalyst material.
The "photocatalytic effect" in the embodiment means decomposition of harmful substances such as ammonia and aldehydes, decomposition and deodorization of unpleasant odors such as cigarette and pet odors, antibacterial effect and antiviral effect on staphylococcus aureus, escherichia coli and the like, and antifouling effect that dirt is hard to adhere to.
As the photocatalyst material, photocatalyst particles having a volume average particle diameter of 2nm to 10 μm can be used. When the volume average particle diameter is within this range, the stability of the dispersion, the processability when applied to a substrate, and the photocatalytic function tend to be good. The volume average particle diameter is more preferably 10nm to 1. Mu.m, still more preferably 20nm to 200nm.
According to the embodiment, the Zeta potential of the base layer is positively charged, and the Zeta potential of the photocatalyst layer is negatively charged, so that the photocatalyst material is firmly fixed to the base layer, and peeling or the like is hardly generated. Here, the pH6 of water is assumed to be slightly acidic in the presence of carbon dioxide in a normal atmosphere, and condensation and rain water are assumed to be wetted. Preferably, even if the pH is changed, the Zeta potential is not liable to change sharply, and the base layer is positive and the photocatalyst material is negative in the pH range of 4 to 7.
The substrate may have a negative Zeta potential. This enhances the bonding between the base material and the base layer. If there is no underlayer, the photocatalyst layer having a negative Zeta potential repels the substrate having a negative Zeta potential, and thus the photocatalyst material is easily peeled off. In addition, if the base layer is present between the photocatalyst material and the base material, the distance between the photocatalyst material and the base material can be maintained, and thus deterioration of the base material due to photocatalytic action can be prevented.
As the base material, an organic material can be used. The organic material is light and flexible. Glass, ceramics, metals, etc. may be used, but an organic material easily chargeable to a negative potential is preferably used. Further, as the substrate, a porous substrate can be used. When a porous base material is used, the surface area of the photocatalyst layer formed via the underlayer increases, and thus the catalytic activity tends to increase. As the organic material, polyethylene terephthalate, polyethylene naphthalate, polyethylene, polypropylene, nylon (registered trademark), polycarbonate, polyimide, acrylic resin, melamine resin, phenol resin, paper, and the like can be used.
In the case of use at high heat conduction or high temperature, a metal or semiconductor material is preferable. Particularly, a material which can easily form an oxide film and can easily form hydrogen bonds with a base layer or can easily form chemical bonds by heat treatment is preferable. As the metal or semiconductor material, aluminum, stainless steel, silicon, carbon, or the like can be used. A material obtained by coating an organic material on a metal or semiconductor substrate can be used.
When the photocatalyst layer contains a photocatalyst material and a promoter material, the photocatalytic activity of the photocatalyst layer tends to be increased. At this time, if the Zeta potential of the cocatalyst material is positively charged, the bonding with the photocatalyst layer having a negative Zeta potential becomes strong. Further, since the Zeta potential of the underlayer is positively charged, the promoter material having the Zeta potential positively charged tends to repel the underlayer and bond with the photocatalyst material easily.
The photocatalyst material may contain tungsten oxide.
Tungsten oxide absorbs visible light, and the Zeta potential is negative over a wide pH range. The tungsten oxide is not limited to individual particles, and particles of various composite materials may be used. The composite material contains a transition metal element and other metal elements in addition to tungsten oxide as a main component. They are also cocatalyst materials. The transition metal element means an element having atomic numbers 21 to 29, 39 to 47, 57 to 79, and 89 to 109. For example, a tungsten oxide composite contains at least one metal element of Ti, sn, zr, mn, fe, pd, pt, cu, ag, zn, al, ru or Ce.
The content of the metal element such as the transition metal element in the composite material may be in the range of 0.01 to 50 mass%. If the content of the metal element exceeds 50 mass%, the photocatalytic property tends to be lowered. The content of the metal element is preferably 10 mass% or less, and more preferably 5 mass% or less. The lower limit of the content of the metal element is not particularly limited, and the content thereof may be 0.01 mass% or more in terms of more effective addition effect of the metal element. The oxides of the above metals are easily positively charged. Noble metal promoter materials such as Pt and Pd may also be used, and if protected by an organic polymer, the Zeta potential is easily positively charged.
As the underlayer, a metal oxide such as aluminum oxide, zirconium oxide, or titanium oxide can be used. Among them, aluminum oxide has a positive Zeta potential in a wide pH range. As the aluminum oxide, hydrated aluminum oxide can be used.The hydrated alumina is made of Al 2 O 3 ·(H 2 The hydrate represented by O) x (0 < x.ltoreq.3) has various forms, and is preferably boehmite (x=1) or pseudoboehmite (1 < x < 2). Boehmite or pseudoboehmite can be easily formed into a strong coating film by coating and drying, and is easily positively charged in water at pH 6. Here, the metal oxide used for the underlayer is referred to as the 1 st metal oxide, and for example, alumina hydrate is referred to as the 1 st alumina hydrate. As the 1 st hydrated alumina, fibrous hydrated alumina can be used. Fibrous alumina is easy to form into a film.
In addition, a 2 nd metal oxide such as a 2 nd hydrated alumina may be further added to the photocatalyst layer. As the 2 nd hydrated alumina, fibrous hydrated alumina can be used. Fibrous hydrated alumina mixed with the photocatalyst material can prevent the photocatalyst particles from agglomerating with each other, forming a uniform and strong film. Further, in the case of hydrated alumina having a positive Zeta potential, the promoter material having a positive Zeta potential tends to repel the hydrated alumina similarly to the underlayer, and to bond with the photocatalyst material more easily. Here, the alumina hydrate used in the photocatalyst layer was referred to as the 2 nd alumina hydrate. The 1 st hydrated alumina and the 2 nd hydrated alumina may be the same or different. The weight ratio of the 2 nd hydrated alumina to the photocatalyst is preferably 1% to 50%. When the amount is less than 1%, the above-mentioned effect is not exhibited in many cases, and when the amount exceeds 50%, the catalytic activity may be lowered. More preferably from 2% to 20%, still more preferably from 5% to 10%.
As the titanium oxide of the base layer, rutile type having a small catalytic activity can be used.
The photocatalyst layer may be partially covered with a curable resin. By partially covering the curable resin, the photocatalyst material surface can be exposed to perform the catalyst function, and the photocatalyst layer is less likely to be peeled off.
(embodiment 2)
Embodiment 2 is an example of a method for producing the photocatalyst-containing substrate of embodiment 1.
Fig. 2 is a flowchart showing a method for producing a photocatalyst-bearing substrate according to embodiment 2.
As shown in fig. 2 (a), a base layer coating liquid 22 containing a 1 st metal oxide having a positive Zeta potential is applied to a substrate 21 having a negative Zeta potential in water having a pH of 6 to form a coating layer. Then, as shown in fig. 2 (b), the coating layer is dried to produce a base layer 23 containing the 1 st metal oxide. Next, as shown in fig. 2 (c), a photocatalyst layer coating liquid 24 containing a photocatalyst material having a negative potential is applied to the base layer 23 to form a coating layer. Further, as shown in fig. 2 (d), the coated layer was dried to prepare a photocatalyst layer 25 containing a photocatalyst material, and a base material 20 with a photocatalyst was obtained.
According to an embodiment, a base layer is formed by applying a base layer coating liquid having a positive Zeta potential to a base material having a negative Zeta potential, and a photocatalyst layer is formed by applying a photocatalyst layer coating liquid having a negative Zeta potential to a base layer having a positive Zeta potential, whereby a base layer is firmly fixed to the base material, a photocatalyst material is firmly fixed to the base layer, and a photocatalyst-carrying base material in which peeling or the like is hardly generated is obtained.
The materials used in the base layer coating liquid and the photocatalyst layer coating liquid are the same as those in embodiment 1.
For example, as the 1 st metal oxide used for the base layer coating liquid, the 1 st hydrated alumina may be used, and the 1 st hydrated alumina may be a fibrous substance.
In addition, a promoter material having a positive Zeta potential may be further added to the photocatalyst layer coating liquid.
If the Zeta potential of the promoter material is positively charged, the binding to the photocatalyst layer, which has a negative Zeta potential, becomes strong. Further, since the Zeta potential of the underlayer is positively charged, the promoter material having the Zeta potential positively charged tends to repel the underlayer and bond with the photocatalyst material easily.
A 2 nd metal oxide, for example, a 2 nd hydrated alumina may be further added to the photocatalyst layer coating liquid.
When the photocatalyst layer is formed by applying a photocatalyst layer coating liquid containing a photocatalyst material and alumina 2, a stable photocatalyst layer can be formed by the binding property of alumina 2. In particular, by using fibrous hydrated alumina, the photocatalytic materials can be prevented from agglomerating with each other, and a uniform and strong photocatalytic layer can be formed. In the case of further containing a promoter material having a positive Zeta potential, the promoter material having a positive Zeta potential tends to repel hydrated alumina having a positive Zeta potential and to bond with a photocatalyst material easily.
In the preparation of the photocatalyst layer coating liquid, tungsten oxide particles having a negative Zeta potential as a photocatalyst material and promoter particles having a positive Zeta potential used as the composite material may be mixed in advance to prepare a dispersion.
In the photocatalyst layer coating liquid, water or an aqueous alcohol solution can be used as a solvent.
Hypochlorous acid may be further added to the photocatalyst layer coating liquid. By containing hypochlorous acid, the dispersion state becomes stable. In addition, hypochlorous acid has the effect of cleaning the substrate.
The temperature at which the coating layer of the photocatalyst layer coating liquid is dried may be 5 ℃ or higher and 60 ℃ or lower. When the temperature is 60 ℃ or lower, particularly, damage to the organic-containing substrate is reduced, and it tends to be difficult to put a load on equipment or workability of the coating step itself. If the temperature exceeds 5 ℃, it takes time but natural drying tends to be possible. More preferably 15℃to 40℃and still more preferably 20℃to 30 ℃.
When a base material having heat resistance such as metal is used, chemical bonds can be formed between the base material and the base layer, between the base layer and the photocatalyst, or the photocatalyst particles themselves can be fused to become stronger at a high temperature of 300 ℃.
As a solvent of the photocatalyst layer coating liquid, water or an aqueous alcohol solution can be used. The aqueous alcohol solution can stably disperse the photocatalytic material and the hydrated alumina. In addition, since the surface tension is small, it can be spread uniformly on the substrate. As the alcohol, ethanol, methanol, and isopropanol can be used. The dispersion may contain a compound having a si—o bond. Among them, silica, siloxane, and the like can improve abrasion resistance and prevent deterioration of the base material due to the photocatalyst material.
The photocatalyst layer coating liquid may further contain graphene oxide or graphite oxide. This prevents the photocatalytic materials from agglomerating with each other, and maintains stability and photocatalytic activity for a long period of time.
After the photocatalyst layer is formed on the base layer, a step of partially covering the photocatalyst layer with a curable resin may be further included. By partially covering the curable resin, the photocatalyst material can be exposed to exhibit a catalyst function while ensuring that the photocatalyst layer is less likely to be peeled off.
Examples of the curable resin used in the embodiment include materials having resistance to oxidation, such as silicone resins and fluorine resins. As part of the coating method, for example, spray coating may be used.
The concentration of the 2 nd hydrated alumina in the photocatalytic layer coating solution may be 0.05 to 1 wt%.
When the amount is less than 0.05 wt%, the coating layer tends to be uneven, and when the amount exceeds 1 wt%, the dispersion state tends to be unstable.
The concentration of the 1 st hydrated alumina in the base layer coating liquid may be 0.1 to 1% by weight.
When the amount is less than 0.1% by weight, the coating layer tends to be uneven, and when the amount exceeds 1% by weight, the coating layer tends to be easily peeled off.
As the coating method used in embodiment 2, a method such as drop coating, spin coating, dip coating, spray coating, applicator coating, doctor blade coating, gravure printing, ink jet printing, or the like can be applied. Among them, spray coating is preferable from the viewpoint of suitability for dosing or roll-to-roll.
Examples of the substrate used in embodiment 2 include metals, ceramics, papers, and polymers. From the viewpoints of coloring and surface modification, it is preferable to contain an organic material.
The polymer can be made into a flexible transparent film, and the application range of the photocatalyst material can be expanded. As the organic material, polyethylene terephthalate, polyethylene naphthalate, polyethylene, polypropylene, nylon (registered trademark), polycarbonate, polyimide, acrylic resin, melamine resin, phenol resin, paper, and the like can be used.
In particular, polyethylene terephthalate is preferable because it has flexibility, transparency, and good adhesion to alumina hydrate. The curable resin is also preferably one which forms a firm surface.
In the case of use requiring high heat conduction or high temperature, a metal or semiconductor material is preferable. Particularly, a material which easily forms an oxide film, easily forms hydrogen bonds with a base layer, or easily forms chemical bonds by heat treatment is preferable. As the metal or semiconductor material, aluminum, stainless steel, silicon, carbon, or the like can be used. A material obtained by coating an organic material on a metal or semiconductor substrate can be used.
The 2 nd hydrated alumina is preferably boehmite or pseudoboehmite. They are also relatively stable with respect to acids or bases.
(embodiment 3)
Embodiment 3 is an example of a photocatalytic device to which the photocatalytic substrate according to embodiment 1 is applied.
Fig. 3 is a schematic diagram showing an example of the structure of the photocatalytic device according to embodiment 3.
As shown in the figure, the photocatalytic device 30 according to embodiment 3 includes a base material 38 having a photocatalyst, a light irradiation unit 34 for generating photocatalytic activity on the base material, and a supply unit 35 for supplying a substance that receives photocatalytic activity to the base material.
The photocatalyst-coated substrate 30 is similar to the photocatalyst-coated substrate of the first embodiment, and includes a substrate 31, a base layer 32 provided on the substrate 31, and a photocatalyst layer 33 provided on the base layer 32.
The photocatalyst-carrying substrate of embodiment 1 has high activity, and the substrate and the photocatalyst are strongly bonded, and the photocatalytic device and the photocatalyst are separated from the substrate, so that the life is long. According to embodiment 3, by using such a catalyst-carrying substrate, effective treatment can be performed with a long lifetime.
The light irradiation unit may be configured to use external light or indoor light, or may be configured to use a lamp, an LED, or the like. In the case of using external light or indoor light, a member for providing the photocatalytic device or a member for moving the photocatalytic device may be further provided at a position where the substrate easily receives light. In the case of using a lamp, an LED, or the like, the LED is preferably used from the viewpoints of low power consumption and miniaturization.
As a supply portion for supplying a substance that receives a photocatalytic action to a substrate, if the substance that receives a photocatalytic action is a gas, natural diffusion, convection by a fan, a pump, or a heater, or the like may be used. In the case of utilizing natural diffusion, a member for providing the photocatalytic device or a member for moving the photocatalytic device may be further provided at a position where the substrate easily receives a substance.
If the substance that receives the photocatalytic action is allowed to pass through the substrate, the amount of the substance that directly contacts the catalyst surface increases, and therefore the efficiency increases. As such a substrate, a porous body may be used, and for example, a cloth-like substrate may be used.
The photocatalytic device according to embodiment 3 may further include an adsorption member for adsorbing a substance that receives a photocatalytic action. By increasing the concentration of the substance in the vicinity of the catalyst, the efficiency of the photocatalyst can be improved. As the adsorption member, for example, activated carbon, alumina, zeolite, silica gel, and the like can be used. The adsorption member may be used in the form of, for example, a pellet, a film, a porous body, or the like, and may be provided under or around the photocatalyst layer of the photocatalytic device.
Examples
Hereinafter, examples are shown, and embodiments are described more specifically.
The various measurements were performed as follows.
(gas decomposition experiment)
In a state where a substrate sample with a photocatalyst was placed in a flow-through device suitable for evaluation of removal performance (decomposing ability) of nitrogen oxides in JIS-R-1701-1 (2004), the gas decomposing rate (%) was determined based on the following formula (1) when the gas concentration before light irradiation was A and the gas concentration after 15 minutes or more from light irradiation and stability was B, among the gas concentrations measured by flowing an acetaldehyde gas having an initial concentration of 10ppm at 140 mL/min.
(A-B)/A×100(1)
The light irradiation was performed using a white fluorescent lamp as a light source, an ultraviolet cut filter, and a visible light having a wavelength of 380nm or more and an illuminance of 6000lux was irradiated.
For comparison, the gas concentration was measured when the light was blocked for 15 minutes or longer.
(E.coli Activity test)
After the photocatalyst-carrying substrate sample was completely immersed in 40ml (1X 10) 5 In/ml), light irradiation was performed for 24 hours.
A white fluorescent lamp was used as a light source, an ultraviolet cut filter was used, and visible light having an illuminance of 6000lux was irradiated with light having a wavelength of only 380nm or more.
After completion, the bacterial cells were inoculated into a "NISSUI CF" (for measuring the number of E.coli) in a microbial test dish (Compact Dry), and the number of bacterial cells was measured after culturing at 37℃for 24 hours.
For comparison, a microbial test dish was prepared in the same state except that the light was blocked for 24 hours.
Example 1
(preparation of the 1 st hydrated alumina Dispersion)
As a dispersion of alumina hydrate 1, an aqueous dispersion F-1000 of fibrous pseudo-boehmite nanoparticles manufactured by Chuanminne Chemical was diluted with water to prepare a dispersion having a concentration of 0.5% by weight.
(preparation of tungsten oxide microparticles)
As a raw material powder, a tungsten trioxide powder having a volume average particle diameter of 0.5 μm was prepared, and argon and RF plasma as carrier gases were sprayed, and further, as a reactive gas, argon was flowed at a flow rate of 40L/min, and air was flowed at a flow rate of 40L/min, so that the pressure in the reaction vessel was 40kPa. The tungsten oxide fine particles are obtained through a sublimation step in which the raw material powder is sublimated and subjected to an oxidation reaction.
(preparation of photocatalyst dispersion liquid)
Tungsten oxide particles having negative Zeta potential in water having room temperature pH6 and 3 wt% of copper oxide particles having positive Zeta potential in water having room temperature pH6 and having a volume average particle diameter of 20 to 100nm were dispersed in water to obtain a 10 wt% aqueous dispersion of tungsten oxide particles and copper oxide particles. As a dispersion of the 2 nd hydrated alumina, a 5% by weight aqueous dispersion of fibrous pseudo-boehmite F-3000 having a longer fiber length manufactured by Chuanminne Chemical Co., ltd was prepared. A10 wt% aqueous dispersion of tungsten oxide and copper oxide fine particles and a 2 nd hydrated alumina dispersion were mixed to prepare a photocatalyst dispersion of 0.5 wt% tungsten oxide and 0.03 wt% pseudoboehmite.
(coating of photocatalyst Material onto PET film)
A PET film (10 cm. Times.10 cm) having a thickness of 150 μm was used as an untreated material, 1g of an aqueous dispersion of 1 st hydrated alumina was dropped onto the PET film, spread over the entire surface, and then dried at room temperature for 1 hour to form a base layer. The Zeta potential of the substrate layer in water at room temperature pH6 is positive.
Then, 2g of a photocatalyst dispersion liquid containing alumina hydrate 2 was dropped, and the photocatalyst coating layer was formed by spreading over the entire surface, and then dried at room temperature for 24 hours, thereby forming a photocatalyst layer, and a photocatalyst-bearing substrate was formed.
(photocatalytic Activity test)
The concentration of acetaldehyde was 0ppm after 30 minutes of light irradiation, relative to the initial concentration of 10ppm. The gas decomposition rate was 100%.
For comparison, an experiment was prepared for shading, and the measurement was performed in the same manner, and as a result, the concentration of acetaldehyde was 10ppm. The gas decomposition rate was 0%.
In the E.coli Activity test, the initial bacterial concentration was 1X 10 5 After 3 hours of irradiation with light from a fluorescent lamp, the bacterial concentration was 0. As a comparison, the concentration of bacteria after 3 hours of shading was measured, and as a result, the concentration of bacteria was measuredDegree of 2X 10 6 /ml。
The photocatalytic activity was hardly changed even after 300 hours of light irradiation.
(Water resistance test)
The substrate with the photocatalyst was immersed in water for 60 minutes, and no peeling was observed, and the photocatalytic activity was hardly changed.
Example 2
(preparation of photocatalyst dispersion liquid)
Tungsten oxide fine particles having a volume average particle diameter of 20nm to 100nm and Pd fine particles (polyvinylpyrrolidone protective colloid) in an amount of 0.01 wt% based on the tungsten oxide fine particles were dispersed in water as a cocatalyst to obtain an aqueous dispersion of 10 wt%. A photocatalyst dispersion of 0.5% by weight of tungsten oxide, 0.02% by weight of pseudoboehmite, 0.1% by weight of a solid content of an emulsion containing silicone, and 60ppm of hypochlorous acid was prepared by mixing the same aqueous dispersion of alumina hydrate 2, the aqueous dispersion of tungsten oxide and Pd fine particles, a reactive silicone-containing emulsion, and hypochlorous acid water as in example 1.
The dispersion was kept in a dark place even when it was sealed in an aluminum can, and the dispersibility was not changed.
(coating of photocatalyst Material onto Melamine resin film)
A melamine resin film (size: 10cm×10 cm) formed on an aluminum plate was used untreated, and a hydrated alumina dispersion was sprayed on the melamine resin film in the same manner as in example 1. After drying at room temperature for 3 hours, the above-mentioned photocatalyst dispersion liquid was sprayed. The mixture was dried at room temperature for 3 hours to form a photocatalyst layer.
(photocatalytic Activity test)
The concentration of acetaldehyde was 0ppm after 30 minutes of light irradiation, relative to the initial concentration of 10ppm. The concentration of acetaldehyde in the light-shielding test was 10ppm.
In the E.coli Activity test, the initial bacterial concentration was 1X 10 5 Per ml, the concentration of the bacteria after 3 hours of light irradiation by a fluorescent lamp was 0. As a comparison, the concentration of the bacteria after 3 hours of shading was measured, and as a result, the concentration of the bacteria was 1X 10 6 /ml。
The photocatalytic activity was hardly changed even after 300 hours of light irradiation.
(peel resistance and Water resistance test)
Rubbing the above base material with photocatalyst with a cloth soaked with water and a dry cloth. No peeling was found and the photocatalytic activity was hardly changed.
Example 3
A base material with a photocatalyst was produced in the same manner as in example 2, except that a nonwoven fabric made of polyethylene was used instead of the melamine resin film.
(photocatalytic Activity test)
The concentration of acetaldehyde was 10ppm relative to the initial concentration, and after irradiation with light for 25 minutes, it became 0ppm. The concentration of the light-shielding test was 10ppm.
In the E.coli Activity test, the initial bacterial concentration was 1X 10 5 Per ml, the concentration of the bacteria after 3 hours of irradiation with light by a fluorescent lamp was 0. As a comparison, the concentration of the bacteria after 3 hours of shading was measured, and as a result, the concentration of the bacteria was 1X 10 6 /ml。
The photocatalytic activity was hardly changed even after 300 hours of light irradiation.
(peel resistance and Water resistance test)
Rubbing the above base material with photocatalyst with a cloth soaked with water and a dry cloth. No peeling was found and the photocatalytic activity was hardly changed.
Example 4
(coating of photocatalyst Material onto high efficiency Filter (HEPA Filter))
The same dispersion of alumina hydrate 1 as in example 1 was used, and it was sprayed on a high efficiency filter and dried with warm air at 60 ℃ for 20 minutes to form a base layer. Then, the photocatalyst dispersion liquid similar to that of example 1 was applied to the base layer by a sprayer, and dried for 20 minutes with warm air at 60 ℃.
(Activity test of photocatalytic device)
Fig. 4 is a schematic diagram showing the configuration of the photocatalytic device used in the example.
As shown in the figure, the photocatalytic device 40 includes a base 48 having a photocatalyst, a fan 45 for supplying a substance that receives a photocatalytic action to the base, and a light irradiation unit 44 including a fluorescent lamp provided opposite to the fan 45 via the base 48. The photocatalyst-containing substrate 48 has a structure in which the same base layer 42 as in example 1 and the same photocatalyst layer 43 as in example 1 are laminated on the substrate 41 composed of the high-efficiency filter.
In this photocatalytic device 40, a fan 45 is driven while the photocatalyst layer 43 of the photocatalyst-containing substrate 48 is irradiated with visible light by a fluorescent lamp 44, and air containing a cigarette smell is introduced into the photocatalytic device 40 from an inlet 46, passes through the photocatalyst-containing substrate 48, and is discharged from an outlet 47.
The smell of the discharged air was investigated by 3 persons. No odor was perceived by 3 persons.
The photocatalytic activity was hardly changed even after 300 hours of light irradiation.
(peel resistance and Water resistance test)
Rubbing the above base material with photocatalyst with a cloth soaked with water and a dry cloth. No peeling was found and the photocatalytic activity was hardly changed.
Example 5
(preparation of hydrated alumina Dispersion)
As a dispersion of alumina hydrate 1, an aqueous dispersion of granular pseudo-boehmite particles 10A produced by Chuanminne Chemical was diluted with water to prepare an aqueous dispersion having a concentration of 0.5% by weight.
(preparation of photocatalyst dispersion liquid)
Tungsten oxide fine particles having a negative Zeta potential in water having a room temperature pH of 20 to 100nm and iron-nickel composite oxide fine particles having a positive Zeta potential in water having a room temperature pH of 6 and having a Zeta potential of 10 wt% relative to tungsten oxide were dispersed in water to obtain a 10 wt% dispersion. A photocatalyst dispersion of 0.5% by weight of tungsten oxide and 0.01% by weight of pseudoboehmite was obtained from an aqueous dispersion of fibrous pseudoboehmite F-1000 and an aqueous dispersion of tungsten oxide, which were manufactured by Chuanyan Fine Chemical Co.
(coating of photocatalyst Material to hydrophobic Japanese paper)
10ml of the 1 st hydrated alumina dispersion was sprayed on a hydrophobic Japanese paper (10 cm. Times.10 cm), and dried at 60℃for 10 minutes to form a base layer. The Zeta potential in water at room temperature pH6 of the basal layer was positive.
Next, the above hydrophobic japanese paper was placed on a polytetrafluoroethylene film, 4g of the photocatalyst dispersion liquid was dropped on a base layer, and the photocatalyst coating layer was formed by spreading over the whole surface, and then dried at room temperature for 24 hours, thereby forming a photocatalyst layer.
(photocatalytic Activity test)
The concentration of acetaldehyde was 0ppm after 20 minutes of light irradiation, relative to the initial concentration of 10ppm. As a comparison, the concentration of acetaldehyde after 20 minutes of shading was measured, and as a result, the concentration of acetaldehyde was 10ppm.
In the E.coli Activity test, the initial bacterial concentration was 1X 10 5 Per ml, the concentration of the bacteria after 2.5 hours of light irradiation with a fluorescent lamp was 0. As a comparison, the concentration of the bacteria after 2.5 hours of shading was measured, and as a result, the concentration of the bacteria was 1X 10 6 /ml。
The photocatalytic activity was hardly changed even after 300 hours of light irradiation.
(Water resistance test)
Even when the above base material with photocatalyst was immersed in water, peeling was not observed, and the photocatalytic activity was hardly changed.
Example 6
(preparation of zirconia Dispersion)
A dispersion having a concentration of 0.5% by weight was prepared by diluting zirconia sol ZR-40BL manufactured by Nissan chemical industry with water.
(preparation of photocatalyst dispersion liquid)
Tungsten oxide fine particles having a volume average particle diameter of 20nm to 100nm and iron-nickel composite oxide fine particles having a Zeta potential of positive in water having a room temperature pH of 6, which is 10% by weight relative to tungsten oxide, were dispersed in water to obtain a 10% by weight aqueous dispersion of tungsten oxide fine particles and iron-nickel composite oxide fine particles. A photocatalyst dispersion of 0.5% by weight of tungsten oxide and 0.01% by weight of pseudoboehmite was obtained from an aqueous dispersion of fibrous pseudoboehmite F-1000 and an aqueous dispersion of tungsten oxide, which were manufactured by Chuanyan Fine Chemical Co.
(coating of photocatalyst Material to hydrophobic Japanese paper)
A dispersion of zirconia sol was sprayed on a hydrophobic Japanese paper (10 cm. Times.10 cm), and dried at 60℃for 10 minutes to form a base layer. The Zeta potential in water at room temperature pH6 of the basal layer was positive.
Next, the above hydrophobic japanese paper was placed on the polytetrafluoroethylene film, and 4g of the photocatalyst dispersion liquid was dropped on the obtained base layer, and the photocatalyst coating layer was formed by spreading over the whole surface, and then dried at room temperature for 24 hours, thereby forming a photocatalyst layer.
(photocatalytic Activity test)
The concentration of acetaldehyde was 0ppm after 20 minutes of light irradiation, relative to the initial concentration of 10ppm. As a comparison, the concentration of acetaldehyde after light shielding was measured, and as a result, the concentration of acetaldehyde was 10ppm.
In the E.coli Activity test, the initial bacterial concentration was 1X 10 5 Per ml, the concentration of the bacteria after 2.5 hours of light irradiation with a fluorescent lamp was 0. As a comparison, the concentration of the bacteria after 2.5 hours of shading was measured, and as a result, the concentration of the bacteria was 1X 10 6 /ml。
The photocatalytic activity was hardly changed even after 300 hours of light irradiation.
(Water resistance test)
Even when the above base material with photocatalyst was immersed in water, peeling was not observed, and the photocatalytic activity was hardly changed.
Example 7
(preparation of titanium dioxide Dispersion)
Granular rutile titanium oxide powder STR-100N produced by the environmental chemical industry was dispersed in water to prepare an aqueous dispersion having a concentration of 0.5% by weight.
(preparation of photocatalyst dispersion liquid)
Tungsten oxide fine particles having a negative Zeta potential in water having a room temperature pH of 20 to 100nm and iron-nickel composite oxide fine particles having a positive Zeta potential in water having a room temperature pH of 6, which are 10 wt% relative to tungsten oxide, are dispersed in water to obtain a 10 wt% dispersion of the tungsten oxide fine particles and the iron-nickel composite oxide fine particles. A photocatalyst dispersion of 0.5% by weight of tungsten oxide and 0.05% by weight of pseudoboehmite was obtained from an aqueous dispersion of fibrous pseudoboehmite F-1000, fine particles of tungsten oxide and an aqueous dispersion of Fine particles of an iron-nickel composite oxide, which were manufactured by Chuanmink Fine Chemical Co.
(coating of photocatalyst Material to PET film)
A titanium dioxide dispersion was sprayed on a PET film (10 cm. Times.10 cm), and the film was dried at 60℃for 10 minutes to form a base layer. The Zeta potential in water at room temperature pH6 of the basal layer was positive. 3g of the photocatalyst dispersion was dropped onto the PET film, and the photocatalyst coating layer was formed by spreading over the entire surface, and then dried at room temperature for 24 hours, thereby forming a photocatalyst layer.
(photocatalytic Activity test)
The concentration of acetaldehyde was 0ppm after 30 minutes of light irradiation, relative to the initial concentration of 10ppm. As a comparison, the concentration of acetaldehyde after light shielding was measured, and as a result, the concentration of acetaldehyde was 10ppm.
In the E.coli Activity test, the initial bacterial concentration was 1X 10 5 Per ml, the concentration of the bacteria after 3 hours of light irradiation with a fluorescent lamp was 0. As a comparison, the concentration of bacteria after light shielding was measured, and as a result, the concentration of bacteria was 1X 10 6 /ml。
The photocatalytic activity was hardly changed even after 300 hours of light irradiation.
(Water resistance test)
Even when the above base material with photocatalyst was immersed in water, peeling was not observed, and the photocatalytic activity was hardly changed.
Example 8
(Activity test of photocatalytic device)
Fig. 5 is a schematic view showing the structure of a photocatalytic device provided in a refrigerator.
As shown in the drawing, in the photocatalytic device 50, an LED that irradiates light of 390nm and an LED that irradiates light of 600nm are provided as the light irradiation section 54 on the top thereof. The photocatalyst-bearing substrate 58 is disposed opposite the LED 54. Around the photocatalyst-bearing base material 58, a teflon (registered trademark) porous film was disposed as an adsorption member, and the porous film was covered on the granular activated carbon aggregate 57. The photocatalyst-containing base material 58 has the same structure as the photocatalyst-containing base material obtained in example 3, and is composed of a base material 51 made of nonwoven fabric, a base layer 52 provided on the base material 51, and a photocatalyst layer 53 provided on the base layer 52, which are laminated in this order from the light irradiation unit 54 side. An air inlet 56 and a small fan 55 for introducing air into the refrigerator between the LED54 and the photocatalyst-containing substrate 58 are provided on the side surface of the photocatalyst device 50. The power supply and the control device are arranged outside the refrigerator.
In the photocatalytic device 50, air in the refrigerator is introduced into the inside of the photocatalytic device through the supply part 55. The light irradiation is performed from the opposite side of the photocatalyst layer 53. The air flow is discharged to the outside of the photocatalytic device 50 through the photocatalyst-carrying substrate made of nonwoven fabric.
The photocatalytic device was driven while light was irradiated with the LED, and as a result, the initial concentration of methyl mercaptan of 10ppm became 0 after 30 minutes.
The photocatalytic activity was hardly changed even after 300 hours of light irradiation.
Example 9
(preparation of base Material with photocatalyst)
The surface of an aluminum plate having a thickness of 1mm and a square of 5cm was treated with UV ozone to form an aluminum oxide film. 0.5g of the alumina dispersion of the 1 st stage of example 1 was added dropwise, spread over the entire surface, and dried at room temperature for 1 hour. Then, 2g of the photocatalyst dispersion liquid containing alumina hydrate 2 was added dropwise, spread over the entire surface, and dried at room temperature for 24 hours. Then, the mixture was heated in air at 500℃for 2 hours to form a photocatalyst-bearing substrate. The hydrated alumina is dehydrated to alumina by high temperature heating.
(photocatalytic Activity test)
The concentration of acetaldehyde was 0ppm after 30 minutes of light irradiation, relative to the initial concentration of 10ppm. The gas decomposition rate was 100%.
(peel resistance and Water resistance test)
Rubbing the above base material with photocatalyst with a cloth soaked with water and a dry cloth. No peeling was found and the photocatalytic activity was hardly changed.
(Heat resistance test)
The above base material with photocatalyst was kept at 200℃for 500 hours in the atmosphere. No peeling or cracking was observed, and the photocatalytic activity was hardly changed.
Comparative example 1
A base material with a photocatalyst was produced in the same manner as in example 1, except that the hydrated alumina base layer was not produced. When the above base material with the photocatalyst was immersed in water, peeling was observed for about 1 hour.
As is apparent from the results of the examples, according to the embodiments, a base material with a photocatalyst, a method for producing the same, and a photocatalytic device, which can stably exhibit stable photocatalytic performance for a long period of time, can be provided.
While several embodiments of the present invention have been described, these embodiments are presented by way of example and are not intended to limit the scope of the invention. These novel embodiments can be implemented in various other modes, and various omissions, substitutions, and changes can be made without departing from the spirit of the invention. These embodiments and modifications thereof are included in the scope and gist of the invention, and are included in the invention described in the claims and their equivalents.

Claims (14)

1. A photocatalyst-bearing substrate comprising: a substrate; a base layer disposed on the substrate, comprising a 1 st hydrated alumina, having a positive Zeta potential in water at pH 6; and a photocatalyst layer provided on the base layer, containing a photocatalyst material having a negative Zeta potential,
the photocatalyst layer further contains a 2 nd hydrated alumina, and the 2 nd hydrated alumina is fibrous.
2. The photocatalyst-bearing substrate of claim 1, wherein the substrate has a negative Zeta potential.
3. The photocatalyst substrate of claim 1, wherein the 1 st hydrated alumina is boehmite or pseudoboehmite.
4. The photocatalyst substrate according to claim 1, wherein the 1 st hydrated alumina is fibrous.
5. The photocatalyst substrate according to any one of claims 1 to 4, wherein the photocatalyst layer further contains a promoter material.
6. The photocatalyst substrate according to any one of claims 1 to 4, wherein the photocatalyst material contains tungsten oxide.
7. The photocatalyst-carrying substrate according to any one of claims 1 to 4, wherein the substrate is porous.
8. The photocatalyst-bearing substrate according to any one of claims 1 to 4, wherein the substrate is an organic material.
9. The photocatalyst substrate of claim 1, wherein the 2 nd hydrated alumina is boehmite or pseudoboehmite.
10. A photocatalytic device comprising the photocatalytic substrate according to any one of claims 1 to 9, a light irradiation unit for generating photocatalytic activity on the photocatalytic substrate, and a supply unit for supplying a substance that receives photocatalytic activity to the substrate.
11. The photocatalytic device according to claim 10, wherein the light irradiation portion is an LED.
12. The photocatalytic device according to claim 10 or 11, wherein the supply portion is a fan.
13. The photocatalytic device according to claim 10 or 11, wherein the substrate is a porous substrate through which the substance permeates.
14. The photocatalytic device according to claim 10 or 11, further comprising an adsorption portion for adsorbing the substance.
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