WO2004062795A1 - Films minces de tio2 optiquement transparents sur du verre possedant des activites anti-bacteriennes et anti-virales et procede de preparation associe - Google Patents

Films minces de tio2 optiquement transparents sur du verre possedant des activites anti-bacteriennes et anti-virales et procede de preparation associe Download PDF

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Publication number
WO2004062795A1
WO2004062795A1 PCT/CN2004/000022 CN2004000022W WO2004062795A1 WO 2004062795 A1 WO2004062795 A1 WO 2004062795A1 CN 2004000022 W CN2004000022 W CN 2004000022W WO 2004062795 A1 WO2004062795 A1 WO 2004062795A1
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Prior art keywords
surfactant
tio
hours
reverse micelle
glass
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PCT/CN2004/000022
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English (en)
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Jimmy Chai-Mei Yu
Jun Lin
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The Chinese University Of Hong Kong
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Publication of WO2004062795A1 publication Critical patent/WO2004062795A1/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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G23/00—Compounds of titanium
    • C01G23/04—Oxides; Hydroxides
    • C01G23/047—Titanium dioxide
    • C01G23/053—Producing by wet processes, e.g. hydrolysing titanium salts
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/30—Treatment of water, waste water, or sewage by irradiation
    • C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
    • C03C17/23—Oxides
    • C03C17/25—Oxides by deposition from the liquid phase
    • C03C17/256—Coating containing TiO2
    • 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
    • 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
    • B01J37/033—Using Hydrolysis
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/84—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by UV- or VIS- data
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2204/00—Glasses, glazes or enamels with special properties
    • C03C2204/02—Antibacterial glass, glaze or enamel
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/20—Materials for coating a single layer on glass
    • C03C2217/21—Oxides
    • C03C2217/212—TiO2
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/70—Properties of coatings
    • C03C2217/71—Photocatalytic coatings
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2218/00—Methods for coating glass
    • C03C2218/10—Deposition methods
    • C03C2218/11—Deposition methods from solutions or suspensions
    • C03C2218/111—Deposition methods from solutions or suspensions by dipping, immersion

Definitions

  • the invention relates to a method for preparing nano-crystalline TiO thin films, and to applications of the thin films in cleaning itself, air and water where the films are located. Particularly, the invention is directed to use of the optically transparent nano-crystalline TiO thin films under ultraviolet irradiation in killing bacteria, germs and viruses in the environment.
  • Glass has been widely used in modern construction industry. It is used as material not only for constituting common windows and doors as well as French windows, but also for constituting walls of buildings such as housings, offices, shopping malls and hospitals. Glass is also an important media with which people can view beauty of the Nature, and enjoy the sunlight under a desired and comfortable environment.
  • TiO 2 thin films on substrates prepared by suitable processes have anti-bacterial and anti-virus activities. Therefore, it is desired that an optically transparent TiO 2 thin film having anti-bacterial and anti- virus activities is formed on the surface of glass used in the buildings mentioned above. It is more preferable if the thin film on glass can not only freshen air of the environment by decomposing organic pollutants existing in the environment but also kill germina and bacteria on contact, in view of more and more serious pollution of the environment. Meanwhile, the thin film does not reduce the transparency of the glass and visible light irradiation in the sunlight any more. This would greatly improve the environment of human livings.
  • the present inventors have disclosed in the Chinese patent application No. 02147089.8 a method f or p reparing n ano-crystalline TiO 2 1 hin films o n a s ubstrate and u se o f t he t hin films .
  • the method in this application includes providing a reverse micelle solution containing highly-dispersed water nano-droplets, which is made from an organic continuous phase, a non-ionic surfactant and water; adding a titanium alkoxide to the reverse micelle solution and subjecting the titanium alkoxide to hydrolysis in the water nano-droplets to form a TiO 2 -containing solution; forming a wet film onto a substrate dipped into the TiO 2 -containing solution by a dip coating technique; and drying the wet film and calcining the dried film.
  • the thin films formed on the substrate disclosed in this application can kill the bacteria and viruses in the environment under ultraviolet irradiation.
  • the inventors have developed a new method for preparing TiO 2 thin film on common glass, and hereby provide the present invention.
  • the thin l film prepared by the method in the present invention exhibits an excellent photocatalytic performance like that in the Chinese patent application.
  • the method also has several advantages that are not achieved in the prior art.
  • the thin film prepared by the method is optically transparent in visible range and very uniform after formed on a glass substrate; the reverse micelle solution used for preparing TiO 2 thin films in the present invention is more thermodynamic stable than that in the prior art.
  • the present invention is provided to address these problems in the art.
  • an object of the invention is to provide a method for preparing an optically transparent TiO 2 thin film on the surface of glass having fungicidal and antivirus activities.
  • the method of the invention comprises the steps of: a) providing a reverse micelle solution containing highly-dispersed water nano-droplets, which is made from an organic continuous phase, a non-ionic surfactant, a co-surfactant and water; b) adding a titanium alkoxide to the reverse micelle solution and subjecting the titanium alkoxide to hydrolysis in the nano-droplets of the reverse micelle solution to form a
  • Another object of the invention is to provide an optically transparent TiO 2 thin film prepared by the method of the invention.
  • the invention has many advantages that the TiO 2 thin film formed onto glass is optically transparent; anatase TiO 2 in the film is highly crystalline and nano-crystalline TiO 2 has an obvious quantum size effect; the thin film can be formed on glass in various shapes in no need of any specific manufacturing apparatus; the phase constitution and composition of the TiO 2 thin film can be readily controlled upon the need, for example, pure anatase TiO 2 in the thin film can be obtained; and the thin film prepared in the presence of different specific surfactants and c o-surfactants has a specific p orous structure and distribution, resulting in a higher content of hydroxyl group at the surface of the thin film.
  • Fig. 1 is the polycrystalline X-ray diffraction patterns of nano-TiO 2 thin films of the present invention on glass;
  • Fig. 2 is an ultraviolet absorption spectrum of nano-TiO 2 thin films of the present invention on glass;
  • Fig. 3 shows the photo-induced antibacterial activities of thin films of the present invention on glass
  • Fig. 4 shows the hydrophilicity of thin films of the present invention on glass
  • Fig. 5 shows the photocatalytic activities of thin films of the present invention on glass for the degradation of acetone in air
  • Fig. 6 shows the formation process of amorphous TiO 2 by controlled hydrolysis and condensation of titanium alkoxide in reverse micelles in a continuous phase in the present invention.
  • the invention provides an effective method for preparing optically transparent TiO 2 thin films on glass.
  • the TiO 2 thin films prepared in the invention are highly optically transparent in the visible range.
  • the thin films can kill all kinds of bacteria on contact, such as colon bacillus, comma bacillus, and pathogenic protoplast, and photocatalytically degrade organic pollutants in the environment, so as to clean the environment where the films are located.
  • water phase is highly dispersed as nano-droplets in an organic continuous phase in the presence of a surfactant and a co-surfactant to form a reverse micelle solution.
  • titanium alkoxide is added to the reverse micelle solution.
  • the titanium alkoxide in the reverse micelle solution penetrates the mono-layer of the surfactants into water nano-droplets to form amorphous TiO 2 by controlled hydrolysis and condensation in the reverse micelles.
  • the formation process of amorphous TiO 2 is shown in Fig.
  • the organic continuous phase may be non-polar or lower-polar organic solvents at the ambient temperature.
  • the organic continuous phases may include: unsubstituted alkanes or alkanes substituted with one or more substituents (substituting groups), unsubstituted alkenes or alkenes substituted with one or more substituents, unsubstituted alkynes or alkynes substituted with one or more substituents, and unsubstituted aromatic hydrocarbons or aromatic hydrocarbons substituted w ith o ne o r more s ubstituents.
  • the s ubstituents o r s ubstituting groups u sed h erein includes, but not limited to, lower alkyl, halide, hydroxyl, lower alkoxyl, cyanide, nitro and the like.
  • the continuous phase used in the invention is C 3 . 8 alkane or cycloalkane, more • preferably, it is C 5 . 6 clycloalkane, and most preferably, it is cyclohexane.
  • the number of the substituents maybe from 1 to 3, and preferably it is 1.
  • alkane, alkene and alkyne used in the invention include both straight chain and branch chain and cyclic alkane, alkene, and alkyne.
  • non-ionic surfactants used include polyols partial fatty acid esters,- poly oxyethylene aliphatic alcohol ether, polyoxyethylene alkyl phenol ether, Triton series.
  • Triton series such as Triton X-100 and Triton X-405 are preferably surfactants, of which Triton X-100 is more preferable.
  • co-surfactant used in the invention means organic agents with a polarity between those of water and the organic continuous phase used in the reverse micelle solution in the invention, and may help the non-ionic surfactant of the invention stabilize water nano-droplets in the reverse micelle solution so as to keep the formed TiO 2 particle as small as possible, hereby to produce the thin film having higher optical transparency.
  • suitable co-surfactants are selected from C 4 . 8 alkanol, and n-hexanol is preferable.
  • alkyl titanate has the same meaning as "titanium alkoxide”.
  • Alkyl titanate according to the invention is selected from those that can be easily hydrolyzed to
  • Alkyl portion in alkyl titanate may be selected from C alkyl, more preferably from C . alkyl, and most preferably ethyl and iso-propyl.
  • the concentration of the non-ionic surfactant in the reverse micelle solution is generally from 0.20 to 0.40M, and preferably 0.3M.
  • concentration of titanium alkoxide in the reverse micelle solution of the invention is generally from 0.1 to 0.25M, and preferably from 0.15 to
  • the molar ratio of water to the surfactant used in the invention may be from 1.0 to 2.5, preferably from 1.5 to 2.0.
  • the molar ratio of the surfactant to the co-surfactant may be from 0.1 to 0.2, preferably 0.15.
  • a small amount of a stabilizer can be added to the reverse micelle solution to control the rate of hydrolysis of the titanium alkoxide.
  • 2,4-diketone may be used as the stabilizer of the invention. It is well-known for those skilled in the art to select a proper stabilizer in the invention and the amount thereof used in the invention.
  • the amount of the stabilizer used in the invention is ranged from 1 to 10% by volume of the reverse micelle solution.
  • acetyl acetone is used in the invention and accounts for
  • the withdrawal speed in step c) of the method of the invention can be adjusted based on desired properties of thin films prepared.
  • the speed is normally set at 3-6mm/s, preferably 4mm/s.
  • the drying temperature of the wet film in step d) is in general at 80°-120°C, and preferably at 100°C for 10 minutes to 1.5 hours.
  • the dried film may be calcined at a temperature ranging from 400° to 580°C, preferably from 470° to 550°C, and more preferably at 550°C.
  • the dried film may be calcined for 1 to 4 hours, preferably 1.5 to 2.5 hours, and more preferably 2 hours.
  • t he i nventors h ave found t hat t he p resence o f a co-surfactant together with a surfactant in a reverse micelle solution can help stabilize the water nano-droplets and inhibit the aggregation and growth of the nano-droplets.
  • the TiO 2 reverse micelle solution formed by controlled hydrolysis and condensation of titanium alkoxide in the reverse micelles exhibits the following advantages: (1) the formed amorphous TiO 2 particles in the reverse micelles are very fine; (2) the formed TiO 2 reverse micelle solution is very thermodynamically stable, and no TiO 2 particles aggregation and precipitation occur; and (3) the formed TiO 2 reverse micelle solution can produce a uniform and optically transparent nano-crystalline TiO thin film on a glass substrate by dip-coating technology.
  • a homogenous amorphous TiO 2 gel layer is formed onto the surface of glass with the dip coating technique.
  • An optically transparent crystalline TiO 2 thin film will be formed after calcined.
  • the substrate of glass used in the invention is preferably cleaned before dipped in the reverse micelle solution so as to achieve a good affinity between the TiO thin film and the substrate.
  • the dip coating technique used in the method of the invention is the same as that used in the prior art. Detailed information on the dip coating technique can be referred to R. Reisfeld and C. K. Jorgensen, 77 Structure and Bonding; Chemistry: Spectroscopy and Applications of Sol-gel Glass, Springer- Verlag, 1992, Berlin, pp91-95.
  • Triton X-100 (.35g), n-hexanol and water, and resultant mixture was stirred for 1 hour to obtain a reverse micelle solution, i the solution, the concentration of Triton X-100 is 0.3M, the molar ratio of Triton X-100 to n-hexanol was 0.15 and that of water to Triton X-100 was 2.
  • isopropyl titanate together with 5ml of acetyl acetone was added to the reverse micelle solution. The concentration of the titanate was kept at 0.2M in the reverse micelle solution.
  • Example 1 was shown in Fig. 2.
  • the thin film is highly transparent in the visible range.
  • the absorption edge starts at a wavelength shorter than 387.5nm (3.2eV) indicating the quantum-sized effect.
  • Photocatalytic antibacterial activities of TiO 2 thin film prepared in Example 1 was evaluated by killing Bacillus pumilusi in an aqueous solution under ultraviolet irradiation.
  • the procedures were shown as follows. 2ml of an aqueous solution of Bacillus pumilusi having a concentration of 1 x 10 7 CFU/ml was pipetted onto the TiO 2 thin film on glass as prepared in
  • Example 1 The glass was illuminated by a 15W 365nm UV lamp (Cole-Parmer Instrument Co.) at a light intensity of 0.63mW/cm 2 . 20 or 40 ⁇ l of diluted solution containing Bacillus pumillusi was dispensed into 1 ml of phosphate buffer. Resultant solution was plated on Luria-Bertani (LB) agar plates. The plate was then incubated at 37°C for 24h, and the number of colonies on the plate was counted at an interval o f 20 minutes. The change in the number of b acteria on the surface TiO 2 thin films on glass was calculated.
  • LB Luria-Bertani
  • Hydrophilicity of a TiO 2 thin film prepared in Example 1 was evaluated with a change of the contact angle between water and the thin film under ultraviolet irradiation (15W 365nm, Cole-Parmer Instrument Co.). The contact angle was measured by an instrument, Model CA-XP, Kyowa Interface Science Co. Ltd., Japan. A thin film on glass as prepared in Example 1 was exposed to air for 2 months to have the contact angle of water on the thin film increased to 43°. Then, the thin film was irradiated by ultraviolet light to measure the contact angle at different time. The results were shown in Fig. 4, which indicated that the contact angle was decreased from 43° to around 5° after the thin film was irradiated for 2 hours. It was understood that thin film of the invention had an excellent hydrophilicity.
  • the photocatalytic activity of the TiO 2 thin film as prepared in Example 1 was evaluated by the degradation of acetone in air under ultraviolet irradiation.
  • the area of the TiO 2 thin film used for experiment was 150cm 2 in a 7,000ml reactor.
  • the equilibrium concentration of acetone was controlled at 407+lppm, and the initial concentration of water vapor was adjusted to 1.2+0.01 vol%, and the temperature was regulated at 25 ⁇ 1°C.
  • the ultraviolet w as generated by a 1 5W 365nm UV lamp (Cole-Parmer Instrument C o.). The UV lamp was positioned 2.5 cm above the glass coated with the TiO 2 thin film.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • Hydrology & Water Resources (AREA)
  • Water Supply & Treatment (AREA)
  • Geology (AREA)
  • Inorganic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Catalysts (AREA)

Abstract

Les modes de réalisation préférés portent sur un procédé de préparation d'un film mince de TiO2 optiquement transparent sur du verre. Les modes de réalisation préférés concernent aussi des films minces préparés selon ce procédé. Les films minces de TiO2 selon l'invention présentent une activité photocatalytique plus élevée, et servent notamment à la dégradation photocatalytique de polluants organiques dans l'air et à l'élimination de bactéries, de germes et de virus dans l'air.
PCT/CN2004/000022 2003-01-08 2004-01-07 Films minces de tio2 optiquement transparents sur du verre possedant des activites anti-bacteriennes et anti-virales et procede de preparation associe WO2004062795A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN03100058.4 2003-01-08
CN03100058.4A CN1245348C (zh) 2003-01-08 2003-01-08 光学透明二氧化钛薄膜的制备方法及其得到的薄膜

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US12/315,040 Continuation-In-Part US8868891B2 (en) 2004-03-18 2008-11-26 Method and apparatus to support booting despite deficient resources

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Cited By (6)

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WO2005121030A1 (fr) * 2004-06-07 2005-12-22 Centro De Investigaciones Energeticas Medioambientales Y Tecnologicas (C.I.E.M.A.T.) Dispositif integre pour la decontamination de l'eau et la production d'energie electrique
CN100410184C (zh) * 2006-03-21 2008-08-13 大连理工大学 一种光催化脱除水中氮的方法
US7534293B2 (en) 2005-05-11 2009-05-19 Agency For Science, Technology And Research Method and solution for forming anatase titanium dioxide, and titanium dioxide particles, colloidal dispersion and film
CN1850691B (zh) * 2006-05-25 2010-10-06 上海交通大学 玻璃基片表面绝缘性二氧化钛纳米薄膜的制备方法
US8273413B2 (en) 2009-07-02 2012-09-25 International Business Machines Corporation Methods of forming metal oxide nanostructures, and nanostructures thereof
CN111620569A (zh) * 2020-06-23 2020-09-04 中建材蚌埠玻璃工业设计研究院有限公司 一种抗病毒玻璃及其制备方法

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CN103586090B (zh) * 2013-01-07 2016-04-06 纳米及先进材料研发院有限公司 一种空气及水净化材料的制备方法
CN106277811B (zh) * 2016-08-12 2019-01-11 海南大学 一种玻璃基板和玻璃表面的镀膜方法

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CN1400185A (zh) * 2001-07-31 2003-03-05 武汉理工大学 制备高活性二氧化钛薄膜自洁净玻璃材料的方法
CN1400186A (zh) * 2001-07-31 2003-03-05 武汉理工大学 提高二氧化钛薄膜自洁净玻璃光催化活性的方法
CN1454474A (zh) * 2002-04-30 2003-11-12 香港中文大学 具有高杀菌光活性介孔二氧化钛薄膜的制备方法
CN1397377A (zh) * 2002-08-14 2003-02-19 清华大学 可用于水和空气净化的二氧化钛光催化薄膜的制备方法
CN1417147A (zh) * 2002-11-26 2003-05-14 复旦大学 一种纳米二氧化钛自清洁玻璃的低温制备方法
CN1433841A (zh) * 2003-01-21 2003-08-06 武汉理工大学 纳晶二氧化钛光催化剂的低温溶剂蒸发诱导结晶方法制备
CN1438071A (zh) * 2003-03-13 2003-08-27 武汉理工大学 表面氟化处理增强二氧化钛光催化活性的方法

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WO2005121030A1 (fr) * 2004-06-07 2005-12-22 Centro De Investigaciones Energeticas Medioambientales Y Tecnologicas (C.I.E.M.A.T.) Dispositif integre pour la decontamination de l'eau et la production d'energie electrique
US7534293B2 (en) 2005-05-11 2009-05-19 Agency For Science, Technology And Research Method and solution for forming anatase titanium dioxide, and titanium dioxide particles, colloidal dispersion and film
CN100410184C (zh) * 2006-03-21 2008-08-13 大连理工大学 一种光催化脱除水中氮的方法
CN1850691B (zh) * 2006-05-25 2010-10-06 上海交通大学 玻璃基片表面绝缘性二氧化钛纳米薄膜的制备方法
US8273413B2 (en) 2009-07-02 2012-09-25 International Business Machines Corporation Methods of forming metal oxide nanostructures, and nanostructures thereof
US8771632B2 (en) 2009-07-02 2014-07-08 International Business Machines Corporation Methods of forming metal oxide nanostructures, and nanostructures thereof
CN111620569A (zh) * 2020-06-23 2020-09-04 中建材蚌埠玻璃工业设计研究院有限公司 一种抗病毒玻璃及其制备方法
CN111620569B (zh) * 2020-06-23 2022-12-27 中建材玻璃新材料研究院集团有限公司 一种抗病毒玻璃及其制备方法

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