CN1323752C - Manufacture of Ag+-Fe+ dosed TiO2 weakly exciting catalytic luminating film - Google Patents
Manufacture of Ag+-Fe+ dosed TiO2 weakly exciting catalytic luminating film Download PDFInfo
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- CN1323752C CN1323752C CNB2005100186567A CN200510018656A CN1323752C CN 1323752 C CN1323752 C CN 1323752C CN B2005100186567 A CNB2005100186567 A CN B2005100186567A CN 200510018656 A CN200510018656 A CN 200510018656A CN 1323752 C CN1323752 C CN 1323752C
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- Prior art keywords
- composite mixed
- butyl titanate
- exciting light
- mixed tio
- film
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Abstract
The present invention relates to a preparation method for photocatalysis TiO2 films. The preparation method for Ag+ and Fe3+ composite doped photocatalyst film excited by weak light is characterized in that the method comprises the procedures that: 1. the molar ratio of butyl titanate to anhydrous alcohol to water to diethanolamine is 1: 26.5: 1: 1, the molar ratio of the doping ionic amount of Ag+ and Fe3+ to the butyl titanate is respectively 0.00043: 1 and 0.0001: 1, and the butyl titanate, the anhydrous alcohol, the water, the diethanolamine, silver nitrate and ferric nitrate are selected so as to prepare the Ag+ and Fe3+ composite doped TiO2 sol by a sol-gel method; 2. chips are cleaned; 3. the Ag+ and Fe3+ composite doped TiO2 sol is coated on the chips by an impregnation pulling method, pulling speed is 5 mm/s, and the impregnation time in the Ag+ and Fe3+ composite doped TiO2 sol is from 35 to 45 s; 4. products are obtained in a resistance furnace after heat treatment. The film prepared by the present invention has the characteristics of low power, long wave ultraviolet excitation or solar light excitation and good photocatalytic performance.
Description
Technical field
The present invention relates to a kind of photocatalysis TiO
2The preparation method of film.
Background technology
So-called photocatalysis film is meant that redox reaction can take place on its surface when this film during by the ultra violet lamp of power necessarily.Coated glass can be placed in the sulculus that methyl orange is housed, use this sulculus a period of time of ultra violet lamp of certain power then, find that the methyl orange color shoals, survey its transmittance and increase.Declaratives methyl orange is decomposed.This photocatalysis film can be used for disposing of sewage, degrading poisonous and harmful organic gas, sterilization, deodorizing etc.
Photocatalysis TiO
2Film is generally and is mixed with single transition metal ions (as Fe
3+, Cu
2+Deng) or silver is ion (Ag
+Deng) single composite mixed film, all can improve TiO to a certain extent
2Photocatalytic.Have now in the doping with Fe
3+Best results, but its excitaton source is the uviol lamp more than 18 watts, and its wavelength is 254nm, bigger to the consumption of the energy, and bigger to the human injury, thereby its range of application is very restricted.
Summary of the invention
At the deficiency of above-mentioned existing photochemical catalyst, the purpose of this invention is to provide a kind of low-power, long wave ultraviolet excitation or day optical excitation, Ag that photocatalysis performance is good
+-Fe
3+Composite mixed TiO
2The preparation method of weak exciting light catalytic film.
The object of the present invention is achieved like this: a kind of Ag
+-Fe
3+Composite mixed TiO
2The preparation method of weak exciting light catalytic film is characterized in that comprising the steps:
1). press butyl titanate: absolute ethyl alcohol: water: the mol ratio of diethanol amine=1: 26.5: 1: 1, the mole proportioning of amounts of dopant ions and butyl titanate is respectively: Ag
+: butyl titanate=0.00043: 1, Fe
3+: butyl titanate=0.0001: 1, choose butyl titanate, absolute ethyl alcohol, water, diethanol amine, silver nitrate, ferric nitrate; Prepare Ag with sol-gel process
+, Fe
3+Composite mixed TiO
2Colloidal sol;
2). substrate cleans;
3). adopt dip-coating method on substrate, to apply Ag
+, Fe
3+Composite mixed TiO
2Colloidal sol, pull rate is 5mm/s, at Ag
+, Fe
3+Composite mixed TiO
2Dip time is 35-45 second in the colloidal sol;
4). heat-treat with resistance furnace, 100 ℃ of insulation 1h, 200 ℃ of insulation 1h, 300 ℃ of insulation 1h, 500 ℃ of insulation 2h, heating rate is controlled at 1 ℃/s; Employing is closed fire door and is cooled off naturally, obtains Ag at substrate
+-Fe
3+Composite mixed TiO
2Weak exciting light catalytic film.
Described substrate is glass or pottery.
Described substrate cleans: clean 15min in the KQ-250DB numerical control supersonic washer, watery hydrochloric acid soaks 30min, and soaked in absolute ethyl alcohol 30min boils 30min, dries stand-by.
Described pull rate is accurate to ± 1mm/s, and dip time is accurate to ± 1s, can not cause liquid level obviously to vibrate when lifting.
Described on-chip Ag
+-Fe
3+Composite mixed TiO
2The thickness of weak exciting light catalytic film is 30～50nm.
The 1st) proportioning of butyl titanate, absolute ethyl alcohol, water, diethanol amine can influence the stability and the photocatalysis TiO of colloidal sol in the step
2The photocatalytic activity of film, the proportioning of amounts of dopant ions and butyl titanate (mole) will influence TiO greatly
2The photocatalytic activity of film, therefore, the proportioning of amounts of dopant ions and butyl titanate must strict control.The 2nd) substrate material must clean up in the step, otherwise can influence the adhesive force of film and substrate and influence the purity of film, finally influences TiO
2The photocatalytic activity of film.The 3rd) coating film thickness is 30-50nm in the step, the thickness of film mainly by pull rate and substrate the dip time in colloidal sol control, pull rate must be strict controlled in 5mm/s, and dip time is 35-45 second (the best is 40 seconds), and precision prescribed is respectively ± 1mm/s, ± 1s; Can not cause the obvious vibration of liquid level when lifting, the vibration of liquid level will influence the uniformity of film forming and then influence quality of forming film.The 4th) heating rate is controlled at 1 ℃/s in the step, adopts during cooling to close fire door and cool off naturally, cools off and may have influence on TiO because of opening fire door
2Crystal formation change and quality of forming film, and then have influence on its photocatalytic activity.
The present invention compared with prior art has following characteristics:
1, the high efficiency of performance can [natural daylight or low wattage uviol lamp (3W)] produce performance efficiently under weak shooting condition.Ag
+-Fe
3+Composite mixed TiO
2Weak exciting light catalytic film surface has more electron-hole pair and low electronics-hole-recombination rate, and this compares with present most of photocatalysis films of reporting, has improved the photosensitivity and the light-catalyzed reaction speed of film.
2, the broad-spectrum degradability under weak shooting condition, the most of harmful organic substance gases in the car of can degrading, and killing bacteria are particularly suitable for the degrading polycyclic aromatic hydrocarbons class, the polychlorinated biphenyl material.
3, the property of can be recycled, Ag
+-Fe
3+Composite mixed TiO
2Weak exciting light catalytic film is subjected to ambient light to intensify the strong active light induced electron of generation, easily invade in the structure of organic matter or microorganism, photohole is then captured the free electron of organic matter or microorganism, destroy organic matter or microorganism structure by redox reaction, realize the answer of self energy level simultaneously, and accept light once more and excite, produce light induced electron and photohole again, the entire reaction continual renovation that goes round and begins again.
Adopt the Ag of the inventive method preparation
+-Fe
3+Composite mixed TiO
2The photocatalytic of weak exciting light catalytic film obviously improves, and use be low-power uviol lamp (3W), wavelength is 376nm, perhaps use daylight under the sunny weather as excitation source, can reach effective utilization, save the energy, enlarge range of application daylight.
The specific embodiment
A kind of Ag
+-Fe
3+Composite mixed TiO
2The preparation method of weak exciting light catalytic film comprises the steps:
1). press butyl titanate: absolute ethyl alcohol: water: the mol ratio of diethanol amine=1: 26.5: 1: 1, the mole proportioning of amounts of dopant ions and butyl titanate is respectively: Ag
+: butyl titanate [(C
4H
9O)
4Ti]=0.00043: 1, Fe
3+: butyl titanate [(C
4H
9O)
4Ti]=0.0001: 1, butyl titanate, absolute ethyl alcohol, water, diethanol amine, silver nitrate, ferric nitrate chosen; Prepare Ag with sol-gel process
+, Fe
3+Composite mixed TiO
2Colloidal sol; It is pure that described butyl titanate, absolute ethyl alcohol, diethanol amine, silver nitrate, ferric nitrate are analysis, and water is redistilled water.
2). substrate cleans: substrate is glass or pottery, cleans 15min in the KQ-250DB numerical control supersonic washer, and watery hydrochloric acid soaks 30min, and soaked in absolute ethyl alcohol 30min boils 30min, dries stand-by.
3). adopt dip-coating method on substrate, to apply Ag
+, Fe
3+Composite mixed TiO
2Colloidal sol, pull rate is 5mm/s, at Ag
+, Fe
3+Composite mixed TiO
2Dip time is 35-45 second (the best is 40 seconds) in the colloidal sol; Pull rate is accurate to ± 1mm/s, and dip time is accurate to ± 1s, can not cause liquid level obviously to vibrate when lifting.
4). heat-treat with resistance furnace (box high temperature resistance furnace), 100 ℃ of insulation 1h, 200 ℃ of insulation 1h, 300 ℃ of insulation 1h, 500 ℃ of insulation 2h, heating rate is controlled at 1 ℃/s; Employing is closed fire door and is cooled off naturally, obtains the Ag that thickness is 30～50nm at substrate
+-Fe
3+Composite mixed TiO
2Weak exciting light catalytic film.
Detect Ag
+-Fe
3+Composite mixed TiO
2Weak exciting light catalytic film under low-power ultraviolet excitation condition to methyl orange solution photocatalytic degradation rate.Testing used methyl orange solution concentration is 10mg/L.The sheet glass of film forming of the present invention (the plated film area is that 5.3cm * 2.5cm) the placement specification is in 17cm * 7cm * 2.5cm clear glass sulculus, and to the methyl orange solution that wherein adds 20ml.Below test the excitation source that is adopted and be Z-F-20C camera bellows formula uv analyzer (the Shanghai Golconda turns round and look at village electric light instrument plant and makes), power is 3 watts, and the ultraviolet wavelength of selection is 365nm.Sheet glass is apart from light source 10cm.Reaction temperature is a room temperature, and the reaction time is the transmittance of a methyl orange solution of survey in per 20 minutes, surveys 4 times.Checkout gear is a 721W microcomputer type visible spectrophotometer (Shanghai Optical Instruments Factory).Its after 20 minutes transmittance be that 144.4,80 minutes transmittances are 179.3.
Between fine 12 noon to 14, test Ag
+-Fe
3+Composite mixed TiO
2The photocatalytic of weak exciting light catalytic film, its after 20 minutes transmittance be that 128.1,80 minutes transmittances are 145.4.
Employing is to colibacillary killing rate test Ag
+-Fe
3+Composite mixed TiO
2Weak exciting light catalytic film, configuration 10
9Original bacterium liquid of (individual)/ml concentration Escherichia coli and 800ml nutrient agar are diluted to 10 with original bacterium liquid
6(individual)/ml concentration (A) is standby as experiment test.To scribble Ag respectively
+-Fe
3+Composite mixed TiO
2Year sheet glass (experimental group) of weak exciting light catalytic film and the blank sheet glass (control group) that carries are put into sterile petri dish, 0.5ml bacterium liquid A is added drop-wise to respectively carries on the sheet glass tiling again.Experimental group and control group are put under the ultraviolet light (3W) behind the irradiation certain hour, in culture dish, add the dilution of 10ml physiological saline, mix.Take out dilution back bacterium liquid test tube stepwise dilution to 10
4, 10
3, 10
2, 10
1Concentration is got 10 of control group and experimental group respectively
2, 10
1Concentration bacterium liquid 1ml is in sterile petri dish, toward filling 10
2, 10
1Add culture medium in the culture dish of concentration bacterium, put into constant incubator after the cooling and cultivate 48h.Bacterium liquid after cultivating is done count of bacteria, contrast experiment's group and control group clump count, colibacillary killing rate reaches 70% in 2 minutes.
Claims (5)
1. Ag
+-Fe
3+Composite mixed TiO
2The preparation method of weak exciting light catalytic film is characterized in that comprising the steps:
1). press butyl titanate: absolute ethyl alcohol: water: the mol ratio of diethanol amine=1: 26.5: 1: 1, the mole proportioning of amounts of dopant ions and butyl titanate is respectively: Ag
+: butyl titanate=0.00043: 1, Fe
3+: butyl titanate=0.0001: 1, choose butyl titanate, absolute ethyl alcohol, water, diethanol amine, silver nitrate, ferric nitrate; Prepare Ag with sol-gel process
+, Fe
3+Composite mixed TiO
2Colloidal sol;
2). substrate cleans;
3). adopt dip-coating method on substrate, to apply Ag
+, Fe
3+Composite mixed TiO
2Colloidal sol, pull rate is 5mm/s, at Ag
+, Fe
3+Composite mixed TiO
2Dip time is 35-45 second in the colloidal sol;
4). heat-treat with resistance furnace, 100 ℃ of insulation 1h, 200 ℃ of insulation 1h, 300 ℃ of insulation 1h, 500 ℃ of insulation 2h, heating rate is controlled at 1 ℃/s; Employing is closed fire door and is cooled off naturally, obtains Ag at substrate
+-Fe
3+Composite mixed TiO
2Weak exciting light catalytic film.
2. a kind of Ag according to claim 1
+-Fe
3+Composite mixed TiO
2The preparation method of weak exciting light catalytic film is characterized in that described substrate is glass or pottery.
3. a kind of Ag according to claim 1
+-Fe
3+Composite mixed TiO
2The preparation method of weak exciting light catalytic film, it is characterized in that described substrate cleaning is: clean 15min in the KQ-250DB numerical control supersonic washer, watery hydrochloric acid soaks 30min, and soaked in absolute ethyl alcohol 30min boils 30min, dries stand-by.
4. a kind of Ag according to claim 1
+-Fe
3+Composite mixed TiO
2The preparation method of weak exciting light catalytic film is characterized in that described pull rate is accurate to ± 1mm/s, and dip time is accurate to ± 1s, can not cause liquid level obviously to vibrate when lifting.
5. a kind of Ag according to claim 1
+-Fe
3+Composite mixed TiO
2The preparation method of weak exciting light catalytic film is characterized in that described on-chip Ag
+-Fe
3+Composite mixed TiO
2The thickness of weak exciting light catalytic film is 30～50nm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100186567A CN1323752C (en) | 2005-04-30 | 2005-04-30 | Manufacture of Ag+-Fe+ dosed TiO2 weakly exciting catalytic luminating film |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100186567A CN1323752C (en) | 2005-04-30 | 2005-04-30 | Manufacture of Ag+-Fe+ dosed TiO2 weakly exciting catalytic luminating film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1712130A CN1712130A (en) | 2005-12-28 |
| CN1323752C true CN1323752C (en) | 2007-07-04 |
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ID=35718032
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005100186567A Expired - Fee Related CN1323752C (en) | 2005-04-30 | 2005-04-30 | Manufacture of Ag+-Fe+ dosed TiO2 weakly exciting catalytic luminating film |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2022219380A1 (en) * | 2021-04-16 | 2022-10-20 | Sri Lanka Institute Of Information Technology | A method of making silver-iron titanate nanoparticles and uses thereof |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102006028429B3 (en) * | 2006-06-21 | 2007-06-28 | Fachhochschule Kiel | Coating production method for producing a solar absorber coating coats a substrate with a titanium precursor solution so as to generate a layer of titanium dioxide according to a sol-gel technique |
| CN101328025B (en) * | 2008-07-17 | 2011-01-05 | 浙江大学 | Preparation of multielement codoped nanaotitania film |
| CN106555178B (en) * | 2016-11-17 | 2019-03-08 | 榆林学院 | One kind mixing iron titanium oxide hydrophobic film and preparation method thereof |
| CN113060801A (en) * | 2021-03-29 | 2021-07-02 | 山东理工大学 | Electrochemical device for treating cyanide-containing wastewater and preparation method and application thereof |
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| JPH08283022A (en) * | 1995-04-11 | 1996-10-29 | Ykk Kk | Titanium dioxide based composite superfine particle and its production |
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-
2005
- 2005-04-30 CN CNB2005100186567A patent/CN1323752C/en not_active Expired - Fee Related
Patent Citations (7)
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|---|---|---|---|---|
| JPH08283022A (en) * | 1995-04-11 | 1996-10-29 | Ykk Kk | Titanium dioxide based composite superfine particle and its production |
| US6077492A (en) * | 1996-01-22 | 2000-06-20 | Petroleum Energy Center | Photocatalyst, process for producing the photocatalyst, and photocatalytic reaction method |
| CN1256868A (en) * | 1998-12-16 | 2000-06-21 | 王志群 | Compound silver series inorganic germifuge |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2022219380A1 (en) * | 2021-04-16 | 2022-10-20 | Sri Lanka Institute Of Information Technology | A method of making silver-iron titanate nanoparticles and uses thereof |
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| Publication number | Publication date |
|---|---|
| CN1712130A (en) | 2005-12-28 |
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