CN1342518A - Process for preparing nm crystal TiO2 photocatalyst carried by metallic wire screen skeleton - Google Patents
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Abstract
A metallic wire screen skeleton material-carried nm-clas cystol TiO2 photocatalyst is prepared through preparing transistion layer sol from n-butyl titanate as precursor, preparing active layer sol from n-butyl titanium or TiCl4 and pore-forming agent, coating the transition layer sol on the cleaned metallic wire screen skeleton-shaped carrier, directly coating the active layer sol, drying and calcining; or preparing nm TiO2 powder suspension, and attaching it the said carrier to form the photocatalyst. Its advantages include high adhesion, low gas resistance and high photocatalytic efficiency and activity.
Description
Technical field:
The present invention relates to a kind of preparation method of nm crystal TiO 2 photocatalyst carried by metallic wire screen skeleton, belong to chemical field.
Background technology:
The method of existing preparation loaded photocatalyst mainly contains three classes: (1) utilizes collosol and gel directly to prepare TiO at carrier surface
2The method of film; (2) utilize nano-powder to be dispersed into suspension, load on the method for carrier surface; (3) utilize inorganic and organic gel that nano-photocatalyst is loaded on method on the silk screen.Wherein in method (1) owing to adopt the TiO of Prepared by Sol Gel Method
2Photocatalyst film, non-porous structure, specific surface is little, and is active very poor.The photochemical catalyst of method (2) preparation is because offspring is very loose with combining of base material, and catalyst is easy to come off, and practicability is difficulty.The catalyst of method (3) preparation, because inorganic and organic gel is to the package action of nanocatalyst, photocatalysis efficiency is low, its bond strength is also poor.In addition, organic gel also the ultraviolet light decomposing phenomenon can occur.
Flaky material such as sheet metal are all used in general preparation, and sheet glass or glass marble etc. in the photochemical catalyst use, exist effective light-receiving area little as carrier, and the little and vapour lock of the contact area of fluid and photochemical catalyst is not suitable for the shortcoming that high-speed reacts greatly.Do not add transition zone in general preparation, make that loaded optic catalyst bond strength easy and base material is bad, base material diffuses into the shortcoming that photochemical catalyst inside makes catalyst activity reduce and be not easy to form crystal phase structure.Practical at present photochemical catalyst adopts ceramic honey comb as carrier substantially, to overcome sheet and pelleted substrate in the difficulty aspect the practicability, but the problem that ceramic monolith exists has: (1) price height, a little less than the mechanical strength, easily broken: (2) are the rigidity structures, are difficult to be prepared into the catalyst assembly of special construction and shape; (3) technology of preparing complexity is difficult to prepare the large tracts of land carrier.
Summary of the invention:
The objective of the invention is to study a kind of preparation method of woven wire framework material loaded nano crystal titanium dioxide film photocatalyst, by the silk screen skeleton structure, solve the light utilization ratio, improve the effective active area of light, fluid and catalyst and reduce the problem that vapour lock improves air speed.Can overcome poor bonding strength and SA shortcoming by transition zone and nanometer.Selection by framework material is can preparation cost low, and technology is simple, and area is big, the high and flexible photochemical catalyst assembly of intensity.
The preparation method of the nm crystal TiO 2 photocatalyst carried by metallic wire screen skeleton that the present invention proposes may further comprise the steps:
(1) preparation transition zone colloidal sol
With the tetrabutyl titanate is presoma, the volume ratio of each composition is in the precursor solution: tetrabutyl titanate: ethanol: diethanol amine: water=1: 8～12: 0.1～0.15: 0.05～0.06 wiring solution-forming, the addition sequence of four kinds of materials is: at first water is added in the ethanolic solution, add diethanol amine again as stabilizing agent, then the tetrabutyl titanate drips of solution is added in the above-mentioned mixed solution, can obtain the solution of faint yellow homogeneous transparent like this, airtight leaving standstill was carried out to gel in 3～7 days, obtained having the vitreosol of certain viscosity.
(2) preparation active layer colloidal sol
With the tetrabutyl titanate is presoma, the volume ratio of each composition is in the precursor solution: tetrabutyl titanate: ethanol: diethanol amine: water=1: 8～12: 0.1～0.15: 0.05～0.06, the addition sequence of four kinds of materials is: at first water is added in the ethanolic solution, add diethanol amine again as stabilizing agent, then the tetrabutyl titanate drips of solution is added in the above-mentioned mixed solution, can obtain the solution of faint yellow homogeneous transparent like this, in this solution, add organic additive at last again as pore creating material, pore creating material is polyethylene glycol or octadecylamine etc., the mass ratio of ethanol is in the addition of pore creating material and the precursor solution: pore creating material: ethanol=0.01～0.3: 1, airtight leaving standstill was carried out to gel in 3～7 days, obtained having the vitreosol of certain viscosity.
Perhaps active layer colloidal sol is presoma with the titanium tetrachloride, the volume ratio of each composition is in the precursor solution: titanium tetrachloride: ethanol: water=1: 8～12: 0.08～0.15, addition sequence is: at first water is added in the ethanolic solution, drip titanium tetrachloride again and form shallow yellow transparent solution, in this solution, add organic additive at last as pore creating material, pore creating material is polyethylene glycol or octadecylamine etc., the mass ratio of ethanol is in the addition of pore creating material and the precursor solution: pore creating material: ethanol=0.01～0.3: 1, airtight leaving standstill was carried out to gel in 3～7 days, obtained having the vitreosol of certain viscosity.
(3) preparation of transition zone
The method that utilization lifts plated film is coated on the transition zone colloidal sol of above-mentioned first step preparation on the woven wire skeleton shape carrier through cleaning, gets rid of unnecessary colloidal sol by rotation, viscosity that can be by regulating colloidal sol and lift the thickness that number of times is controlled thin layer.The wet gel film that obtains in air atmosphere, with the heating rate of 2～5 ℃/min, is warming up to 350～550 ℃ again through behind the cold air drying, is incubated 0.5～3 hour, just can form TiO
2Film, the thickness of transition zone are 100～300 nanometers, for uniformity and the compactness that guarantees transition layer film, can lift 1～3 time.
(4) preparation of active photocatalyst layer
The method that utilization lifts plated film directly has been coated on mesh-like skeleton carrier through cleaning or preplating on the mesh-like skeleton carrier of transition zone with the active layer colloidal sol of above-mentioned second step preparation, get rid of unnecessary colloidal sol by rotation, viscosity that can be by regulating colloidal sol and lift the thickness that number of times is controlled thin layer.The wet gel film that obtains in air atmosphere, with the heating rate of 2～5 ℃/min, is warming up to 350～550 ℃ again through behind the cold air drying, is incubated 0.5～5 hour, just can form TiO
2Film, the thickness of active layer are 300～600 nanometers, for uniformity and the compactness that guarantees the active layer film, can lift 3～6 times.
More than the transition zone and the active layer of preparation gained all have photocatalytic activity, all have certain photocatalysis effect, and difference is: the photocatalysis efficiency of active layer is higher relatively; And the bond strength that adds the active layer of transition zone and substrate is better, and since transition zone stop that base material reduces the diffusion of catalyst layer, make easier one-tenths of catalyst layer brilliant perfect, active raising.
In addition, when above-mentioned second step prepares active layer colloidal sol, also can replace active layer colloidal sol with preparation active layer suspension.Detailed process is as follows: be the nano-titanium dioxide powder of 5～50nm with particle diameter, be made into suspension with deionized water by 1～5% mass percent concentration, about 0.5～the 2ml of nitric acid that adds 2mol/L concentration then by every 500ml hanging drop, then 40～80 ℃ of insulations, added hot reflux 2～24 hours, be prepared into nano-titanium dioxide powder suspension: with this suspension at the mesh-like skeleton carrier or be coated with on the mesh-like skeleton carrier of transition zone of above-mentioned first step preparation and lift, unnecessary suspension is got rid of in rotation, cold air drying, again in air atmosphere, 250～500 ℃ of insulations 0.5～5 o'clock, just can form TiO
2Powder attached type photochemical catalyst.
The nanocrystalline TiO of silk screen skeleton structure that utilizes method of the present invention to prepare
2Photochemical catalyst has the bond strength height, and vapour lock is little, advantages such as photocatalysis efficiency height and high activity.In whole preparation method, raw material is inexpensive, and technology is simple, has therefore reduced product cost, has very high practical value and application prospect.
The specific embodiment:
Embodiment one:
(1) preparation of transition zone colloidal sol: with the tetrabutyl titanate is presoma, and the proportioning of precursor solution is a tetrabutyl titanate: ethanol: diethanol amine: water=1: 8: 0.1: 0.05 (volume ratio) wiring solution-forming.The addition sequence of four kinds of materials is: at first water is added in the ethanolic solution, add diethanol amine again as stabilizing agent, then the tetrabutyl titanate drips of solution is added in the above-mentioned mixed solution, can obtain the solution of faint yellow homogeneous transparent like this.Airtight leaving standstill was carried out to gel in 3 days, obtained having the vitreosol of certain viscosity.
(2) at room temperature, clean the stainless steel metal silk screen, use washed with de-ionized water at last, oven dry by cleaning agent.Woven wire is immersed in the transition zone colloidal sol, and the speed with 20cm/min lifts then, the centrifugal unnecessary colloidal sol that gets rid of attachment removal on the silk screen surface, air dry.Again immerse then in the transition zone colloidal sol, the speed with 20cm/min lifts then, gets rid of the colloidal sol of attachment removal on the silk screen surface, air dry.Repeat this process, prepare 2 layers of transition zone.In heating furnace, 400 ℃, calcining in 2 hours forms final transition layer film at last.Auger electron spectroscopy studies show that base material and transition layer film exist physical diffusion and chemical bond, have the good binding performance.The THICKNESS CONTROL of transition zone is in 200 nanometers.
Embodiment two:
(1) preparation of transition zone colloidal sol: with the tetrabutyl titanate is presoma, and the proportioning of precursor solution is: tetrabutyl titanate: ethanol: diethanol amine: water=1: 10: 0.12: 0.055 (volume ratio) wiring solution-forming.The addition sequence of four kinds of materials is: at first water is added in the ethanolic solution, add diethanol amine again as stabilizing agent, then the tetrabutyl titanate drips of solution is added in the above-mentioned mixed solution, airtight the leaving standstill of solution that can obtain faint yellow homogeneous transparent like this was carried out to gel in 5 days, obtained having the vitreosol of certain viscosity.
(2) at room temperature,, use washed with de-ionized water at last, oven dry by the clear common aluminum alloy silk screen of cleaning agent.Woven wire is immersed in the transition zone sol solutions, and the speed with 20cm/min lifts then, the centrifugal unnecessary colloidal sol that gets rid of attachment removal on the silk screen surface, air dry.Again immerse then in the transition zone sol solutions, the speed with 20cm/min lifts then, gets rid of the colloidal sol of attachment removal on the silk screen surface, air dry.Repeat this process, prepare 3 layers of transition zone.In heating furnace, 500 ℃, calcining in 1 hour forms final transition layer film at last.Auger electron spectroscopy studies show that base material and transition layer film exist physical diffusion and chemical bond, have the good binding performance.The THICKNESS CONTROL of transition zone is in 320 nanometers.
Embodiment three:
(1) preparation of transition zone colloidal sol: with the tetrabutyl titanate is presoma, and the proportioning of precursor solution is: tetrabutyl titanate: ethanol: diethanol amine: water=1: 12: 0.15: 0.06 (volume ratio) wiring solution-forming.The addition sequence of four kinds of materials is: at first water is added in the ethanolic solution, add diethanol amine again as stabilizing agent, then the tetrabutyl titanate drips of solution is added in the above-mentioned mixed solution, can obtain the solution of faint yellow homogeneous transparent like this.Airtight leaving standstill was carried out to gel in 7 days, obtained having the vitreosol of certain viscosity.
(2) preparation of active layer suspension: the 1g nano-titanium dioxide powder is added in the 50ml deionized water, and the about 3-4 of nitric acid that adds 2mol/1 again drips, and stirs 24 hours under 50 ℃ of heat-retaining conditions, obtains active suspension.
(3) at room temperature, clean the stainless steel metal silk screen, use washed with de-ionized water at last, oven dry by cleaning agent.Woven wire is immersed in the transition zone colloidal sol, and the speed with 20cm/min lifts then, the centrifugal unnecessary colloidal sol that gets rid of attachment removal on the silk screen surface, air dry.Again immerse then in the transition zone colloidal sol, the speed with 20cm/min lifts then, gets rid of the colloidal sol of attachment removal on the silk screen surface, air dry.Repeat this process, prepare 2 layers of transition zone.In heating furnace, 400 ℃, calcining in 2 hours forms final transition layer film at last.
(4) with preplating TiO
2The stainless steel metal silk screen of transition zone immerses in the active suspension of above-mentioned preparation, and the speed with 10cm/min lifts then, the centrifugal liquid that removes attached to the silk screen surface, air dry.Again immerse then in the active suspension, the speed with 10cm/min lifts then, the centrifugal liquid that gets rid of attachment removal on the silk screen surface, air dry.Repeat this process, prepare 3 layers of active layer.In heating furnace, 250 ℃, calcining in 5 hours forms final TiO at last
2Powder attached type photochemical catalyst.The electron microscopy study result shows that this catalyst has the good binding state; The photocatalysis performance evaluation shows that this catalyst has very high catalytic activity.
Embodiment four:
(1) preparation of transition zone colloidal sol: with the tetrabutyl titanate is presoma, and the proportioning of precursor solution is: tetrabutyl titanate: ethanol: diethanol amine: water=1: 10: 0.12: 0.055 (volume ratio) wiring solution-forming.The addition sequence of four kinds of materials is: at first water is added in the ethanolic solution, add diethanol amine again as stabilizing agent, then the tetrabutyl titanate drips of solution is added in the above-mentioned mixed solution, can obtain the solution of faint yellow homogeneous transparent like this.Airtight leaving standstill was carried out to gel in 5 days, obtained having the vitreosol of certain viscosity.
(2) preparation of active layer colloidal sol: with the titanium tetrachloride is presoma, and the proportioning of precursor solution is a titanium tetrachloride: ethanol: water=1: 10: 0.12 (volume ratio).Addition sequence: at first water is added in the ethanolic solution, drip titanium tetrachloride again and form shallow yellow transparent solution, add 10%PEG400 at last in this solution, airtight leaving standstill was carried out to gel in 5 days, obtained having the vitreosol of certain viscosity.
(3) at room temperature,, use washed with de-ionized water at last, oven dry by cleaning agent cleaning aluminum alloy silk screen.Woven wire is immersed in the transition zone colloidal sol, and the speed with 20cm/min lifts then, the centrifugal unnecessary colloidal sol that gets rid of attachment removal on the silk screen surface, air dry.Again immerse then in the transition zone colloidal sol, the speed with 20cm/min lifts then, gets rid of the colloidal sol of attachment removal on the silk screen surface, air dry.Repeat this process, prepare 2 layers of transition zone.In heating furnace, 350 ℃, calcining in 3 hours forms final transition layer film at last.
(4) with preplating TiO
2The woven wire of transition zone immerses in the above-mentioned active layer colloidal sol, and the high speed with 150cm/min lifts then, and the 1500rpm high speed centrifugation removes the colloidal sol attached to the silk screen surface, air dry.Again immerse then in the active layer sol solutions, the high speed with 150cm/min lifts then, and the 1500rpm high speed centrifugation gets rid of the colloidal sol of attachment removal on the silk screen surface, air dry.Repeat this process, prepare 5 layers of active layer.In heating furnace, 450 ℃ of calcinings form final TiO at last
2Film photocatalyst.The electron microscopy study result shows that this catalyst film has the good binding state; The photocatalysis performance evaluation shows that this catalyst has very high catalytic activity.The THICKNESS CONTROL of active layer is in 540 nanometers.
Embodiment five:
(1) preparation of transition zone colloidal sol: with the tetrabutyl titanate is presoma, and the proportioning of precursor solution is: tetrabutyl titanate: ethanol: diethanol amine: water=1: 12: 0.15: 0.06 (volume ratio) wiring solution-forming.The addition sequence of four kinds of materials is: at first water is added in the ethanolic solution, add diethanol amine again as stabilizing agent, then the tetrabutyl titanate drips of solution is added in the above-mentioned mixed solution, can obtain the solution of faint yellow homogeneous transparent like this.Airtight leaving standstill was carried out to gel in 7 days, obtained having the vitreosol of certain viscosity.
(2) preparation of active layer glue: with the tetrabutyl titanate is presoma, the volume ratio of each composition is in the precursor solution: tetrabutyl titanate: ethanol: diethanol amine: water=1: 12: 0.15: 0.06, the addition sequence of four kinds of materials is: at first water is added in the ethanolic solution, add diethanol amine again as stabilizing agent, then the tetrabutyl titanate drips of solution is added in the above-mentioned mixed solution, can obtain the solution of faint yellow homogeneous transparent like this, in this solution, add 8%PEG400 at last again as pore creating material, airtight leaving standstill was carried out to gel in 7 days, obtained having the vitreosol of certain viscosity.
(3) at room temperature, clean stainless steel cloth, use washed with de-ionized water at last, oven dry by cleaning agent.Woven wire is immersed in the transition zone colloidal sol, and the speed with 10cm/min lifts then, the centrifugal unnecessary colloidal sol that gets rid of attachment removal on the silk screen surface, air dry.Again immerse then in the transition zone colloidal sol, the speed with 10cm/min lifts then, gets rid of the colloidal sol of attachment removal on the silk screen surface, air dry.Repeat this process, prepare 3 layers of transition zone.In heating furnace, 450 ℃, calcining in 1 hour forms final transition layer film at last.
(4) with preplating TiO
2The stainless steel metal silk screen of transition zone immerses in the above-mentioned active layer colloidal sol, and the speed with 10cm/min lifts then, the centrifugal colloidal sol that removes attached to the silk screen surface, air dry.Again immerse then in the active layer sol solutions, the speed with 10cm/min lifts then, the centrifugal colloidal sol that gets rid of attachment removal on the silk screen surface, air dry.Repeat this process, prepare 4 layers of active layer.In heating furnace, 400 ℃ of calcinings form final TiO at last
2Film photocatalyst.The electron microscopy study result shows that this catalyst film has the good binding state; The photocatalysis performance evaluation shows that this catalyst has very high catalytic activity.The THICKNESS CONTROL of active layer is in 440 nanometers.
Claims (3)
1, the preparation method of woven wire framework material loaded nano crystal titanium dioxide film photocatalyst is characterized in that this method may further comprise the steps:
(1) preparation transition zone colloidal sol
With the tetrabutyl titanate is presoma, the volume ratio of each composition is in the precursor solution: tetrabutyl titanate: ethanol: diethanol amine: water=1: 8～12: 0.1～0.15: 0.05～0.06 wiring solution-forming, the addition sequence of four kinds of materials is: at first water is added in the ethanolic solution, add diethanol amine again as stabilizing agent, then the tetrabutyl titanate drips of solution is added in the above-mentioned mixed solution, airtight leaving standstill was carried out to gel in 3～7 days, obtained vitreosol;
(2) preparation active layer colloidal sol
With the tetrabutyl titanate is presoma, the volume ratio of each composition is in the precursor solution: tetrabutyl titanate: ethanol: diethanol amine: water=1: 8～12: 0.1～0.15: 0.05～0.06 wiring solution-forming, the addition sequence of four kinds of materials is: at first water is added in the ethanolic solution, add diethanol amine again as stabilizing agent, then the tetrabutyl titanate drips of solution is added in the above-mentioned mixed solution, can obtain the solution of faint yellow homogeneous transparent like this, in this solution, add organic additive at last again as pore creating material, pore creating material is polyethylene glycol or octadecylamine etc., the mass ratio of ethanol is in the addition of pore creating material and the precursor solution: pore creating material: ethanol=0.01～0.3: 1, airtight leaving standstill was carried out to gel in 3～7 days, obtained vitreosol;
Perhaps active layer colloidal sol is presoma with the titanium tetrachloride, the volume ratio of each composition is in the precursor solution: titanium tetrachloride: ethanol: water=1: 8～12: 0.08～0.15, addition sequence is: at first water is added in the ethanolic solution, drip titanium tetrachloride again and form shallow yellow transparent solution, in this solution, add organic additive at last as pore creating material, pore creating material is polyethylene glycol or octadecylamine etc., the mass ratio of ethanol is in the addition of pore creating material and the precursor solution: pore creating material: ethanol=0.01～0.3: 1, airtight leaving standstill was carried out to gel in 3～7 days, obtained vitreosol;
(3) preparation of transition zone
The method that utilization lifts plated film is coated on the transition zone colloidal sol of above-mentioned first step preparation on the woven wire skeleton shape carrier through cleaning, get rid of unnecessary colloidal sol by rotation, viscosity that can be by regulating colloidal sol and lift the thickness that number of times is controlled thin layer, the wet gel film that obtains is through behind the cold air drying, in air atmosphere,, be warming up to 350～550 ℃ again with the heating rate of 2～5 ℃/min, be incubated 0.5～3 hour, just can form TiO
2Film, the thickness of transition zone are 100～300 nanometers;
(4) preparation of active photocatalyst layer
The method that utilization lifts plated film is with on the active layer colloidal sol of above-mentioned second step preparation mesh-like skeleton carrier of transition zone in above-mentioned second step that directly has been coated on mesh-like skeleton carrier through cleaning or preplating, unnecessary colloidal sol is got rid of in rotation, the wet gel film that obtains is through behind the cold air drying, again in air atmosphere, heating rate with 0.5～5 ℃/min, be warming up to 350～550 ℃, be incubated 0.5～5 hour, just can form TiO
2Film, active layer thickness are 300～600 nanometers.
2, a kind of preparation method of woven wire framework material loaded nano crystal titanium dioxide powder attached type photochemical catalyst may further comprise the steps:
(1) preparation transition zone colloidal sol
With the tetrabutyl titanate is presoma, the volume ratio of each composition is in the precursor solution: tetrabutyl titanate: ethanol: diethanol amine: water=1: 8～12: 0.1～0.15: 0.05～0.06 wiring solution-forming, the addition sequence of four kinds of materials is: at first water is added in the ethanolic solution, add diethanol amine again as stabilizing agent, then the tetrabutyl titanate drips of solution is added in the above-mentioned mixed solution, airtight leaving standstill was carried out to gel in 3～7 days, obtained vitreosol;
(2) with particle diameter be the nano-titanium dioxide powder of 5～50nm, be made into suspension with deionized water by 1～5% mass percent concentration, about 0.5～the 2ml of nitric acid that adds 2mol/L concentration then by every 500ml hanging drop, then 40～80 ℃ of insulations, add hot reflux 2～24 hours, and be prepared into the active suspension of nano titanium oxide;
(3) preparation of transition zone
The method that utilization lifts plated film is coated on the transition zone colloidal sol of above-mentioned first step preparation on the woven wire skeleton shape carrier through cleaning, viscosity by regulating colloidal sol and lift the thickness that number of times is controlled thin layer, the wet gel film that obtains is through behind the cold air drying, again in air atmosphere, heating rate with 2～5 ℃/min, be warming up to 350～550 ℃, be incubated 0.5～3 hour, just can form TiO
2Film, the thickness of transition zone are 100～300 nanometers;
(4) with the suspension of the above-mentioned second step preparation at the mesh-like skeleton carrier or be coated with on the mesh-like skeleton carrier of transition zone of above-mentioned second step preparation and lift, unnecessary suspension is got rid of in rotation, and cold air drying is again in air atmosphere, 250～500 ℃ of insulations 0.5～5 o'clock, just can form TiO
2Powder attached type photochemical catalyst.
3, the preparation method of woven wire framework material loaded nano crystal titanium dioxide film photocatalyst is characterized in that this method may further comprise the steps:
(1) with the tetrabutyl titanate is presoma, the volume ratio of each composition is in the precursor solution: tetrabutyl titanate: ethanol: diethanol amine: water=1: 8～12: 0.1～0.15: 0.05～0.06 wiring solution-forming, the addition sequence of four kinds of materials is: at first water is added in the ethanolic solution, add diethanol amine again as stabilizing agent, then the tetrabutyl titanate drips of solution is added in the above-mentioned mixed solution, airtight leaving standstill was carried out to gel in 3～7 days, obtained vitreosol;
(2) utilize the method lift plated film that the transition zone colloidal sol of above-mentioned first step preparation is coated on the woven wire skeleton shape carrier through cleaning, get rid of unnecessary colloidal sol by rotation, viscosity that can be by regulating colloidal sol and lift the thickness that number of times is controlled thin layer, the wet gel film that obtains is through behind the cold air drying, in air atmosphere,, be warming up to 350～550 ℃ again with the heating rate of 2～5 ℃/min, be incubated 0.5～3 hour, just can form TiO
2Film, its thickness are 100～300 nanometers.
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| WO2004007070A1 (en) * | 2002-07-12 | 2004-01-22 | Tsinghua University | Method of making photocatalysts by loading titanium dioxide film on flexible substrates |
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| CN100435936C (en) * | 2005-12-20 | 2008-11-26 | 中国科学院合肥物质科学研究院 | Foamed aluminum carried titanium dioxide catalyst, its preparation method and uses |
| CN100460060C (en) * | 2005-01-05 | 2009-02-11 | 中国科学院过程工程研究所 | Supported TiO2 photocatalyst, its preparation method and photocatalytic water purifier |
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- 2001-09-21 CN CN 01131093 patent/CN1119203C/en not_active Expired - Fee Related
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| CN1314484C (en) * | 2002-07-12 | 2007-05-09 | 清华大学 | Method of making photocatalyst by loading titanium dioxide film on surface of flexible substrate |
| WO2004007070A1 (en) * | 2002-07-12 | 2004-01-22 | Tsinghua University | Method of making photocatalysts by loading titanium dioxide film on flexible substrates |
| CN100460060C (en) * | 2005-01-05 | 2009-02-11 | 中国科学院过程工程研究所 | Supported TiO2 photocatalyst, its preparation method and photocatalytic water purifier |
| CN1321739C (en) * | 2005-06-09 | 2007-06-20 | 上海交通大学 | Production of TiO2 naometer light catalyzing net from foam metal carrier |
| CN100435936C (en) * | 2005-12-20 | 2008-11-26 | 中国科学院合肥物质科学研究院 | Foamed aluminum carried titanium dioxide catalyst, its preparation method and uses |
| CN102219281B (en) * | 2010-04-13 | 2013-07-10 | 中国水利水电科学研究院 | Photocatalytic water purification device and manufacturing method of photocatalytic water purification device |
| CN102219281A (en) * | 2010-04-13 | 2011-10-19 | 中国水利水电科学研究院 | Photocatalytic water purification device and manufacturing method of photocatalytic water purification device |
| CN102513249A (en) * | 2011-12-15 | 2012-06-27 | 无锡威孚环保催化剂有限公司 | Belt type metal material surface coating process and equipment |
| CN104626680A (en) * | 2015-03-03 | 2015-05-20 | 中国科学院上海硅酸盐研究所 | Composite black titanium dioxide film and preparation method thereof |
| CN106390998A (en) * | 2016-08-30 | 2017-02-15 | 陈劲夫 | Nanometer titania based composite catalyst and preparation method thereof |
| CN106390998B (en) * | 2016-08-30 | 2019-06-21 | 惠州市登高达电业有限公司 | A kind of nm TiO 2-base composite catalyst and preparation method thereof |
| CN106895510A (en) * | 2017-02-23 | 2017-06-27 | 诺曼利尔（青岛）环境能源技术有限公司 | Air cleaning unit and nanometer light purify the preparation method of coating |
| CN109603920A (en) * | 2018-12-18 | 2019-04-12 | 同济大学 | Cellulose-the TiO of excited by visible light2Composite photo-catalyst |
| CN109603920B (en) * | 2018-12-18 | 2020-04-07 | 同济大学 | Visible light excited cellulose-TiO2Composite photocatalyst |
| CN110639485A (en) * | 2019-10-11 | 2020-01-03 | 南京大学昆山创新研究院 | Preparation of supported TiO by distributed deposition method2Method for preparing photocatalyst |
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