WO2006074697A1 - Photocatalyseur bloque en tant qu'agent de clarification de l'environnement - Google Patents

Photocatalyseur bloque en tant qu'agent de clarification de l'environnement Download PDF

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Publication number
WO2006074697A1
WO2006074697A1 PCT/EP2005/000355 EP2005000355W WO2006074697A1 WO 2006074697 A1 WO2006074697 A1 WO 2006074697A1 EP 2005000355 W EP2005000355 W EP 2005000355W WO 2006074697 A1 WO2006074697 A1 WO 2006074697A1
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WIPO (PCT)
Prior art keywords
photocatalyst
carpet
caged
weight
finishing composition
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PCT/EP2005/000355
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English (en)
Inventor
Jan De Clerck
Original Assignee
Domo Oudenaarde Nv
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Application filed by Domo Oudenaarde Nv filed Critical Domo Oudenaarde Nv
Priority to PCT/EP2005/000355 priority Critical patent/WO2006074697A1/fr
Publication of WO2006074697A1 publication Critical patent/WO2006074697A1/fr

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    • 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
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/88—Handling or mounting catalysts
    • B01D53/885—Devices in general for catalytic purification of waste gases
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/46—Oxides or hydroxides of elements of Groups 4 or 14 of the Periodic Table; Titanates; Zirconates; Stannates; Plumbates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/80—Type of catalytic reaction
    • B01D2255/802—Photocatalytic

Definitions

  • the present invention relates to an environmental clarifying agent suitable for removing unpleasant odors, decomposing and removing harmful substances and contaminants in the air by a photocatalytic action.
  • the present invention relates to products treated with such clarifying agent.
  • VOC volatile organic compounds
  • the main cause is solvents used for adjustment of synthetic adhesives, for example, formaldehyde (it is also a carcinogen) derived from formalin.
  • surface treatments are often used in order to protect floor coverings and/or to polish them.
  • synthetic resin for example, acryl resin emulsified polishing agent and a product filled in a synthetic resin bottle with a nozzle for spray is generally used.
  • polishing agents often contain solvents harmful for human body.
  • living spaces of residences and offices may carry airborne malodorous substances including sulfur compounds such as hydrogen sulfide and methyl mercaptan, nitrogen compounds such as ammonia, and other compounds such as fatty acid. To provide a comfort of living environment, it is desirable to treat the contaminated air for removal of the malodorous substances.
  • titanium oxide When irradiated with light, titanium oxide produces electrons with a powerful reductive action and holes with a powerful oxidative action, and decomposes any molecular species with which it comes into contact by a redox action.
  • This action of titanium oxide namely, its photocatalytic action, has been utilized for removing unpleasant odors, decomposing and removing harmful substances and contaminants in the air.
  • This method has the advantages that it can be repeated over and over merely by utilizing titanium oxide and light, the reaction products are harmless carbon dioxide and so on, and titanium dioxide itself is a safe and nontoxic substance, so it affords safe and easy antibacterial action, and in principle it can be used semi-permanently.
  • titanium oxide when titanium oxide is mixed into a substrate, its powerful photocatalytic action can decompose not only harmful substance but even the substrate, leading to deterioration of the substrate coated or treated therewith so these products cannot be used repeatedly or over extended periods.
  • the present invention provides a caged photocatalyst as an environmental clarifying agent said caged photocatalyst comprising a nano photocatalyst enclosed in a calcium carbonate casing.
  • said nano photocatalyst can be selected from the group comprising nano size TiO 2 , ZnO, SiO 3 ; Ti 1-x Sn x O 2 , SrTiO 3 , Fe 2 O 3 , CdS, CdSe, WO 3 , FeTiO 3 , GaP, GaAs, GeAs, RuO 2 , MoS 3 , LaRhO 3 , CdFeO 3 , Bi 2 O 3 , MoS 2 , In 2 O 3 , CdO, SnO 2 , SiC, InP and/or mixture thereof.
  • the calcium carbonate casing is provided with specific pore size wherein harmful substances in the air, or unpleasant odors, can be easily decomposed and eliminated by the photocatalytic action of titanium oxide.
  • said substrate When using the caged photocatalyst to impart air clarifying properties to a substrate, said substrate will not be in contact with the photocatalyst, and will therefore not be degraded not decomposed by its photocatalytic action.
  • the substrate in contact with the caged photocatalyst is protected by the calcium carbonate casing.
  • the caged photocatalyst or a composition comprising it exhibits an efficient catalytic decomposing action under irradiation not only with ultraviolet rays but also visible light, allowing the removal of unpleasant odors, the decomposition and removal of harmful substances and contaminants in the air and furthermore, when a substrate is treated with such caged photocatalyst or a composition comprising it, the substrate will not be prone to decomposition and it's the deodorizing properties of the substrate can be sustained for an extended period of time.
  • the present caged photocatalyst when added to a substrate or kneaded into a binder provides excellent durability, with no degradation of the binder or the substrate.
  • the present caged photocatalyst not only adsorbs unpleasant odors or harmful substances in the air, but also decomposes and removes them, and allows an environment to be cleaned effectively, economically, and safely, without modifying or degrading the substrate provided therewith.
  • the present invention also provides a photocatalyst composition comprising the caged photocatalyst according to the invention, together with a binder and a solvent.
  • the present invention also encompasses the use of a photocatalyst composition according to the invention for imparting air clarifying properties to a substrate.
  • the substrate is a carpet.
  • the present invention also provides a finishing composition for floor coverings such as carpets comprising the caged photocatalyst according to the invention.
  • the finishing composition according to the invention comprises (a) the photocatalyst composition according to the invention (b) a liquid carrier and optionally (c) a coarcervate.
  • said finishing composition comprises the photocatalyst composition in an amount between 1 to 50 % by weight, preferably from 5 to 35 % by weight, more preferably from 7 to 20 % by weight, yet more preferably from 7 to 13 % by weight, most preferably from 8 to 9 %.
  • the present invention also encompasses the use of a finishing composition according to the invention, for the treatment of carpets.
  • the present invention further provides a method for the preparation of a carpet having air clarifying properties wherein said method comprising the steps of: providing a finishing composition according to the present invention, and applying said finishing composition onto a carpet thereby obtaining a carpet having air clarifying properties.
  • the present invention also encompasses subtrates such as floor coverings for example carpet having air clarifying properties obtained by the methods according to the invention.
  • subtrates such as floor coverings for example carpet having air clarifying properties obtained by the methods according to the invention.
  • FIG 1 illustrates the experimental arrangement for the assessment of degradation of volatile organic compound (VOC) by the floor covering according to the invention.
  • Figure 2 illustrates the results of an experiment measuring the catalytic activity of TiO2 coated carpet by the analysis of the effect of the coated carpets on formaldehyde degradation under continuous aeration.
  • Figure 3 illustrates the results of an experiment measuring the catalytic activity of TiO2 coated carpet by the analysis of the effect of the coated carpets on benzene degradation under continuous aeration.
  • Figure 4 illustrates the results of olfactory evaluation of the tobacco odor deodorant property of the carpets according to the invention.
  • Figure 5 illustrates the results of olfactory evaluation of the tobacco odor deodorant property of the carpets according to the invention.
  • Figure 6 illustrates determination of the catalytic degradation of total volatile organic compound (TVOC) by the carpets according to the invention under continuous aeration.
  • TVOC total volatile organic compound
  • Figure 7 illustrates the results of an experiment measuring the effect of the duration of UV light illumination on the catalytic formaldehyde degradation property of the carpets according to the invention under continuous aeration.
  • Figure 8 illustrates the results of an experiment determining the air cleaning durability of a carpet according to the invention under conditions intended to simulate a 5 year cycle of maintenance.
  • the present invention provides solutions to indoor air problems by providing a caged photocatalyst useful for manufacturing substrates having air clarifying properties such as floor covering having anti staining, self-cleaning, antimicrobial and deodorizing properties.
  • air clarifying properties means that the substrate showing such properties can remove unpleasant odors, and/or removes and decompose harmful substances and contaminants in the air.
  • the present invention provides a caged photocatalyst as an environmental clarifying agent said caged photocatalyst comprising a nano photocatalyst enclosed in a calcium carbonate casing.
  • a process for preparing the caged photocatalyst there can be mentioned, for example, a process of dispersing nano sized particles of photocatalyst such as titanium dioxide particles in a solution of calcium chloride, and adding Na 2 CO 3 to the solution to enclose the photocatalyst in a casing of calcium carbonate.
  • Another process comprises dispersing nano sized particles of photocatalyst such as titanium dioxide particles in aqueous calcium chloride-alcohol solution, and growing the calcium carbonate casing around the photocatalyst by diffusion of gaseous carbon dioxide into the solution.
  • photocatalyst such as titanium dioxide particles
  • the calcium carbonate casing exhibit specific pore size wherein harmful substances in the air, or unpleasant odors, can be easily decomposed and eliminated by the photocatalytic action of titanium oxide, while the substrate treated or coated with said caged photocatalyst is not decomposed.
  • a substrate When a substrate is treated or coated with a caged photocatalyst according to the invention it will exhibit a deodorant function, an antimicrobial function or an antistain function without being prone to decomposition.
  • the substrate is provided with deodorant function, an antimicrobial function or an antistain functions by treating or coating the surface of the substrate with the caged photocatalyst optionally in the presence of a binder.
  • the caged photocatalyst is used to treat or coat a substrate, and can be used in combination with a binder, whereby since the part in contact with the substrate or the binder is the calcium carbonate casing there is no decomposition of said substrate or binder, the organic compounds contaminating an environment, such as unpleasant odors, harmful substances can be quickly and continuously decomposed and removed by the decomposition properties of the photocatalyst.
  • the present invention further provides a photocatalyst composition
  • a photocatalyst composition comprising the caged photocatalyst, a binder and a solvent.
  • the caged photocatalyst comprises a photocatalyst enclosed in a calcium carbonate casing.
  • Non-limiting examples of suitable photocatalyst enclosed in the calcium carbonate casing include nano-size oxide and non-oxide semiconductors such as TiO 2 , ZnO, SiO 3 ; Ti 1- x Sn x O 2 , SrTiO 3 , Fe 2 O 3 , CdS, CdSe, WO 3 , FeTiO 3 , GaP, GaAs, GeAs, RuO 2 , MoS 3 , LaRhO 3 , CdFeO 3 , Bi 2 O 3 , MoS 2 , In 2 O 3 , CdO, SnO 2 , SiC, InP and/or mixture thereof.
  • nano-size oxide and non-oxide semiconductors such as TiO 2 , ZnO, SiO 3 ; Ti 1- x Sn x O 2 , SrTiO 3 , Fe 2 O 3 , CdS, CdSe, WO 3 , FeTiO 3 , GaP, GaAs, GeA
  • the photocatalysts are used on a nanoscale size.
  • the photocatalysts have an average particle size of less than 55 nm.
  • the nano-crystalline photocatalyst is in anatase form and have a particle size of 10-55 nm They are excellent in the points that they show a deodorant function, an antimicrobial function or an antistain function due to decomposition of an organic compound by oxidation.
  • nano TiO 2 , Fe 2 O 3 , ZnO, SnO 2 , and the like are available in the point that starting materials are obtained cheaply, and further an anatase type TiO 2 and SnO 2 are more preferred in the point that nano particles having higher activity can be easily obtained.
  • the photocatalyst may be used either any one kind of these or in combination of two kinds or more by mixing.
  • said nano photocatalyst is anatase TiO 2 .
  • Photocatalyst described herein are able to break down many organic pollutants totally or partially.
  • nano TiO 2 as anatase is preferred since high photocatalytic purification has been observed because of its strong oxidation power, high chemical durability and non-toxicity.
  • TiO 2 is an inorganic oxide, showing no absorption of any fraction of the visible light, thus it is not colored. In the region of shorter wavelength a strong absorption of UV radiation is observed. This is due to the promotion of an electron out of the valence band into the conductive band. In its anatase modification the band gap is 3.05 eV. In its tuned form the band gap is 2.8 eV. In this process photo energy is transferred into chemical energy.
  • said photocatalyst may be doped or tuned by adding one or more element within the crystal lattice of said photocatalyst.
  • said photocatalyst can be doped with elements selected from the group comprising Nb, Mo, Cr, V, Cu, Mg, Ag, Ru, Au, N, Nd, Pd, Pt, Fe, Ni, Mn and the like.
  • Said elements can be the atom as such or ion form of said atoms. They can be implanted from the surface to deep inside of the bulk of the photocatalyst in an amount of at least 10 15 ions per g of the photocatalyst.
  • the present invention also provides a photocatalyst composition comprising the caged photocatalyst according to the invention, together with a binder and a solvent.
  • the caged photocatalyst according to the invention is used in the photocatalyst composition in an amount ranging from 0.01 to 5 % by weight, preferably from 0.01 to 1% by weight and most preferably from 0.05 to 0.3 %.
  • Non-limiting examples of suitable binder include melamine resin, urethane resin, celluloid, chitin, starch sheet, polyvinyl alcohol, polyester resins, urea-formaldehyde, dicyandiamide-formaldehyde, epoxy resins, polyurethane resins, (poly)silane resins, (poly)siloxane resins, silazane resins, acrylamide resins, acrylic silicon resins, acrylurethane resins, polyacrylamide resins and the like and mixtures thereof.
  • the binder may be employed in an amount ranging from 0.01 to 5 % by weight, for example in an amount ranging from 0.01 to 1% by weight and for example in an amount ranging from 0.05 to 0.3 %.
  • the binders for use according to the invention may be modified so as to impart hydrophobic and/or oleophobic surface properties to a substrate to be treated with therewith.
  • the photocatalyst enclosed in the calcium carbonate casing permit to prevent the degradation or decomposition of the binder.
  • the caged photocatalyst may be employed in an amount ranging from 0.01 to 5 % by weight, for example in an amount ranging from 0.01 to 1 % by weight and for example in an amount ranging from 0.05 to 0.3 %.
  • said photocatalyst composition comprises a solvent.
  • Suitable solvents can be selected from the group comprising water, ethylene glycol butyl ether, aliphatic linear, branched or cyclic or mixed aromatic-aliphatic alcohols having 4 to 20 carbon atoms, such as methanol, ethanol, butanol, 2-propanol, isobutanol, isopropanol. benzyl alcohol, methoxypropanol or furfuryl alcohol; and the like, and/or mixture thereof.
  • said solvent is selected from the group comprising water, ethylene glycol butyl ether, ethanol and the like, and/or mixture thereof.
  • said solvent is water.
  • the photocatalyst composition may further comprise additional solvent such as for example ethylene glycol butyl ether.
  • said photocatalyst composition is a suspension comprising the caged photocatalyst, a binder and at least one solvent.
  • said solvent is selected from the group comprising water, alkylene glycols, polyalkylene glycols, alkylene carbonates, ethanol, propanol and isopropanol and mixtures thereof.
  • the solvent can be employed individually or as a mixture, and in particular in a amount ranging from 50 to 99 % by weight, for example in an amount ranging from 80 to 99% by weight and for example in an amount ranging from 90 to 99 %.
  • the caged photocatalyst can be dispersed or otherwise introduced into a molten, uncrosslinked, uncured or dissolved form of a suitable binder.
  • the photocatalyst composition for use in the present invention may further comprise antimicrobial agents. Although not limiting, up to 1 % by weight of antimicrobial agents may be added to the photocatalyst composition.
  • Antimicrobial agents suitable for said photocatalyst composition may be any chemical capable of preventing the growth of or killing microorganisms.
  • suitable antimicrobial agents include, but are not limited to, quaternary ammonium, phenolic, amide, acid, and nitro compounds, and mixtures thereof.
  • quaternary ammonium compounds include, but are not limited to, 2-(3-anilinovinylul)3,4-dimethyl- oxazolinium iodide, alkylisoquinolium bromide, benzalkonium chloride, benzethonium chloride, cetylpyridinium chloride, chlorhexidine gluconate, chlorhexidine hydrochloride, lauryl trimethyl ammonium compounds, methylbenzethonium chloride, stearyltrimethyl ammonium chloride, and mixtures thereof.
  • Suitable phenolic compounds include, but are not limited to, benzyl alcohol, p-chlorophenol, chlorocresol, chloroxylenol, cresol, o-cymene-ol (BIOSOL), hexachlorophene, hinokitiol, isopropylmethylphenol, parabens (having methyl, ethyl, propyl, butyl, isobutyl, isopropyl, and/or sodium methyl substituents), phenethyl alcohol, phenol, phenoxyethanol, o-phynylphenol, resorcin, resorcin monoacetate, sodium parabens, sodium phenolsulfonate, thioxolone, 2,4,4'- trichloro hydroxidiphenyl ether, zinc phenolsuflonate, di-tert.-butyl phenole, hydrochinone, and mixtures thereof.
  • benzyl alcohol p
  • Suitable amides include, but are not limited to, diazolidinyl urea, 2,4-imidazolidinedione (HYDATOIN), 3,4,4'-trichlorocarbanilide, 3- trifluoromethyl-4,41-dichlorocarbanilide, undecylenic acid monoethanolamide, and mixtures thereof, more preferably still 2,4-imidazolidinedione.
  • HYDATOIN 2,4-imidazolidinedione
  • 3,4,4'-trichlorocarbanilide 3,4,4'-trichlorocarbanilide, 3- trifluoromethyl-4,41-dichlorocarbanilide, undecylenic acid monoethanolamide, and mixtures thereof, more preferably still 2,4-imidazolidinedione.
  • suitable acids include, but are not limited to, ascorbic acid, benzoate, benzoic acid, citric acid, dehydroacetic acid, potassium sorbate, salicylic acid derivatives such as acetyl salicylic acid, salicylic acid aldehyde, sodium citrate, sodium dehydroacetate, sodium salicylate, sodium salicylic acid, sorbic acid, undecylenic acid, zinc undecylenate, and mixtures thereof.
  • suitable nitro compounds include, but are not limited to, 2-bromo nitro-2,3-propanediol (BRONOPOL), and methyldibromo glutaronitrile and propyulene glycol (MERGUARD), and mixtures thereof.
  • said antimicrobial agent is hinokitiol.
  • the photocatalyst composition according to the present invention may also contain auxiliaries or additives such as absorbents, rheological modifiers, plasticizers, antifoaming agents, antifouling agents, thixotropic agents, pigments, fillers, aggregates, extenders, reinforcing agents, flow control agents, catalysts, pigment pastes, mineral oils, wetting agents, adhesion promoters, thickening agents, flame-retarding agents, antioxidants, elastomers, antisettling agents, diluents, UV light stabilizers, air release agents, solvents, dispersing aids, and mixtures thereof, additional hardeners and additional curable compounds, depending on the application.
  • auxiliaries or additives such as absorbents, rheological modifiers, plasticizers, antifoaming agents, antifouling agents, thixotropic agents, pigments, fillers, aggregates, extenders, reinforcing agents, flow control agents, catalysts, pigment pastes, mineral oils, wetting agents
  • the photocatalyst composition can be formulated as comprising 0.10 to 0.15 % by weight of caged photocatalyst, 0.10 to 0.20 % by weight of antimicrobial agent, 0.10 to 0.15% by weight of a binder, 0.03 to 0.05 % by weight of a solvent and above 98 % by weight of water.
  • the photocatalyst composition can be formulated as comprising 0.10 to 0.15 % by weight of caged TiO 2 , 0.10 to 0.20 % by weight of hinokitiol,
  • Non-limiting examples of substrate which can be treated with said the caged photocatalyst or with the photocatalyst composition according to the invention include textile products, paper products, interior products such as floor covering including carpets, rugs, mats and the like.
  • the substrate treated, coated and or produced therewith exhibits an environmental cleaning function such as removing unpleasant odors, decomposing and removing harmful substances or contaminants in the air.
  • the substrate can be treated with the caged photocatalyst as such or with the photocatalyst composition comprising said caged photocatalyst by impregnation, dipping, flooding, coil coating, spraying, centrifuging, screen printing, or vacuum infiltrating and the like.
  • the treated substrate can be further cured or dried.
  • said drying step may be performed by thermal hardening such as by heating, by infra red treatment, using laser and the like.
  • Said drying step may also be performed using radiation hardening such as UV, VIS, laser hardening, electron beam hardening and the like.
  • the temperature may range from room temperature to 350 0 C.
  • the present invention is intended for treating substrates which are so-called floor coverings, and can be applied to carpets, rugs and mats such as car mats and the like.
  • said floor covering is a carpet which has undergone a post-treatment with a finishing composition.
  • the present invention also provides a finishing composition for floor coverings such as carpets comprising the caged photocatalyst according to the invention.
  • the finishing composition according to the invention comprises (a) the photocatalyst composition according to the invention (b) a liquid carrier and optionally (c) a coarcervate.
  • the carpet can be submitted to a treatment with a finishing composition comprising a photocatalyst composition comprising the caged photocatalyst described above, optionally in combination with stain resists such as grease and water stain fluoride-based repellent.
  • stain resists such as grease and water stain fluoride-based repellent.
  • the term "carpet” encompasses carpets, rug, mats and the like.
  • the finishing composition comprises (a) the photocatalyst composition according to the invention (b) a liquid carrier and optionally (c) a coarcervate.
  • Said composition may further comprise soil resists products such as fluorocarbon to impart water and oil repellency.
  • the finishing composition may also comprise a stain resists.
  • the finishing composition may further comprise a softener for extra bulk.
  • the liquid carrier is preferably an aqueous system.
  • the carrier can also contain a low molecular weight organic solvent that is highly soluble in water, e.g., C1 to C4 monohydric alcohols, C2 to C6 polyhydric alcohols, such as alkylene glycols and polyalkylene glycols, alkylene carbonates, and mixtures thereof.
  • water-soluble solvents examples include ethanol, propanol and isopropanol.
  • said liquid carrier is selected from the group comprising water, alkylene glycols, polyalkylene glycols, alkylene carbonates, ethanol, propanol and isopropanol and mixtures thereof.
  • Water is a preferred liquid carrier due to its low cost, availability, safety, and environmental compatibility. The water can be distilled, deionized, or tap water.
  • Highly preferred materials of this class of liquid carriers are those that do not cause any significant color change, nor impart any discoloration, such as graying or yellowing, to the carpets to which they are applied, either during treatment followed by drying and/or curing, or after the drying and/or curing step followed by normal exposure to the elements, such as air, moisture or sunlight exposure.
  • the level of liquid carrier to be used in the finishing composition can typically be from 50% to 99% of the composition, for example from 75% to 95%, and preferably from 80% to 90 % of the composition, for example 87 to 89 %.
  • the amount of photocatalyst composition to be used in the finishing composition can typically vary from 1 to 50 %, for example from 5 to 35 %, for example from 7 to 20 % and preferably from 7 to 13 %, for example 8 to 9 %.
  • the coacervate for use in the finishing composition assists in solubilising the particles provides a uniform film at the fiber surface.
  • Said coacervate can be selected form the group comprising Levalin VKU-N (Bayer), Primasol SD (BASF), lrgapadol PN New (Ciba), Lyogen AF (Clariant AG), Intratex AF (Crompton & Knowles) and the like.
  • the amount of coacervate to be used in the finishing composition can typically vary from 0 to 15 %, for example from 1 to 10 %, for example from 2 to 5 % and preferably from 2 to 4 %.
  • the present invention further provides a method for the preparation of a carpet having air clarifying properties wherein said method comprising the step of treating said carpet with a caged photocatalyst according to the invention.
  • the method comprises the steps of treating said carpet with a photocatalyst composition according to the invention.
  • the method of the present invention comprises the steps of: providing a finishing composition according to the present invention, and applying said finishing composition onto a carpet thereby obtaining a carpet having air clarifying properties.
  • Suitable carpet fiber material which can be treated with the finishing composition are materials comprising for example, wool, polyamide, polyurethanes, polyester, polyacrylonitrile, polypropylene, polyethylene and cellulose-containing fiber materials of all kinds, for example natural cellulose fibers, such as cotton, linen, jute and hemp, and also regenerated cellulose.
  • the materials may also be used as blends of natural fibers like cotton, wool or jute with each other or with synthetic fiber materials like PES, Nylon or polypropylene or blends of synthetic fiber materials with each other.
  • Typical fiber blends are of polyacrylonitrile-polyester, polyamide/polyester, polyester/cotton, polyester/viscose and polyester/wool.
  • stain resists and soil resists may be used in the finishing composition.
  • Suitable stain resists are polymers containing phenol-formaldehyde, methacrylic acid, maleic acid, sulfonated fatty acids, and blends of the above.
  • Suitable soil resists are polymers containing fluorochemical residues with the most preferred being cationically dispersed. The use of cationic fluorochemicals in combination with anionic stain resists typically gives better fluorine retention.
  • Suitable stain resists for the practice of this invention include, but are not limited to, phenol formaldehyde polymers or copolymers such as CEASESTAIN and STAINAWAY (from American Emulsions Company, Inc., Dalton, Ga.), MESITOL (from Bayer Corporation, Pittsburgh, Pa.), ERIONAL (from Ciba Corporation, Greensboro, N. C), TAMOL (from Rohm & Haas Co.), BAYPROTECT CL or CSDTM (from Bayer AG), INTRATEX (from Crompton & Knowles Colors, Inc., Charlotte, N. C), NYLOFIXANTM P (from Sandoz Corp.), ACRYSOLTM (from Rohm and Haas Company) and CARBOPOLTM (from B.
  • phenol formaldehyde polymers or copolymers such as CEASESTAIN and STAINAWAY (from American Emulsions Company, Inc., Dalton, Ga.), MESITOL (from Bayer Corporation, Pittsburgh, Pa.), ER
  • LEUKOTANTM family of materials such as LeukotanTM 970, LeukotanTM 1027, LeukotanTM 1028, and LeukotanTM QR 1083 (from Rohm and Haas Company), and sulfonated fatty acids from Rockland React-Rite, Inc., Rockmart, Ga.).
  • Suitable soil resists for the practice of the present invention include, but are not limited to, fluorochemical emulsions such as AMGUARD (from American Emulsions Company, Inc., Dalton, Ga.), SOFTECH (from Dyetech, Inc., Dalton, Ga.), LANAPOL (from Lenmar Chemical Corporation, Dalton, Ga.), SCOTCHGARD FC series carpet protectors (from 3M Company, St. Paul, Minn.), NK GUARD (from Nicca USA, Inc., Fountain Head, N. C), UNIDYNE (from Diakin America, Inc., Decatur, Ala.), and ZONYL such as Zonyl 555, N-130 and N-119 (from E. I. du Pont de Nemours and Company, Wilmington, Del.).
  • fluorochemical emulsions such as AMGUARD (from American Emulsions Company, Inc., Dalton, Ga.), SOFTECH (from Dyetech, Inc., Dalton, Ga.), LANAPOL (from Le
  • the amount of the stain resists and/or soils resists used in the preparations of the finishing composition of the present invention are the amounts typically employed in the carpet and fabric industry and would be well known to those skilled in the art. Ordinarily, depending upon the nature of the stain resist and/or soils resist and the carpet being treated and its location, the resists are applied to the material in an amount to result in a treatment rate of 0.1 wt % to 20 wt % based upon the weight of the weight of the carpet being treated and the amount of stain resists and/or soils resists.
  • the treatment rate will be from 0.15 wt % to 10 wt %, preferably from 0.2 wt % to 4 wt %, more preferably from 0.25 wt % to 2 wt %.
  • the stain resists and/or soils resists is applied to give a treat rate of 0.25 wt % to 1.0 wt % based upon the weight of the carpet being treated.
  • the finishing composition of the present invention may be provided with other active ingredients depending upon the application or surface to be treated.
  • One such additional ingredient which may be utilized in the finishing composition depending upon the application is a foaming agent for producing a foam composition for treating the relatively absorbent surfaces of the carpet.
  • foaming agents include lauryl sulphate, ammonium lauryl sulphate, sodium lauryl sulphate.
  • the additional ingredients would be utilized in the compositions at the usually employed concentrations, generally 5 % by weight or less based upon the total weight of the finishing composition.
  • the finishing composition is prepared by emulsifying the photocatalyst composition in water, using equipment such as a sonnicator, homogenizer, microfluidizer, high shear blending equipment and the like.
  • the finishing composition may be applied to the surface at any stage during its manufacture.
  • the finishing composition may be utilized to treat the precursor filaments, yarns or fibers prior to their use in the conventional manufacturing process.
  • the filament or yarn may be run through a bath containing the finishing composition or the finishing composition may be sprayed on the filament. After the treatment, the filaments or yarns are dried and then further processed into carpet in the normal manner.
  • the carpet during the manufacturing process may be immersed, sprayed or otherwise treated with the finishing composition.
  • the carpet fibers may be sprayed or otherwise treated with the finishing composition prior to being inserted into the primary backing.
  • the fibers may also be treated once they have been inserted into the primary backing, either before or after the backing adhesive and secondary backing material have been applied.
  • the finishing composition may also be applied to the finished carpet as a final step prior to drying and rolling.
  • the carpet would be sprayed or otherwise treated with the finishing composition, after which time the carpet would be dried in the usual manner and rolled onto the roll.
  • the finishing composition can be applied to the carpet in an amount ranging from 10 g/m 2 to 100 g/m 2 of surface, for example from 20 g/m 2 to 70 g/m 2 , preferably from 40 g/m 2 to 60 g/m 2 , and preferably in an amount of 50 g/m 2 .
  • the finishing compositions according to the present invention can be applied to the carpets by a variety of methods. Examples of such methods include, but are not limited to, beck dying procedures, continuous dyeing procedures, brushing, dipping, spraying, padding, roll-coating, foaming or the like.
  • the finishing compositions can be applied to the carpet as such or in combination with other fluorofinishes, stainblockers, processing aids, lubricants, anti-stains, etc.
  • the compositions can also be blended with other agents that have oil/water repellency and soil release properties and applied to the carpets. They can be applied to dyed and undyed carpeting.
  • the finishing composition is formulated as foam and can be roll-coated on the carpet. Once the finishing composition applied the coated carpets exhibit fibers having uniform and even coating of photocatalyst particles of an average size of 2 ⁇ m with a spread of 0,5 to 4 ⁇ m.
  • said finishing composition is provided as a foam.
  • the finishing composition can then beapplied by means of a foam applicator.
  • Foam application has several advantages, it allows exact quantity controllable application and an even application without any stripes. Low wet pick-up is observed and an adjustable penetration of the composition can be obtained. In addition this mode of application requires only little space. It is also ecologically beneficial and has a minimum impact on speed.
  • the finishing composition can be applied after dyeing, before drying. In another embodiment the finishing composition can be applied during finishing.
  • the finishing composition can be applied as aqueous formulation in diluted, solubilised, emulsified or dispersed form.
  • finishing composition Another option would be to apply the finishing composition to an installed carpet.
  • the finishing composition When applying the finishing composition to an installed carpet, it is not essential, but preferred that the finishing composition be applied thoroughly and evenly throughout the length of the pile, especially reaching down to the base of the pile fiber. This is generally achieved by applying an aqueous foaming finishing composition to the carpet and then working the fibers to improve the contact, distribution and penetration of the finishing composition. This is most commonly achieved by use of a pile brush operated either by hand or automatically for example, utilizing a cleaning device such as is commonly available commercially.
  • the fibers of the carpet may initially be wetted through an application of a detergent solution. This is most commonly applied where the installed carpet is cleaned using a cleaning machine prior to the application of the finishing composition .
  • the finishing composition may be applied and worked into the carpet, utilizing the pile brush. Once the carpet has been so treated, it is dried, either by allowing it to dry in the air at ambient temperature or through the use of hot air blown through the pile of the carpet to increase the speed of drying of the carpet.
  • the finishing composition may be applied in many different ways. The composition may be applied by dipping the material in the finishing composition or by spraying the composition onto the fibrous material. In any of these cases, once the fiber or carpet is treated with the finishing composition , the treated carpet material is allowed to dry by way of applied heat or simply by ambient drying.
  • the carpet backing and/or carpet cushion underlayment may also be treated with the finishing composition.
  • the carpet backing and/or carpet cushion underlayment may be treated during the manufacturing process, or prior to its installation.
  • the carpet cushion underlayment may also be similarly treated during the installation of the carpet cushion underlayment.
  • the present invention provides a caged photocatalyst capable of exhibiting durable photocatalytic activity as described herein, a process for producing the above- mentioned caged photocatalyst, a photocatalyst composition comprising the caged photocatalyst, a finishing composition comprising said caged photocatalyst or said photocatalyst composition and a substrate comprising or treated with said caged photocatalyst or a composition comprising it.
  • the surprising properties of the floor covering coated with the caged photocatalyst according to the invention are shown in the present examples. The following examples illustrate the use of the present invention but are not to be construed as limiting the scope of the present invention.
  • VOC degradation properties of the floor covering according to the invention are determined.
  • the tested VOC reference substances for indoor air were benzene, Formaldehyde (HCHO), TVOC (total volatile organic compound) and cigarette smoke polluted indoor air (tobacco odor).
  • the tested gas 4 flows out a container 15 comprising said gas in a concentrated form.
  • the gas flows out of tube 6 through a regulation valve 8 into tube 9 which is connected to the test chamber 2.
  • the concentrated gas is diluted and adjusted to the wanted concentration by means of pure air 6 flowing trough tube 7 connected to the regulation valve 8.
  • the air/gas mixture flows into tube 9 which is connected to the test chamber 2.
  • the sample 1 to be analyzed is placed in the test chamber 2 which comprise a UV bulb 3.
  • the gas flows out of the test chamber 2 through tube 10.
  • a data logger 11 is connected to the arrangement and control and/or measure the temperature, humidity and/or flow rate.
  • the tested gas flowing out of the test chamber 2 through tubing 10 is sampled through a valve 12 which is connected 17 to an olfactometer 13 and is also connected 16 to a sampling tube 4 for gas analysis.
  • Example 1 Determination of the catalytic formaldehyde degradation property of the carpets according to the invention under continuous aeration
  • the catalytic activity of TiO2 coated carpet was measured by the analysis of the effect of the coated carpets on formaldehyde degradation under continuous aeration.
  • the carpet samples were made from 40 cm x 40 cm carpet pieces. From these carpet pieces, carpet samples of 7.8 cm x 7.8 cm were manufactured and masked by means of an aluminum tape in order to avoid edge effects during the measurement of the catalytic degradation of the formaldehyde. Formaldehyde degradation was investigated under continuous aeration by chamber testing and compared with uncoated carpet samples, and with a control measurement performed in the test chamber without sample.
  • test chambers are airtight aluminum boxes which have a volume of 49.58 I 1 the proportion between the tested sample and the chamber volume amounts to 1.23 m 2 /m 3 in a standard inspection surface of 61 cm 2 .
  • the carpet samples were placed in the center of the test chambers and locked therein.
  • a UV lamp of 80 W was fixed in the chamber on the top.
  • a defined formaldehyde concentration of 220 ⁇ g/m 3 +/- 30 ⁇ g/m 3 (which corresponds to the average formaldehyde content in a smoker room) was applied in the test chamber by means of a continuous air supply over a Teflon hose at an air exchange rate of 0.5/h.
  • the test chambers were operated at a temperature of 20°C and a relative humidity of 50 %.
  • the formaldehyde originates from a 50 NI content high-grade steel container containing a concentrated formaldehyde atmosphere of 54000 ⁇ g/m 3 , in constant equilibrium between liquid and gaseous state at 20 0 C and 50 % relative humidity.
  • the formaldehyde flows out of this container at an air flow of 3.0 l/h (50 ml/min) and is mixed with pure air in ratio of 1 :245.
  • the air flows out of the test chambers at a flow rate of 180 l/h, wherein 24.8 I were sampled by means of diaphragm pumps.
  • the initial fluctuations in formaldehyde content observed in the test chamber are due mainly to errors due for examples to sampling point, time needed to adjust the concentration inside the test chamber and the like. This is verifyed by the measurements performed in the test chambers without samples. A clear difference between the samples according to the invention and the controls can be seen after 8 h.
  • Example 2 Determination of the catalytic benzene degradation property of the carpets according to the invention under continuous aeration .
  • a concentration of 45 ⁇ g/m 3 +/- 15 ⁇ g/m 3 was applied in the test chamber by means of a continuous air supply over a Teflon hose at an air exchange rate of 0.5/h.
  • the test chambers were operated at a temperature of 20°C and a relative humidity of 50 %.
  • the benzene originates from a 50 NI content high-grade steel container containing a concentrated benzene atmosphere of 11200 ⁇ g/m 3 , in constant equilibrium between liquid and gaseous state at 20 0 C and 50 % relative humidity.
  • the benzene flows out of this container at an air flow of 3.0 l/h (50 ml/min) and is mixed with pure air in ratio of 1:26.
  • the air flows out of the test chambers at a flow rate of 180 l/h, wherein 24.8 I were sampled by means of diaphragm pumps.
  • the laboratory tests were performed according to the respective DIN procedures and/or regulations wherein the benzene concentration was measured by use of the Tenax absorbent. Subsequently, the samples were examined by gas chromatography with the GG/FID/ECD.
  • Example 3 Olfactory evaluation of tobacco odor deodorant property of the carpets according to the invention
  • cigarette smoke -corresponding to the content of a room wherein 50 cigarettes are consumed daily- was applied in the test chamber by means of a continuous air supply over a Teflon hose at an air exchange rate of 0.5/h.
  • the test chambers were operated at a temperature of 20 0 C and a relative humidity of 50 %.
  • the cigarette smoke originates from a 50 NI content high-grade steel container containing a concentrated cigarette smoke atmosphere at 20 0 C and 50 % relative humidity.
  • the cigarette smoke flows out of this container at an air flow of 5.2 l/h (87 ml/min) and is mixed with pure air in ratio of 1 :3.6 so as to obtain in the test chamber a concentration equivalent to the smoke of 50 cigarettes consumed daily.
  • the olfactometry measurements were performed according to the respective VDI recommendation 388I, Sheet I and II, whereby the odor intensity (Gl with a scaling from 0 to 5 corresponding to 5: intense odor, 4: strong odor, 3: readily perceptible, 2: weak odor perceptible, 1 : barely perceptible odor, 0: no odor) and the odor development/ Hedonik (GA with a scaling from -5 to +5 ) were evaluated.
  • Three independent test persons made the respective odor evaluation and means values were calculated.
  • Example 4 Determination of the catalytic TVOC degradation property of the carpets according to the invention under continuous aeration.
  • cigarette smoke -corresponding to the content of a room wherein 50 cigarettes are consumed daily- was applied in the test chambers by means of a continuous air supply over a Teflon hose at an air exchange rate of 0.5/h.
  • the test chambers were operated at a temperature of 20 0 C and a relative humidity of 50 %.
  • the cigarette smoke originates from a 50 NI content high-grade steel container containing a concentrated cigarette smoke atmosphere at 20 0 C and 50 % relative humidity.
  • the cigarette smoke flows out of this container at an air flow of 5.2 l/h (87 ml/min) and is mixed with pure air in ratio of 1:3.6 so as to obtain in the test chamber a concentration equivalent to the smoke of 50 cigarettes consumed daily.
  • the air flowed out of the test chambers and 24.8 I were sampled by means of diaphragm pumps.
  • TVOC content The determination of the total content of volatile organic compounds (TVOC content) was performed by a portable gas chromatograph PE Photovac Voyager. In order to obtain representative values, 5 measurements were performed every 10 min. Calibration of the chromatograph was performed using a defined toluol standard. The detection used a photoionization detector with quick-change electrodeless discharge UV lamp, 10.6 eV.
  • Example 5 Determination of the catalytic formaldehyde degradation property of the carpets according to the invention under continuous aeration: Influence of the UV irradiation duration
  • the catalytic degradation property was measured by the analysis of the effect of the coated carpets on formaldehyde degradation under different UV light expositions.
  • the carpet samples were made from 40 cm x 40 cm carpet pieces. From these carpet pieces, carpet samples of 7.8 cm x 7.8 cm were manufactured and masked by means of an aluminum tape in order to avoid edge effects during the measurement of the catalytic degradation of the formaldehyde. Formaldehyde degradation was investigated under continuous aeration by chamber testing and compared with uncoated carpet samples, and with a control without sample.
  • test chambers are airtight aluminum boxes which have a volume of 49.58 I 1 the proportion between the tested sample and the chamber volume amounts to 1.23 m 2 /m 3 in a standard inspection surface of 61 cm 2 .
  • the carpet samples were placed in the center of the test chambers and locked therein.
  • a UV lamp 3 mW/cm 2 was fixed in the chamber on the top.
  • the experiment was set up in accordance with the usual daily light intensities which can be expected during the different seasons and weather conditions. The experiment started by simulating winter conditions consisting of 10-hour light exposure under cloudy conditions which is estimated at 0.15 Won 2 for 10 hours, with half-hour irradiation of 3 mW/cm 2 .
  • the experiment carried on by extending the daily irradiating duration by 1 , 2, 4, 6 and 8 hours, in order to simulate irradiation expected during the transition periods of spring and autumn in the as well as maximum exposure in the summer time area.
  • the results were compared to those obtained using uncoated carpet samples or control measurements without samples.
  • a defined formaldehyde concentration of 220 ⁇ g/m 3 +/- 30 ⁇ g/m 3 (which corresponds to the average formaldehyde content in a smoker room) was applied in the test chamber by means of a continuous air supply over a Teflon hose at an air exchange rate of 0.5/h.
  • the test chambers were operated at a temperature of 20 0 C and a relative humidity of 50 %.
  • the formaldehyde originates from a 50 NI content high-grade steel container containing a concentrated formaldehyde atmosphere of 54000 ⁇ g/m 3 , in constant equilibrium between liquid and gaseous state at 20 0 C and 50 % relative humidity.
  • the formaldehyde flows out of this container at an air flow of 3.0 l/h (50 ml/min) and is mixed with pure air in ratio of 1 :245.
  • the air flows out of the test chambers at a flow rate of 130 l/h, wherein 24.8 I were sampled by means of diaphragm pumps.
  • Example 6 Determination of the air cleaning durability of a carpet according to the invention under conditions intended to simulate a 5 year cycle of maintenance.
  • the air cleaning durability of a carpet according to the invention was evaluated under conditions intended to simulate a 5 year cycle of maintenance.
  • the catalytic formaldehyde degradation properties of the carpets according to the invention which have been vacuum cleaned and/or 1 time laundered, was investigated by chamber testing and compared with untreated samples.
  • the carpet samples were made from 200 cm x 100 cm carpet pieces which were vacuum cleaned.
  • the carpet pieces were vacuumed 500 times each with a back and forth motion using a usual household-vacuum cleaner of 1200 Watt. This treatment corresponds to a usual regular cycle 2 times weekly carpet care over 5 years. Subsequently, a laundering took place at 30 0 C with the addition of a commercial carpet preservative agent.
  • carpet samples of 7.8 cm x 7.8 cm were manufactured and masked by means of an aluminum tape in order to avoid edge effects during the measurement of the catalytic degradation of the formaldehyde.
  • the test chambers are airtight aluminum boxes which have a volume of 49.58 I, the proportion between the tested sample and the chamber volume amounts to 1.23 m 2 /m 3 in a standard inspection surface of 61 cm 2 .
  • the carpet samples were placed in the center of the test chambers and locked therein.
  • a UV lamp 3 mW/cm 2 was fixed in the chamber on the top.
  • the samples were incubated over a period of 14 days with constant irradiation by a UV lamp with a radiation intensity of 3 mW/cm 2 .
  • As a control sample a carpet according to the invention which had not been vacuumed was used.
  • a defined formaldehyde concentration of 220 ⁇ g/m 3 +/- 30 ⁇ g/m 3 was applied in the test chamber by means of a continuous air supply over a Teflon hose at an air exchange rate of 0.5/h.
  • the tests chambers were operated at a temperature of 20 0 C and a relative humidity of 50 %.
  • the formaldehyde originates from a 50 NI content high-grade steel container containing a concentrated formaldehyde atmosphere of 54000 ⁇ g/m 3 , in constant equilibrium between liquid and gaseous state at 20 0 C and 50 % relative humidity.
  • the formaldehyde flows out of this container at an air flow of 3.0 l/h (50 ml/min) and is mixed with pure air in ratio of 1 :245.
  • the air flows out of the test chambers at a flow rate of 180 l/h, wherein 24.8 I are sampled by means of diaphragm pumps.

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Abstract

Cette invention concerne un photocatalyseur bloqué contenant un nano photocatalyseur renfermé dans une enveloppe de carbonate de calcium. Le photocataylseur bloqué est utile en tant qu'agent de clarification de l'environnement convenant à l'élimination des odeurs désagréables, à la décomposition et à la suppression de substances nocives et de contaminants de l'air par action photocatalytique. Cette invention concerne également des produits traités au moyen dudit agent de clarification.
PCT/EP2005/000355 2005-01-14 2005-01-14 Photocatalyseur bloque en tant qu'agent de clarification de l'environnement WO2006074697A1 (fr)

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CN103170369A (zh) * 2013-02-28 2013-06-26 安徽大学 氧化锌/聚苯胺复合光催化剂的制备方法
WO2013109599A1 (fr) * 2012-01-19 2013-07-25 Nestec Sa Systèmes de gestion de déchets utilisant des composés éliminant les mauvaises odeurs activés par un rayonnement ultraviolet
CN105642314A (zh) * 2016-01-18 2016-06-08 武汉理工大学 一种硫化镉-氧化锌核壳多层纳米棒阵列光催化材料及其制备方法
CN106111161A (zh) * 2016-06-21 2016-11-16 武汉理工大学 一种多孔核壳结构的ZnO/ZnS/CdS复合材料及其制备方法
CN106423223A (zh) * 2016-09-20 2017-02-22 中国计量大学 一种饼状多孔结构MoSe2@TiO2光催化剂及其制备方法
CN106799247A (zh) * 2017-01-25 2017-06-06 宁德师范学院 一种Bi24O31Br10/In2O3异质结光催化剂
CN106807410A (zh) * 2017-01-25 2017-06-09 宁德师范学院 一种Bi24O31Br10/In2O3异质结光催化剂的制备方法
CN107597155A (zh) * 2017-09-27 2018-01-19 大连民族大学 一种一锅法合成具有可见光响应的光催化剂BiPO4/WO3纳米片的制备方法
CN109851706A (zh) * 2018-12-21 2019-06-07 昆明理工大学 一种可见光降解甲醛的水性丙烯酸树脂及其制备方法
CN113318758A (zh) * 2021-06-22 2021-08-31 淮北师范大学 一种光催化剂及其制备方法和应用
CN115350729A (zh) * 2022-07-13 2022-11-18 润赢科技(郑州)有限公司 一种新型高效环保光催化甲醛清除剂及其制备方法

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Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013109599A1 (fr) * 2012-01-19 2013-07-25 Nestec Sa Systèmes de gestion de déchets utilisant des composés éliminant les mauvaises odeurs activés par un rayonnement ultraviolet
CN103170369A (zh) * 2013-02-28 2013-06-26 安徽大学 氧化锌/聚苯胺复合光催化剂的制备方法
CN105642314B (zh) * 2016-01-18 2019-01-25 武汉理工大学 一种硫化镉-氧化锌核壳多层纳米棒阵列光催化材料及其制备方法
CN105642314A (zh) * 2016-01-18 2016-06-08 武汉理工大学 一种硫化镉-氧化锌核壳多层纳米棒阵列光催化材料及其制备方法
CN106111161A (zh) * 2016-06-21 2016-11-16 武汉理工大学 一种多孔核壳结构的ZnO/ZnS/CdS复合材料及其制备方法
CN106111161B (zh) * 2016-06-21 2019-08-23 武汉理工大学 一种多孔核壳结构的ZnO/ZnS/CdS复合材料及其制备方法
CN106423223A (zh) * 2016-09-20 2017-02-22 中国计量大学 一种饼状多孔结构MoSe2@TiO2光催化剂及其制备方法
CN106807410A (zh) * 2017-01-25 2017-06-09 宁德师范学院 一种Bi24O31Br10/In2O3异质结光催化剂的制备方法
CN106799247B (zh) * 2017-01-25 2019-07-05 宁德师范学院 一种Bi24O31Br10/In2O3异质结光催化剂
CN106799247A (zh) * 2017-01-25 2017-06-06 宁德师范学院 一种Bi24O31Br10/In2O3异质结光催化剂
CN106807410B (zh) * 2017-01-25 2019-09-24 宁德师范学院 一种Bi24O31Br10/In2O3异质结光催化剂的制备方法
CN107597155A (zh) * 2017-09-27 2018-01-19 大连民族大学 一种一锅法合成具有可见光响应的光催化剂BiPO4/WO3纳米片的制备方法
CN109851706A (zh) * 2018-12-21 2019-06-07 昆明理工大学 一种可见光降解甲醛的水性丙烯酸树脂及其制备方法
CN113318758A (zh) * 2021-06-22 2021-08-31 淮北师范大学 一种光催化剂及其制备方法和应用
CN113318758B (zh) * 2021-06-22 2022-02-25 淮北师范大学 一种光催化剂及其制备方法和应用
CN115350729A (zh) * 2022-07-13 2022-11-18 润赢科技(郑州)有限公司 一种新型高效环保光催化甲醛清除剂及其制备方法

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