CN101190828B - Method for forming metal composite titanium dioxide nano particle film on glass surface - Google Patents
Method for forming metal composite titanium dioxide nano particle film on glass surface Download PDFInfo
- Publication number
- CN101190828B CN101190828B CN2006101147507A CN200610114750A CN101190828B CN 101190828 B CN101190828 B CN 101190828B CN 2006101147507 A CN2006101147507 A CN 2006101147507A CN 200610114750 A CN200610114750 A CN 200610114750A CN 101190828 B CN101190828 B CN 101190828B
- Authority
- CN
- China
- Prior art keywords
- titanium dioxide
- nano particle
- dioxide nano
- metal composite
- composite titanium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Images
Abstract
The invention pertains to the application field of nano material and photocatalysis technology, in particular to a method for forming a serials of metal titanium dioxide nanoparticle film with functions of sterilization, anti-mildew, deodorant, degradation of organic pollutants, decomposition of harmful gases and good hydrophilic property. The method comprises: hydro-thermal synthesis method is adopted, which is of high crystallinity; the crystalline phases make up of the metal titanium dioxide nanoparticles which are then dispersed to form sol; thereby, the nanoparticles are solidified to form a layer of film on glass surface. The film has good performances of degradation organics, hydrophile and self-cleaning.
Description
Technical field
The invention belongs to nano material and light-catalysed applied technical field, be particularly related to the use hydrothermal method, synthetic crystallization degree height, titanium dioxide nano-particle with specific crystal formation, form colloidal sol behind the nanoparticle redispersion, on glass surface, form a series of methods after the plated film thermofixation with metal composite titanium dioxide nano particle film of sterilization, mildew-resistant, deodorizing, degradable organic pollutant, resolving harmful gas function and good hydrophilic ability.
Background technology
In recent years, the office block of Highrise buildings, glass curtain wall formula etc. are Beijing especially in the city, big cities such as Shanghai emerge in multitude like the mushrooms after rain.It is that the cleaning of glass must working aloft that the appearing as of these high-rises brought new problem keeping a public place clean of building glass.Like this, the routine cleaning of glass is dangerous high, with high costs.In addition, in the cleaning course of glass, also need to use a large amount of washing composition, undoubtedly, will bring harm for environment.For solving this problem, the research based on the self-cleaning glass of optically catalytic TiO 2 performance has in recent years attracted the great interest of investigator.At present, several method below preparation titanium dioxide automatically cleaning film mainly contains on substrate of glass: (1) magnetron sputtering method; (2) high temperature pyrolytic cracking (HTP); (3) sol-gel method.Magnetron sputtering method needs the environment for use of specific equipment and high temperature, high vacuum, and the cost during enforcement is higher.Simultaneously, the glasswork outward appearance of using magnetron sputtering method to obtain is turned white, and there are certain gap in apparent property and simple glass.High temperature pyrolytic cracking (HTP) generally uses the alkoxide of titanium as precursor, and the alkoxide of pyrolysis titanium prepares titanium dioxide nano particle film under the high temperature of three or four hundred degree, and in general, film is dense, is unfavorable for the hydrophilic long-term maintenance of titanium dioxide nano particle film.Sol-gel method is the most a kind of method for preparing self-cleaning glass of studying at present.As precursor,, again TiO 2 sol is supported on the film of nanoparticles that obtains titanium dioxide on the substrate of glass with the alkoxide of titanium by the stable TiO 2 sol of Prepared by Sol Gel Method.The report of this respect can be referring to " nature " 1997 the 388th volumes 431 pages of (Wang, R., Hashimoto, K., Fujishima, A., Nature, 1997,388,431), " new The Chemicals " 1996 20 volumes 233 pages of (Sitkiewiitz, S., Heller, A., New J.Chem., 1996,20,233) and 726 pages of (Sunada of " environmental science and technology " 1998 the 32nd volume, K., Kikuchi, Y., Hashimoto, K., Fujishima, A., Eviron.Sci.Techno., 1998,32,726) etc.TiO 2 particles in the TiO 2 sol that uses in this method is undefined structure, titanium dioxide film in the elevated temperature heat solidification process, particulate growth highly significant; Simultaneously, the particulate crystal formation also may bring the cracking of film from unformed crystal transition in opposite directions in the sintering process.Existing studies show that, the obvious reduction that particulate is significantly grown and brought glass visible region transmittance in the sintering process.Weathering resistance is investigated and is also shown, use the hydrophilic hold-time of titanium dioxide film of sol-gel method preparation very short, this may be relevant with underlying cause: contain a large amount of organism in coating liquid-TiO 2 sol, the sintering caudacoria is better relatively to organic affinity; The crystallization degree of titanium dioxide is lower, thereby has influenced the photocatalytic activity of TiO 2 particles.Because the shortcoming of sol-gel method for obtaining being enough to the self-cleaning glass of practicability, also need be developed new technology.
Summary of the invention
One of purpose of the present invention provides a kind of method that forms the metal composite titanium dioxide nano particle film with specific crystalline phase composition on glass surface, in order to preparation photocatalytic activity height, the self-cleaning glass goods that the wetting ability hold-time is long.
Two of purpose of the present invention is that metal inorganic salt-titanium tetrachloride more cheap with relative metal alkoxide, that be easy to get is a main raw material, use the pH value of alkali regulation system, the synthetic crystalline phase of utilization hydrothermal method is formed certain, the metal composite titanium dioxide nano particle that crystallization degree is high; Disperse to obtain colloidal sol behind this particle, as the raw material of realizing the inventive method,, improve the performance and the weathering resistance of goods in order to overcome the shortcoming that particle size significantly increases in the sintering process that common method brings with this colloidal sol.
Three of purpose of the present invention is to add metal-salt or metal complex when the hydrothermal preparation metal composite titanium dioxide nano particle, makes the particle membrane of glass surface have certain assassination bacterium function and certain visible light catalytic performance.
The use crystalline state is good, crystalline phase is formed the colloidal solution of certain titanium dioxide nano-particle as coated solution, the preparation self-cleaning glass both can overcome the remarkable growth question of titanium dioxide nano-particle in the high-temperature sintering process that sol-gel method brings, and was favourable to the photocatalysis performance that improves titanium dioxide again.Based on this principle, the inventor has proposed method of the present invention, and this method comprises:
(1) the synthetic crystalline phase of hydrothermal method is formed certain metal composite titanium dioxide nano particle;
(2) washing redispersion metal composite titanium dioxide nano particle;
(3) thermofixation behind the glass surface plated film.
Metal composite titanium dioxide nano particle of the present invention is prepared by following method, and this method may further comprise the steps, and related amount is in parts by weight:
(1) gets 15～65 parts of titanium tetrachlorides addings and place 35～85 portions of frozen water of 0～10 ℃ of water-bath, continue to stir after 30 minutes～5 hours, filter, obtain transparent, clarifying titanium tetrachloride aqueous solution after the collection lower floor filtrate;
(2) with 0.0001～3 part water miscible transition metal salt, 0～10 part complexing agent joins in 87～99.9999 parts the deionized water, obtains transition metal salt solution or by the transition metal salt solution of complexing agent complexing;
(3) 10～40 parts mineral alkali is joined in 60～90 parts the deionized water and obtain alkaline solution after the dissolving;
(4) under stirring fast, add the transition metal salt of 0.1～30 part of step (2) in the titanium tetrachloride aqueous solution of 10～50 parts of steps (1) or by the transition metal salt solution of complexing agent complexing, after continuing stirred for several minute, the alkaline solution that adds 0.05～30 part of step (3) is added to continue behind the deionized water to stir and was made it uniform mixing in 1 minute～2 hours; Above-mentioned solution is transferred to middle the pressure in the still, in 100～300 ℃ of constant temperature;
(5) behind the solution naturally cooling that step (4) is obtained, the supernatant liquid that inclines filters lower sediment, after the washing lower sediment 1～10 time, use small amount of deionized water that precipitation is transferred to and obtain the crystallization degree height in the container, crystalline phase is formed certain metal composite titanium dioxide nano particle slurries;
(6) 0.5～20 part tensio-active agent is joined in 80～99.5 parts the deionized water and obtain water phase surfactant mixture;
(7) under vigorous stirring, in the metal composite titanium dioxide nano particle slurry of 5～50 parts of steps (5), add 0～94 part the deionized water and the water phase surfactant mixture of 1～50 part of step (6), 10～60 ℃ continue down to stir 5 minutes～5 hours, ultra-sonic dispersion stirred 0～10 hour after 2 minutes～4 hours, leave standstill, obtain metal composite titanium dioxide nano particle colloidal sol after the filtration.
The deionized water that described step (4) was added before constant temperature is 30～89.95 parts.
Described step (4) constant temperature time is 30 minutes～24 hours.
The described transition metal of step (2) is iron, silver, nickel, platinum, iridium, zinc, palladium or copper etc.
The described complexing agent of step (2) is ammoniacal liquor, oxalate, thiosulphate, thiocyanate-, citric acid, tartrate, trolamine, diethanolamine or amino acid etc.
The described alkali of step (3) is sodium hydroxide, potassium hydroxide, yellow soda ash, salt of wormwood, sodium bicarbonate, saleratus or ammoniacal liquor.
The described tensio-active agent of step (6) is polyoxyethylene glycol, polyvinyl alcohol, polyvinylpyrrolidone or polyoxyethylene glycol-b-polypropylene glycol-b-polyoxyethylene glycol amphipathic three block copolymer.
The crystalline phase of described metal composite titanium dioxide nano particle consists of the duplex grain structure of Detitanium-ore-type, rutile-type, Detitanium-ore-type and rutile-type or the duplex grain structure of Detitanium-ore-type and brookite type (content of brookite is not more than 20%).
The particle size of described metal composite titanium dioxide nano particle is 3～100 nanometers.
After deionized water is regulated the concentration of the certain metal composite titanium dioxide nano particle colloidal sol of crystalline phase composition, in glass surface spraying, dip-coating or brushing, drying repeats to film, and elevated temperature heat can form metal composite titanium dioxide nano particle film at glass surface after solidifying.
The method that forms metal composite titanium dioxide nano particle film at glass surface of the present invention may further comprise the steps, and related amount is in weight part:
(1) under agitation, in 10～100 parts metal composite titanium dioxide nano particle colloidal sol, add 0～90 part deionized water after, stir;
(2) colloidal sol with step (1) is applied to glass surface, room temperature～200 ℃ drying 1 minute～5 hours;
(3), be 300～700 ℃ of following constant temperature 1 minute～10 hours in temperature with the above-mentioned glass that is covered with metal composite titanium dioxide nano particle film.
Be to guarantee the thickness of film of nanoparticles, but repeating step (2) 1 times or more than 1 time.
By the metal composite titanium dioxide nano particle film that the inventive method forms, have antibiotic, mildew-resistant, deodorizing, decomposing pollutant function with photo-catalysis function on glass surface.Simultaneously, glass surface can keep good hydrophilicity for a long time under the natural light condition, and this point has important effect to keeping of glass automatically cleaning effect.
Advantage of the present invention and positively effect:
Adopt the technology of the present invention to prepare metal composite titanium dioxide nano particle film, compare, have the following advantages with the method for using always at present especially sol-gel method at glass surface:
(1) starting material are cheap and easy to get
The present invention adopts titanium tetrachloride as main raw material, compares as precursor with the alkoxide that uses titanium, and material cost is cheaper.
(2) can effectively suppress remarkable growth of particulate and because the cracking problem of the film that the crystalline phase conversion causes in the sintering process
The TiO 2 sol that use the inventive method obtains is by the crystallization degree height, and crystalline phase is formed certain metal composite titanium dioxide nano particle and formed.The TiO 2 sol that common method obtains then is made up of unbodied titanium dioxide nano-particle.Therefore, use the inventive method, can obviously suppress the growth of particle in the sintering process, improve the optical property and the photocatalytic activity of film of nanoparticles.
(3) using method of the present invention to form the crystalline phase of film of nanoparticles effectively adjusts
The existing titanium dioxide optical catalyst of duplex grain structure such as the P25 of studies show that shown better photocatalysis performance.Use method of the present invention, can obtain crystalline phase and consist of Detitanium-ore-type/rutile-type, Detitanium-ore-type/brookite type duplex grain structure metal composite titanium dioxide nano particle film, form single photocatalyst with the crystalline phase that common method obtains and compare and to have more superior performance.
(4) preparation method is simple
Adopt the technology of the present invention to prepare metal composite titanium dioxide nano particle film, use simple brushing technology at glass surface, the equipment less investment, it is little to implement difficulty.
(5) hold-time of hydrophilicity is more of a specified duration
As shown in Figure 5, under the natural light condition, use the inventive method to obtain titanium dioxide nano particle film and shown the good hydrophilicity energy.This may be better with employing crystal property among the present invention, and it is relevant as coating solution that crystalline phase is formed certain metal composite titanium dioxide nano particle colloidal sol.
(6) optical property of film is better
Adopt method of the present invention, can effectively suppress particulate growth in the sintering process.Therefore, the scattering of light owing to large-size particle will be resolved with the optical property reduction problem that reflection causes.
(7) owing to the effect of doped metal salt, film has dark antibacterial, and responds certain visible light.
Description of drawings
Fig. 1. the stereoscan photograph of the glass surface metal composite titanium dioxide nano particle film of the embodiment of the invention 6.
Fig. 2. the XRD figure of the metal composite titanium dioxide nano particle that the embodiment of the invention 3 obtains.
Fig. 3. the surface of the embodiment of the invention 3 is covered with the test result of the glass transmittance of metal composite titanium dioxide nano particle film;
A blank glass sheet; B is covered with the sheet glass of metal composite titanium dioxide nano particle film.
Fig. 4. the sheet glass that is covered with the silver ions composite titanium dioxide nano particle film of the embodiment of the invention 5 and blank glass sheet, illumination be after 3 hours, the ultra-violet absorption spectrum of remaining tropeolin-D;
B-illumination 0 hour; D-is covered with the sheet glass illumination 3 hours of silver ions composite titanium dioxide nano particle film; F-blank glass sheet illumination 3 hours.
Fig. 5. the surface of the embodiment of the invention 7 is covered with the variation of the contact angle of the glass of metal composite titanium dioxide nano particle film and water with storage period.
Embodiment
Embodiment 1
Get 25 weight part titanium tetrachlorides and be dissolved in the 75 weight part frozen water, in 0～5 ℃ of ice-water bath, continue to stir 30 minutes, obtain transparent, clarifying titanium tetrachloride aqueous solution.1 weight part iron trichloride is dissolved in the aqueous solution that generates molysite in the deionized water of 99 weight parts.25 weight part sodium hydroxide add in the deionized water of 75 weight parts and obtain alkaline solution.Under stirring fast, the molysite aqueous solution that in the above-mentioned titanium tetrachloride aqueous solution of 40 weight parts, adds 20 weight parts, after continuing stirred for several minute, add 10 weight part alkaline solutions again, continue to stir after 10 minutes, add 30 parts deionized water, stir, be transferred in the teflon-lined and press in the still, 150 ℃ of constant temperature 2 hours naturally cools to room temperature.The supernatant liquid that inclines filters lower sediment, after the deionized water wash lower sediment 5 times, solid precipitation is transferred to container obtains iron ion compound nano titania slurry, and the particle size of titanium dioxide is about 10～50 nanometers in the slurry.
10 weight part polyoxyethylene glycol add in the deionized water of 90 weight parts and obtain the polyoxyethylene glycol aqueous solution.Get the above-mentioned iron ion composite titanium dioxide of 20 weight parts nano pulp, under vigorous stirring, add 70 weight parts waters and the 10 weight part polyoxyethylene glycol aqueous solution, continue to stir 3 hours, after ultrasonic 20 minutes, leave standstill, filter and obtain metal composite titanium dioxide nano particle colloidal sol.This colloidal sol is sprayed on glass, after the drying at room temperature, repeats 2 times and film, in the retort furnace in 400 ℃ of constant temperature after 8 hours, naturally cooling.Obtain having the metal composite titanium dioxide nano particle film of light purification function at glass surface.
Embodiment 2
Get 60 weight part titanium tetrachlorides and be dissolved in the 40 weight part frozen water, in 0～5 ℃ of ice-water bath, continue to stir 2 hours, obtain transparent, clarifying titanium tetrachloride aqueous solution.2 weight part cupric nitrates are dissolved in the deionized water of 99 weight parts and generate copper salt solution.10 weight part sodium hydroxide add in the deionized water of 90 weight parts and obtain alkaline solution.Under stirring fast, in 14 weight part titanium tetrachloride aqueous solutions, add 10 weight part copper salt solutions, after continuing stirred for several minute, the alkaline solution that adds 0.5 weight part, add the deionized water of 75.5 weight parts, continue to stir after 1 hour, transfer in the teflon-lined autoclave, 100 ℃ of constant temperature 2 hours naturally cools to room temperature.The supernatant liquid that inclines filters lower sediment, deionized water wash lower sediment 2 times.Solid precipitation is transferred to container obtains cupric ion compound nano titania slurry, the particle size of titanium dioxide is about 10～50 nanometers in the slurry.
20 weight account polyethylene pyrrolidone add in the deionized water of 80 weight parts and obtain polyvinylpyrrolidonesolution solution.Get the above-mentioned cupric ion composite titanium dioxide of 50 weight parts nano pulp, under vigorous stirring, add 48 weight parts waters and 2 weight account polyethylene pyrrolidone solution, continue to stir 30 minutes, stirred 3 hours after ultrasonic 10 minutes, leave standstill, obtain cupric ion composite titanium dioxide nano particle colloidal sol after the filtration.This colloidal sol is sprayed on glass, after 60 ℃ of dryings, in the retort furnace in 500 ℃ of constant temperature 30 minutes, naturally cooling.Obtain having the metal composite titanium dioxide nano particle film of light purification function at glass surface.
Embodiment 3
Get 22 weight part titanium tetrachlorides and be dissolved in the 78 weight part frozen water, in 0～5 ℃ of ice-water bath, continue to stir 4 hours, filter, obtain titanium tetrachloride aqueous solution; 0.1 weight part Silver Nitrate, 5 weight part ammoniacal liquor add and obtain ammino in 94.9 parts by weight of deionized water and close silver-colored solution.37 weight part potassium hydroxide add in the water of 63 weight parts and obtain alkaline solution.Under vigorous stirring, in the above-mentioned titanium tetrachloride aqueous solution of 45 weight parts, add 5 weight parts silver solution, the alkaline solution of 30 weight parts, after add the deionized water of 20 weight parts, continue to stir after 10 minutes, be transferred in the teflon-lined and press in the still, 250 ℃ of constant temperature 1 hour naturally cools to room temperature.The supernatant liquid that inclines filters lower sediment.After the deionized water wash precipitation 10 times, deionized water is transferred to container with it, obtains silver ions compound titania slurry, and the particle size of titanium dioxide is about 5～20 nanometers in the slurry.
The polyoxyethylene glycol of 20 weight parts-b-polypropylene glycol-b-polyoxyethylene glycol amphipathic three block copolymer P123 adds in the deionized water of 80 weight parts and obtains water phase surfactant mixture.Get the above-mentioned silver ions composite titanium dioxide of 40 weight parts slurry, under vigorous stirring, add the water phase surfactant mixture of 30 parts by weight of deionized water and 20 weight parts, 50 ℃ continue to stir 5 hours, stirred 5 hours after ultrasonic 2 hours minutes, obtain silver ions composite titanium dioxide nano particle colloidal sol.The deionized water of 50 weight part silver ions composite titanium dioxide nano particle colloidal sols and 50 weight parts mixes, and is sprayed at glass surface, after the drying at room temperature, repeat 3 times and be coated with membrane process, in the retort furnace in 650 ℃ of constant temperature after 10 minutes, naturally cooling.
Embodiment 4
Get 35 weight part titanium tetrachlorides and be dissolved in the 65 weight part frozen water, in 0～5 ℃ of ice-water bath, continue to stir 2 hours, filter, obtain titanium tetrachloride aqueous solution.0.02 being dissolved in, weight part chloro-iridic acid ammonia generates iridium solution in the deionized water of 99.8 weight parts.
40 weight parts of sodium carbonate add in the deionized water of 60 weight parts and obtain alkaline solution.Under vigorous stirring, in the above-mentioned titanium tetrachloride aqueous solution of 15 weight parts, add the iridium solution of 0.5 weight part, continue stirred for several minute after, add the alkali lye of 5 weight parts.Add deionized water 79.5 weight parts, stir after 30 minutes, be transferred in the teflon-lined and press in the still, 180 ℃ of constant temperature 1 hour naturally cools to room temperature.Incline behind the supernatant liquid, filter lower sediment, be transferred to container after deionized water wash precipitates 1 time and obtain iridium ion compound titanium dioxide nano-particle slurry, the particle size of titanium dioxide is about 10～50 nanometers in the slurry.
5 weight account polyethylene pyrrolidone add in the deionized water of 95 weight parts and obtain water phase surfactant mixture.Get 10 weight part iridium ion composite titanium dioxide slurries, under violent vigorous stirring, add the water phase surfactant mixture of 70 parts by weight of deionized water and 20 weight parts, 30 ℃ continue to stir 1 hour, stirred 5 hours after ultrasonic 30 hours minutes, obtain iridium ion composite titanium dioxide nano particle colloidal sol.The deionized water of 10 weight part iridium ion composite titanium dioxide nano particle colloidal sols and 90 weight parts mixes, and is sprayed at glass surface, after the drying at room temperature, repeat 3 times and be coated with membrane process, in the retort furnace in 300 ℃ of constant temperature 8 hours, naturally cooling.
Embodiment 5
Get 50 weight part titanium tetrachlorides and be dissolved in the 50 weight part frozen water, in 0～5 ℃ of water-bath, continue to stir 2 hours, filter, obtain transparent, clarifying titanium tetrachloride aqueous solution.1 weight part Silver Nitrate, 2 weight part citric acids add and obtain silver-colored solution in 97 parts by weight of deionized water.30 weight parts of sodium carbonate add in the deionized water of 70 weight parts and obtain alkaline solution.Under stirring fast, in the above-mentioned titanium tetrachloride aqueous solution of 20 weight parts, add the silver-colored solution of 19 weight parts, continue stirred for several minute after, add the alkali lye of 10 weight parts.Add the deionized water of 51 weight parts, stir after 10 minutes, be transferred in the teflon-lined and press in the still, 120 ℃ of constant temperature 3 hours naturally cools to room temperature.Filter lower sediment, be transferred to container after deionized water wash precipitates 2 times and obtain silver ions compound titanium dioxide nano-particle slurry, the particle size of titanium dioxide is about 10～50 nanometers in the slurry.
The polyvinyl alcohol of 1 weight part adds in 99 parts by weight of deionized water and obtains polyvinyl alcohol water solution.Get 50 weight part silver ions composite titanium dioxide slurries, under vigorous stirring, add the polyvinyl alcohol water solution of 50 weight parts, 20 ℃ continue to stir 1 hour, stir 5 hours after ultrasonic 1 hour, obtain silver ions composite titanium dioxide nano particle colloidal sol.After the deionized water of 50 weight part silver ions composite titanium dioxide nano particle colloidal sols and 50 weight parts mixes, be sprayed on glass.40 ℃ of dryings repeat 2 times and are coated with membrane process, in the retort furnace in 500 ℃ of constant temperature after 3 hours, naturally cooling.
Embodiment 6
Get 17 weight part titanium tetrachlorides and be dissolved in the 83 weight part frozen water, in 0～10 ℃ of water-bath, continue to stir 3 hours, filter, obtain transparent, clarifying titanium tetrachloride aqueous solution.2 weight part cupric nitrates, 10 weight part ammoniacal liquor add and generate the cupric ion aqueous solution that ammino closes in the deionized water of 88 weight parts.25 weight part sodium bicarbonates add in the deionized water of 75 weight parts and obtain alkaline solution.Under vigorous stirring, the cupric ion aqueous solution that in the above-mentioned titanium tetrachloride aqueous solution of 40 weight parts, adds 2 parts, after continuing stirred for several minute, after adding the alkaline solution of 15 weight parts, add deionized water 20 weight parts, continue to stir after 10 minutes, be transferred to and press in the still in the teflon-lined, 250 ℃ of constant temperature 5 hours naturally cools to room temperature.The supernatant liquid that inclines filters lower sediment.Deionized water wash is transferred to container after precipitating 7 times, obtains cupric ion compound titanium dioxide nano-particle slurry, and the particle size of titanium dioxide is about 10～50 nanometers in the slurry.
The polyvinyl alcohol of 15 weight parts adds in 85 parts by weight of deionized water and obtains polyvinyl alcohol water solution.Get the cupric ion composite titanium dioxide slurry of 30 weight parts, under vigorous stirring, add the polyvinyl alcohol water solution of 60 parts by weight of deionized water and 10 weight parts, 10 ℃ continue to stir 3 hours, stirred 30 minutes after ultrasonic 15 hours, obtain cupric ion composite titanium dioxide nano particle colloidal sol.Be sprayed at after the deionized water of 50 weight part cupric ion composite titanium dioxide nano particle colloidal sols and 50 weight parts mixes on glass, 150 ℃ of dryings, after repeating to be coated with membrane process 5 times, in the retort furnace in 550 ℃ of constant temperature after 3 hours, naturally cooling.
Embodiment 7
Get 35 weight part titanium tetrachlorides and be dissolved in the 65 weight part frozen water, in 0～10 ℃ of water-bath, continue to stir 1 hour, filter, obtain transparent, clarifying titanium tetrachloride aqueous solution.0.1 the weight part Platinic chloride, 3 weight part ammoniacal liquor add and generate the platinum ion solution that ammino closes in the deionized water of 96.9 weight parts.The sodium hydroxide of 18 weight parts adds in the deionized water of 82 weight parts and obtains alkaline solution.Under vigorous stirring, the platinum ion solution that in the above-mentioned titanium tetrachloride aqueous solution of 23 weight parts, adds 25 weight parts, after continuing stirred for several minute, after adding the alkaline solution of 15 weight parts, add deionized water 37 weight parts, continue to stir after 2 hours, be transferred to and press in the still in the teflon-lined, 250 ℃ of constant temperature 0.5 hour naturally cools to room temperature.The supernatant liquid that inclines filters lower sediment.Be transferred to container after deionized water wash precipitates 4 times and obtain platinum ion compound titanium dioxide nano-particle slurry, the particle size of titanium dioxide is about 10～50 nanometers in the slurry.
10 weight account polyethylene pyrrolidone add and obtain the polyvinylpyrrolidone aqueous solution in 90 parts by weight of deionized water.Get 30 weight part platinum ion composite titanium dioxide slurries, under vigorous stirring, the polyvinylpyrrolidone polyvinyl alcohol water solution that adds 60 parts by weight of deionized water and 10 weight parts, 10 ℃ continue to stir 1 hour, stirred 5 hours after ultrasonic 30 minutes, obtain platinum ion composite titanium dioxide nano particle colloidal sol.Be sprayed at after the deionized water of 50 weight part platinum ion composite titanium dioxide nano particle colloidal sols and 50 weight parts mixes on glass, 100 ℃ of dryings, after repeating to be coated with membrane process 1 time, in the retort furnace in 550 ℃ of constant temperature after 3 hours, naturally cooling.
Claims (9)
1. one kind forms the method for metal composite titanium dioxide nano particle film at glass surface, it is characterized in that this method may further comprise the steps, and related amount is in weight part:
(1) under agitation, in 10～100 parts metal composite titanium dioxide nano particle colloidal sol, add 0～90 part deionized water after, stir;
(2) colloidal sol with step (1) is applied to glass surface, drying;
(3), be 300～700 ℃ of following constant temperature in temperature with the above-mentioned glass that is covered with metal composite titanium dioxide nano particle film;
Described metal composite titanium dioxide nano particle colloidal sol is prepared by following method:
(1) gets 15～65 parts of titanium tetrachlorides addings and place 35～85 portions of frozen water of 0～10 ℃ of water-bath, continue to stir, filter, obtain transparent, clarifying titanium tetrachloride aqueous solution after the collection lower floor filtrate;
(2) with 0.0001～3 part water miscible transition metal salt, 0～10 part complexing agent joins in 87～99.9999 parts the deionized water, obtains transition metal salt solution or by the transition metal salt solution of complexing agent complexing;
(3) 10 parts～40 parts mineral alkali is joined in 60～90 parts the deionized water and obtain alkaline solution after the dissolving;
(4) under stirring fast, add the transition metal salt of 0.1～30 part of step (2) in the titanium tetrachloride aqueous solution of 10～50 parts of steps (1) or by the transition metal salt solution of complexing agent complexing, after continuing to stir, the alkaline solution that adds 0.05～30 part of step (3) is added and is continued behind the deionized water to stir to make it uniform mixing; Above-mentioned solution is transferred to middle the pressure in the still, in 100～300 ℃ of constant temperature;
(5) behind the solution naturally cooling that step (4) is obtained, the supernatant liquid that inclines filters lower sediment, the washing lower sediment, use deionized water that precipitation is transferred to and obtain the crystallization degree height in the container, crystalline phase is formed certain metal composite titanium dioxide nano particle slurries;
(6) 0.5～20 part tensio-active agent is joined in 80～99.5 parts the deionized water and obtain water phase surfactant mixture;
(7) under vigorous stirring, in the metal composite titanium dioxide nano particle slurry of 5～50 parts of steps (5), add 0～94 part the deionized water and the water phase surfactant mixture of 1～50 part of step (6), 10～60 ℃ continue down to stir, ultra-sonic dispersion, stir, leave standstill, obtain metal composite titanium dioxide nano particle colloidal sol after the filtration;
The crystalline phase of described metal composite titanium dioxide nano particle consists of the duplex grain structure of Detitanium-ore-type, rutile-type, Detitanium-ore-type and rutile-type or the duplex grain structure of Detitanium-ore-type and brookite type, wherein, the brookite type content in the mixed crystal of Detitanium-ore-type and brookite type is not more than 20 weight parts.
2. method according to claim 1 is characterized in that: the deionized water that the step of described preparation metal composite titanium dioxide nano particle (4) was added before constant temperature is 30～89.95 weight parts.
3. method according to claim 1 is characterized in that: the step of described preparation metal composite titanium dioxide nano particle (4) constant temperature time is 30 minutes～24 hours.
4. method according to claim 1 is characterized in that: the ultra-sonic dispersion of the step of described preparation metal composite titanium dioxide nano particle (7) is 2 minutes～4 hours.
5. method according to claim 1 is characterized in that: the transition metal of the step of described preparation metal composite titanium dioxide nano particle (2) is iron, silver, nickel, platinum, iridium, zinc, palladium or copper.
6. method according to claim 1 is characterized in that: the described network of step (2) and the agent of preparation metal composite titanium dioxide nano particle are ammoniacal liquor, oxalate, thiosulphate, thiocyanate-, citric acid, tartrate, trolamine, diethanolamine or amino acid.
7. method according to claim 1 is characterized in that: the described alkali of step (3) of preparation metal composite titanium dioxide nano particle is sodium hydroxide, potassium hydroxide, yellow soda ash, salt of wormwood, sodium bicarbonate, saleratus or ammoniacal liquor.
8. method according to claim 1 is characterized in that: the described tensio-active agent of step (7) of preparation metal composite titanium dioxide nano particle is polyoxyethylene glycol, polyvinyl alcohol, polyvinylpyrrolidone or polyoxyethylene glycol-b-polypropylene glycol-b-polyoxyethylene glycol amphipathic three block copolymer.
9. method according to claim 1 is characterized in that: the particle size of described metal composite titanium dioxide nano particle is 3～100 nanometers.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2006101147507A CN101190828B (en) | 2006-11-22 | 2006-11-22 | Method for forming metal composite titanium dioxide nano particle film on glass surface |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2006101147507A CN101190828B (en) | 2006-11-22 | 2006-11-22 | Method for forming metal composite titanium dioxide nano particle film on glass surface |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101190828A CN101190828A (en) | 2008-06-04 |
| CN101190828B true CN101190828B (en) | 2011-01-12 |
Family
ID=39486050
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2006101147507A Expired - Fee Related CN101190828B (en) | 2006-11-22 | 2006-11-22 | Method for forming metal composite titanium dioxide nano particle film on glass surface |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101190828B (en) |
Families Citing this family (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102464499A (en) * | 2010-11-08 | 2012-05-23 | 赵正坤 | Titaniferous composition, method for forming nano particle film on ceramic or glass surface from titaniferous composition and application of titaniferous composition |
| CN102000594B (en) * | 2010-11-26 | 2012-05-16 | 大连理工大学 | Preparation method of visible light photo catalyst silver and silver phosphate and application thereof |
| CN102220039B (en) * | 2011-04-26 | 2012-10-10 | 福州大学 | Interior photocatalytic coating, preparation method and application thereof |
| CN103539967B (en) * | 2012-07-16 | 2017-10-20 | 上海市肿瘤研究所 | Core shell structure Polymer/nano gold composite nano materials and its preparation method and application |
| CN104016592A (en) * | 2014-06-16 | 2014-09-03 | 滁州市宏源喷涂有限公司 | Glass for greenhouse and spraying process of glass |
| CN104190458B (en) * | 2014-07-16 | 2016-08-24 | 上海工程技术大学 | A kind of low temperature preparation technology of dual element modified nano-titanium dioxide colloidal sol |
| CN104195534B (en) * | 2014-09-16 | 2019-10-22 | 中国建材国际工程集团有限公司 | The preparation method of the self-cleaning film of titanium dioxide |
| CN106311195A (en) * | 2015-07-06 | 2017-01-11 | 新加坡国立大学 | Catalyst for photocatalytic degradation of antibiotic as well as preparation method and application thereof |
| CN107140850A (en) * | 2017-05-02 | 2017-09-08 | 江苏秀强玻璃工艺股份有限公司 | A kind of plated film antibacterial safety glass and preparation method thereof |
| CN107827343A (en) * | 2017-10-31 | 2018-03-23 | 孟凡志 | A kind of semi-tempered glass treatment fluid and preparation method thereof |
| CN108722435A (en) * | 2018-06-07 | 2018-11-02 | 高志远 | Five yuan are co-doped with nano-titanium dioxide modified plated film functional material, preparation and film plating process |
| CN108947268B (en) * | 2018-07-26 | 2021-06-18 | 安徽朗旭玻璃器皿有限公司 | Self-cleaning glass for glass curtain wall and preparation method thereof |
| CN109115818B (en) * | 2018-08-30 | 2021-03-02 | 浙江省交通运输科学研究院 | Method for evaluating amount of glass bead surface pre-loaded with nano titanium dioxide |
| CN110436792A (en) * | 2019-08-21 | 2019-11-12 | 吉林大学 | A method of preparing the quartz capillary with titanium dioxide nano-particle coating |
| CN110711573A (en) * | 2019-09-17 | 2020-01-21 | 上海市政工程设计研究总院（集团）有限公司 | Method for preparing multifunctional nano composite material dustproof antifouling mildew inhibitor |
| CN113475521A (en) * | 2021-07-08 | 2021-10-08 | 安徽江淮汽车集团股份有限公司 | Composite efficient antibacterial automobile disinfectant and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1382521A (en) * | 2001-04-25 | 2002-12-04 | 中国科学院理化技术研究所 | Nano composite metal-TiO2 particle and its preparing process and usage |
| CN1539772A (en) * | 2003-10-29 | 2004-10-27 | 王玉震 | Self-cleaning glass |
| CN1686951A (en) * | 2005-04-07 | 2005-10-26 | 福州大学 | Method for manufacturing anti pollution flashover high tension ceramic and glass insulators |
-
2006
- 2006-11-22 CN CN2006101147507A patent/CN101190828B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1382521A (en) * | 2001-04-25 | 2002-12-04 | 中国科学院理化技术研究所 | Nano composite metal-TiO2 particle and its preparing process and usage |
| CN1539772A (en) * | 2003-10-29 | 2004-10-27 | 王玉震 | Self-cleaning glass |
| CN1686951A (en) * | 2005-04-07 | 2005-10-26 | 福州大学 | Method for manufacturing anti pollution flashover high tension ceramic and glass insulators |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101190828A (en) | 2008-06-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101190828B (en) | Method for forming metal composite titanium dioxide nano particle film on glass surface | |
| JP4803180B2 (en) | Titanium oxide photocatalyst, its production method and use | |
| CN106582892B (en) | Nano-TiO2Coating structure and its preparation method and application | |
| Sayılkan et al. | Photocatalytic performance of Sn-doped TiO2 nanostructured mono and double layer thin films for Malachite Green dye degradation under UV and vis-lights | |
| CN100509148C (en) | Method for synthesizing attapulgite composite photocatalyst | |
| CN108295830B (en) | TiO with 001, 101 crystal face exposed2Sepiolite composite gel and preparation method thereof | |
| CN107522169A (en) | A kind of normal temperature prepares pure organic homogeneous precipitation method of nano-oxide | |
| JP2013208589A (en) | Visible light-responsive photocatalyst coating agent and coating film | |
| CN104226287A (en) | Preparation method of nano titanium dioxide photocatalyst thin film | |
| CN101857390A (en) | Composite powder with antibacterial and heat insulation functions and preparation method and purposes thereof | |
| CN110201655B (en) | One-step method for preparing hollow TiO2Method and application of nano-microspheres | |
| CN101585552A (en) | Method for fabricating porous TiO2 thin film by utilizing nano-crystalline TiO2 hydrosol | |
| CN1636879A (en) | Prepn process of nanometer mesoporous TiO2 powder | |
| CN101947439B (en) | Novel indoor air purifying agent and preparation method thereof | |
| CN109650439B (en) | Large-size self-assembled titanium dioxide microsphere and preparation method and application thereof | |
| CN1296274C (en) | Composite microballoon of monodisperse SiO2 and TiO2 and its prepn process | |
| US20210213437A1 (en) | Linear titanium-oxide polymer, titanium dioxide coating, photocatalytic coating and preparation method therefor | |
| CN103691414A (en) | Preparation method of high-stability neutral photocatalyst sol for cement-based material | |
| CN101716501B (en) | Zinc titanate micro-nano photocatalysis material and preparation method thereof | |
| CN109772373A (en) | A kind of preparation method with visible light-responded rGO/ black bismuth oxychloride-bismuth-bismuth oxide heterojunction photocatalyst | |
| CN103521247B (en) | A kind of preparation method of self assembly Silver-phosphate-bascomposite composite visible light photocatalytic material | |
| CN105399138A (en) | Perovskite SrTiO3 tetragonal nanoparticle preparation method and product | |
| CN101391211A (en) | Alumina substrate shaped titanium dioxide-nucleus/shell structure composite microsphere photocatalyst and preparation method thereof | |
| CN102786080A (en) | Indium tin oxide compound, its preparation method and its photocatalytic application | |
| CN107486203B (en) | Recyclable floating type composite photocatalytic ball and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20110112 Termination date: 20181122 |