WO2013094574A1 - 混合原子価銅化合物担持酸化タングステンおよびその製造方法 - Google Patents

混合原子価銅化合物担持酸化タングステンおよびその製造方法 Download PDF

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WO2013094574A1
WO2013094574A1 PCT/JP2012/082708 JP2012082708W WO2013094574A1 WO 2013094574 A1 WO2013094574 A1 WO 2013094574A1 JP 2012082708 W JP2012082708 W JP 2012082708W WO 2013094574 A1 WO2013094574 A1 WO 2013094574A1
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tungsten oxide
copper
mixed
supported
compound
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French (fr)
Japanese (ja)
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康弘 細木
靖 黒田
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Resonac Holdings Corp
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Showa Denko KK
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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K33/00—Medicinal preparations containing inorganic active ingredients
    • A61K33/24—Heavy metals; Compounds thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K33/00—Medicinal preparations containing inorganic active ingredients
    • A61K33/24—Heavy metals; Compounds thereof
    • A61K33/34—Copper; Compounds thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P31/00—Antiinfectives, i.e. antibiotics, antiseptics, chemotherapeutics
    • A61P31/04—Antibacterial agents
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P31/00—Antiinfectives, i.e. antibiotics, antiseptics, chemotherapeutics
    • A61P31/12—Antivirals
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P43/00—Drugs for specific purposes, not provided for in groups A61P1/00-A61P41/00
    • 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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/06—Halogens; Compounds thereof
    • B01J27/132—Halogens; Compounds thereof with chromium, molybdenum, tungsten or polonium
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/39—Photocatalytic properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
    • B01J35/45—Nanoparticles
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/70—Catalysts, in general, characterised by their form or physical properties characterised by their crystalline properties, e.g. semi-crystalline
    • 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
    • B01J37/03—Precipitation; Co-precipitation
    • B01J37/031—Precipitation
    • 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
    • B01J2235/00—Indexing scheme associated with group B01J35/00, related to the analysis techniques used to determine the catalysts form or properties
    • 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
    • B01J2235/00—Indexing scheme associated with group B01J35/00, related to the analysis techniques used to determine the catalysts form or properties
    • B01J2235/15—X-ray diffraction
    • 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
    • B01J2235/00—Indexing scheme associated with group B01J35/00, related to the analysis techniques used to determine the catalysts form or properties
    • B01J2235/30—Scanning electron microscopy; Transmission electron microscopy

Definitions

  • the present invention relates to tungsten oxide carrying a mixed valence copper compound, a method for producing the same, an antiviral agent, and a photocatalyst. More specifically, it has high photocatalytic activity for antibacterial, antiviral, deodorizing, deodorizing, air purification, water purification, etc. under irradiation of visible light having a wavelength of 400 nm or more, and antibacterial and antiviral in the dark.
  • the present invention relates to a useful tungsten oxide supporting a mixed valence copper compound, a method for producing the same, an antiviral agent, and a photocatalyst.
  • a photocatalyst using tungsten oxide particles alone generates holes and electrons in the valence band and the conduction band by photoexcitation when irradiated with visible light, but the conduction band is lower than the redox level of oxygen. Therefore, oxygen cannot be reduced by electrons excited in the conduction band. Therefore, the amount of active oxygen species produced is insufficient, and does not exhibit photocatalytic activity in an environment where visible light is irradiated.
  • a catalyst having a promoter supported on the surface of tungsten oxide has been proposed.
  • a tungsten oxide photocatalyst carrying copper hydroxide or copper oxide can exhibit photocatalytic activity under irradiation with visible light (Patent Documents 1 and 2).
  • tungsten oxide supporting a noble metal such as platinum functions as an antiviral agent (Patent Document 3).
  • these photocatalysts have excellent functions such as deodorization, their catalytic functions as antiviral agents are not so high. Furthermore, there is no catalytic function as an antiviral agent under dark conditions.
  • An object of the present invention is to provide a copper compound-supported tungsten oxide having a deodorizing function under visible light irradiation and high antiviral activity under dark conditions, and a method for producing the same.
  • the present inventors have carried out a high deodorizing function under visible light irradiation by supporting a mixed valence copper iodide as a copper compound on tungsten oxide particles. It has been found that a copper compound-supported tungsten oxide having high antiviral properties under dark conditions can be obtained.
  • the present invention has been completed based on such findings.
  • a photocatalyst is a substance having a semiconductor property, which generates holes and electrons by absorbing light of a band gap or more and exhibits a catalytic action by participating in a chemical reaction.
  • the co-catalyst refers to a substance that captures holes or electrons generated by the photocatalyst, increases the amount of adsorption of the reaction substrate, or lowers the activation energy of the chemical reaction that occurs on the photocatalyst surface.
  • the divalent component of the copper compound functions as a promoter for the tungsten oxide photocatalyst.
  • a compound having a mixed valence means a compound that does not follow the law of constant proportion, such as an interstitial compound or a lattice defect compound such as an oxide, sulfide, hydride, carbide, boride, etc. of a transition metal.
  • the virus means a DNA virus and an RNA virus, but also includes a bacteriophage (hereinafter also abbreviated as “phage”) which is a virus that infects bacteria. In general, it refers to animal viruses, plant viruses, and bacterial viruses, and is not particularly limited.
  • the present invention provides the following [1] to [13].
  • [1] A mixed valence copper compound-supported tungsten oxide comprising tungsten oxide supporting monovalent and divalent mixed valence copper iodide.
  • [2] The mixed valence copper compound-supported tungsten oxide according to [1], wherein the composition ratio of the copper iodide is CuIx (1 ⁇ x ⁇ 2).
  • [3] The mixed valence copper compound-supported tungsten oxide according to [2], wherein the composition ratio of the copper iodide is CuIx (1.05 ⁇ x ⁇ 1.8).
  • [4] The mixed valence copper compound supported according to any one of [1] to [3], wherein the crystal structure of the copper iodide is at least one of zinc blende structure, wurtzite structure, and sodium chloride structure Tungsten oxide.
  • [5] The mixed valence copper compound-supported tungsten oxide according to any one of [1] to [4], wherein the copper iodide has a particle size of 100 nm or less.
  • the amount of the mixed-valence copper compound supported is 0.1 to 50 parts by mass in terms of copper metal with respect to 100 parts by mass of the tungsten oxide, according to any one of [1] to [5].
  • a mixed valence copper compound-supported tungsten oxide is 0.1 to 50 parts by mass in terms of copper metal with respect to 100 parts by mass of the tungsten oxide, according to any one of [1] to [5].
  • tungsten oxide powder and copper (II) chloride are added to a polar solvent and mixed, and sodium iodide is added to precipitate copper iodide on the tungsten oxide surface.
  • a virus inactivation and deodorization method wherein the mixed valence copper compound-supported tungsten oxide according to any one of [1] to [6] is used to inactivate and deodorize a virus.
  • the present invention it is possible to provide a mixed valence copper compound-supported tungsten oxide excellent in virus inactivation (antiviral properties) in the dark and photocatalytic activity in visible light, and a method for producing the same.
  • FIG. 2 is an X-ray diffraction pattern of mixed oxide copper compound-supported tungsten oxide of Example 1.
  • FIG. 2 is an electron image photograph of the mixed valence copper compound-supported tungsten oxide of Example 1 using a scanning electron microscope. The white part is a mixed-valence copper compound.
  • FIG. 3 is a diagram showing the antiviral performance of Example 1.
  • the mixed valence copper compound-supported tungsten oxide of the present invention (simply referred to as “copper compound-supported tungsten oxide”) will be described.
  • the copper compound-supported tungsten oxide of the present invention is made of tungsten oxide supporting monovalent and divalent mixed valence copper iodide.
  • the mixed valence copper compound-supported tungsten oxide of the present invention since monovalent and divalent mixed valence copper iodide is supported on the surface of tungsten oxide, copper has both a monovalent component and a divalent component. Have. Therefore, it has excellent antiviral properties in the dark due to the monovalent copper component, and the copper in the divalent state functions as a promoter for the tungsten oxide photocatalyst, so that it also has a photocatalytic function such as deodorization by visible light absorption. Excellent.
  • Monovalent and divalent mixed valence copper iodides may be supported as a single compound, that is, as a compound in a mixed valence state. Supporting as one compound is preferable because it is simple in the production process. In addition to the compound in the mixed valence state, a monovalent copper compound and / or a divalent copper compound may be further supported. Next, each component of the mixed valence copper compound-supported tungsten oxide will be described.
  • copper iodide is known to have a zinc blend structure, a wurtzite structure, and a sodium chloride structure
  • copper iodide having any crystal structure may be supported.
  • a zinc-blende structure is preferably used because of the simplicity of the manufacturing method.
  • a solid solution of a compound having the same structure such as ZnO or GaN and copper iodide may be formed.
  • the molar ratio of Cu to I (I / Cu) is not particularly limited. That is, monovalent and divalent mixed valence copper iodide is a zinc blende structure, a wurtzite structure structure, or a sodium chloride structure, but has a 1: 1 ratio of Cu to I. It is preferable that the mixed valence copper compound CuIx (1 ⁇ x ⁇ 2) deviates from the copper compound CuI which is (molar ratio). Although the state of excess iodine is unknown, it may be substituted or penetrated into the crystal structure of CuI or may be adsorbed on the surface.
  • the crystal structure of the mixed valence compound CuIx (1 ⁇ x ⁇ 2) can be identified by XRD. If a diffraction peak is observed in the vicinity of 25.5 ° in addition to the X-ray diffraction peak of WO 3 , it can be confirmed that CuIx having a zinc flash structure exists. Further, when the amount of copper iodide supported is small, an X-ray diffraction peak may not be observed. However, by detecting Cu and I in elemental analysis such as fluorescent X-ray and SEM-EDX, CuIx (1 ⁇ X ⁇ 2) exists and the value of x can be verified.
  • the size of CuIx (1 ⁇ x ⁇ 2) particles supported on tungsten oxide is not particularly limited, but is preferably 1 ⁇ m or less, more preferably 500 nm or less, and even more preferably 100 nm or less. preferable. When the thickness is 100 nm or less, the contact probability of CuIx (1 ⁇ x ⁇ 2) with a virus increases, and high antiviral performance is exhibited.
  • the supported amount of CuIx (1 ⁇ x ⁇ 2) is preferably 0.1 to 50 parts by mass, and 0.3 to 20 parts by mass in terms of copper metal with respect to 100 parts by mass of tungsten oxide. More preferred is 1 to 5 parts by mass.
  • the presence of 0.1 part by mass or more is preferable because the abundance ratio of CuIx (1 ⁇ x ⁇ 2) is increased and high antiviral performance is exhibited.
  • the amount is 50 parts by mass or less, inhibition of light absorption by CuIx (1 ⁇ x ⁇ 2) occurs, and the photocatalytic activity is prevented from being lowered.
  • the monovalent component of CuIx (1 ⁇ x ⁇ 2) supported on the surface of tungsten oxide exhibits high inactivation performance against viruses, and the covalent divalent Cu is present.
  • the component supplements the excited electrons of WO 3 and exhibits high photocatalytic performance.
  • x should be larger than 1 and smaller than 2, more preferably from 1.05 to 1.8, still more preferably from 1.1 to 1.7, and from 1.15 to 1.6. Is even more preferable.
  • the copper compound-supported tungsten oxide of the present invention is one in which monovalent and divalent mixed valence copper iodide is supported on tungsten oxide (WO 3 ). These components may be supported. However, from the viewpoint of improving antiviral performance and photocatalytic performance, the amount of other components supported is preferably 10 parts by mass or less, more preferably 100 parts by mass relative to the amount of mixed valence copper iodide supported by 100 parts by mass. It is 5 parts by mass or less, more preferably 1 part by mass or less, and it is further preferred that no other components are supported.
  • the specific surface area of the tungsten oxide particles constituting the copper compound-supported tungsten oxide is not particularly limited, but is preferably 3 to 100 m 2 / g. When it is 100 m 2 / g or less, handleability is excellent, and when it is 3 m 2 / g or more, antiviral properties and photocatalytic performance are excellent. From this point of view, the particle size of the tungsten oxide is more preferably 5 ⁇ 80m 2 / g, 7 ⁇ 40m 2 / g is more preferable.
  • support tungsten oxide of this invention includes the process of suspending a tungsten oxide in the solution which melt
  • Methods for supporting copper iodide on tungsten oxide include a kneading method in which WO 3 powder and CuI powder are mixed, a colloid adsorption method in which CuI colloid is adsorbed on WO 3 powder, and a copper salt is reacted with iodine in a liquid phase. Any of the liquid phase precipitation methods for depositing on WO 3 may be used, but a simple liquid phase precipitation method is preferred in terms of the production method.
  • tungsten oxide powder and a copper divalent salt (copper chloride, copper acetate, copper sulfate, copper nitrate, etc.), preferably copper (II) chloride
  • a copper divalent salt copper chloride, copper acetate, copper sulfate, copper nitrate, etc.
  • copper (II) chloride preferably copper (II) chloride
  • an iodine compound hydrogen iodide, iodate
  • sodium, ammonium iodide, sodium iodide, potassium iodide, etc. preferably sodium iodide is added to deposit copper iodide on the tungsten oxide surface.
  • the Cu: I ratio deviates from the stoichiometric ratio of CuI, and the mixed-valence copper-supported tungsten oxide coexists with monovalent and divalent copper.
  • the polar solvent only needs to dissolve the copper divalent salt and the iodine compound, and is, for example, water.
  • the amount of iodine ion added is preferably 1.1 times or more, more preferably 1.2 times or more, and further preferably 1.5 times or more with respect to the number of moles of copper. By adding 1.1 times or more, crystalline copper iodide can be efficiently produced on tungsten oxide. On the other hand, when the amount of iodine ion added is large, there is no problem if x of CuIx (1 ⁇ x ⁇ 2) is less than 2.
  • a solution in which tungsten oxide powder and a copper divalent salt (copper chloride, copper acetate, copper sulfate, copper nitrate, etc.), preferably copper (II) chloride, are added to a polar solvent causes aggregation of the formed CuI.
  • the pH of the solution is preferably 2 to 8, and more preferably 3 to 7. When the pH is 8 or less, the dissolution of tungsten oxide is satisfactorily prevented.
  • the pH of the solution is an alkaline component (sodium hydroxide aqueous solution, potassium hydroxide aqueous solution, calcium hydroxide aqueous solution, lime water, sodium carbonate aqueous solution, ammonia aqueous solution, triethylamine aqueous solution, pyridine aqueous solution, ethylenediamine aqueous solution, sodium hydrogen carbonate aqueous solution, etc. ), Acidic components (hydrochloric acid, sulfuric acid, nitric acid, citric acid, oxalic acid, etc.) can be added to obtain a desired value. Further, a dispersing agent such as gelatin or glucose may coexist.
  • a dispersing agent such as gelatin or glucose may coexist.
  • the application form of the mixed valence copper compound-supported tungsten oxide of the present invention thus obtained is not particularly limited, and can be used in a dark place in the presence of an arbitrary light beam.
  • the mixed valence copper compound-supported tungsten oxide of the present invention can be used in the presence of water (for example, in water or seawater), in a dry state (for example, in a low humidity state in winter), in a high humidity state, or in an organic matter. Even in the presence of coexistence, it has high virus inactivating ability and photocatalytic ability such as deodorization, and can inactivate viruses continuously.
  • buildings such as hospitals and factories, machine tools and measuring devices, interiors and parts of electrical appliances (inside refrigerators, washing machines, dishwashers, etc. It can be applied to any object such as a filter.
  • dark places include the inside of machines, storage rooms for refrigerators, and hospital facilities (waiting rooms, operating rooms, etc.) that become dark places at night or when not in use, but are limited to these. There is no.
  • a product incorporating a light source for irradiating ultraviolet rays by coating titanium oxide on a ceramic filter of an air washer has been proposed.
  • the present invention also provides a virus inactivation and deodorization method in which a mixed valence copper compound-supported tungsten oxide is used to inactivate and deodorize a virus.
  • the present invention also provides the use of mixed valence copper compound-supported tungsten oxide as an antiviral agent.
  • the present invention provides the use of mixed valence copper compound-supported tungsten oxide as a photocatalyst. Further, in order to improve the activity of the mixed valence copper compound-supported tungsten oxide, it may be used in combination with an adsorption aid such as TiO 2 or zeolite.
  • the mixed valence copper compound-supported tungsten oxide of the present invention when there are substances that adversely affect the environment, such as organic compounds such as aldehydes, the mixed valence copper compound-supported tungsten oxide of the present invention has a concentration of organic matter when compared with a dark place under light irradiation. And increase the concentration of carbon dioxide, which is an oxidative decomposition product. In addition, when brought into contact with bacteriophage, it can inactivate the bacteriophage in both dark and light places.
  • Carbon dioxide generation rate (deodorization function)
  • a glass petri dish having a diameter of 1.5 cm was placed in a sealed glass reaction vessel (capacity 0.5 L), and 0.3 g of the powder obtained in each of the examples and comparative examples was placed on the petri dish. .
  • the inside of the reaction vessel was replaced with a mixed gas having a volume ratio of oxygen and nitrogen of 1: 4, and 5.2 ⁇ L of water (corresponding to a relative humidity of 50% (25 ° C.)) and 5.1% acetaldehyde (25 ° C. ⁇ 5.0 mL) was sealed and irradiated with visible light from the outside of the reaction vessel.
  • a light source in which a filter (trade name: L-42, Asahi Techno Glass Co., Ltd.) that cuts ultraviolet rays having a wavelength of 400 nm or less was attached to a xenon lamp was used.
  • the evolution rate of carbon dioxide which is an oxidative decomposition product of acetaldehyde, was measured over time by gas chromatography.
  • the photocatalytic activity was evaluated by the amount of carbon dioxide generated per hour.
  • a glass plate having a thickness of about 5 mm was placed on the filter paper, and a glass plate (50 mm ⁇ 50 mm ⁇ 1 mm) coated with the powder obtained in each example and comparative example was placed thereon.
  • the powder is dispersed in an ethanol solvent, and the dispersion is prepared so that the solid content is 2.0 mg / 25 (cm) 2 over the entire surface of the glass plate (50 mm ⁇ 50 mm ⁇ 1 mm). What applied and evaporated the solvent on a glass plate was used.
  • a white fluorescent lamp is used as a light source, light of 400 nm or less is cut by an ultraviolet cut filter (N-113 manufactured by Nitto Resin Industry Co., Ltd.), and the illuminance is 800 lux (illuminance meter manufactured by Topcon Corporation: TOPCON IM A plurality of sets for measurement were allowed to stand at the position of (measured at -5). After a predetermined time, the phage concentration of the sample on the glass plate was measured.
  • the phage concentration was measured by the following method.
  • the sample on the glass plate was infiltrated into 10 mL of a recovery liquid (SM Buffer) and shaken for 10 minutes with a shaker.
  • the phage recovery solution was appropriately diluted, mixed with a separately cultured culture solution of E. coli (NBRC13965) (OD 600 > 1.0, 1 ⁇ 10 8 CFU / mL), and then stirred at 37 ° C.
  • the phages were infected with E. coli by standing in a thermostatic chamber for 10 minutes. This solution was spread on an agar medium and cultured at 37 ° C. for 15 hours, and the number of phage plaques was visually measured.
  • the phage concentration N was determined by multiplying the number of plaques obtained by the dilution factor of the phage recovery solution.
  • the relative phage concentration (LOG (N / N 0 )) was determined from the initial phage concentration N 0 and the phage concentration N after a predetermined time.
  • the apparatus used for the measurement was X'pert PRO made by Panallytical.
  • Example 1 5 g of tungsten oxide powder was added to 200 mL of an aqueous copper chloride solution having a concentration of 0.125% by mass (corresponding to 5 parts by mass as copper with respect to tungsten oxide). Next, NaOHaq was added to adjust the pH to 5.5, and then a 2-fold molar amount of sodium iodide was added to copper, followed by stirring for 30 minutes (iodine ion addition step). Then, it was washed and collected by suction filtration, dried at 120 ° C. for one day and night, and then pulverized in an agate mortar to obtain a copper compound-supported tungsten oxide powder. X measured by elemental analysis was 1.3. The results are shown in Table 1.
  • Example 2 A tungsten compound-supported tungsten oxide powder was obtained in the same manner as in Example 1 except that the equivalent of 1 part by mass of copper as tungsten was used. The x measured by elemental analysis was 1.2.
  • Example 3 A copper compound-supported tungsten oxide powder of the present invention was obtained in the same manner as in Example 2 except that HClaq was added instead of NaOHaq to adjust the pH to 2.1.
  • the x measured by elemental analysis was 1.2.
  • Example 4 5 g of tungsten oxide powder was added to 200 mL of a copper chloride aqueous solution having a concentration of 0.025 mass% (corresponding to 1 mass part as copper with respect to tungsten oxide) to obtain a mixed solution having a pH of 4.4. To this mixed solution, without adjusting the pH, a 2-fold molar amount of sodium iodide was added to copper and stirred for 30 minutes (iodine ion addition step). Then, it was washed and collected by suction filtration, dried at 120 ° C. for one day and night, and then pulverized in an agate mortar to obtain a copper compound-supported tungsten oxide powder. The x measured by elemental analysis was 1.2.
  • Example 5 A copper compound-supported tungsten oxide powder was obtained in the same manner as in Example 1 except that the equivalent of 20 parts by mass of copper as tungsten was used. X measured by elemental analysis was 1.5.
  • Comparative Example 1 5 g of tungsten oxide powder was added to 200 mL of a copper chloride aqueous solution having a concentration of 0.0025% by mass (equivalent to 0.1 part by mass as copper with respect to tungsten oxide). Next, after heat treatment at 90 ° C. for 1 hour with stirring, it was washed and collected by suction filtration, dried at 120 ° C. for one day and night, and then pulverized in an agate mortar to obtain a tungsten oxide powder modified with copper ions. .
  • Comparative Example 3 5 g of tungsten oxide powder was added to 200 mL of a copper chloride aqueous solution having a concentration of 0.025 mass% (corresponding to 1 mass part as copper with respect to tungsten oxide) to obtain a mixed solution having a pH of 4.4. Without adjusting the pH to this mixed solution, an equimolar amount of sodium iodide was added to copper and stirred for 30 minutes (iodine ion addition step). Then, it was washed and collected by suction filtration, dried at 120 ° C. for one day and night, and then pulverized in an agate mortar to obtain a tungsten oxide photocatalyst supported on CuIx (x ⁇ 1) 1%. X measured by elemental analysis was 0.9.
  • Comparative Example 4 5 g of tungsten oxide powder was added to 200 mL of an aqueous copper chloride solution having a concentration of 0.125% by mass (corresponding to 5 parts by mass as copper with respect to tungsten oxide) to obtain a mixed solution having a pH of 4.4. Without adjusting the pH to this mixed solution, an equimolar amount of sodium iodide was added to copper and stirred for 30 minutes (iodine ion addition step). Then, it was washed and collected by suction filtration, dried at 120 ° C. for one day and night, and then pulverized in an agate mortar to obtain a tungsten oxide photocatalyst supported on CuIx (x ⁇ 1) 5%. X measured by elemental analysis was 1.0.
  • Comparative Example 5 5 g of titanium oxide powder is added to 200 mL of an aqueous copper chloride solution having a concentration of 0.0125% by mass (corresponding to 0.5 parts by mass as copper with respect to tungsten oxide), and 4 times the amount of glucose and 8 times the amount of mol of copper. Of NaOH was added and stirred at 90 degrees for 1 hour (iodine ion addition step). Then, it was washed and collected by suction filtration, dried at 80 ° C. for one day and night, and then pulverized in an agate mortar to obtain a CuxO-supported titanium oxide photocatalyst.
  • Table 1 shows the evaluation results of carbon dioxide generation rate (deodorizing function) and anti-phage performance (antiviral activity) obtained for the photocatalyst powders of Examples 1 to 5 and Comparative Examples 1 to 4 described above.
  • the mixed valence copper compound-supported tungsten oxide of the present invention is a copper ion-supported tungsten oxide photocatalyst (Comparative Example 1), a stoichiometric compound CuI-supported tungsten oxide photocatalyst.
  • the generation rate of carbon dioxide was almost the same level, but the antiviral performance was up to 3 times higher under visible light irradiation.
  • the mixed valence copper compound-supported tungsten oxide of the present invention (Examples 1 to 5) exhibited high antiviral performance even in the dark.
  • Comparative Examples 1, 3, and 4 show almost no antiviral performance in the dark. This is because Comparative Example 1 does not contain any copper monovalent component, and Comparative Examples 3 and 4 are insufficient in generating CuIx (1 ⁇ x ⁇ 2).
  • Comparative Example 2 shows high antiviral performance at the same level as Example 1 in both the dark place and the light place, but shows almost no activity in the decomposition of acetaldehyde. This indicates that CuI alone does not show visible light responsive photocatalysis.
  • Example 5 the antiviral performance was lower than that of Example 1 in both the dark place and the light place, and the acetaldehyde degradation activity was about 60% lower than that of the Example. This indicates that the photocatalytic action of CuxO / TiO 2 is lower than that of the mixed-valence copper compound-supported tungsten oxide of the present invention.
  • the mixed valence copper compound-supported tungsten oxide of the present invention has high productivity, can exhibit high catalytic activity under visible light irradiation, and can exhibit high antiviral performance in the dark. Recognize.
  • the mixed valence copper compound-carrying tungsten oxide of the present invention is a photocatalyst that can express high catalytic activity under irradiation with visible light, and a catalyst that can express antiviral performance in the dark. Effective for deodorization, deodorization, air purification, water quality purification, etc.

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US10213780B2 (en) * 2014-09-12 2019-02-26 Nitto Denko Corporation Multivalence semiconductor photocatalytic materials
CN111613521B (zh) * 2020-05-08 2022-04-05 中国科学院宁波材料技术与工程研究所 一种化合物薄膜、制备方法及其应用

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