CN102407105B - Nanometer titanium dioxide modified film and gradient doping modification method of nanometer titanium dioxide film - Google Patents
Nanometer titanium dioxide modified film and gradient doping modification method of nanometer titanium dioxide film Download PDFInfo
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- CN102407105B CN102407105B CN2011103306871A CN201110330687A CN102407105B CN 102407105 B CN102407105 B CN 102407105B CN 2011103306871 A CN2011103306871 A CN 2011103306871A CN 201110330687 A CN201110330687 A CN 201110330687A CN 102407105 B CN102407105 B CN 102407105B
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Abstract
The invention discloses a nanometer titanium dioxide modified film, comprising multiple layers of titanium dioxide films doped with modifying ions, wherein the modifying ions are all doped on the surfaces of the titanium dioxide films, and the doping amount of the modifying ions is increased along with the increase of the layer number of the titanium dioxide films; and the modifying ions are selected from transition metal, noble metal, rare-earth metal or nonmetal. The invention also discloses a gradient doping modification method of the nanometer titanium dioxide modified film. The method is simple to operate, low in cost and easy for realization of large-scale production. Ions distributed in each film layer in a gradient mode are conducive to transport and transfer of photon-generated carriers, can effectively prompt separation of photon-generated electronics and cavities, and enables the light absorption wavelength of TiO2 to be transferred to a visible light region through red shift. The modified film is in a layer structure, and the photo catalysis performance of the film can be effectively improved by gradient doping of ions.
Description
Technical field
The present invention relates to a kind of nano titanium oxide doping vario-property film and nano-titanium dioxide film is carried out the grade doping modification, belong to catalysis material and preparing technical field thereof.
Background technology
TiO
2Because nontoxic, stable chemical nature, the characteristics such as cheap and easy to get are widely used in the fields such as function ceramics, cosmetics, environmental pollution improvement, solar cell.At present, TiO
2The semiconductor-based photochemical catalyst that is considered to organic pollution in a kind of degrading waste water of tool DEVELOPMENT PROSPECT and the air.Under illumination condition, TiO
2Can be carbon dioxide, water and small-molecule substance with most organic substance decomposings, thereby reach the purpose of environmental protection.But TiO
2Greater band gap (the anatase: 3.2eV of itself, rutile: 3.0eV), only just can be excited under less than the ultraviolet lighting of 388nm and degradation of organic substances at wavelength, and ultraviolet light only accounts for about 4% of sunshine total amount, thereby limited its application under sunshine and/or visible light; On the other hand, TiO
2The electron-hole with photocatalytic activity that produces under illumination condition is very easily again compound, causes quantum efficiency lower, and photocatalytic activity descends.
For overcoming above shortcoming, generally adopt at TiO at present
2This method of modifying of middle doping metals and/or nonmetallic ion.By at TiO
2One or more ions of middle doping not only can effectively reduce the recombination probability in light induced electron and hole, and can make TiO
2Light absorption wavelength enter visible-range, increase the absorbing amount of visible region, and then improve TiO
2Photocatalytic activity.At present, for TiO
2The ion doping method that film the most often adopts is that the doping ion is directly added TiO
2Precursor solution in, be called bulk phase-doped or interior doping; What this project team adopted is that the doping ion is mixed at TiO
2Film surface is called surface doping or outer the doping.Experimental result shows, surface doping is than the TiO after bulk phase-doped
2Film has more excellent photocatalysis performance.But ion surface mixes and also easily makes TiO
2Doping ion on every side is too concentrated, and unnecessary ion might become new electron-hole complex centre, has reduced on the contrary TiO
2Photocatalytic activity.Therefore, the control surface ions dosage is also effectively utilized the surface doping ion, makes gained TiO
2Film keeps best catalytic performance that photocatalysis field is had great practical value.
Summary of the invention
For the problems referred to above, the invention provides a kind of modified film by nanometer titanium dioxide, this modified film has excellent photocatalysis performance.
The present invention also provides a kind of grade doping method of modifying of modified film by nanometer titanium dioxide, the method makes modification ion distribution gradient in each layer of film, help transportation and the transmission of photo-generated carrier, can effectively promote the separation in light induced electron-hole, make TiO
2The light absorption wavelength red shift to visible region, improve the utilization rate of photon, therefore, gained modified film excellent performance.
The present invention is achieved by the following technical solutions:
A kind of modified film by nanometer titanium dioxide, comprise that multi-layer doping has the titanium deoxid film of modification ion, is characterized in that: the modification ion all is entrained in the titanium deoxid film surface, along with the addition content of the increase modification ion of the titanium deoxid film number of plies is the change main trend.
Fig. 1 is the ion gradient doping vario-property nano-TiO by the present invention's preparation
2The schematic cross-section of film.The ion that stain representative is mixed among the figure increases with the increase amounts of dopant ions of the film number of plies thereupon.
Modification ion described in the above-mentioned modified film by nanometer titanium dioxide is selected from transition metal, noble metal, rare earth metal or nonmetal.
In the above-mentioned modified film by nanometer titanium dioxide, described transition metal is Fe, Co, W or V, and described noble metal is Ag, Pt or Au, and described rare earth metal is Ce or La, described nonmetal be B, F or S.
In the above-mentioned modified film by nanometer titanium dioxide, modification ion and TiO
2Mass ratio be 0.002-0.03:1.
The present invention has mainly improved the admixture form of doping ion, make its addition content in every layer film different, concrete for being increase tendency, the ion of gradient distribution helps transportation and the transmission of photo-generated carrier in each layer of film, can effectively promote the separation in light induced electron-hole, make TiO
2The light absorption wavelength red shift to visible region, improve the utilization rate of photon, thereby effectively promote photocatalysis performance.The admixture ion that the present invention selects (is the modification ion, down together) transition metal ions, precious metal ion, rare earth ion and nonmetallic ion are arranged, its gradient ratio at every layer is closely not identical when selecting different ions, and with the variation of admixture ion, the content of each layer intermediate ion also changes.Different admixture ions has different best admixture gradient ratios, and the difference of each layer of admixture ion admixture gradient ratio can change the photocatalysis performance of modified film.Can find out from Fig. 2-7, different admixture ions, different admixture gradient ratios have different performances, but generally, are better than that existing ion surface mixes or the performance of bulk phase-doped film according to the performance of the modified film of gradient admixture gained.In the whole modified film, the number of plies of titanium deoxid film is generally the 3-6 layer, and the thickness of final gained modified film has certain influence to film performance, and general final thickness is 0.1-0.5 μ m, and thickness can make the performance of film weaken above this scope even disappear.
The present invention has made modified film by nanometer titanium dioxide of the present invention with the method for surface doping ion, but distinct with existing surface doping method.The ion surface of general indication mixes or the outer meaning of mixing is: the substrate surface dipping lift plated film repeatedly after, in the end coat a certain amount of solion on the skim with a kind of solution injection device, it is dispersed on the film surface, and namely ion all is entrained in the surface of final formed film.The present invention improves the method, the film that each dipping is lifted gained carries out surface doping, so repeatedly ion just is distributed in the surface of every layer film behind the plated film, and the ionic weight that mixes at every tunic increases with the increase of rete number, but it once is the same that total ion concentration mixes with ion surface, and the inventive method is simple to operate, and cost is low, be fit to very much large-scale production, specifically may further comprise the steps:
(1) ethanol, butyl titanate and nitric acid are mixed the preparation colloidal tio 2;
(2) adopt dip-coating method to plate titanium deoxid film at substrate, the complete film of every plating applies a modification ion, and the coated weight of modification ion increases with the increase of coating layers, stops plated film after reaching thickness;
(3) with the substrate behind the plated film at 400-500 ℃ of roasting 1-3h, obtain modified film by nanometer titanium dioxide.
In the said method, the process of preparation colloidal tio 2 is: add the 1-5mL butyl titanate in the 10-50mL absolute ethyl alcohol, add rapidly the rarer nitric acid of 10-50mL, stir 10-120min, then at 20-25 ℃ of lower ageing 1-3 days, get colloidal tio 2, the molar concentration of nitric acid is 0.2mol/L.
In the said method, the modification ion doping is on the surface of every layer of titanium deoxid film, modification ion (ion namely mixes) generally is to carry out surface doping with the form of solution, difference according to the modification ion, the raw material of introducing the modification ion is also different, and those skilled in the art can select as required.For example, Fe and Co can carry out surface doping with the form wiring solution-forming of nitrate, and W can carry out surface doping with the form of sodium tungstate, and V can be with ammonium metavanadate (NH
4VO
3) form carry out surface doping, Ag can carry out surface doping with the form of silver nitrate, Pt can be with chloroplatinic acid (H
2PtCl
6) form carry out surface doping, Au can be with gold chloride (HAuCl
4) form carry out surface doping, rare earth metal can carry out surface doping with the form of its nitrate, B can carry out surface doping with the form of boric acid, F can carry out surface doping with the form of ammonium fluoride, S can be with thiocarbamide (CH
4N
2S) form is carried out surface doping.
When the preparation modified film, when also namely the modification ion being carried out grade doping, modified film general thickness, doping total ion concentration, ion gradient doping ratio all have considerable influence to the performance of film, will pay special attention in the preparation to control these influence factors, its media thickness is determined by colloidal nature, dip time, pull rate and number of times.
In the said method, during the dip-coating method plated film, pull rate 0.5-1mm/s, each plated film time is 1-10min.
In the said method, described substrate is glass, alloy, pottery or stainless steel substrates.
The present invention has the following advantages owing to taking above technical scheme:
1, the ion that gradient distributes in each layer of film helps transportation and the transmission of photo-generated carrier, can effectively promote the separation in light induced electron-hole, makes TiO
2The light absorption wavelength red shift to visible region;
2, can change the photocatalysis performance of film by the mix ratio of ion of regulating gradient;
3, the grade doping method is simple to operate, and cost is low, is easy to large-scale production;
4, the gained modified film is layer structure, and the amount of the doping ion that adds in every layer is different, Effective Raise TiO
2The photocatalysis performance of film.
Description of drawings
Fig. 1 is the ion gradient doping vario-property nano-TiO by the present invention's preparation
2The schematic cross-section of film.
Fig. 2 is the nano-TiO of grade doping and surface doping W element
2The uv-visible absorption spectra of film degradation acid fuchsin (ANR) solution.Wherein, 1. be acid fuchsin at the absorption spectrum of 400-600nm, 2. be the nano-TiO of Comparative Examples 1 gained surface doping W element
23. the uv-visible absorption spectra of film degradation acid fuchsin is the TiO of embodiment 2 gained grade doping W elements
24. the uv-visible absorption spectra of film degradation acid fuchsin is the TiO of embodiment 1 gained grade doping W element
2The uv-visible absorption spectra of film degradation acid fuchsin.
Fig. 3 is the nano-TiO by the grade doping La element of embodiment 3-5 and Comparative Examples 2-3 preparation
2Film, non-gradient surface doping La and pure TiO
2The uv-visible absorption spectra of film degradation acid fuchsin.
Fig. 4 is the nano-TiO by the grade doping F element of embodiment 6-8 and Comparative Examples 4 preparations
2The TiO of film, non-gradient surface doped F element
2The uv-visible absorption spectra of film degradation acid fuchsin.
Fig. 5 is the nano-TiO by the grade doping Ag element of embodiment 9-11 and Comparative Examples 5 preparations
2The TiO of film, non-gradient surface doping Ag element
2The uv-visible absorption spectra of film degradation acid fuchsin.
Fig. 6 is the nano-TiO by the grade doping B element of embodiment 12-14 and Comparative Examples 6 preparations
2The TiO of film, non-gradient surface doping B element
2The uv-visible absorption spectra of film degradation acid fuchsin.
Fig. 7 is the nano-TiO by the grade doping F element of embodiment 15-17 and Comparative Examples 7 preparations
2The TiO of film, non-gradient surface doped F element
2The uv-visible absorption spectra of film degradation acid fuchsin.
The specific embodiment
Following examples are used for specifically setting forth the present invention, but the present invention is not limited to embodiment, and all equivalences of doing according to the content of patent application of the present invention change and modify, and all should belong to the category of the present invention's protection.
The present invention adopts sol-gel process and dip-coating method to prepare nano-TiO
2Film, it carries out modification to adopt the grade doping ion pair, specifically carries out according to following steps:
A: get a clean beaker, to wherein pipetting the 10-50mL absolute ethyl alcohol, then under stirring condition, add the 1-5mL butyl titanate, add rapidly the rarer nitric acid of 10-50mL 0.2mol/L.Continue to stir 10-120min, put into incubator 20-25 ℃ ageing 1-3 days, obtain TiO
2Colloid;
B: the sheet glass (2.5cm * 2.5cm * 0.1cm) that gets a cleaning, with dip-coating method to the sheet glass plated film, the complete film of every plating applies primary ions, and the volume distribution gradient of Coating Ions solution, total coating layers is the 3-6 layer, pull rate is 0.5-1mm/s, and each plated film time is 1-10min;
C: the sheet glass behind the plated film is placed Muffle furnace, and 400-500 ℃ of roasting 1-3h namely obtains nano-TiO
2Modified film.
Embodiment 1
In the beaker of a cleaning, pipette the 20mL absolute ethyl alcohol, under the magnetic agitation condition, add the butyl titanate of 1mL and rare nitric acid of 30mL 0.2mol/L, continue to stir 30min, place 25 ℃ of incubator ageings 2 days, obtain TiO
2Colloid; Get a clean glass sheet, lift plated film with the speed of 1mm/s, each dip time in colloid is 1min, carries out 3 times and lifts, and applies 9 * 10 on the film surface after lifting plated film at every turn
-3The sodium tungstate solution of mol/L, liquor capacity is than being 1:3:6, total amount is 0.1mL(W and TiO
2Mass ratio be 0.03); Sheet glass behind the plated film is placed Muffle furnace, and 450 ℃ of roasting 1h can obtain the nano-TiO of grade doping W ion
2Film (be designated as W 136, wherein the numeral of W back is the gradient mix ratio of W).
The modified film (W 127) for preparing grade doping W ion according to the method for embodiment 1, different is that every layer film coated with tungsten acid sodium solution volume ratio is 1:2:7 (W 127).
Comparative Examples 1
The nano-TiO for preparing non-gradient admixture W ion according to the method for embodiment 1
2Modified film, different is after lifting plated film three times on the sheet glass, in the end applies the sodium tungstate solution (W external doping) of 0.1mL on the skim.
Embodiment 3
In the beaker of a cleaning, pipette the 30mL absolute ethyl alcohol, under the magnetic agitation condition, add the butyl titanate of 2mL and rare nitric acid of 50mL 0.2mol/L, continue to stir 60min, place 20 ℃ of incubator ageings 3 days, obtain TiO
2Colloid; Get a clean glass sheet, lift plated film with the speed of 1mm/s, the dip time in colloid is respectively 5min, 2min, 1min, carries out 3 times and lifts, and applies 7 * 10 on the film surface after lifting plated film at every turn
-3The lanthanum nitrate hexahydrate of mol/L, liquor capacity is than being 1:3:6, total amount is 0.1mL(La and TiO
2Mass ratio be 0.02); Sheet glass behind the plated film is placed Muffle furnace, and 400 ℃ of roasting 2h can obtain the nano-TiO of grade doping La ion
2Film (La 136).
Embodiment 4
The modified film for preparing grade doping La ion according to the method for embodiment 3, different is that it is 1:4:5 (La 145) that every layer film applies the lanthanum nitrate hexahydrate volume ratio.
The modified film for preparing grade doping La ion according to the method for embodiment 3, different is that it is 2:3:5 (La 235) that every layer film applies the lanthanum nitrate hexahydrate volume ratio.
Comparative Examples 2
The nano-TiO for preparing non-gradient admixture La ion according to the method for embodiment 3
2Modified film, different is after lifting plated film three times on the sheet glass, in the end applies the lanthanum nitrate hexahydrate (La external doping) of 0.1mL on the skim.
Comparative Examples 3
Method according to embodiment 3 prepares pure nano-TiO
2Film (TiO
2), different is directly at TiO with sheet glass
2Lift plated film in the colloid.
Embodiment 6
In the beaker of a cleaning, pipette the 50mL absolute ethyl alcohol, under the magnetic agitation condition, add the butyl titanate of 5mL and rare nitric acid of 50mL 0.2mol/L, continue to stir 120min, place 25 ℃ of incubator ageings 2 days, obtain TiO
2Colloid; Get a clean glass sheet, lift plated film with the speed of 1mm/s, the dip time in colloid is respectively 10min, 2min, 1min, 1min, carries out 4 times and lifts, and applies 5 * 10 on the film surface after lifting plated film at every turn
-3The ammonium fluoride solution of mol/L, liquor capacity is than being 1:2:3:4, total amount is 0.2mL(F and TiO
2Mass ratio be 0.003); Sheet glass behind the plated film is placed Muffle furnace, and 500 ℃ of roasting 1h can obtain the nano-TiO of grade doping F ion
2Film (F 1234).
Embodiment 7
The modified film for preparing grade doping F ion according to the method for embodiment 6, different is that it is 2:3:7:8 (F 2378) that every layer film applies the ammonium fluoride solution volume ratio.
Embodiment 8
The modified film for preparing grade doping F ion according to the method for embodiment 6, different is that it is 1:4:6:9 (F 1469) that every layer film applies the ammonium fluoride solution volume ratio.
Comparative Examples 4
The nano-TiO for preparing non-gradient admixture F ion according to the method for embodiment 6
2Modified film, different is after lifting plated film three times on the sheet glass, in the end applies the ammonium fluoride solution solution (F external doping) of 0.2mL on the skim.
Embodiment 9
In the beaker of a cleaning, pipette the 10mL absolute ethyl alcohol, under the magnetic agitation condition, add butyl titanate and the rare nitric acid of 10mL 0.2mol/L of 1mL, continue to stir 10min, place 25 ℃ of incubator ageings 1 day, obtain TiO
2Colloid; Get a clean glass sheet, lift plated film with the speed of 0.5mm/s, the dip time in colloid is respectively 5min, 2min, 1min, 1min, 1min, 1min, carries out 6 times and lifts, and applies 5 * 10 on the film surface after lifting plated film at every turn
-3The mol/L liquor argenti nitratis ophthalmicus, liquor capacity is than being 1:2:3:6:7:11, total amount is 0.3mL(Ag and TiO
2Mass ratio be 0.03); Sheet glass behind the plated film is placed Muffle furnace, and 400 ℃ of roasting 3h can obtain the nano-TiO of grade doping Ag ion
2Film (Ag 12367-11).
The modified film for preparing grade doping Ag ion according to the method for embodiment 9, different is that it is 1:2:4:5:8:10 (Ag 12458-10) that every layer film applies the liquor argenti nitratis ophthalmicus volume ratio.
Embodiment 11
The modified film for preparing grade doping Ag ion according to the method for embodiment 9, different is that it is 1:2:5:6:7:9 (Ag 125679) that every layer film applies the liquor argenti nitratis ophthalmicus volume ratio.
Comparative Examples 5
The nano-TiO for preparing non-gradient admixture Ag ion according to the method for embodiment 9
2Modified film, different is after lifting plated film six times on the sheet glass, in the end applies the liquor argenti nitratis ophthalmicus (Ag external doping) of 0.3mL on the skim.
In the beaker of a cleaning, pipette the 50mL absolute ethyl alcohol, under the magnetic agitation condition, add the butyl titanate of 2mL and rare nitric acid of 40mL 0.2mol/L, continue to stir 40min, place 25 ℃ of incubator ageings 2 days, obtain TiO
2Colloid; Get a clean glass sheet, lift with the speed of 1mm/s, the dip time in colloid is respectively 5min, 1min, 1min, carries out 3 times and lifts, and lifting at every turn and applying concentration on the film surface behind the plated film is 3 * 10
-3The BAS of mol/L, liquor capacity is than being 1:3:6, total amount is 0.3mL(B and TiO
2Mass ratio be 0.002); Sheet glass behind the plated film is placed Muffle furnace, and 450 ℃ of roasting 1h can obtain the nano-TiO of grade doping B ion
2Film (B 136).
Embodiment 13
The modified film for preparing grade doping B ion according to the method for embodiment 12, different is that it is 1:2:7 (B 127) that every layer film applies the BAS volume ratio.
The modified film for preparing grade doping B ion according to the method for embodiment 12, different is that it is 1:4:5 (B 145) that every layer film applies the BAS volume ratio.
Comparative Examples 6
The nano-TiO for preparing non-gradient admixture B ion according to the method for embodiment 12
2Modified film, different is after lifting plated film three times on the sheet glass, in the end applies the BAS (B external doping) of 0.3mL on the skim.
Embodiment 15
In the beaker of a cleaning, pipette the 30mL absolute ethyl alcohol, under the magnetic agitation condition, add the butyl titanate of 2mL and rare nitric acid of 20mL 0.2mol/L, continue to stir 60min, place 25 ℃ of incubator ageings 2 days, obtain TiO
2Colloid; Get a clean glass sheet, lift with the speed of 1mm/s, the dip time in colloid is respectively 3min, 2min, 1min, carries out 3 times and lifts, and lifting at every turn and applying concentration on the film surface behind the plated film is 5 * 10
-3The ammonium fluoride solution of mol/L, liquor capacity is than being 1:3:6, total amount is 0.2mL(F and TiO
2Mass ratio be 0.003); Sheet glass behind the plated film is placed Muffle furnace, and 450 ℃ of roasting 1h can obtain the nano-TiO of grade doping F ion
2Film (F 136).
Embodiment 16
The modified film for preparing grade doping F ion according to the method for embodiment 15, different is that it is 1:2:7 (F 127) that every layer film applies the ammonium fluoride solution volume ratio.
Embodiment 17
The modified film for preparing grade doping F ion according to the method for embodiment 15, different is that it is 2:3:5 (F 235) that every layer film applies the ammonium fluoride solution volume ratio.
Comparative Examples 7
The nano-TiO for preparing non-gradient admixture F ion according to the method for embodiment 15
2Modified film, different is after lifting plated film three times on the sheet glass, in the end applies the ammonium fluoride solution (F external doping) of 0.2mL on the skim.
Fig. 2 is the nano-TiO of grade doping and surface doping W element
2The uv-visible absorption spectra of film degradation acid fuchsin (ANR) solution.As can be seen from the figure, with the standby W ion-doped nano TiO of grade doping legal system of the present invention
2The W ion-doped nano TiO of film specific surface doping method preparation
2Film has better photocatalytic activity, and doping ion gradient ratio is different, and its catalytic activity is also different, and photocatalysis performance sequentially is: W surface doping＜W 136＜W 127.
Fig. 3 is the nano-TiO by the grade doping La element of embodiment 3-5 and Comparative Examples 2-3 preparation
2Film, non-gradient surface doping La and pure TiO
2The uv-visible absorption spectra of film degradation acid fuchsin.As can be seen from the figure, photocatalysis performance La 235＜La surface doping＜La 145＜La 136.
Fig. 4 is the nano-TiO by the grade doping F element of embodiment 6-8 and Comparative Examples 4 preparations
2The TiO of film, non-gradient surface doped F element
2The uv-visible absorption spectra of film degradation acid fuchsin.As can be seen from the figure, photocatalysis performance F surface doping＜F 2468＜F 2378＜F 1469.
Fig. 5 is the nano-TiO by the grade doping Ag element of embodiment 9-11 and Comparative Examples 5 preparations
2The TiO of film, non-gradient surface doping Ag element
2The uv-visible absorption spectra of film degradation acid fuchsin.As can be seen from the figure, photocatalysis performance Ag 12458-10＜Ag surface doping＜Ag 125679＜Ag 12367-11.
Fig. 6 is the nano-TiO by the grade doping B element of embodiment 12-14 and Comparative Examples 6 preparations
2The TiO of film, non-gradient surface doping B element
2The uv-visible absorption spectra of film degradation acid fuchsin.As can be seen from the figure, photocatalysis performance B 127＜B surface doping＜B 145＜B 136.
Fig. 7 is the nano-TiO by the grade doping F element of embodiment 15-17 and Comparative Examples 7 preparations
2The TiO of film, non-gradient surface doped F element
2The uv-visible absorption spectra of film degradation acid fuchsin.As can be seen from the figure, photocatalysis performance F 127＜F 235＜F surface doping＜F 136.
Can find out from Fig. 2-7, the prepared modified film photocatalysis performance of grade doping method of the present invention is much better than the film of existing surface dopping method gained.
Claims (12)
1. modified film by nanometer titanium dioxide, comprise that multi-layer doping has the titanium deoxid film of modification ion, it is characterized in that: the modification ion all is entrained in the titanium deoxid film surface, along with the addition content of each layer of increase modification ion of the titanium deoxid film number of plies is the change main trend.
2. modified film by nanometer titanium dioxide according to claim 1, it is characterized in that: described modification ion is selected from transition metal, rare earth metal or nonmetal.
3. modified film by nanometer titanium dioxide according to claim 2, it is characterized in that: described transition metal is Fe, Co, W or V, described rare earth metal is Ce or La, described nonmetal be B, F or S.
4. modified film by nanometer titanium dioxide according to claim 1, it is characterized in that: described modification ion is selected from noble metal.
5. modified film by nanometer titanium dioxide according to claim 4 is characterized in that described noble metal is Ag, Pt or Au.
6. modified film by nanometer titanium dioxide according to claim 1 is characterized in that: modification ion and TiO
2Mass ratio be 0.002-0.03:1.
7. modified film by nanometer titanium dioxide according to claim 1, it is characterized in that: described titanium deoxid film is the 3-6 layer, general thickness is 0.1-0.5 μ m.
8. the grade doping method of modifying of a nano-titanium dioxide film is characterized in that may further comprise the steps:
(1) ethanol, butyl titanate and nitric acid are mixed the preparation colloidal tio 2;
(2) adopt dip-coating method to plate titanium deoxid film at substrate, the complete film of every plating applies a modification ion, and the coated weight of each layer modification ion increases with the increase of coating layers, stops plated film after reaching thickness;
(3) with the substrate behind the plated film at 400-500 ℃ of roasting 1-3h, obtain modified film by nanometer titanium dioxide.
9. method according to claim 8, it is characterized in that: the process of preparation colloidal tio 2 is: add the 1-5mL butyl titanate in the 10-50mL absolute ethyl alcohol, add rapidly the rarer nitric acid of 10-50mL, stir 10-120min, then at 20-25 ℃ of lower ageing 1-3 days, get colloidal tio 2.
10. method according to claim 9, it is characterized in that: the molar concentration of nitric acid is 0.2mol/L.
11. method according to claim 8 is characterized in that: during the dip-coating method plated film, pull rate 0.5-1mm/s, each plated film time is 1-10min.
12. method according to claim 8 is characterized in that: described substrate is glass, alloy, pottery or stainless steel substrates.
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| CN103055905A (en) * | 2012-12-20 | 2013-04-24 | 河海大学 | Preparation method of modified titanium dioxide photocatalysts of platinum metal and fluorin ions |
| CN105669043B (en) * | 2015-12-29 | 2018-12-28 | 安徽理工大学 | La3+Adulterate TiO2Electrochomeric films and preparation method thereof |
| CN106268765B (en) * | 2016-07-15 | 2019-01-08 | 辽宁大学 | A kind of metal ion doped titanium dioxide method for manufacturing thin film |
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| CN113913795A (en) * | 2021-10-11 | 2022-01-11 | 成都先进金属材料产业技术研究院股份有限公司 | Method for preparing iron element doped titanium-based nano corrosion-resistant film |
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| CN102172522A (en) * | 2011-03-11 | 2011-09-07 | 陕西科技大学 | Method for preparing samarium-doped titanium dioxide thin film |
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| CN1502405A (en) * | 2002-11-26 | 2004-06-09 | 中国科学院广州能源研究所 | TiO2 photocatalyst film with inhomogeneously-doped metal ions on base body and preparation process thereof |
| CN102172522A (en) * | 2011-03-11 | 2011-09-07 | 陕西科技大学 | Method for preparing samarium-doped titanium dioxide thin film |
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