WO2002053284A1 - Procédé d'activation de photocatalyseur et dispositif à cet effet - Google Patents

Procédé d'activation de photocatalyseur et dispositif à cet effet Download PDF

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Publication number
WO2002053284A1
WO2002053284A1 PCT/JP2001/011576 JP0111576W WO02053284A1 WO 2002053284 A1 WO2002053284 A1 WO 2002053284A1 JP 0111576 W JP0111576 W JP 0111576W WO 02053284 A1 WO02053284 A1 WO 02053284A1
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Prior art keywords
light
emitting diode
visible light
responsive photocatalyst
light emitting
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PCT/JP2001/011576
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English (en)
Japanese (ja)
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Shinichi Sugihara
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Ecodevice Laboratory Co., Ltd.
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Priority to KR10-2003-7008845A priority Critical patent/KR20030072373A/ko
Priority to JP2002554228A priority patent/JPWO2002053284A1/ja
Publication of WO2002053284A1 publication Critical patent/WO2002053284A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
    • C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
    • C07C45/37—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of >C—O—functional groups to >C=O groups
    • C07C45/39—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of >C—O—functional groups to >C=O groups being a secondary hydroxyl group
    • 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
    • B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation

Definitions

  • the present invention relates to a method for activating a photocatalyst and an apparatus comprising a photocatalyst and a light source.
  • photocatalysts composed of anatase-type titanium dioxide can be used for antibacterial tiles, self-cleaning building materials, superhydrophilic materials, deodorizing and deodorizing materials, water purification, cancer treatment, etc.
  • the Lean Revolution (Akira Fujishima et al.) Has been actively developing various applications.
  • WO94 / 11092 discloses an air treatment method using a photocatalyst under indoor lighting.
  • Japanese Patent Application Laid-Open No. 7-102678 discloses a method for preventing hospital-acquired infection using a photocatalyst. JP 8 6 7 8 3 5 and JP Hei 8 - 1 6 4 3 3 4 No.
  • 2000-218784 describes a dental light irradiation device used for sterilization and treatment of the oral cavity such as periodontal disease or decolorization of teeth by light irradiation, This is a dental irradiation device that uniformly irradiates the entire dentition with light and decolorizes using a plurality of light-emitting diodes arranged curved along the front surface of the dentition.
  • ultraviolet light is not contained as much as possible in consideration of adverse effects on the human body.
  • the conventional photocatalyst shows little activity, and the effect of the photocatalyst is very weak.
  • an object of the present invention is to provide a method and apparatus for activating a photocatalyst, which uses a light emitting diode containing a high content of visible light or a light emitting diode containing only visible light as a light source. Disclosure of the invention
  • the present invention relates to a method for activating a photocatalyst, in which a photocatalyst (visible light responsive photocatalyst) having activity by the action of light having a wavelength of 420 nm or more is irradiated with light from a light emitting diode. Further, the present invention provides an apparatus having a layer containing a visible light responsive photocatalyst on a light emitting diode substrate, a light emitting diode, a visible light responsive photocatalyst, and light from the light emitting diode being applied to the visible light responsive photocatalyst. Apparatus including light transport means for transport About. BRIEF DESCRIPTION OF THE FIGURES
  • FIG. 1 is an ESR spectrum of the visible light responsive photocatalyst (Reference Example 1) used in the present invention measured at 77K in vacuum.
  • the upper row shows the spectrum in the dark
  • the middle row shows the spectrum under irradiation of light having a wavelength of 420 nm or more (cut off the light of less than 420 nm out of the mercury lamp light)
  • the lower row shows the spectrum. This is a spectrum when a light of a mercury lamp is irradiated without cutting off light of less than 420 nm.
  • FIG. 2 is an ESR spectrum of the visible light responsive photocatalyst (Reference Example 1) used in the present invention measured at room temperature in a vacuum.
  • the upper part is a spectrum in the dark
  • the middle part is a spectrum under irradiation of light having a wavelength of 420 nm or more (the light of 420 nm or less of the light of a mercury lamp is cut off)
  • the lower part is a spectrum.
  • the spectrum is obtained when the light of a mercury lamp is irradiated without cutting off light of less than 420 nm.
  • Figure 3 shows the XRD measurement results of the product of Reference Example 1 (upper) and the hydrolyzate (dried at 50 ° C) (lower).
  • Figure 4 shows the emission spectra of the blue light emitting diode (B LUE), the green light emitting diode (GREEN), and the white light emitting diode (WHITE).
  • FIG. 5 shows the results of oxidation of isopropanol by a blue light emitting diode in Example 3.
  • Fig. 6 shows the product of Reference Example 4 (visible light responsive photocatalyst) in a vacuum at 77 K: light with a wavelength of 420 nm or more (of the mercury lamp, the light less than 420 nm is turned off).
  • 2 is an ESR spectrum measured under the irradiation of FIG.
  • Figure 7 shows that the product (visible light responsive photocatalyst) of Reference Example 5 under vacuum at 77K, with light having a wavelength of 420 nm or more (of the light of a mercury lamp, the light of less than 420 nm was cut off). It is an ESR spectrum measured under irradiation.
  • Figure 8 shows that the product of Reference Example 6 (visible light responsive photocatalyst) was irradiated with light having a wavelength of more than 420 nm at 77K (power of the mercury lamp was less than 420 nm) in a vacuum. ESR spectrum measured under irradiation. BEST MODE FOR CARRYING OUT THE INVENTION
  • the visible light responsive photocatalyst used in the present invention contains at least anatase-type titanium dioxide and has a g-value of ESR measured in a vacuum at 77 K under irradiation of light having a wavelength of 420 nm or more at 77 K.
  • the main signal with S2.004 to 2.07 and the two subsignals with g-values of 1.985 to 1.986 and 2.024 are observed.
  • the above three signals (main signal and two subsignals) are minutely observed or substantially observed in vacuum at 77K and in darkness. That is not done.
  • the visible light-responsive photocatalyst used in the present invention preferably contains anatase type titanium dioxide as a main component, and may further contain rutile type titanium dioxide and / or amorphous titanium dioxide. Also, the anatase type titanium dioxide does not necessarily have to have high crystallinity.
  • FIG. 1 shows a typical spectrum of the visible light responsive photocatalyst used in the present invention measured at 77 in a vacuum. In the figure, the upper row shows the spectrum under black, and the middle row shows the spectrum under irradiation of light having a wavelength of 420 nm or more (light of less than 420 nm of the mercury lamp light is cut off). It is.
  • the lower part shows the spectrum when the light of the mercury lamp is irradiated without cutting off the light of less than 420 nm.
  • the upper, middle, and lower rows are all the results measured under the same gain (GA IN).
  • Comparison of the upper and middle spectrums in Fig. 1 clearly shows that in the middle spectrum, the main signal with a g-value force of S 2.004 to 2.007 and a g-value of 1.985-1.
  • the two sub-signals, 986 and 2.024 are stronger than in the upper spectrum.
  • the main signals with g values of 2.004 to 2.007 and the g values of 1.985 to 1.986 and 2.024 2 The intensities of the two sub-signals are substantially the same whether or not the irradiation light contains light of 420 nm or less.
  • the visible light responsive photocatalyst used in the present invention is also measured by ESR under irradiation of light having a wavelength of at least 420 nm in black and at room temperature in the vacuum at room temperature. It can be done.
  • ESR ESR under irradiation of light having a wavelength of at least 420 nm in black and at room temperature in the vacuum at room temperature. It can be done.
  • the upper row shows the spectrum in the dark
  • the middle row shows the spectrum under the irradiation of light having a wavelength of 420 nm or more (cut off the light of less than 420 nm out of the mercury lamp light). ⁇ It is a kutor.
  • the lower part is a spectrum when the light of a mercury lamp is irradiated without cutting off light of less than 420 nm.
  • GAIN gain
  • the visible light responsive photocatalyst used in the present invention has, in addition to the above signals, a g-value force of S 2 .7 in ESR measured in vacuum at 77 K under irradiation with light having a wavelength of 420 nm or more. It may further have a side signal that is between 09 and 2.010. The side signal having a g value of 2.009 to 2.010 is shown in the middle ESR spectrum of FIG.
  • the visible light responsive photocatalyst used in the present invention can be oxygen-deficient titanium oxide having a bond ratio between Ti (titanium) and 0 (oxygen) less than 2. Whether or not it is oxygen-deficient titanium oxide can be measured by X-ray photoelectron spectroscopy (XPS).
  • XPS X-ray photoelectron spectroscopy
  • the Ti-0 of titanium oxide with close binding energy is used.
  • 530 ⁇ 0.5 eV and 532 belonging to the 0-0 bond of adsorbed oxygen It is preferable to separate ⁇ 0.5 eV and obtain by calculation. From the results of measurement and calculation by this method, it can be seen that the visible light responsive photocatalyst described in Reference Examples described later is of an oxygen deficient type.
  • the commercially available titanium oxide catalysts ST-01 manufactured by Ishihara Sangyo
  • other JRC-IT03 catalogs referred to by the Catalysis Society of Japan
  • P- 25 manufactured by Nippon Aerosil
  • the visible light responsive photocatalyst used in the present invention can be produced using amorphous or imperfect crystalline titanium dioxide as a raw material.
  • This raw material titanium dioxide can be produced by a sulfuric acid method, a chloride method, or the like. It can be obtained by a wet method using oxide as a raw material.
  • the raw material titanium dioxide can be obtained by hydrolyzing titanium chloride with ammonium hydroxide. This hydrolysis is suitably performed by adjusting the amount of ammonium hydroxide added so that the pH of the reaction solution is 6 or more.
  • the titanium chloride may be any of titanium trichloride, titanium tetrachloride, titanium oxychloride and the like, and a mixture thereof may be used.
  • the hydrolysis can be performed, for example, under cooling or at a temperature in the range of room temperature to 90 ° C., but the hydrolysis at room temperature is relatively low in crystallinity or non-crystalline dioxidation. It may be preferable from the viewpoint that titanium is obtained.
  • the hydrolyzate of titanium chloride with ammonium hydroxide is preferably used as a raw material titanium dioxide after being washed with an aqueous solution of ammonium hydroxide.
  • the remaining amount of ammonium chloride generated during hydrolysis is appropriate. It can be performed to reduce the amount, and preferably can be performed a plurality of times.
  • the amorphous or incompletely crystalline titanium dioxide may be a commercially available product, for example, incompletely crystalline titanium dioxide such as ST-01 or C-02 manufactured by Ishihara Sangyo. There may be.
  • a hydrolyzate obtained by hydrolyzing titanium sulfate or titanyl sulfate was washed with water to remove at least a part of sulfate ions contained in the hydrolyzate.
  • the method can be carried out by a method comprising at least titanium oxide containing anatase-type titanium oxide, which comprises heating in the presence of ammonia or a derivative thereof.
  • the above hydrolyzate can be washed with water or aqueous ammonia, but as a result of the subsequent studies, it has been found that a product with a higher BET specific surface area can be obtained by water washing as compared with ammonia water washing.
  • the present invention employs water washing. More specifically, when the heating conditions are the same, the product obtained by water washing can obtain a product having a BET specific surface area that is almost twice that of ammonia water washing.
  • the washing with water is carried out by washing the sulfate ion concentration in the washing filtrate. It is preferable to carry out until the degree becomes 2000 ppm or less. More preferably, the washing with water is performed until the sulfate ion concentration in the washing filtrate becomes 1500 ppm or less.
  • the production of the visible light responsive photocatalyst used in the present invention can be performed, for example, as follows, in addition to the above method.
  • Amorphous or incompletely crystalline titanium dioxide is heated in the presence of ammonia or its derivatives.
  • Ammonia may be liquid or gaseous.
  • ammonia gas the raw material titanium dioxide is heated in an atmosphere gas atmosphere.
  • the ammonia derivative include an ammonium salt such as ammonium chloride.
  • the raw material titanium dioxide is heated in the presence of ammonium chloride.
  • the absorption of light at a wavelength of 45 O nm of the material generated by heating is greater than the absorption of light at a wavelength of 45 O nm of the raw titanium dioxide This is done by terminating the heating at that point.
  • the raw material titanium dioxide is white, and the light absorption at a wavelength of 45 O nm is around 10%.
  • the raw material titanium dioxide when the raw material titanium dioxide is heated in the presence of ammonia or its derivative, it gradually turns yellow. However, this coloring fades to a peak at a certain point in time, and eventually shows an absorption similar to that of the starting titanium dioxide.
  • Types of raw material titanium dioxide and species of ammonia (derivative) to coexist Depending on the type and amount, heating temperature, time, etc., the absorption of light at a wavelength of 450 nm may reach up to about 60%.
  • the characteristic of visible light responsive photocatalyst is wavelength
  • the wavelength 4 Although not uniquely determined by the light absorption intensity at 45 O nm, the wavelength 4
  • the material clearly shows visible light response.
  • the heating conditions cannot necessarily be defined only by the temperature, but may be, for example, a temperature in the range of 300 to 500 ° C. This heating can be performed under normal pressure.
  • the heating time can be appropriately determined based on the absorption of light at a wavelength of 45 O nm of the material generated by heating.
  • a rotary kiln, a tunnel kiln, a Matsufur furnace, or the like which is generally used in this field, can be used.
  • individual particles of titanium oxide are aggregated or sintered by heating, they may be ground by a crusher as necessary.
  • the material obtained by heating as described above can be washed with water or an aqueous solution as needed. This washing may improve the visible light responsiveness of the obtained visible light responsive photocatalyst in some cases.
  • amorphous or incompletely crystalline titanium dioxide material before heating
  • ammonium hydroxide a considerable amount of chloride is added to the hydrolyzate. Ammonia remains, resulting in amorphous or imperfectly crystalline titanium dioxide as described above. Can be converted to a visible light responsive photocatalyst.
  • a considerable amount of ammonium chloride may remain in the obtained material.
  • washing with water or an appropriate aqueous solution may remove ammonium chloride and improve the visible light responsiveness of the visible light responsive photocatalyst in some cases.
  • the material obtained by heating can be washed with water or an aqueous solution such that the pH of the washed water or aqueous solution is, for example, 5 or more.
  • the visible light responsive photocatalyst used in the present invention includes silicon, aluminum, tin, zirconium, antimony, phosphorus, platinum, gold, silver, copper, iron, niobium, tungsten, on its surface and / or inside depending on the application. Elements such as tantalum and compounds containing them can be coated, supported, or doped.
  • the above visible light responsive photocatalyst can be carried using a transparent activated alumina described in JP-A-2000-119017 as a carrier.
  • a transparent visible light responsive photocatalyst can be obtained, and a transparent paint can be provided.
  • the visible light responsive photocatalyst may be contained in a coating film.
  • This coating film can be formed using a paint containing at least the above visible light responsive photocatalyst, a binder and a solvent.
  • the binder may be either an organic binder or an inorganic binder.
  • the inorganic binder include alkyl silicate and silicon halide. And products obtained by hydrolyzing hydrolyzable silicon compounds such as partially hydrolyzed products thereof, silica, colloidal silica, water glass, silicon compounds such as organopolysiloxane, and organic polysiloxane compounds.
  • Examples include inorganic binders such as condensates, phosphates such as zinc phosphate and aluminum phosphate, heavy phosphates, cement, lime, gypsum, frit for enamel, glaze for glass lining, and plaster.
  • examples of the organic binder include organic binders such as a fluorine-based polymer, a silicon-based polymer, an acrylic resin, an epoxy resin, a polyester resin, a melamine resin, a urethane resin, and an alkyd resin. Since the binder is degraded or decomposed by the photocatalytic function of the photocatalyst, it is necessary to appropriately select the type of binder according to the use scene, the degree of the photocatalytic function, and the application.
  • a visible light responsive photocatalyst is used as the photocatalyst, so that the photocatalyst function is much less deteriorated compared to a conventional paint using an ultraviolet type photocatalyst, and the photocatalyst is used indoors where there is almost no ultraviolet light. Has almost no deterioration due to the photocatalytic function.
  • organic binders such as acrylic resins, epoxy resins, polyester resins, melamine resins, urethane resins, and alkyd resins, which cannot be used in paints using an ultraviolet-type photocatalyst, can also be used favorably.
  • these binders can be used alone or in combination of two or more.
  • the alkyl silicates e.g., S i as a general formula n O n _! (OR) 2n + 2 (where S i is Keimoto, O is oxygen, R represents an alkyl group.)
  • the compound represented by N is, for example, 1 to 6, and R is, for example, an alkyl group having 1 to 4 carbon atoms. However, it is not limited to these.
  • cement examples include Portland cement, such as early-strength cement, ordinary cement, moderate heat cement, sulfate-resistant cement, white cement, oil well cement, geothermal well cement, fly ash cement, high sulfate cement, Mixed cements such as silica cement and blast furnace cement, and alumina cement can be used.
  • Portland cement such as early-strength cement, ordinary cement, moderate heat cement, sulfate-resistant cement, white cement, oil well cement, geothermal well cement, fly ash cement, high sulfate cement, Mixed cements such as silica cement and blast furnace cement, and alumina cement can be used.
  • plaster for example, secco plaster, lime plaster, doloma plaster and the like can be used.
  • fluorinated polymer examples include polyvinyl fluoride, polyvinylidene fluoride, polychlorinated trifluoroethylene, polytetrafluoroethylene, polytetrafluoroethylene propylene copolymer, ethylene-polytetrafluoroethylene copolymer, and ethylene-polytetrafluoroethylene copolymer.
  • Crystalline fluororesins such as ethylene monochloride trifluorene ethylene copolymer, tetrafluoroethylene monofluoroalkylbier ether copolymer, perfluoro-norelocyclopolymer, vinylinoleatenorreolenorreolefin copolymer, An amorphous fluororesin such as a nylester-fluorofluorin copolymer, various fluororubbers, and the like can be used.
  • a fluoropolymer mainly composed of a vinyl ether-fluorene copolymer and a vinylinestenolefinolefluorene copolymer is preferred because it has little degradation and deterioration and is easy to handle.
  • Silicone polymers include linear silicone resin and acrylic-modified silicone resin Fats and various types of silicone rubber can be used.
  • the organic polysiloxane compound used for the polycondensate of the organic polysiloxane compound is a substance known as a hydrolyzate of an organic silicon compound.
  • Japanese Patent Application Laid-Open Nos. 8-164, 334 and 8-6 Nos. 7 835, JP-A-8-155030, JP-A-10-66830, Patent No. 2756474, etc. Can be used.
  • the organic polysiloxane compound is a hydrolyzate of an organic silicon compound, and examples of the organic silicon compound include those having an alkyl group and an alkoxy group.
  • a hydrolyzate of an organosilicon compound having an alkyl group and an alkoxy group is also known, and is obtained, for example, by hydrolyzing an organosilicon compound represented by R ⁇ Si (OR 2 ) 4 — n .
  • R 1 and R 2 can each be, for example, a lower alkyl group having 1 to 8 carbon atoms.
  • R 1 is a lower alkyl group having 1 to 3 carbon atoms, preferably Is suitably a methyl group.
  • N in the above formula is an integer of 0 to 2, and specifically, a film obtained by using a hydrolyzate (three-dimensionally crosslinked product) of a mixture of organic silicon compounds in which at least n is 1 or 2 is used.
  • a hydrolyzate three-dimensionally crosslinked product
  • the organosilicon compound include methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, and methyltributanol.
  • Kishishiran methylol tri chrono Les silane, methylcarbamoyl Honoré tribromomethyl silane; Echinoretori main Tokishishiran, E triethoxysilane, E tilt re-isopropoxyphenyl Sila down, E Ji ⁇ tri t one butoxysilane, E Chino Les trichlorosilane, Echinoretoribu port Mushiran; n-propyltrimethoxysilane, n-propyltriethoxysilane, n-propyltriisopropoxysilane, n-propyltributoxysilane, n-propyltrichlorosilane, n-propyltribromosilane; n-hexyl / trime Toxoxysilane, n-hexinoletriethoxysilane, n-hexyltriisopropoxysilane, n-hexyltri-t-poxysi
  • Gurishidokishipuro pills triethoxysilane, .gamma.-glycidoxypropyltrimethoxysilane isopropoxyphenyl Sila down, y- glycidoxypropyltrimethoxysilane t Ru can be given an butoxysilane like.
  • the compounding amount of the binder is about 100 to 2000% by weight, preferably 25 to 100% by weight, and preferably 25 to 100% by weight, based on the solid matter, based on the visible light-responsive photocatalyst particles. 500% by weight is more preferable, and 25 to 250% by weight is more preferable.
  • the visible light responsive photocatalyst can be maintained without desorbing the visible light responsive photocatalyst when a coating film is formed.
  • the solvent an inorganic solvent, an organic solvent, or a mixture thereof can be used. Water is preferred as the inorganic solvent.
  • the organic solvent alcohols such as methanol, ethanol, 2-propanol, and ethylene glycol, and ketones can be used. Those containing alcohol are preferred from the viewpoints of handleability and coatability.
  • the compounding amount of the solvent can be appropriately set according to the workability. If necessary, the paint and the coating film can contain at least one compound selected from the group consisting of dicarboxylic acids and derivatives thereof.
  • Dicarponic acid is an organic compound having two olepoxyl groups COOH in the molecule.
  • aliphatic unsaturated dicarboxylic acids such as maleic acid and fumaric acid
  • aromatic dicarboxylic acids such as phthalic acid, isophthalic acid and terephthalic acid.
  • the dicarboxylic acid derivative is an esterified product of the dicarboxylic acid, Dicarboxylic acids such as salts, dicarboxylic anhydrides, dicarboxylic acid azides, dicarboxylic acid amides, dicarbonic acid imides, etc. Ethyl dicarboxylate, propyl dicarbonate, butyl dicarboxylate, sodium dicarboxylate, ammonium dicarboxylate and the like can be used. Further, a product containing dicarboxylic acid or a derivative thereof, for example, Rhodiasolve (trade name, manufactured by Rhone Pourin Japan Co., Ltd.) containing three kinds of dicarboxylic acid esters may be used.
  • Dicarboxylic acids such as salts, dicarboxylic anhydrides, dicarboxylic acid azides, dicarboxylic acid amides, dicarbonic acid imides, etc. Ethyl dicarboxylate, propyl dicarbonate, butyl dicarboxylate
  • the content of the dicarboxylic acid and the derivative thereof is about 0.5 to 500% by weight, preferably 5 to 500% by weight, and more preferably 10 to 50% by weight based on the visible light responsive photocatalyst particles in the paint or coating film. ⁇ 500 wt% is more preferred, and 25 ⁇ 250 wt% is even more preferred.
  • the content of the dicarboxylic acid and its derivative is less than the above range, the effect of adding is difficult to be exhibited, and when the content is more than the above range, a further remarkable effect is hardly recognized. Note that a coating film formed using a visible light responsive coating composition containing a dicarboxylic acid or a derivative thereof becomes porous, and the visible light responsive photocatalytic function can be improved.
  • visible light-responsive photocatalyst particles in addition to at least one compound selected from the group consisting of dicarboxylic acids and derivatives thereof, visible light-responsive photocatalyst particles, binders, and solvents, dispersants, surfactants, curing agents, Various additives such as a crosslinking agent may be contained.
  • the thickness of the visible light responsive photocatalyst coating film can be appropriately set according to the application, and can be, for example, about 0.01 to 1.
  • the coating film can be formed by applying or spraying a paint on the substrate.
  • the visible light responsive photocatalyst particles and the binder are dispersed in a solvent to form a coating composition, and then the coating composition is applied or sprayed on a substrate to form the visible light responsive photocatalyst particles and the binder.
  • a solvent water, an organic solvent such as toluene and alcohol can be used.
  • the coating method include, for example, impregnation method, die coating method, spinner coating method, blade coating method, roller coating method, wire per coating method, lino-slowno coating method, brush coating method, and sponge coating method. It can be applied by a conventional method or sprayed by a usual method such as a spray coating method.
  • the solvent is removed by drying or baking.
  • the drying or firing is preferably performed at a temperature lower than 500 ° C., more preferably at a temperature from room temperature to 400 ° C. In this case, if the temperature is higher than 500 ° C., the visible light responsive photocatalytic function tends to decrease, which is not preferable.
  • a method such as ultraviolet irradiation may be used to solidify the binder used.
  • the above-mentioned organic binder such as ataryl resin, epoxy resin, polyester resin, melamine resin, urethane resin, alkyd resin, etc.
  • the organic binder or the inorganic binder described above may be applied or sprayed on the article in advance as a primer or a coating.
  • the paints and coatings described above include particulate matter, adsorbents, carriers and / or condensed phosphates. Can be included.
  • the particulate matter has, for example, an average particle diameter of 1 ⁇ ⁇ ! It can be up to 100 m of inorganic or organic particles.
  • the photocatalytic particles can also have the function of adsorbing and / or supporting the substance to be treated. preferable.
  • adsorbent and carrier general adsorbents and carriers can be used.
  • activated carbon for example, activated carbon, zeolite, silica gel, transparent activated alumina (for example, JP-A-2000-119017), amorphous or Titanium dioxide, diatomaceous earth, etc. with low crystallinity
  • Titanium dioxide of amorphous or low crystallinity is hydrolyzed with ammonium hydroxide after titanium sulfate or titanium sulfate is obtained, and then sulfated ions remain, for example, calcined at 400 ° C, and then washed if necessary. Can be obtained by doing so.
  • the paint is a paint containing a binder, a condensed phosphate, a visible light responsive photocatalyst, and a solvent, and the solvent is preferably water.
  • a paint containing water as a solvent and containing a condensed phosphate has good dispersibility of visible light-responsive photocatalyst particles, and a coating film obtained from this paint shows excellent visible light response.
  • the present invention includes a coating containing a binder, a condensed phosphate, and a visible light-responsive photocatalyst, and the coating shows hydrophilicity under light irradiation.
  • Conventional hydrophilic paints and coatings (for example, JP-A-11-1659) contain silica and silicone to obtain weather resistance.
  • a coating film having excellent weather resistance can be obtained without containing silica-silicone.
  • a coating film with excellent weather resistance can be obtained without containing silica or silicone, so that there is more freedom in composition, for example, increasing the amount of binder or increasing the content of visible light responsive photocatalyst It is also possible.
  • the paint and the coating film in the present invention may contain silica or silicone.
  • the amount of the condensed phosphate is 0.5 to 5%, preferably 1 to 1.2%, based on the weight of the visible light responsive photocatalyst, whereby dispersibility, viscosity, Good paint is obtained in terms of stability and the like.
  • the larger the specific surface area of the visible light responsive photocatalyst and the larger the amount of the surface coating agent the larger the optimal amount of the condensed phosphate.
  • the optimum amount of condensed phosphate varies depending on the method of producing the visible light responsive photocatalyst and the type of surface coating agent.
  • the condensed phosphate need not be limited to one kind, and two or more kinds may be used in combination.
  • the paint and the coating film of the present invention may further contain a colloidal oxide in addition to the above components.
  • the colloidal oxide include colloidal silica. Since the colloidal oxide is a fine particle, it can increase the surface area of the coating (make it porous) and increase the frequency of contact between the visible light responsive photocatalyst and the reactant. However, colloidal oxides are not Is not an essential component to show Further, in the present invention, a first layer comprising a binder and containing no visible light responsive photocatalyst particles is provided on a substrate, and further, a binder and visible light responsive photocatalyst particles are formed on the first layer.
  • the first layer By providing the first layer not containing the visible light responsive photocatalyst particles, the connection between the substrate and the second layer containing the visible light responsive photocatalyst particles is strengthened. Can be adhered to the substrate more firmly and for a longer period of time.
  • a binder an organic binder is preferable.
  • the first layer preferably contains, as a filler, inorganic particles having no visible light responsive photocatalytic function.
  • inorganic particles include titanium oxide, silicon oxide, and aluminum oxide that have been surface-treated with silicon oxide, aluminum oxide, zirconium oxide, or the like so as not to have a visible light responsive photocatalytic function. And magnesium oxide.
  • the amount of the visible light responsive photocatalyst particles in the coating composition is 5 to 98%, preferably 20 to 90% by volume based on the total amount of the visible light responsive photocatalyst particles and the binder. It is 98%, more preferably 50-98%, and most preferably 70-98%.
  • the coating composition may contain a crosslinking agent, a dispersing agent, a filler and the like.
  • a cross-linking agent a normal cross-linking agent such as an isocyanate-based or melamine-based cross-linking agent can be used, and as the dispersing agent, a coupling agent or the like can be used.
  • the content of the visible light responsive photocatalyst particles in the coating composition is determined by the When the content is 40 to 98% by volume based on the total amount of the acidic photocatalyst particles and the binder, it is preferable to add a coupling agent to the coating composition.
  • the addition amount of the coupling agent is preferably 5 to 50%, more preferably 7 to 30%.
  • the reaction is preferably carried out at a temperature from room temperature to 200 ° C. In this case, if the temperature is higher than 400 ° C., the binder is thermally degraded, and the visible light-responsive photocatalyst particles are easily removed, which is not preferable.
  • a method of solidifying using an isocyanate-based or melamine-based cross-linking agent is preferable.
  • the light emitting diode used in the method of the present invention is a light emitting diode having an emission wavelength at least in the visible light region or having an emission wavelength only in the visible light region.
  • Examples of such a light emitting diode include a purple light emitting diode, a blue light emitting diode, a green light emitting diode, a yellow light emitting diode, and a white light emitting diode.
  • the violet emission diode has an emission wavelength from the ultraviolet region to the visible light region.
  • a blue light emitting diode, a green light emitting diode, a yellow light emitting diode, or a white light emitting diode has an emission wavelength only in a visible light region.
  • the photocatalyst activated by the photocatalyst activation method of the present invention can be used in, for example, a chemical reaction method, an environmental purification method, a sterilization method, a hydrophilization method, a cell growing method, an antifouling method, and the like. Further, the amount of light irradiation and the irradiation time can be appropriately set depending on the amount of the substance to be treated.
  • the method of the present invention can also be used in a reaction system such as a microchemical chip.
  • the present invention relates to a device having a layer containing a visible light responsive photocatalyst on a light emitting diode substrate.
  • the light-emitting diode substrate may include, for example, at least a light-emitting diode and a light-transmitting layer provided thereon, and a layer including the visible light-responsive photocatalyst provided on the light-transmitting layer. it can.
  • the light emitting diode is a violet light emitting diode, and light having a wavelength of 400 nm or less is transmitted between the light transmitting layer and the layer containing the visible light responsive photocatalyst.
  • a layer that does not transmit light may be further provided.
  • the violet light emitting diode also contains ultraviolet rays of 400 nm or less, but by providing a layer (one layer of filter) that does not transmit light of wavelengths of 400 nm or less, the ultraviolet rays are cut off, for example, visible light response.
  • This filter layer can be a layer that does not transmit light having an arbitrary wavelength of 410 to 550 nm or less. Also, two types of filters having different transmission characteristics can be combined. Further, the present invention relates to an apparatus including a light emitting diode, a visible light responsive photocatalyst, and a light transfer means for transferring light from the light emitting diode to the visible light responsive photocatalyst.
  • the light transfer means may be, for example, an optical fiber.
  • the layer containing the visible light responsive photocatalyst can be a coating film formed by using a paint, and for example, the visible light responsive photocatalyst in a powder state is provided on a light emitting diode.
  • the visible light-responsive photocatalyst is the above-mentioned visible light-responsive photocatalyst
  • a raw material titanium compound such as amorphous or incompletely crystalline titanium oxide on a base material is added together with a suitable binder if necessary.
  • a layer containing a visible light responsive photocatalyst can also be formed by applying the above and heating the film by applying an ammonia or a derivative thereof in an atmosphere or by including an ammonia or a derivative thereof in an atmosphere. .
  • the device of the present invention described above can be used for chemical reaction, environmental purification, sterilization, decolorization, hydrophilization, cell growth, or imparting antifouling properties.
  • the device of the present invention is useful as a microchemical reactor.
  • the device of the present invention can also be used as illumination such as an illumination lamp or an indicator lamp.
  • Example 1 Example 1
  • 0.2 g of the powder produced in Reference Example 3 was uniformly applied to a glass plate (6 ⁇ 6 cm) using water, and dried at room temperature. About 2 ml of a 0.05 wt% aqueous solution of methylene blue was dropped near the center of the plate glass and dried at room temperature.
  • the light source was set so as to be 1 cm relative to the sample.
  • the light source was a blue LED (Nichia Chemical Industry Co., Ltd., Model No. NS SB 450), a 2 x 2 grid of 4 pieces, so that one side could fit into 1.5 cm. Lighting was performed by applying a voltage to the light emitting diode to 3.7 V. The light irradiation time for the sample was 1 hour. Table 1 shows the color change of the light-irradiated part of each sample after light irradiation. Comparative Example 1
  • Example 2 A methylene blue decolorization test was performed in the same manner as in Example 1 except that a commercially available ultrafine titanium oxide powder (ST-01 manufactured by Ishihara Sangyo) was used instead of the powder produced in Reference Example 3. Table 1 shows the results. Comparative Example 2
  • a decolorization test of methylene blue was performed in the same manner as in Example 2 except that a commercially available ultrafine titanium oxide powder (ST-01 manufactured by Ishihara Sangyo) was used instead of the powder produced in Reference Example 3. Table 1 shows the results.
  • a decolorization test of methylene blue was performed in the same manner as in Example 2 except that commercially available titanium oxide powder for photocatalyst P-25 (manufactured by Dedasa) was used instead of the powder produced in Reference Example 3. Table 2 shows the results.
  • Example 2 The color was completely erased.
  • Nichia Chemical's model NSPB500S was illuminated and placed in a checkerboard shape with a total of 9 pieces of 3x3 so as to fit into a 1.5 cm square on each side.
  • One light emitting diode Lighting was applied by applying a voltage so that the voltage became 3 V with respect to the diode.
  • the illuminance at the position of the sample was 250001X.
  • isopropanol was added so that the inside of the reaction system became 540 ppm.
  • the inside of the reaction system was set at 1 atm in an air atmosphere, and the humidity was 30%.
  • the respective concentrations of isopropanol, acetone, and carbon dioxide in the reaction system were collected from the reaction system using a syringe, and measured using FID and TCD.
  • Figure 5 shows the results of the reaction after irradiation with light.
  • a water-based sealer layer (30 ⁇ ) and an acrylic silicon-based paint layer (100 ⁇ 2 layer) are provided on a glass substrate, and the above paint is applied on one layer (30 ⁇ m: coating film 1) or two layers (30 ⁇ ). 2: Coating film 2) was provided.
  • the NO oxidation activity (removal rate) of the obtained coating film was measured by the same method as that described in the above Test Example.
  • Table 3 shows the NO removal rate (%) (coating area 5 X 5 cm).
  • titanium tetrachloride (special grade, manufactured by Kanto Chemical Co., Ltd.) was added to pure water of ice water (2 liters as water), stirred and dissolved to obtain an aqueous solution of titanium tetrachloride. While stirring 200 g of the aqueous solution with a stirrer, about 50 ml of aqueous ammonia (containing 13 wt% as NH 3 ) was added as quickly as possible. The addition amount of aqueous ammonia was adjusted so that the final pH of the aqueous solution was about 8. This turned the aqueous solution into a white slurry. After further stirring for 15 minutes, the mixture was filtered with a suction filter.
  • the precipitate collected by filtration was dispersed in 2 Om 1 of aqueous ammonia (containing 6 wt% as NH 3 ), stirred for about 20 hours with a stirrer, and suction-filtered again to obtain a white hydrolyzate.
  • the obtained white hydrolyzate was transferred to a crucible and heated at 400 ° C. for 1 hour in the air using an electric furnace to obtain a yellow product.
  • the XRD measurement results of the obtained product are shown in the upper part of FIG.
  • the lower part of Fig. 3 also shows the XRD measurement results of the white hydrolyzate dried at 50 ° C. From these results, it can be seen that the white hydrolyzate dried at 50 ° C. is amorphous, and the obtained product is anatase-type titanium dioxide.
  • the absorption spectrum of the obtained product and the white hydrolyzate dried at 50 ° C was measured under the following conditions using a Hitachi autograph spectrophotometer (U-3210) equipped with an integrating sphere.
  • the white hydrolyzate was dried at 50 ° C, whereas the reflectance at 450 nm was 61% when the reflectance at 700 nm of the obtained product was 100%.
  • the reflectance at 450 nm was 95% when the reflectance at 700 nm was 100%.
  • the ESR spectrum of the obtained product was measured. The measurement was carried out in a vacuum (0.1 Torr) at 77K or at room temperature. The measurement conditions are as follows.
  • H mn field of Mn 2 + markers
  • .DELTA..eta H variation Figure 1 (measurement temperature 77 K) of the magnetic field from ⁇ n and 2 (Measurement temperature room temperature)
  • E SR spectrum of in the dark in the upper part
  • the ESR spectrum measured with a 500W high-pressure mercury lamp irradiated without using a filter (L-42) is shown below. Comparing the upper and middle spectrums in Fig.
  • the visible light responsive photocatalyst of Reference Example 1 was also measured by ESR when the three signals were in the air, at room temperature, in the dark, and under light irradiation having a wavelength of 420 nm or more. It was a thing to be done.
  • the cloudy solution was subjected to suction filtration.
  • the amount of the white precipitate remaining on the filter paper was 131 kg.
  • the white precipitate was dispersed in 200 kg of aqueous ammonia (6%), stirred for 24 hours, and subjected to suction filtration. After filtration, the white precipitate was 108 kg.
  • the white precipitate was placed in a forced-air-type shelf dryer set at 50 ° C and dried for 4 days. The sample after drying was 17 kg.
  • the dried sample was placed in an alumina crucible (20 x 20 x 5 cm) at lkg, placed in a gas furnace, a thermocouple was placed on the sample surface, and the sample was fired for 1 hour at a temperature of 400 ° C.
  • the white matter attached to the filter paper was stirred eight times in ammonia water adjusted to pH 11 and filtered again eight times, and washed to obtain a white powder.
  • the obtained powder was dried at 50 ° C. to obtain a sample powder.
  • the BET surface area of the obtained hydrolyzate (sample powder) was 308.7 m 2 / g. 8 g of the obtained sample powder was placed in a crucible, transferred to an electric furnace, and baked at 400 ° C for 60 minutes to obtain 6.3 g of a bright yellow powder having a BET surface area of 89.4 m 2 / g. Was.
  • An X-ray diffraction (XRD) test of this powder shows that it contains anatase-type titanium oxide.
  • the ESR spectrum of the obtained powder was measured.
  • the measurement was performed at 77 K in a vacuum (0.
  • the measurement conditions are the same as in Reference Example 1.
  • Fig. 6 shows the ESR spectrum measured with light irradiated through a filter (L-42) that cuts light below 420 nm (using a high-pressure mercury lamp of 500 W). .
  • the ESR spectrum under ⁇ black was also measured, but practically no signal was observed.
  • a main signal with a g-value of 2.004 to 2.007 and two sub-signals with a g-value of 1.985 to 1.986 and 2.024 were observed. .
  • the ESR spectrum of the obtained material was measured.
  • the measurement was performed at 77 K in a vacuum (00 ⁇ ⁇ rr).
  • the measurement conditions are the same as in Reference Example 1.
  • Fig. 7 shows the ESR spectrum measured under the condition that light was irradiated through a filter (L-42) that cuts light of 420 nm or less (using a high-pressure mercury lamp of 500 W). .
  • the main signal whose g-value power is S2.004 to 2.007 is And two sub-signals with g-values of 1.895 to 1.896 and 2.024.
  • Fig. 8 ESR measured with light irradiated through a filter (L-42) that cuts light below 420 nm (using a 500 W high-pressure mercury lamp) Indicates the spectrum.
  • the main signal has a g value of 2.004 to 2.007, and g values of 1.985 to 1.986 and 2.024. Two minor signals were observed.
  • the present invention it is possible to provide a method and an apparatus for activating a photocatalyst using a light-emitting diode having a high visible light content or containing only visible light as a light source.

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Abstract

La présente invention concerne un procédé d'activation de photocatalyseur conçu pour l'application d'un faisceau de diode électroluminescente sur un photocatalyseur sensible à la lumière visible et s'activant à une lumière d'au moins 420 nm. L'invention concerne également un dispositif comportant une couche contenant un photocatalyseur sensible à la lumière visible appliquée sur un substrat de diode électroluminescente. L'invention concerne enfin un dispositif comprenant une diode électroluminescente, un photocatalyseur sensible à la lumière visible, et un organe de transfert de la lumière servant au transfert de la lumière de la diode électroluminescente sur le photocatalyseur sensible à la lumière visible.
PCT/JP2001/011576 2000-12-28 2001-12-27 Procédé d'activation de photocatalyseur et dispositif à cet effet WO2002053284A1 (fr)

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JP2007298328A (ja) * 2006-04-28 2007-11-15 Shunichi Nakai 光触媒活性度評価装置
US8746929B2 (en) 2011-10-14 2014-06-10 GE Lighting Solutions, LLC Device with combined features of lighting and air purification

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CN101485958B (zh) * 2009-01-15 2012-03-14 浙江大学 用于降解烟气二恶英的光催化反应器及光催化剂活化方法
CN102091644B (zh) * 2010-12-27 2012-12-12 湖北工业大学 一种碳-氮-氯共掺杂纳米二氧化钛光催化剂的制备方法
CN102267768A (zh) * 2011-07-06 2011-12-07 西北农林科技大学 一种石灰-粉煤灰联合处理高浓度含氟废水的方法

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JPH11328743A (ja) * 1998-05-20 1999-11-30 Victor Co Of Japan Ltd 光ディスク及びその記録再生装置
JPH11333304A (ja) * 1998-05-22 1999-12-07 Kankyo Device Kenkyusho:Kk 光触媒及びその利用
JP2000037615A (ja) * 1998-07-23 2000-02-08 Mitsubishi Electric Corp 光源一体型光触媒装置およびその製法
WO2000010706A1 (fr) * 1998-08-21 2000-03-02 Ecodevice Laboratory Co., Ltd. Photocatalyseur de type a rayonnement visible et son procede de production
JP2000143241A (ja) * 1998-11-11 2000-05-23 Nippon Alum Co Ltd 酸化チタン微粒子の製造方法
JP2000325799A (ja) * 1999-05-20 2000-11-28 Sony Corp 光触媒装置
EP1095908A1 (fr) * 1999-10-29 2001-05-02 Sumitomo Chemical Company, Limited Oxide de titane, photocatalyseur et composition utilisant le photocatalysateur
JP3215698B1 (ja) * 2000-01-31 2001-10-09 有限会社環境デバイス研究所 可視光応答材料及びその製造方法

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US5919422A (en) * 1995-07-28 1999-07-06 Toyoda Gosei Co., Ltd. Titanium dioxide photo-catalyzer
JPH11328743A (ja) * 1998-05-20 1999-11-30 Victor Co Of Japan Ltd 光ディスク及びその記録再生装置
JPH11333304A (ja) * 1998-05-22 1999-12-07 Kankyo Device Kenkyusho:Kk 光触媒及びその利用
JP2000037615A (ja) * 1998-07-23 2000-02-08 Mitsubishi Electric Corp 光源一体型光触媒装置およびその製法
WO2000010706A1 (fr) * 1998-08-21 2000-03-02 Ecodevice Laboratory Co., Ltd. Photocatalyseur de type a rayonnement visible et son procede de production
JP2000143241A (ja) * 1998-11-11 2000-05-23 Nippon Alum Co Ltd 酸化チタン微粒子の製造方法
JP2000325799A (ja) * 1999-05-20 2000-11-28 Sony Corp 光触媒装置
EP1095908A1 (fr) * 1999-10-29 2001-05-02 Sumitomo Chemical Company, Limited Oxide de titane, photocatalyseur et composition utilisant le photocatalysateur
JP3215698B1 (ja) * 2000-01-31 2001-10-09 有限会社環境デバイス研究所 可視光応答材料及びその製造方法

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007298328A (ja) * 2006-04-28 2007-11-15 Shunichi Nakai 光触媒活性度評価装置
US8746929B2 (en) 2011-10-14 2014-06-10 GE Lighting Solutions, LLC Device with combined features of lighting and air purification

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