CN114308050A - Base material with photocatalyst and photocatalytic device - Google Patents
Base material with photocatalyst and photocatalytic device Download PDFInfo
- Publication number
- CN114308050A CN114308050A CN202210049033.XA CN202210049033A CN114308050A CN 114308050 A CN114308050 A CN 114308050A CN 202210049033 A CN202210049033 A CN 202210049033A CN 114308050 A CN114308050 A CN 114308050A
- Authority
- CN
- China
- Prior art keywords
- photocatalyst
- substrate
- layer
- zeta potential
- hydrated alumina
- Prior art date
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- Granted
Links
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 171
- 239000000463 material Substances 0.000 title claims abstract description 102
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 68
- 239000000758 substrate Substances 0.000 claims abstract description 102
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 47
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 55
- 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 32
- 229910001930 tungsten oxide Inorganic materials 0.000 claims description 32
- 239000000126 substance Substances 0.000 claims description 18
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 16
- 239000003426 co-catalyst Substances 0.000 claims description 13
- 239000011368 organic material Substances 0.000 claims description 10
- 229910001593 boehmite Inorganic materials 0.000 claims description 5
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 5
- 239000012466 permeate Substances 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 239000010410 layer Substances 0.000 description 101
- 239000006185 dispersion Substances 0.000 description 58
- 238000000576 coating method Methods 0.000 description 39
- 239000011248 coating agent Substances 0.000 description 37
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 32
- 238000012360 testing method Methods 0.000 description 29
- 239000007788 liquid Substances 0.000 description 26
- 239000002245 particle Substances 0.000 description 26
- 239000010419 fine particle Substances 0.000 description 22
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- 239000002184 metal Substances 0.000 description 16
- 230000000694 effects Effects 0.000 description 13
- -1 polyethylene terephthalate Polymers 0.000 description 13
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- 239000011247 coating layer Substances 0.000 description 12
- 238000002360 preparation method Methods 0.000 description 12
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- 241000894006 Bacteria Species 0.000 description 11
- 239000002131 composite material Substances 0.000 description 11
- 239000007789 gas Substances 0.000 description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 10
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- 238000000354 decomposition reaction Methods 0.000 description 9
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- 229910044991 metal oxide Inorganic materials 0.000 description 8
- 150000004706 metal oxides Chemical class 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 229920002799 BoPET Polymers 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 230000002209 hydrophobic effect Effects 0.000 description 6
- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical compound [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 239000004065 semiconductor Substances 0.000 description 6
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 6
- 239000004640 Melamine resin Substances 0.000 description 5
- 229920000877 Melamine resin Polymers 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 235000019645 odor Nutrition 0.000 description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 4
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 3
- 239000005751 Copper oxide Substances 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 229910000431 copper oxide Inorganic materials 0.000 description 3
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 2
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- 238000002338 electrophoretic light scattering Methods 0.000 description 2
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- 238000002474 experimental method Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 230000001678 irradiating effect Effects 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
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- 229920001778 nylon Polymers 0.000 description 2
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- 230000001590 oxidative effect Effects 0.000 description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 2
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- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229910018557 Si O Inorganic materials 0.000 description 1
- 241000191967 Staphylococcus aureus Species 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
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- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
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- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- 230000000840 anti-viral effect Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
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- 239000000084 colloidal system Substances 0.000 description 1
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- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
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- 229910052802 copper Inorganic materials 0.000 description 1
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- 238000005336 cracking Methods 0.000 description 1
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- 238000007865 diluting Methods 0.000 description 1
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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
- 238000003618 dip coating Methods 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
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- 230000031700 light absorption Effects 0.000 description 1
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- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
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- 239000000741 silica gel Substances 0.000 description 1
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- 239000000377 silicon dioxide Substances 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
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- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 238000000733 zeta-potential measurement Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Images
Classifications
-
- A—HUMAN NECESSITIES
- 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
- 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
- A61L9/16—Disinfection, sterilisation or deodorisation of air using physical phenomena
- A61L9/18—Radiation
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D3/00—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- 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
-
- B01J35/39—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0215—Coating
-
- A—HUMAN NECESSITIES
- 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
- A61L2202/00—Aspects relating to methods or apparatus for disinfecting or sterilising materials or objects
- A61L2202/10—Apparatus features
- A61L2202/13—Biocide decomposition means, e.g. catalysts, sorbents
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- 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
- A62D2101/20—Organic substances
- A62D2101/28—Organic substances containing oxygen, sulfur, selenium or tellurium, i.e. chalcogen
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- 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
- A62D2101/40—Inorganic substances
Abstract
Embodiments of the present invention relate to a photocatalyst-carrying substrate, a method for producing the same, and a photocatalytic device. The invention provides a photocatalyst-carrying substrate which can be easily produced and is difficult to peel. The photocatalyst-bearing substrate of the embodiment comprises: a substrate; a base layer disposed on a substrate, the base layer having a positive Zeta potential in water at a pH of 6; and a photocatalyst layer provided on the base layer, the photocatalyst layer containing a photocatalyst material having a negative Zeta potential.
Description
The present application is a divisional application of an invention patent application having an application date of 2018, 12 and 14, and an application number of 201811532251.9, entitled "photocatalyst-containing substrate, method for producing same, and photocatalytic device".
The present application is based on Japanese patent application laid-open No. 2017 and No. 239740 (application date: 12/14/2017), and enjoys a preferential interest from the application. This application is incorporated by reference into this application in its entirety.
Technical Field
Embodiments of the present invention relate to a photocatalyst-carrying substrate, a method for producing the same, and a photocatalytic device.
Background
The photocatalyst generates holes excited by light, and has a strong oxidizing ability. This oxidizing ability is used for decomposition and removal of harmful organic molecules, sterilization, maintenance of hydrophilicity of a base material, and the like. As a substrate on which such a photocatalyst is supported, for example, there is a method in which a liquid obtained by dispersing titanium oxide particles and a thermoplastic resin in an organic solvent is applied to a substrate and dried to form a coating film containing titanium oxide. Further, as for a photocatalyst-processed body obtained by fixing a photocatalyst to a base material with a binder resin, there is a method of: by applying the binder resin, the photocatalyst powder is dispersed while the applied resin has adhesiveness, thereby fixing the photocatalyst on the substrate.
However, in these substrates, the coating film containing titanium oxide is likely to contain photocatalyst particles in the binder resin, and the photocatalyst particles are not likely to come into contact with the external environment, and the photocatalytic activity is likely to be inhibited. In addition, the binder resin in which the photocatalyst powder is dispersed is likely to cause the photocatalyst particles to be detached.
Disclosure of Invention
An object of an embodiment of the present invention is to provide a photocatalyst-carrying substrate which has sufficient photocatalytic activity and is difficult to peel off.
The photocatalyst-bearing substrate of the embodiment comprises: a substrate; a base layer disposed on the substrate having a positive Zeta potential in water at a pH of 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 configuration, a photocatalyst-carrying substrate which can be easily produced and is difficult to peel off can be obtained.
Drawings
Fig. 1 is a sectional view showing the structure of a photocatalyst-equipped substrate according to embodiment 1.
Fig. 2 is a flowchart showing a method for producing a photocatalyst-equipped 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.
Description of the symbols
10. 20 … photocatalyst-carrying base material, 11, 21, 31, 41, 51 … base material, 12, 23, 32, 42, 52 … basal layer, 13, 25, 33, 43, 53 … photocatalyst layer, 20 … photocatalyst-carrying base material, 21 … base material, 22 … basal layer coating liquid, 24 … photocatalyst layer coating liquid, 30, 40, 50 … photocatalyst device, 38, 48, 58 … photocatalyst-carrying base material, 34, 44, 54 … light irradiation mechanism, 35, 45, 55 … supply section, 57 … activated carbon
Detailed description of the preferred embodiments
Hereinafter, embodiments will be described with reference to the drawings.
In the embodiments, the same reference numerals are used for the common components, and redundant description is omitted. The drawings are schematic views for explaining the embodiments and facilitating understanding thereof, and the shapes, dimensions, ratios, and the like of the drawings are different from those of actual apparatuses, but these may be appropriately designed and changed by referring to the following description and known techniques.
The number of embodiments is 3 as follows.
(first embodiment)
Fig. 1 is a sectional view showing the structure of a photocatalyst-equipped substrate according to embodiment 1.
As shown in the drawing, the photocatalyst-carrying substrate 10 of embodiment 1 includes a substrate 11, a foundation layer 12 provided on the substrate 11, and a photocatalyst layer 13 provided on the foundation layer 12.
The base 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 base material or the underlayer can be measured by electrophoretic light scattering using a Zetasizer Nano ZS manufactured by Malvern corporation, using a flat-plate sample cell (cell) for Zeta potential measurement, using polystyrene latex as tracer particles.
The pH at the time of measuring the Zeta potential of the substrate or the foundation layer can be adjusted by adding dilute hydrochloric acid and a dilute aqueous potassium hydroxide 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, co-catalyst material, can be measured by electrophoretic light scattering using a Zetasizer Nano ZS manufactured by Malvern corporation through a capillary sample cell (capillary cell).
The pH at which the Zeta potential of the photocatalyst material or the co-catalyst material is measured can be adjusted by adding dilute hydrochloric acid and a dilute aqueous solution of potassium hydroxide to pure water in which the photocatalyst material or the co-catalyst material is dispersed.
The "photocatalytic action" in the embodiment refers to decomposition of harmful substances such as ammonia and aldehydes, decomposition and deodorization of unpleasant odors of cigarette and pet odors, antibacterial action and antiviral action against staphylococcus aureus, escherichia coli, and the like, and antifouling action in which dirt is less likely to adhere.
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 μm, and still more preferably 20nm to 200 nm.
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 less likely to occur. Here, the reason why the pH of water is set to 6 is that the pH of water is slightly shifted to the acidic side in the presence of carbon dioxide in normal atmosphere, and condensation and rain water are assumed to be wet. Preferably, the Zeta potential is not liable to change rapidly even if the pH is changed, and the base layer is positive and the photocatalyst material is negative within the range of pH4 to 7.
The substrate may have a negative Zeta potential. This strengthens the bonding between the base material and the foundation layer. Without the base layer, the photocatalyst layer having a negative Zeta potential repels the base material having a negative Zeta potential, and therefore the photocatalyst material is easily peeled off. Further, if the undercoat 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 substrate, an organic material can be used. Organic materials are light and flexible. Glass, ceramic, metal, or the like may also be used, but an organic material that easily carries a negative potential is preferably used. Further, as the substrate, a porous substrate can be used. When a porous substrate is used, the surface area of the photocatalyst layer formed via the base layer increases, and thus the catalytic activity tends to be improved. As the organic material, polyethylene terephthalate, polyethylene naphthalate, polyethylene, polypropylene, nylon (registered trademark), polycarbonate, polyimide, acrylic resin, melamine resin, phenol resin, paper, or the like can be used.
In the case of use at high heat conduction or high temperature, a metal or semiconductor material is preferable. In particular, a material which easily forms an oxide film, easily forms a hydrogen bond with the underlying layer, or easily forms a chemical bond 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 a metal or semiconductor substrate with an organic material can be used.
When the photocatalyst layer contains the photocatalyst material and the co-catalyst material, the photocatalytic activity of the photocatalyst layer tends to increase. At this time, if the Zeta potential of the co-catalyst material is positively charged, the binding with the photocatalyst layer whose Zeta potential is negative becomes strong. Further, since the Zeta potential of the base layer is positively charged, the co-catalyst material having a positively charged Zeta potential tends to repel the base layer and to be easily bonded to the photocatalyst material.
The photocatalyst material may contain tungsten oxide.
Tungsten oxide has visible light absorption, and in addition, 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 can 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 promoter materials. The transition metal element has an atomic number of 21 to 29, 39 to 47, 57 to 79, 89 to 109. For example, the tungsten oxide composite material 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 a transition metal element in the composite material may be set to a range of 0.01 to 50 mass%. When the content of the metal element exceeds 50 mass%, photocatalytic properties tend to be lowered. The content of the metal element is preferably 10% by mass or less, and more preferably 5% by mass or less. The lower limit of the content of the metal element is not particularly limited, and the content may be 0.01 mass% or more in order to more effectively exhibit the effect of adding the metal element. Oxides of the above metals are easily positively charged. Noble metal promoter materials such as Pt and Pd can also be used, and when 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. Wherein the aluminum oxide has a positive Zeta potential over a wide pH range. As the aluminum oxide, hydrated alumina may be used. The hydrated alumina is made of Al2O3·(H2Hydrates represented by O) x (0 < x.ltoreq.3) have various forms, and boehmite (x ═ 1) or pseudoboehmite (1 < x < 2) is preferable. Boehmite or pseudoboehmite can easily form a strong coating film by coating and drying, and is easily positively charged in water having a pH of 6. Here, the metal oxide used in the underlayer is referred to as a 1 st metal oxide, and for example, hydrated alumina is referred to as a 1 st hydrated alumina. As the 1 st hydrated alumina, fibrous hydrated alumina can be used. Fibrous alumina is easily formed into a film.
In addition, a 2 nd metal oxide such as 2 nd hydrated alumina may be further added to the photocatalyst layer. As the 2 nd hydrated alumina, fibrous hydrated alumina can be used. The fibrous hydrated alumina mixed with the photocatalyst material can prevent the photocatalyst particles from agglomerating with each other, and form a uniform and strong film. Further, with respect to hydrated alumina having a positive Zeta potential, a co-catalyst material having a positive Zeta potential tends to repel hydrated alumina as in the base layer, and to be more easily bonded to a photocatalyst material. Here, the hydrated alumina used in the photocatalyst layer was defined as the 2 nd hydrated alumina. 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%. If the content is less than 1%, the above-mentioned effects are not exhibited in many cases, and if the content exceeds 50%, the catalytic activity may be lowered. More preferably 2% to 20%, and still more preferably 5% to 10%.
The titanium oxide used as the underlayer may be a rutile type having a small catalytic activity.
The photocatalyst layer may be partially covered with a curable resin. By partially covering the curable resin, the surface of the photocatalyst material is surely exposed to exhibit a 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-carrying substrate of embodiment 1.
Fig. 2 is a flowchart showing a method for producing a photocatalyst-equipped substrate according to embodiment 2.
As shown in fig. 2(a), an undercoat 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 at a pH of 6 to form a coating layer. Then, as shown in fig. 2(b), the coating layer is dried to produce an underlayer 23 containing the 1 st metal oxide. Next, as shown in fig. 2(c), a coating layer is formed by applying a photocatalyst layer coating liquid 24 containing a photocatalyst material having a negative potential on the undercoat layer 23. Further, as shown in fig. 2(d), the coating layer is dried to produce a photocatalyst layer 25 containing a photocatalyst material, and the photocatalyst-equipped substrate 20 is obtained.
According to the embodiment, the photocatalyst-carrying base material in which the undercoat layer is firmly fixed to the base material, the photocatalyst material is firmly fixed to the undercoat layer, and peeling or the like is less likely to occur is obtained by forming the undercoat layer by applying the undercoat layer coating liquid having a positive Zeta potential to the base material having a negative Zeta potential and forming the photocatalyst layer by applying the photocatalyst layer coating liquid having a negative Zeta potential to the undercoat layer having a positive Zeta potential.
The materials used in the undercoat 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 one.
In addition, a co-catalyst material having a positive Zeta potential may be further added to the photocatalyst layer coating liquid.
If the Zeta potential of the cocatalyst material is positively charged, the binding to the photocatalyst layer whose Zeta potential is negative becomes stronger. Further, since the Zeta potential of the base layer is positively charged, the co-catalyst material having a positively charged Zeta potential tends to be repelled from the base layer and to be easily bonded to the photocatalyst material.
A 2 nd metal oxide, for example, a 2 nd hydrated alumina, may be further added to the photocatalyst layer coating liquid.
When a photocatalyst layer coating solution containing a photocatalyst material and 2 nd hydrated alumina is applied to form a photocatalyst layer, a stable photocatalyst layer can be formed by the binding property of the 2 nd hydrated alumina. In particular, by using fibrous hydrated alumina, the aggregation of the photocatalyst materials can be prevented, and a uniform and strong photocatalyst layer can be formed. When a co-catalyst material having a positive Zeta potential is further contained, the co-catalyst material having a positive Zeta potential tends to be repelled from the hydrated alumina having a positive Zeta potential and to be easily bonded to the photocatalyst material.
In the preparation of the photocatalyst layer coating liquid, the tungsten oxide particles having a negative Zeta potential as the photocatalyst material and the promoter particles having a positive Zeta potential used as the composite material may be mixed in advance to prepare a dispersion liquid.
In the photocatalyst layer coating liquid, water or an alcohol aqueous solution may be used as a solvent.
Hypochlorous acid may be further added to the photocatalyst layer coating liquid. The dispersion state becomes stable by containing hypochlorous acid. In addition, hypochlorous acid has an 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, damage to the substrate containing an organic material in particular is reduced, and it tends to be difficult to increase the load on the equipment and workability of the coating step itself. When 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 undercoat layer, between the undercoat layer and the photocatalyst, or the photocatalyst particles can be fused to each other and made stronger at a high temperature of 300 ℃.
As the solvent of the photocatalyst layer coating liquid, water or an alcohol aqueous solution can be used. The aqueous alcohol solution can stably disperse the photocatalytic material and the hydrated alumina. Further, since the surface tension is small, the base material can be uniformly spread. As the alcohol, ethanol, methanol, and isopropanol can be used. The dispersion may contain a compound having an 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 aggregating with each other, and can maintain stability and photocatalytic activity for a long period of time.
The method may further include a step of partially covering the photocatalyst layer with a curable resin after forming the photocatalyst layer on the base layer. By partially covering the curable resin, the surface of the photocatalyst material is surely exposed to exhibit a catalyst function, and the photocatalyst layer is less likely to be peeled off.
Examples of the curable resin used in the embodiment include materials resistant to oxidation, such as silicone resins and fluorine-based resins. As a partial coating method, for example, spray coating may be used.
The concentration of the 2 nd hydrated alumina in the photocatalytic layer coating liquid may be 0.05 to 1% by weight.
When the content is less than 0.05% by weight, the coating layer tends to become uneven, and when the content exceeds 1% by weight, the dispersion state tends to become 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 content is less than 0.1% by weight, the coating layer tends to become uneven, and when the content is more than 1% by weight, the coating layer tends to be easily peeled off.
As the coating method used in embodiment 2, a method such as droplet coating, spin coating, dip coating, spray coating, applicator coating, blade coating, gravure printing, inkjet printing, or the like can be applied. Among them, spraying is preferable from the viewpoint of suitability for metering or roll-to-roll.
Examples of the substrate used in embodiment 2 include metals, ceramics, paper, and polymers. From the viewpoint of coloring and surface modification, the organic material is preferably contained.
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, or the like can be used.
In particular, polyethylene terephthalate is preferable because it has flexibility, transparency, and good adhesion to hydrated alumina. Also preferred is a curable resin which forms a strong surface.
In the case of use requiring high heat conduction or high temperature, a metal or semiconductor material is preferable. In particular, a material which easily forms an oxide film, easily forms a hydrogen bond with the base layer, or easily forms a chemical bond 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 photocatalyst-carrying substrate of 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 drawing, the photocatalyst apparatus 30 according to embodiment 3 includes a base material 38 having a photocatalyst, a light irradiation unit 34 for generating photocatalytic activity to the base material, and a supply unit 35 for supplying a substance that receives photocatalytic action to the base material.
The photocatalyst-containing substrate 30 includes a substrate 31, a foundation layer 32 provided on the substrate 31, and a photocatalyst layer 33 provided on the foundation layer 32, as in the photocatalyst-containing substrate of the first embodiment.
The photocatalyst-carrying substrate of embodiment 1 has high activity, strong binding between the substrate and the photocatalyst, and long life because the photocatalyst device and the photocatalyst are separated from the substrate. According to embodiment 3, by using such a substrate with a catalyst, efficient treatment can be performed over a long life.
The light irradiation unit may be an external light or an indoor light, or a lamp or an LED. When external light or indoor light is used, a member for installing the photocatalyst device or a member for moving the photocatalyst device may be further provided at a position where the substrate easily receives light. When a lamp, an LED, or the like is used, the LED is preferably used from the viewpoint of low power consumption and downsizing.
As the supply portion for supplying the substance which receives the photocatalytic action to the base material, if the substance which receives the photocatalytic action is a gas, natural diffusion, convection by a fan, a pump, or a heater, or the like can be used. In the case of using natural diffusion, a member for installing the photocatalytic device or a member for moving the photocatalytic device may be further provided at a position where the substrate easily receives the substance.
If a substance that receives a photocatalytic effect is able to pass through the substrate, the amount of the substance that is in direct contact with the catalyst surface increases, and therefore the efficiency increases. As such a substrate, a porous body can be used, and for example, a cloth-like substrate can be used.
The photocatalytic device of embodiment 3 may further include an adsorbing 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 adsorbing member, for example, activated carbon, alumina, zeolite, silica gel, or the like can be used. The adsorbing member may be used in the form of, for example, a granular form, a film form, a porous body, or the like, and may be provided below or around the photocatalyst layer of the photocatalyst device.
Examples
Hereinafter, embodiments will be described more specifically by way of examples.
Various measurements were performed as follows.
(gas decomposition experiment)
In a state where a substrate sample with a photocatalyst is placed in a flow-through apparatus suitable for evaluation of nitrogen oxide removal performance (decomposition ability) according to JIS-R-1701-1(2004), a gas decomposition rate (%) is determined based on the following formula (1) when the gas concentration before light irradiation is A and the gas concentration after 15 minutes or more from light irradiation and at a steady state is B, of the gas concentrations measured by flowing acetaldehyde gas having an initial concentration of 10ppm at 140 mL/minute.
(A-B)/A×100(1)
The light irradiation was performed by irradiating visible light having an illuminance of 6000lux with light having a wavelength of 380nm or more using a white fluorescent lamp as a light source and an ultraviolet cut filter.
For comparison, the gas concentration when 15 minutes or more has elapsed after light shielding is measured.
(E.coli Activity test)
The photocatalyst-carrying substrate sample was completely immersed in 40ml (1X 10) of the bacterial suspension5/ml), light irradiation was performed for 24 hours.
A white fluorescent lamp was used as a light source, and a visible light having an illuminance of 6000lux was irradiated with light having a wavelength of 380nm or more using an ultraviolet cut filter.
After completion of the dilution, the bacterial suspension was inoculated into a microorganism test dish (Compact Dry) "NISSUI CF" (for measuring the number of Escherichia coli), and the bacterial count was measured after 24 hours of culture at 37 ℃.
For comparison, a microbial test dish in the same state was prepared except that the light was shielded for 24 hours.
(example 1)
(preparation of No. 1 hydrated alumina Dispersion)
As the 1 st dispersion of hydrated alumina, an aqueous dispersion F-1000 of fibrous pseudo-boehmite nanoparticles manufactured by Kagawa Fine Chemical company was diluted with water to prepare a dispersion having a concentration of 0.5% by weight.
(preparation of Fine tungsten oxide particles)
Tungsten trioxide powder having a volume average particle diameter of 0.5 μm was prepared as a raw material powder, and argon and RF plasma were sprayed as a carrier gas, and further, argon was flowed at a flow rate of 40L/min and air was flowed at a flow rate of 40L/min as a reactive gas, and the pressure in the reaction vessel was set to 40 kPa. The tungsten oxide fine particles are obtained through a sublimation step of carrying out an oxidation reaction while sublimating the raw material powder.
(preparation of photocatalyst Dispersion liquid)
Tungsten oxide fine particles having a negative Zeta potential in water at room temperature pH6 and a volume average particle diameter of 20 to 100nm and copper oxide fine particles having a positive Zeta potential in water at room temperature pH6 in an amount of 3 wt% relative to the tungsten oxide fine particles are dispersed in water to obtain a 10 wt% aqueous dispersion of the tungsten oxide fine particles and the copper oxide fine particles. As a dispersion of the 2 nd hydrated alumina, a 5 wt% aqueous dispersion of fibrous pseudoboehmite F-3000 having a longer fiber length manufactured by Kagawa Fine Chemical was prepared. A photocatalyst dispersion containing 0.5% by weight of tungsten oxide and 0.03% by weight of pseudoboehmite was prepared by mixing a 10% by weight aqueous dispersion of tungsten oxide and copper oxide particles with a 2 nd hydrated alumina dispersion.
(coating of photocatalyst Material onto PET film)
A150 μm thick PET film (10 cm. times.10 cm) was used without treatment, and 1g of the 1 st aqueous dispersion of hydrated alumina was dropped onto the PET film, developed on the entire surface, and then dried at room temperature for 1 hour to form an underlayer. The Zeta potential of the substrate layer in water at room temperature pH6 is positive.
Subsequently, 2g of a photocatalyst dispersion containing 2 nd hydrated alumina was dropped to spread and form a photocatalyst coating layer over the entire surface, and then dried at room temperature for 24 hours to form a photocatalyst layer, thereby forming a photocatalyst-carrying substrate.
(photocatalytic activity test)
The acetaldehyde concentration was 0ppm after 30 minutes of light irradiation, relative to the initial concentration of 10 ppm. The gas decomposition rate was 100%.
For comparison, a light-shielding experiment was prepared, and the concentration of acetaldehyde was measured in the same manner as described above, and found to be 10 ppm. The gas decomposition rate was 0%.
In the activity test of Escherichia coli, the initial bacteria concentration is 1 × 105Ml, the bacterial concentration was 0 after 3 hours of light irradiation with a fluorescent lamp. For comparison, the bacterial concentration after 3 hours of light-shielding was measured and found to be 2X 106/ml。
The photocatalytic activity was hardly changed even after 300 hours of light irradiation.
(Water resistance test)
The photocatalyst-carrying substrate 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% relative to the tungsten oxide fine particles were dispersed in water as a co-catalyst to obtain a 10 wt% aqueous dispersion. An aqueous dispersion of the same 2 nd hydrated alumina as in example 1, an aqueous dispersion of the above-mentioned tungsten oxide and Pd fine particles, a reactive silicone-containing emulsion, and hypochlorous acid water were mixed to prepare a photocatalyst dispersion containing 0.5 wt% of tungsten oxide, 0.02 wt% of pseudoboehmite, 0.1 wt% of the solid content of the silicone-containing emulsion, and 60ppm of hypochlorous acid.
The dispersion was stored in a dark place while being sealed in an aluminum can, and the dispersibility did not change.
(coating photocatalyst Material on Melamine resin film)
The same hydrated alumina dispersion as in example 1 was sprayed on a melamine resin film (size 10 cm. times.10 cm) formed on an aluminum plate without treatment. After drying at room temperature for 3 hours, the photocatalyst dispersion was sprayed. Dried at room temperature for 3 hours to form a photocatalyst layer.
(photocatalytic activity test)
The acetaldehyde concentration was 0ppm after 30 minutes of light irradiation, relative to the initial concentration of 10 ppm. The acetaldehyde concentration in the light-shielding test was 10 ppm.
In the activity test of Escherichia coli, the initial bacteria concentration is 1 × 105And/ml, the bacterial concentration was 0 after 3 hours of light irradiation by a fluorescent lamp. For comparison, the concentration of the bacteria after 3 hours of light-shielding was measured and found to be 1X 106/ml。
The photocatalytic activity was hardly changed even after 300 hours of light irradiation.
(Peel resistance and Water resistance test)
The above base material with photocatalyst was rubbed with a dry cloth and a water-soaked cloth. No peeling was observed, and the photocatalytic activity was hardly changed.
(example 3)
A photocatalyst-equipped substrate was produced in the same manner as in example 2, except that a polyethylene nonwoven fabric was used instead of the melamine resin film.
(photocatalytic activity test)
The acetaldehyde concentration was 0ppm after 25 minutes of light irradiation, relative to the initial concentration of 10 ppm. The concentration of the test for light shielding was 10 ppm.
In the activity test of Escherichia coli, the initial bacteria concentration is 1 × 105Ml, the bacterial concentration after 3 hours of irradiation with fluorescent light was 0. For comparison, the concentration of the bacteria after 3 hours of light-shielding was measured and found to be 1X 106/ml。
The photocatalytic activity was hardly changed even after 300 hours of light irradiation.
(Peel resistance and Water resistance test)
The above base material with photocatalyst was rubbed with a dry cloth and a water-soaked cloth. No peeling was observed, and the photocatalytic activity was hardly changed.
(example 4)
(coating of photocatalyst Material onto high efficiency Filter (HEPA filter))
The same dispersion of the 1 st hydrated alumina as in example 1 was sprayed on a high efficiency filter and dried with warm air at 60 ℃ for 20 minutes to form a base layer. Next, the same photocatalyst dispersion as in example 1 was applied to the base layer by a spray gun, and dried with warm air at 60 ℃ for 20 minutes to form a photocatalyst-carrying substrate.
(Activity test of photocatalytic device)
FIG. 4 is a schematic view showing the structure of a photocatalyst apparatus used in examples.
As shown in the drawing, the photocatalytic device 40 includes a base material 48 having a photocatalyst, a fan 45 for supplying a substance that receives a photocatalytic effect to the base material, and a light irradiation unit 44 made of a fluorescent lamp and disposed to face the fan 45 with the base material 48 interposed therebetween. The photocatalyst-equipped substrate 48 has a structure in which the same underlayer 42 as in example 1 and the same photocatalyst layer 43 as in example 1 are stacked on the substrate 41 made of the high efficiency filter.
In the photocatalyst apparatus 40, the fan 45 is driven while the fluorescent lamp 44 irradiates the photocatalyst layer 43 of the photocatalyst-equipped base material 48 with visible light, and air containing cigarette smell is introduced into the photocatalyst apparatus 40 from the inlet 46, passes through the photocatalyst-equipped base material 48, and is discharged from the outlet 47.
The odor of the discharged air was investigated by 3 persons. No odor was perceived by any of 3 people.
The photocatalytic activity was hardly changed even after 300 hours of light irradiation.
(Peel resistance and Water resistance test)
The above base material with photocatalyst was rubbed with a dry cloth and a water-soaked cloth. No peeling was observed, and the photocatalytic activity was hardly changed.
(example 5)
(preparation of alumina hydrate dispersion)
As the 1 st dispersion of hydrated alumina, an aqueous dispersion 10A of granular pseudo-boehmite particles manufactured by kansui Fine Chemical company was diluted with water to prepare an aqueous dispersion having a concentration of 0.5 wt%.
(preparation of photocatalyst Dispersion liquid)
Tungsten oxide fine particles having a negative Zeta potential in water at room temperature pH6 and a volume average particle diameter of 20nm to 100nm, and iron-nickel composite oxide fine particles having a positive Zeta potential in water at room temperature pH6 and a volume average particle diameter of 10 wt% with respect to tungsten oxide were dispersed in water to obtain a 10 wt% dispersion. A photocatalyst dispersion containing 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 manufactured by Kagawa Fine Chemical Co.
(coating of hydrophobic Japanese paper with photocatalyst Material)
10ml of the 1 st hydrated alumina dispersion was sprayed on 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 base layer is positive.
Next, the hydrophobic japanese paper was placed on the polytetrafluoroethylene film, 4g of the photocatalyst dispersion was dropped onto the base layer, and the entire surface was developed to form a photocatalyst coating layer, followed by drying at room temperature for 24 hours to form a photocatalyst layer.
(photocatalytic activity test)
The acetaldehyde concentration was 0ppm after 20 minutes of light irradiation, relative to the initial concentration of 10 ppm. For comparison, the acetaldehyde concentration after shading for 20 minutes was measured, and the acetaldehyde concentration was 10 ppm.
In the activity test of Escherichia coli, the initial bacteria concentration is 1 × 105And/ml, the bacterial concentration was 0 after 2.5 hours of light irradiation with a fluorescent lamp. For comparison, the concentration of the bacteria after 2.5 hours of light-shielding was measured, and the concentration was 1X 106/ml。
The photocatalytic activity was hardly changed even after 300 hours of light irradiation.
(Water resistance test)
The photocatalyst-carrying substrate was not peeled off even when immersed in water, and the photocatalytic activity was hardly changed.
(example 6)
(preparation of zirconium oxide Dispersion)
A dispersion having a concentration of 0.5% by weight was prepared by diluting daily chemical industrial zirconia sol ZR-40BL 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 positive Zeta potential in water at room temperature pH6 in an amount of 10 wt% relative to tungsten oxide are dispersed in water to obtain a 10 wt% aqueous dispersion of tungsten oxide fine particles and iron-nickel composite oxide fine particles. A photocatalyst dispersion containing 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 manufactured by Kagawa Fine Chemical Co.
(coating of hydrophobic Japanese paper with photocatalyst Material)
The zirconia sol dispersion was sprayed on 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 base layer is positive.
Next, the hydrophobic japanese paper was placed on the polytetrafluoroethylene film, 4g of the photocatalyst dispersion was dropped onto the obtained base layer, and the entire surface was developed to form a photocatalyst coating layer, followed by drying at room temperature for 24 hours to form a photocatalyst layer.
(photocatalytic activity test)
The acetaldehyde concentration was 0ppm after 20 minutes of light irradiation, relative to the initial concentration of 10 ppm. For comparison, the acetaldehyde concentration after light shielding was measured, and as a result, the acetaldehyde concentration was 10 ppm.
In the activity test of Escherichia coli, the initial bacteria concentration is 1 × 105And/ml, the bacterial concentration was 0 after 2.5 hours of light irradiation with a fluorescent lamp. As a comparison, the bacterial concentration after 2.5 hours of shading is measured, and the result shows that the bacterial concentration is 1 in a predetermined amount106/ml。
The photocatalytic activity was hardly changed even after 300 hours of light irradiation.
(Water resistance test)
The photocatalyst-carrying substrate was not peeled off even when immersed in water, and the photocatalytic activity was hardly changed.
(example 7)
(preparation of titanium dioxide Dispersion)
Granular rutile titanium oxide powder STR-100N produced by the 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 at room temperature pH6 and a volume average particle diameter of 20nm to 100nm, and iron-nickel composite oxide fine particles having a positive Zeta potential in water at room temperature pH6 and a volume average particle diameter of 10 wt% with respect to tungsten oxide were dispersed in water to obtain a 10 wt% dispersion of tungsten oxide fine particles and iron-nickel composite oxide fine particles. A photocatalyst dispersion containing 0.5 wt% of tungsten oxide and 0.05 wt% of pseudoboehmite was obtained from an aqueous dispersion of fibrous pseudoboehmite F-1000, an aqueous dispersion of Fine particles of tungsten oxide and Fine particles of iron-nickel composite oxide, manufactured by Kagawa Fine Chemical Co.
(coating of photocatalyst Material on PET film)
The titanium dioxide dispersion was sprayed on a PET film (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 base layer is positive. 3g of the photocatalyst dispersion was dropped onto the PET film, and the entire surface was developed to form a photocatalyst coating layer, which was then dried at room temperature for 24 hours to form a photocatalyst layer.
(photocatalytic activity test)
The acetaldehyde concentration was 0ppm after 30 minutes of light irradiation, relative to the initial concentration of 10 ppm. For comparison, the acetaldehyde concentration after light shielding was measured, and as a result, the acetaldehyde concentration was 10 ppm.
In the activity test of Escherichia coli, the initial bacteria concentration is 1 × 105Ml, irradiated with light for 3 hours by a fluorescent lampThe bacterial concentration after the treatment was 0. For comparison, the concentration of the bacteria after shading was measured, and as a result, the concentration of the bacteria was 1X 106/ml。
The photocatalytic activity was hardly changed even after 300 hours of light irradiation.
(Water resistance test)
The photocatalyst-carrying substrate was not peeled off even when immersed in water, and the photocatalytic activity was hardly changed.
(example 8)
(Activity test of photocatalytic device)
Fig. 5 is a schematic diagram showing a structure of a photocatalytic device provided in a refrigerator.
As shown in the figure, the photocatalyst apparatus 50 is provided with an LED for emitting 390nm light and an LED for emitting 600nm light as the light emitting unit 54 at the top thereof. The photocatalyst-bearing substrate 58 is disposed opposite the LED 54. Around the photocatalyst-carrying substrate 58, a member obtained by coating the granular activated carbon aggregate 57 with a teflon (registered trademark) porous film was disposed as an adsorbing member. The photocatalyst-carrying substrate 58 has the same configuration as the photocatalyst-carrying substrate obtained in example 3, and is formed by laminating a substrate 51 made of a nonwoven fabric, a foundation layer 52 provided on the substrate 51, and a photocatalyst layer 53 provided on the foundation layer 52 in this order from the light irradiation section 54 side. An air inlet 56 and a small fan 55 are provided on the side surface of the photocatalyst device 50, the air inlet facing the space between the LED54 and the photocatalyst-carrying substrate 58, and the air is sent into the refrigerator. The power supply and the control device are disposed outside the refrigerator.
In the photocatalyst apparatus 50, air in the refrigerator is introduced into the inside of the photocatalyst apparatus through the supply portion 55. The light irradiation is performed from the opposite side of the photocatalyst layer 53. The airflow passes through the photocatalyst-carrying substrate made of nonwoven fabric and is discharged to the outside of the photocatalyst apparatus 50.
The photocatalytic device was driven while irradiating light 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 a photocatalyst-carrying substrate)
An aluminum oxide film was formed by treating the surface of an aluminum plate having a thickness of 1mm and a square of 5cm with UV ozone. 0.5g of the 1 st alumina dispersion of example 1 was dropped and spread over the entire surface, and then dried at room temperature for 1 hour. Subsequently, 2g of a photocatalyst dispersion containing 2 nd hydrated alumina was dropped and developed over the entire surface, followed by drying at room temperature for 24 hours. Subsequently, the substrate was heated at 500 ℃ for 2 hours in air to form a photocatalyst-carrying substrate. By heating at high temperature, the hydrated alumina is dehydrated into alumina.
(photocatalytic activity test)
The acetaldehyde concentration was 0ppm after 30 minutes of light irradiation, relative to the initial concentration of 10 ppm. The gas decomposition rate was 100%.
(Peel resistance and Water resistance test)
The above base material with photocatalyst was rubbed with a dry cloth and a water-soaked cloth. No peeling was observed, and the photocatalytic activity was hardly changed.
(Heat resistance test)
The photocatalyst-carrying substrate 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 photocatalyst-equipped substrate was produced in the same manner as in example 1, except that the hydrated alumina base layer was not produced. When the photocatalyst-carrying substrate was immersed in water, peeling was observed for about 1 hour.
As is clear from the results of the above examples, according to the embodiments, it is possible to provide a photocatalyst-carrying substrate, a method for producing the same, and a photocatalyst apparatus, which can stably exhibit stable photocatalytic performance over a long period of time.
Several embodiments of the present invention have been described, but these embodiments are presented as examples and are not intended to limit the scope of the invention. These new embodiments can be implemented in other various ways, 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 the equivalent scope thereof.
Claims (17)
1. A photocatalyst-bearing substrate comprising: a substrate; a base layer disposed on the substrate comprising alumina hydrate 1 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.
2. The photocatalyst-bearing substrate according to claim 1, wherein the substrate has a negative Zeta potential.
3. The photocatalyst-bearing substrate according to claim 1, wherein the 1 st hydrated alumina is boehmite or pseudo-boehmite.
4. The photocatalyst-bearing substrate according to claim 1, wherein the 1 st hydrated alumina is fibrous.
5. The photocatalyst-bearing substrate according to any one of claims 1 to 4, wherein the photocatalyst layer further contains a co-catalyst material.
6. The photocatalyst-bearing substrate of claim 5, wherein the promoter material has a positive Zeta potential.
7. The photocatalyst-bearing substrate according to any one of claims 1 to 4, wherein the photocatalyst material contains tungsten oxide.
8. The photocatalyst-provided substrate according to any one of claims 1 to 4, wherein the substrate is porous.
9. The photocatalyst-bearing substrate according to any one of claims 1 to 4, wherein the substrate is an organic material.
10. The photocatalyst-bearing substrate according to any one of claims 1 to 4, wherein the photocatalyst layer further contains 2 nd hydrated alumina.
11. The photocatalyst-bearing substrate according to claim 10, wherein the 2 nd hydrated alumina is boehmite or pseudo-boehmite.
12. The photocatalyst-bearing substrate according to claim 10, wherein the 2 nd hydrated alumina is fibrous.
13. A photocatalytic device comprising the photocatalyst-carrying substrate according to any one of claims 1 to 12, a light irradiation unit for generating photocatalytic activity on the photocatalyst-carrying substrate, and a supply unit for supplying a substance that receives photocatalytic activity to the substrate.
14. The photocatalytic device according to claim 13, wherein the light irradiation section is an LED.
15. The photocatalytic device according to claim 13 or 14, wherein the supply part is a fan.
16. The photocatalytic device according to claim 13 or 14, wherein the substrate is a porous substrate, and the substance permeates the porous substrate.
17. The photocatalyst apparatus according to claim 13 or 14, further comprising an adsorbing portion for adsorbing the substance.
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