CN100438973C - Method for preparing TiO2 visible light photocatalyst - Google Patents
Method for preparing TiO2 visible light photocatalyst Download PDFInfo
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- CN100438973C CN100438973C CNB2007101395520A CN200710139552A CN100438973C CN 100438973 C CN100438973 C CN 100438973C CN B2007101395520 A CNB2007101395520 A CN B2007101395520A CN 200710139552 A CN200710139552 A CN 200710139552A CN 100438973 C CN100438973 C CN 100438973C
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Abstract
The invention relates to a preparing method for the TiO2 visible light catalyst. The method is to make the titanium salt react with the ethanol to get the transparent liquid, drop the liquid into the deionized water to form the white suspension, adjust the pH value with the inorganic acid, and then process with the ultra sound in eighty to one hundred and sixty DEG C for five to twenty hours to get the TiO2 nanometer crystal sol; and then drop the ammonium bromide into the TiO2 nanometer crystal sol, implement circumfluent reaction for five to ten hours, then decompress and evaporate the solvent to get the dry gel, extract the dry gel taking the ethanol as the solvent, and dry in one hundred to one hundred and twenty DEG C to obtain the TiO2 visible light catalyst. The invention has the advantages of simple operation, gentle reaction condition, and low cost of device, strong visible light absorbing and good visible light catalyzing capability, etc.
Description
Technical field
The invention belongs to a kind of TiO
2The preparation method of visible-light photocatalyst.
Technical background
TiO
2It is most widely used photochemical catalyst, but its energy gap (anatase Eg=3.2eV) broad can only utilize the ultraviolet light that accounts for sunshine 3-4%, has seriously restricted its effective utilization to solar energy, must carry out modification to it, make its ABSORPTION EDGE extend to visible region.Numerous results of study show, TiO
2Non-metal N anion dopedly can make it have excellent visible light to absorb and TiO
2Halide anion mix and can produce Ti
3+, improve TiO greatly
2The quantum efficiency of photochemical catalyst.Therefore, the anion codope TiO of halogen and N
2Photochemical catalyst is a kind of very desirable visible-light photocatalyst.But prior preparation method is that (Spray Pyrolysis SP), need the hot conditions up to 900 ℃ could realize high temperature sputter decomposition method, and simple equipment and technical conditions are difficult to satisfy, and this has limited codope TiO greatly
2The application of visible-light photocatalyst, thereby room temperature and be worth expectation especially a little more than the low temperature preparation method of room temperature.
Summary of the invention
The object of the invention provides a kind of simple to operate, the following preparation of cryogenic conditions TiO
2The method of visible-light photocatalyst.
The object of the present invention is achieved like this: at first make titanium alkoxide complete hydrolysis with a large amount of water, add the inorganic acid peptization then, form TiO through water-heat process
2Nanocrystalline colloidal sol is again with the direct prepared in reaction N-Br codope of amine bromide TiO
2Visible-light photocatalyst.
Preparation method of the present invention is as follows:
(1) TiO
2The nanocrystalline colloidal sol preparation:
Titanium alkoxide and ethanol 0.5～1: 1 reaction in molar ratio obtained after the transparency liquid in 2～10 minutes, this fluid drips is added in the deionized water, the mol ratio that makes titanium alkoxide and water is 1: 80～120, the while strong agitation, form behind the white suspension with inorganic acid for adjusting pH value between 1～3, through ultrasonic processing in 10～30 minutes,, obtain TiO then 80～160 ℃ of reactions 5～20 hours
2Nanocrystalline colloidal sol;
(2) photochemical catalyst preparation:
Under stirring fast, amine bromide is by the mol ratio 1～3 of amine bromide and titanium alkoxide: 1 is added drop-wise to TiO
2In the nanocrystalline colloidal sol, dropwise and continued back flow reaction 5～10 hours, then solvent evaporated under reduced pressure, obtain pale brown look xerogel, with ethanol is that solvent carries out extracting extraction 5～20 hours to the gained xerogel, descends dry 10～30 minutes at 100～120 ℃ again, obtains TiO
2Visible-light photocatalyst.
Aforesaid titanium alkoxide is tetraethyl titanate, tetraisopropyl titanate or butyl titanate.
Aforesaid inorganic acid is HCl or HNO
3
Aforesaid amine bromide is tetramethylammonium bromide, teabrom, cetyl trimethyl
Ammonium bromide or amyl group trimethylammonium bromide
The TiO of the present invention's preparation
2Visible-light photocatalyst has in the visible region of 400～600nm more by force and to absorb, and under the visible light irradiation of＞420nm, and the methylene blue degradation rate is higher than 50% in 16 hours.
The present invention compared with prior art has following advantage:
1. simple to operate, reaction condition is gentle, equipment cost is low;
2. has stronger visible absorption;
3. has the excellent visible light photocatalysis performance.
The specific embodiment
Embodiment 1
The reaction in 0.5: 1 in molar ratio of tetraisopropyl titanate and ethanol obtained transparency liquid in 2 minutes.Afterwards, this fluid drips is added in the deionized water, the mol ratio that makes tetraisopropyl titanate and water is 1: 80, simultaneously strong agitation.After forming white suspension, regulating the pH value with HCl is 1, then through ultrasonic processing in 10 minutes, 160 ℃ of reactions 5 hours, obtains TiO
2Nanocrystalline colloidal sol.
Under stirring fast, tetramethylammonium bromide is added drop-wise to TiO by the mol ratio of tetramethylammonium bromide and tetraisopropyl titanate at 1: 1
2In the nanocrystalline colloidal sol, dropwise and continued back flow reaction 5 hours, solvent evaporated under reduced pressure obtains pale brown look xerogel then.With ethanol is that solvent carries out extracting extraction 5 hours to the gained xerogel, descends dry 30 minutes at 100 ℃ again, obtains pale brown toner end TiO
2Visible-light photocatalyst.This pale brown toner end has in the visible region of 400～600nm more by force and to absorb, and under the visible light irradiation of＞420nm, and the methylene blue degradation rate is 50.6% in 16 hours.
Embodiment 2
The reaction in 0.5: 1 in molar ratio of tetraisopropyl titanate and ethanol obtained transparency liquid in 5 minutes.Afterwards, this fluid drips is added in the deionized water, the mol ratio that makes tetraisopropyl titanate and water is 1: 100, simultaneously strong agitation.After forming white suspension, regulating the pH value with HCl is 2, then through ultrasonic processing in 15 minutes, 100 ℃ of reactions 10 hours, obtains TiO
2Nanocrystalline colloidal sol.
Under stirring fast, teabrom is added drop-wise to TiO by the mol ratio of teabrom and tetraisopropyl titanate at 1.5: 1
2In the nanocrystalline colloidal sol, dropwise and continued back flow reaction 5 hours, solvent evaporated under reduced pressure obtains pale brown look xerogel then.With ethanol is that solvent carries out extracting extraction 8 hours to the gained xerogel, descends dry 25 minutes at 110 ℃ again, obtains pale brown toner end TiO
2Visible-light photocatalyst.This pale brown toner end has in the visible region of 400～600nm more by force and to absorb, and under the visible light irradiation of＞420nm, and the methylene blue degradation rate is 51.3% in 16 hours.
Embodiment 3
The reaction in 1: 1 in molar ratio of tetraethyl titanate and ethanol obtained transparency liquid in 3 minutes.Afterwards, this fluid drips is added in the deionized water, the mol ratio that makes tetraethyl titanate and water is 1: 100, simultaneously strong agitation.After forming white suspension, use HNO
3Regulating the pH value is 1.5, then through ultrasonic processing in 15 minutes, 150 ℃ of reactions 5 hours, obtains TiO
2Nanocrystalline colloidal sol.
Under stirring fast, softex kw is added drop-wise to TiO by the mol ratio of softex kw and tetraethyl titanate at 3: 1
2In the nanocrystalline colloidal sol, dropwise and continued back flow reaction 10 hours, solvent evaporated under reduced pressure obtains pale brown look xerogel then.With ethanol is that solvent carries out extracting extraction 10 hours to the gained xerogel, descends dry 30 minutes at 110 ℃ again, obtains pale brown toner end TiO
2Visible-light photocatalyst.This pale brown toner end has in the visible region of 400～600nm more by force and to absorb, and under the visible light irradiation of＞420nm, and the methylene blue degradation rate is 52.6% in 16 hours.
Embodiment 4
The reaction in 0.8: 1 in molar ratio of butyl titanate and ethanol obtained transparency liquid in 5 minutes.Afterwards, this fluid drips is added in the deionized water, the mol ratio that makes butyl titanate and water is 1: 120, simultaneously strong agitation.After forming white suspension, regulating the pH value with HCl is 2, then through ultrasonic processing in 30 minutes, 150 ℃ of reactions 6 hours, obtains TiO
2Nanocrystalline colloidal sol.
Under stirring fast, softex kw is added drop-wise to TiO by the mol ratio of softex kw and butyl titanate at 2: 1
2In the nanocrystalline colloidal sol, dropwise and continued back flow reaction 8 hours, solvent evaporated under reduced pressure obtains pale brown look xerogel then.With ethanol is that solvent carries out extracting extraction 15 hours to the gained xerogel, descends dry 10 minutes at 120 ℃ again, obtains pale brown toner end TiO
2Visible-light photocatalyst.This pale brown toner end has in the visible region of 400～600nm more by force and to absorb, and under the visible light irradiation of＞420nm, and the methylene blue degradation rate is 51.9% in 16 hours.
Embodiment 5
The reaction in 0.8: 1 in molar ratio of tetraethyl titanate and ethanol obtained transparency liquid in 5 minutes.Afterwards, this fluid drips is added in the deionized water, the mol ratio that makes tetraethyl titanate and water is 1: 100, simultaneously strong agitation.After forming white suspension, use HNO
3Regulating the pH value is 2, then through ultrasonic processing in 15 minutes, 80 ℃ of reactions 20 hours, obtains TiO
2Nanocrystalline colloidal sol.
Under stirring fast, tetramethylammonium bromide is added drop-wise to TiO by the mol ratio of tetramethylammonium bromide and tetraethyl titanate at 2: 1
2In the nanocrystalline colloidal sol, dropwise and continued back flow reaction 9 hours, solvent evaporated under reduced pressure obtains pale brown look xerogel then.With ethanol is that solvent carries out extracting extraction 20 hours to the gained xerogel, descends dry 25 minutes at 110 ℃ again, obtains pale brown toner end TiO
2Visible-light photocatalyst.This pale brown toner end has in the visible region of 400～600nm more by force and to absorb, and under the visible light irradiation of＞420nm, and the methylene blue degradation rate is higher than 53.6% in 16 hours.
Embodiment 6
The reaction in 1: 1 in molar ratio of butyl titanate and ethanol obtained transparency liquid in 10 minutes.Afterwards, this fluid drips is added in the deionized water, the mol ratio that makes butyl titanate and water is 1: 110, simultaneously strong agitation.After forming white suspension, regulating the pH value with HCl is 1.5, then through ultrasonic processing in 15 minutes, 120 ℃ of reactions 8 hours, obtains TiO
2Nanocrystalline colloidal sol.
Under stirring fast, the amyl group trimethylammonium bromide is added drop-wise to TiO by the mol ratio of amyl group trimethylammonium bromide and butyl titanate at 1.5: 1
2In the nanocrystalline colloidal sol, dropwise and continued back flow reaction 8 hours, solvent evaporated under reduced pressure obtains pale brown look xerogel then.With ethanol is that solvent carries out extracting extraction 15 hours to the gained xerogel, descends dry 15 minutes at 120 ℃ again, obtains pale brown toner end TiO
2Visible-light photocatalyst.This pale brown toner end has in the visible region of 400～600nm more by force and to absorb, and under the visible light irradiation of＞420nm, and the methylene blue degradation rate is 51.8% in 16 hours.
Embodiment 7
The reaction in 0.5: 1 in molar ratio of tetraisopropyl titanate and ethanol obtained transparency liquid in 5 minutes.Afterwards, this fluid drips is added in the deionized water, the mol ratio that makes tetraisopropyl titanate and water is 1: 120, simultaneously strong agitation.After forming white suspension, use HNO
3Regulating the pH value is 3, then through ultrasonic processing in 10 minutes, 150 ℃ of reactions 5 hours, obtains TiO
2Nanocrystalline colloidal sol.
Under stirring fast, softex kw is added drop-wise to TiO by the mol ratio of softex kw and tetraisopropyl titanate at 3: 1
2In the nanocrystalline colloidal sol, dropwise and continued back flow reaction 10 hours, solvent evaporated under reduced pressure obtains pale brown look xerogel then.With ethanol is that solvent carries out extracting extraction 15 hours to the gained xerogel, descends dry 20 minutes at 110 ℃ again, obtains pale brown toner end TiO
2Visible-light photocatalyst.This pale brown toner end has in the visible region of 400～600nm more by force and to absorb, and under the visible light irradiation of＞420nm, and the methylene blue degradation rate is 52.2% in 16 hours.
Claims (4)
1, a kind of TiO
2The preparation method of visible-light photocatalyst is characterized in that comprising the steps:
(1) TiO
2The nanocrystalline colloidal sol preparation:
Titanium alkoxide and ethanol 0.5～1: 1 reaction in molar ratio obtained after the transparency liquid in 2～10 minutes, this fluid drips is added in the deionized water, the mol ratio that makes titanium alkoxide and water is 1: 80～120, the while strong agitation, form behind the white suspension with inorganic acid for adjusting pH value between 1～3, through ultrasonic processing in 10～30 minutes,, obtain TiO then 80～160 ℃ of reactions 5～20 hours
2Nanocrystalline colloidal sol;
(2) photochemical catalyst preparation:
Under stirring fast, amine bromide is by the mol ratio 1～3 of amine bromide and titanium alkoxide: 1 is added drop-wise to TiO
2In the nanocrystalline colloidal sol, dropwise and continued back flow reaction 5～10 hours, then solvent evaporated under reduced pressure, obtain pale brown look xerogel, with ethanol is that solvent carries out extracting extraction 5～20 hours to the gained xerogel, descends dry 10～30 minutes at 100～120 ℃ again, obtains TiO
2Visible-light photocatalyst.
2, a kind of TiO as claimed in claim 1
2The preparation method of visible-light photocatalyst is characterized in that described titanium alkoxide is tetraethyl titanate, tetraisopropyl titanate or butyl titanate.
3, a kind of TiO as claimed in claim 1
2The preparation method of visible-light photocatalyst is characterized in that described inorganic acid is HCl or HNO
3
4, a kind of TiO as claimed in claim 1
2The preparation method of visible-light photocatalyst is characterized in that described amine bromide is tetramethylammonium bromide, teabrom, softex kw or amyl group trimethylammonium bromide.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007101395520A CN100438973C (en) | 2007-09-29 | 2007-09-29 | Method for preparing TiO2 visible light photocatalyst |
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|---|---|---|---|
| CNB2007101395520A CN100438973C (en) | 2007-09-29 | 2007-09-29 | Method for preparing TiO2 visible light photocatalyst |
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| CN100438973C true CN100438973C (en) | 2008-12-03 |
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| CN109911933A (en) * | 2019-03-08 | 2019-06-21 | 广东工业大学 | A kind of black titanium dioxide nano material and its preparation method and application |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020006865A1 (en) * | 2000-07-17 | 2002-01-17 | Kabushiki Kaisha Toyota Chuo Kenkyusho | Photocatalytic substance |
| CN1363521A (en) * | 2001-01-09 | 2002-08-14 | 攀枝花市永禄科技开发有限责任公司 | Process for preparing anatase crystal type nano TiO2 |
| US20060210798A1 (en) * | 2005-03-16 | 2006-09-21 | Clemens Burda | Doped metal oxide nanoparticles and methods for making and using same |
| CN1903436A (en) * | 2006-08-08 | 2007-01-31 | 南开大学 | Method for preparing nitrogen-doped nanometer titanium dioxide catalyst with high activity for visible light range |
| CN1962459A (en) * | 2006-12-01 | 2007-05-16 | 浙江大学 | Method for preparing modified titanium oxide sol, powder and film |
-
2007
- 2007-09-29 CN CNB2007101395520A patent/CN100438973C/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020006865A1 (en) * | 2000-07-17 | 2002-01-17 | Kabushiki Kaisha Toyota Chuo Kenkyusho | Photocatalytic substance |
| CN1363521A (en) * | 2001-01-09 | 2002-08-14 | 攀枝花市永禄科技开发有限责任公司 | Process for preparing anatase crystal type nano TiO2 |
| US20060210798A1 (en) * | 2005-03-16 | 2006-09-21 | Clemens Burda | Doped metal oxide nanoparticles and methods for making and using same |
| CN1903436A (en) * | 2006-08-08 | 2007-01-31 | 南开大学 | Method for preparing nitrogen-doped nanometer titanium dioxide catalyst with high activity for visible light range |
| CN1962459A (en) * | 2006-12-01 | 2007-05-16 | 浙江大学 | Method for preparing modified titanium oxide sol, powder and film |
Non-Patent Citations (2)
| Title |
|---|
| Preparation of high efficient photoelectrode of N-F-codopedTiO2 nanotubes. Yaling Su, etc.Journal of Photochemistry and Photobiology A: Chemistry,Vol.194 . 2007 * |
| 铁、氮共掺杂二氧化钛粉末的制备及光催化活性. 黄东升，程朝凤，李玉花，曾人杰.无机化学学报，第23卷第4期. 2007 * |
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