WO2020084169A1 - Composition photocatalytique comprenant du dioxyde de titane et un support - Google Patents

Composition photocatalytique comprenant du dioxyde de titane et un support Download PDF

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Publication number
WO2020084169A1
WO2020084169A1 PCT/EP2019/079439 EP2019079439W WO2020084169A1 WO 2020084169 A1 WO2020084169 A1 WO 2020084169A1 EP 2019079439 W EP2019079439 W EP 2019079439W WO 2020084169 A1 WO2020084169 A1 WO 2020084169A1
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WIPO (PCT)
Prior art keywords
photocatalytic
composition according
titanium dioxide
carrier
photocatalytic composition
Prior art date
Application number
PCT/EP2019/079439
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English (en)
Inventor
Daniel Lucas
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Lucas UK Group Limited
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Publication of WO2020084169A1 publication Critical patent/WO2020084169A1/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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/063—Titanium; Oxides or hydroxides thereof
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0215—Coating
    • B01J37/0219—Coating the coating containing organic compounds
    • 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
    • B01J37/024—Multiple impregnation or coating
    • 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
    • B01J37/024—Multiple impregnation or coating
    • B01J37/0244—Coatings comprising several layers

Definitions

  • the present invention relates to a photocatalytic coating composition, in particular a photocatalytic coating composition comprising Ti0 2 for photocatalysis of NOx, and uses thereof.
  • Photocatalysis is the acceleration of a photoreaction in the presence of a catalyst. In catalysed photolysis, light is absorbed by an adsorbed substrate. In photogenerated catalysis, the
  • PCA photocatalytic activity
  • Titanium dioxide is a semiconductor material with a band gap of about 3.2 eV, which corresponds to the energy of near UV light with a wavelength of about 390 nm. Higher energy (shorter wavelength) light is therefore able to produce electron-hole pairs that can potentially initiate both oxidation and reduction reactions on the surface of the material.
  • Ti0 2 occurs naturally as the minerals anatase, rutile and brookite, which possess different crystalline structures and different photocatalytic activities (Chen, H., Nanayakkara, C. E. and Grassian, V. H.: Titanium dioxide photocatalysis in atmospheric chemistry, Chem. Rev., 112, 5919-5948, 2012).
  • the activity of a particular sample or form of Ti0 2 is therefore reported to depend on the contributions of these different minerals, and is also potentially influenced by the presence of other materials which may be included deliberately (i.e. doping) or as a result of ageing or soiling processes.
  • VOCs VOCs
  • NO or N0 2 are ideally oxidised to surface- bound nitrate, which is then removed by wash-off.
  • a VOC e.g. benzene
  • the reaction products are almost certainly influenced by the mineral composition of the Ti0 2 material and the presence of other materials.
  • NOx is a generic term for molecules containing one nitrogen and one or more oxygen atom. In particular in the context of environmental chemistry, it refers to the nitrogen oxides that are most relevant for air pollution, namely nitric oxide (NO) and nitrogen dioxide (N0 2 ). These gases contribute to the formation of smog and acid rain, as well as affecting tropospheric ozone. Nitrous oxide (N 2 0) has a limited, if any, role in air pollution, although it may have a significant impact on the ozone layer, and is a significant greenhouse gas.
  • NOx gases are usually produced from the reaction among nitrogen and oxygen during combustion of fuels, such as hydrocarbons, in air; especially at high temperatures, such as occur in car engines. In areas of high motor vehicle traffic, such as in large cities, the nitrogen oxides emitted can be a significant source of air pollution.
  • This invention seeks to provide a photocatalytic composition, in particular comprising Ti0 2 for photocatalysis of NOx, which is suitable for application to horizontal and vertical surfaces.
  • paint compositions include titanium dioxide as a pigment.
  • paint manufacturers desire the titanium dioxide used as a pigment to be as photo-catalytically inactive as possible. This is because photo-catalytically active pigments would photo-oxidise the polymer-based binders of the paint composition, which would cause an effect known as chalking in which the particles of titanium dioxide protrude through the film surface to produce a white, chalky appearance.
  • titanium dioxide particles which (1) have the low active or non-active rutile crystal structure; (2) have a particle size which in the range 0.2 to 0.3 microns (200-300nm); and/or (3) are treated with alumina, silica, zirconia or similar materials which form a coating around the Ti0 2 core to shield its photocatalytic activity.
  • a photocatalytic composition for photocatalysis of NOx wherein the coating composition comprises titanium dioxide in an anatase form and optionally also in a rutile form, and a carrier:
  • the ratio of rutile:anatase is between 95:5 and 0:100.
  • the photocatalytic composition of the invention comprises Ti0 2 nanoparticles.
  • the anatase form has greater photocatalytic activity, but the rutile form has a greater thermodynamic stability.
  • the incorporation of the anatase form of the titanium dioxide particles increases the photocatalytic activity of the composition.
  • the use of smaller particles also increases the photocatalytic activity of the composition.
  • the particle-size distribution (PSD) of a powder, or granular material, or particles dispersed in a fluid is a list of values or a mathematical function that defines the relative amount of particles present according to size.
  • the ratio of D90 value to the D10 value is an indication of the uniformity of particle sizes.
  • PSD is typically defined in the context of the method by which it is determined.
  • particle size is determined using transmission electron microscopy in accordance with ISO 13322-1:2014 which provides electron microscope operating conditions for particle size imaging and a measurement uncertainty analysis specifically for lognormal distributions, which would be the most common reference model for nanoparticle distributions.
  • the particle size is reported as an area-equivalent diameter.
  • the area-equivalent mean particle diameter of the Ti0 2 is less than lOOnm, in particular less than 50nm, in particular less than 25nm.
  • the D90 value of the TI0 2 is less than lOOnm, in particular less than 50nm, in particular less than 30nm, in particular less than 25nm.
  • the titanium dioxide particles have a mean particle diameter which is less than or equal to lOnm.
  • the D90 value of the titanium dioxide particles is equal to or less than lOnm.
  • the ratio of rutile:anatase is between 75:25 and 90:10, in particular between 80:20 and 90:10.
  • the ratio of rutile:anatase is from 0:100 to 5:95
  • the ratio of rutile:anatase in the Ti0 2 can be determined by quantitative analysis using X-ray diffraction techniques (for example K. Sakurai et al., Anal. Chem. 2010, 82, 9, 3519-3522).
  • the ratio between the different forms of the Ti0 2 in the formulation is typically a balance between the desired photocatalytic activity and the thermodynamic stability of the Ti0 2 in the formulation.
  • the composition comprises between 0.05 and 20 w/w% Ti0 2 , in particular between 0.5 and 15 w/w% Ti0 2 , more particularly between 1 and 15 w/w% Ti0 2 ; more particularly between 2.5 and 15 w/w% Ti0 2 ; more particularly between 5 and 15 w/w% TiO 3 ⁇ 4 more particularly between 10 and 15 w/w% Ti0 2 .
  • w/w% Ti0 2 is weight of Ti0 2 as a percentage of the total weight of the composition.
  • 'carrier' means a substance, typically inert, which serves as a vehicle for the Ti0 2 .
  • the composition must be suitable for application to a surface.
  • the carrier must be capable of being applied to the surface and must be compatible with the surface.
  • the composition is typically suitable for application to horizontal and vertical surfaces.
  • the carrier may comprise one or more surface active agents (surfactants).
  • the carrier may comprise a cationic surfactant.
  • the carrier may further comprise a non-ionic surfactant.
  • the non-ionic surfactant may comprise a fluoro-surfactant.
  • the carrier may comprise a cationic surfactant and a non-ionic surfactant.
  • the cationic surfactant my form the major surfactant component of the carrier.
  • the cationic surfactant may comprise more than 50% of the surfactant components in the carrier.
  • the carrier may comprise a cationic surfactant and a non-ionic surfactant (e.g. a fluoro- surfactant), wherein the ratio of cationic surfactant to non-ionic surfactant is from 2:1 to 100:1.
  • the ratio of cationic surfactant to non-ionic surfactant may be from 5:1 to 50:1; from 10:1 to 40:1; from 20:1 to 40:1; or from 25:1 to 35:1.
  • the carrier is a surfactant-based carrier which comprises one or more surfactant components and non-active solvents, such as water.
  • a surfactant-based carrier is able to carry the titanium dioxide particles to the substrate without necessarily encapsulating the titanium dioxide particles, which may decrease their ability to create a Ti0 2 -NOx interface.
  • a carrier which comprises surface active agents is less likely to be photo-catalysed by the titanium dioxide particles in the composition, which are selected for their photo-catalytic activity.
  • the carrier may be a polymeric carrier.
  • the polymer may selected from vinyl acetate-based polymers, such as polyvinyl acetate (PVA) or vinyl acetate/ethylene copolymer (VAE); acrylic polymers, polyurethane polymer; polyalkylene polymers; and mixtures thereof.
  • PVA polyvinyl acetate
  • VAE vinyl acetate/ethylene copolymer
  • acrylic polymers acrylic polymers, polyurethane polymer
  • polyalkylene polymers polyalkylene polymers
  • the carrier may be in the form of an aqueous solution, dispersion or emulsion.
  • An aqueous carrier is useful as organic carriers are more tightly regulated and controlled. Coating processes tend to use aqueous components where possible to avoid the health and safety issues relating to the storage, handling, use and disposal of organic compounds.
  • the carrier may also include a silicate binder.
  • silicate binder may be in the form of sodium silicate, lithium silicate, potassium silicate, calcium silicate or magnesium silicate.
  • silicate includes metasilicates, orthosilicates and pyrosilicates.
  • composition may further comprise an emulsifier, such as a sodium phosphate.
  • an emulsifier such as a sodium phosphate.
  • the composition may further comprise an anti-microbial agent, such as an anti-fungal agent and/or an anti-bacterial agent, wherein the anti-microbial agent is different to the Ti0 2 .
  • an anti-microbial agent such as an anti-fungal agent and/or an anti-bacterial agent, wherein the anti-microbial agent is different to the Ti0 2 .
  • the anti-microbial agent may include a zinc compound or complex, a silver compound or complex and/or a heterocyclic compound including nitrogen and sulphur heteroatoms.
  • the anti-microbial agent includes a zinc compound or complex.
  • the anti-microbial agent includes a heterocyclic compound formed from a heterocycle core containing one or more nitrogen heteroatoms and a heterocyclic substituent containing one or more sulphur heteroatoms.
  • Example anti-microbial agents include, but are not limited to, zinc oxide, Bis[l-Hydroxy-2(lH)-pyridinethionato-0,S]-T-4 zinc and 2-(4-thiazolyl)benzimidazole.
  • the zinc compound comprises a pair of pyridine-based ligands in which the sulphur and oxygen atoms of the ligands are bound to the zinc.
  • the composition may further comprise a rheology modifier.
  • a rheology modifier may control the viscosity of the composition and therefore shelf stability, ease of application, open time/wet edge and sagging.
  • the rheology may also influence levelling, settling and film forming.
  • Rheology modifiers include, but are not limited to: cellulosic modifiers, such as Methyl cellulose, Hydroxy ethyl cellulose (HEC), Carboxy methyl cellulose (CMC), Hydroxy propyl cellulose (HPC), and Hydrophobically modified HEC; Acrylates such as alkali-swellable emulsions (ASE) or Hydrophobically modified alkali-swellable emulsions (HASE); associative thickeners such as Hydrophobically modified polyurethanes (HEUR) and Hydrophobically modified polyethers (HMPE); and clays.
  • cellulosic modifiers such as Methyl cellulose, Hydroxy ethyl cellulose (HEC), Carboxy methyl cellulose (CMC), Hydroxy propyl cellulose (HPC), and Hydrophobically modified HEC
  • Acrylates such as alkali-swellable emulsions (ASE) or Hydrophobically modified alkali-swellable emul
  • open time/ wet edge of a coating is a measure of how much time an air-dry composition takes to reach a stage where it can no longer be applied the same "wet” coating without leaving an indication on drying that the "wet” and newly applied coating did not quite flow together.
  • composition may further comprise one or more additional functional additives, for example to improve fire retardant or UV resistant properties or to improve the mechanical properties or increase durability.
  • the composition is a paint composition.
  • the term "paint” is any liquid, liquefiable, or mastic composition that, after application to a substrate in a thin layer, converts to a solid film.
  • the composition is an architectural coating composition suitable for use in coating buildings.
  • the composition is an architectural paint composition suitable for coating buildings.
  • the composition is an exterior architectural paint composition suitable for coating the exterior of buildings.
  • the photocatalytic composition is applied to a substrate to provide the substrate with a photo-catalytic agent on a surface thereof.
  • the photocatalytic agent forms a transparent coating.
  • coating is intended to mean an adhered layer of the photocatalytic titanium dioxide particles.
  • the coating may comprise a single continuous layer of the titanium dioxide particles (for example when the particles are encapsulated within a polymeric film) or it may contain a discontinuous layer where the individual particles are effectively adhered to the substrate (for example where the carrier is a surfactant-based carrier).
  • the air-purification performance of a substrate coated with the photocatalytic coating composition of the present invention in terms of NOx abatement may be determined according to methods set forth in ISO 22197-1:2016.
  • ISO 22197-1:2016 specifies a test method for the determination of the air- purification performance of materials that contain a photocatalyst or have photocatalytic films on the surface, usually made from semiconducting metal oxides, such as titanium dioxide or other ceramic materials, by continuous exposure of a test piece to the model air pollutant under illumination with ultraviolet light.
  • the composition contains substantially no volatile organic compounds (VOCs).
  • VOCs volatile organic compounds
  • a VOC is defined as“any organic compound having an initial boiling point less than or egual to 250°C (482°F), measured at a standard atmospheric pressure of 101.3kPa” .
  • substantially no VOCs it is meant that the composition comprises less than 5%, suitably less than 3%, suitably less than 1%, suitably less than 0.1% or suitably 0% volatile organic compounds as defined above.
  • the composition of the invention may also provide protection for the substrate to which it is applied. Such protection may arise as a result of the composition being able to break down acidic components in the environment (for example, so-called "acid rain”) which may otherwise damage the substrate over time.
  • the coating may provide a protective layer over the substrate.
  • composition once applied to a substrate, it may provide a "self-cleaning" effect, whereby dirt or other particulate contaminants in the environment are prevented from adhering to the substrate and are washed off by rain or other precipitation.
  • photocatalytic particles on a substrate comprising: i) applying a composition as defined anywhere herein in relation to the first aspect of the invention to the substrate;
  • drying may be passive or active drying.
  • layer includes one or more layers, which may be continuous or discontinuous.
  • the carrier is a surfactant-based carrier and the coating comprises a discontinuous layer of the photocatalytic particles.
  • the photocatalytic coating is in the form of one or more substantially continuous polymeric layers.
  • at least some of the titanium dioxide particles applied to the substrate are exposed to the environment.
  • at least 10% of the applied titanium dioxide particles are exposed to the environment, at least 25% of the applied titanium dioxide particles are exposed to the environment, at least 50% of the applied titanium dioxide particles are exposed to the environment, at least 60% of the applied titanium dioxide particles are exposed to the environment, or at least 70% of the applied titanium dioxide particles are exposed to the environment.
  • the photocatalytic coating is transparent.
  • the coating is typically applied in liquid form in a solvent or water base, which evaporates to leave a dried coating.
  • the liquid may require thickening to prevent sagging, or an anti-foaming agent to aid processing.
  • the thickness of the coating, or amount of product applied is controlled. Bonding typically occurs either through the drying process
  • Polymers which may be used in the or each coating include, but are not limited to: vinyl acetate- based polymers, such as polyvinyl acetate (PVA) or vinyl acetate/ethylene copolymer (VAE); acrylic polymers, polyurethane polymer; polyalkylene polymers; and mixtures thereof.
  • PVAm polyvinyl acetate
  • VAE vinyl acetate/ethylene copolymer
  • the substrate may be coated with two or more layers.
  • the substrate may be coated with the photocatalytic coating and a second polymeric coating.
  • the substrate is coated with an intermediate coating which comprises a substantially continuous polymeric layer and the intermediate coating is located between the substrate and an outer layer formed from the photocatalytic coating.
  • the intermediate coating may be in the form of a substantially continuous layer and the outer layer comprising the T1O2 may also be substantially continuous.
  • the "outer layer” means the layer which is the furthest of the layers from the substrate. Thus, there may be more than one intermediate layer.
  • the substrate may include, but is not limited to: an interior or exterior wall, an interior or exterior floor, ceiling and roof.
  • the substrate may be an exterior wall, exterior floor or roof.
  • This example generates the titanium dioxide particles in situ, then incorporates the particles into a surfactant-based carrier.
  • the 5.84kg of amorphous titanium dioxide from Step 1 is mixed with 40kg of deionised water and 260g of tartaric acid. This mixture is then heated to 95°C and stirred for 4-6 hours after which time the mixture is clear. The mixture is then allowed to cool to 20°C.
  • the pH of the mixture produced in Step 2 is then adjusted to 8.1 to 8.6 by the addition of a 10% sodium silicate solution with stirring at 20°C.
  • Step 3 To the neutralised mixture of Step 3 is added a first part of the carrier composition comprising 3.39kg of a cationic surfactant (Varisoft TA 100 solution (0.105% active in water)). The mixture is stirred for 30 minutes, followed by the addition of a second part of the carrier composition comprising llOg of a non-ionic fluoro surfactant (Capstone FS30). The resultant composition is stirred for a further 15 minutes, after which it is ready for application or transfer to a suitable storage container.
  • a cationic surfactant Varisoft TA 100 solution (0.105% active in water
  • the titanium dioxide particles of Example 1 had a mean particle size diameter of less than lOnm.
  • This example generates the titanium dioxide particles in situ, then incorporates the particles into a surfactant-based carrier.
  • the 5.84kg of amorphous titanium dioxide from Step 1 is mixed with 40kg of deionised water and 260g of tartaric acid. This mixture is then heated to 95°C and stirred for 4-6 hours after which time the mixture is clear. The mixture is then allowed to cool to 20°C.
  • Step 2 To the mixture produced in Step 2 is added 2.33kg of triethylamine solution, and the resultant mixture is stirred for 4 hours. After this time, the mixture is heated to 50°C and mixed for a further 3 hours to drive off the remaining triethylamine. The pH of the resultant mixture is adjusted to 8.1 to 8.6 with sodium silicate solution.
  • Step 3 To the neutralised mixture of Step 3 is added a first part of the carrier composition comprising 3.39kg of a cationic surfactant (Varisoft TA 100 solution (0.105% active in water)). The mixture is stirred for 30 minutes, followed by the addition of a second part of the carrier composition comprising llOg of a non-ionic fluoro surfactant (Capstone FS30). The resultant composition is stirred for a further 15 minutes, after which it is ready for application or transfer to a suitable storage container.
  • a cationic surfactant Varisoft TA 100 solution (0.105% active in water
  • the titanium dioxide particles of Example 2 had a mean particle size diameter of less than lOnm.
  • This example uses commercially available titanium dioxide and a polymeric carrier. The components are mixed together to form a composition having the following composition:
  • Example 3 This example is similar to Example 3, but with a simplified composition:
  • the air-purification performance of a substrate coated with the photocatalytic composition of the present invention in terms of NOx abatement was determined according to methods set forth in ISO 22197-1:2016.
  • ISO 22197-1:2016 specifies a test method which includes the continuous exposure of a test piece to the model air pollutant under illumination with ultraviolet light.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Catalysts (AREA)

Abstract

L'invention concerne une composition photocatalytique pour photocatalyse de NOx, la composition comprenant du dioxyde de titane sous une forme d'anatase et éventuellement également sous une forme de rutile, et un support; le diamètre moyen des particules du TiO2 étant inférieur à 100 nm; et le rapport rutile:anatase étant compris entre 95:5 et 0:100.
PCT/EP2019/079439 2018-10-26 2019-10-28 Composition photocatalytique comprenant du dioxyde de titane et un support WO2020084169A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GBGB1817500.0A GB201817500D0 (en) 2018-10-26 2018-10-26 Coating composition
GB1817500.0 2018-10-26

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WO2020084169A1 true WO2020084169A1 (fr) 2020-04-30

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005075354A2 (fr) * 2004-02-06 2005-08-18 Kemira Pigments Oy Produit de dioxyde de titane, procede de production de celui-ci, et son utilisation en tant que photocatalyseur
WO2008048765A2 (fr) * 2006-10-18 2008-04-24 Millennium Inorganic Chemicals, Inc. COMPOSITION de revêtement dépolluant amélioré
WO2009029856A1 (fr) * 2007-08-31 2009-03-05 Millennium Inorganic Chemicals, Inc. Sols de dioxyde de titane, stables, transparents
WO2016207697A1 (fr) * 2015-06-24 2016-12-29 Am Technology Limited Composition photocatalytique à base de liant aérien et son utilisation pour la fabrication de peintures à base d'eau, en particulier pour applications intérieures

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005075354A2 (fr) * 2004-02-06 2005-08-18 Kemira Pigments Oy Produit de dioxyde de titane, procede de production de celui-ci, et son utilisation en tant que photocatalyseur
WO2008048765A2 (fr) * 2006-10-18 2008-04-24 Millennium Inorganic Chemicals, Inc. COMPOSITION de revêtement dépolluant amélioré
WO2009029856A1 (fr) * 2007-08-31 2009-03-05 Millennium Inorganic Chemicals, Inc. Sols de dioxyde de titane, stables, transparents
WO2016207697A1 (fr) * 2015-06-24 2016-12-29 Am Technology Limited Composition photocatalytique à base de liant aérien et son utilisation pour la fabrication de peintures à base d'eau, en particulier pour applications intérieures

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
A. FUJISHIMAK. HONDA, NATURE, vol. 238, 1972, pages 37
CHEN, H.NANAYAKKARA, C. E.GRASSIAN, V. H.: "Titanium dioxide photocatalysis in atmospheric chemistry", CHEM. REV., vol. 112, 2012, pages 5919 - 5948
K. SAKURAI ET AL., ANAL. CHEM., vol. 82, no. 9, 2010, pages 3519 - 3522

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