CN1623653A - Preparation process of photocatalyzing active nano TiO2 collosol - Google Patents
Preparation process of photocatalyzing active nano TiO2 collosol Download PDFInfo
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- CN1623653A CN1623653A CN 200410060994 CN200410060994A CN1623653A CN 1623653 A CN1623653 A CN 1623653A CN 200410060994 CN200410060994 CN 200410060994 CN 200410060994 A CN200410060994 A CN 200410060994A CN 1623653 A CN1623653 A CN 1623653A
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Abstract
A photocatalytic nano-TiO2 sol for degradating the environmental pollutant, cleaning air and suppresing growth of bacteria is prepared through dissolving its precursor in alcohol, dropping water in the solution while stirring, reacting no acid solution under heating and stirring to obtain raw sol, diluting and regulating pH value. Its advantages are high photocatalytic activity and high stability.
Description
Technical field
The present invention relates to the crossing domain of subjects such as material, nanometer, chemistry, environmental science and biology, more specifically relate to a kind of photocatalytic activity nano-TiO
2The preparation method of colloidal sol.
Background technology
Since Fujishima and Honda found the photocatalysis performance of nano semiconductor material first in 1972, this field had caused great interest of scientists and research enthusiasm, becomes one of current direction of active research the most.Semiconductor particle has band structure, and generally (Valence Band, VB) (Conduction Band CB) constitutes, and has the forbidden band between valence band and the conduction band with empty high energy conduction band by the low energy valence band of filling up electronics.When semiconductor is penetrated in the illumination that is equal to or greater than energy gap (Eg) with energy, the electronics (e on the valence band
-) being excited transits to conduction band, produces corresponding hole (h on valence band
+), and under electric field action, separate and move to particle surface.Photohole has the very strong electronic capability that gets, and has strong oxidizing property, can capture the electronics in semiconductor grain adsorbed material or the solvent, makes the not light absorbing material of script be activated oxidation, and electron acceptor is reduced by the electronics of accepting the surface.Since in employed semiconductor light-catalyst, TiO
2Photochemical catalyst because of its have inexpensive, nontoxic, catalytic activity is high, oxidability is strong, chemical stability is good, abrasion resistance and can be recycling etc. advantage, and become catalyst ideal in the environmental treatment.
Yet in actual application, what people used always is through heat treated TiO
2Powder or film are though people such as Zhao Jincai adopt liquid-gel method or the synthetic TiO of hydro-thermal method
2Powder or film have obtained using widely aspect photocatalysis degradation organic contaminant, yet their building-up process all needs inevitably through muffle furnace high-temperature calcination, the TiO that obtains like this
2Cost height not only, and because the particle agglomeration of calcining when heating up influences nano-TiO
2Dispersiveness, thus limit its application.
Summary of the invention
The object of the present invention is to provide a kind of photocatalytic activity nano-TiO
2The preparation method of colloidal sol, this is easy to implement the method, and raw material is easy to get, and is cheap, operates fast and convenient.
To achieve these goals, the present invention adopts following technical measures:
Its step is as follows:
(a) because presoma viscosity is bigger, form hard aggregate for preventing localized precipitation, the inorganic or organic precursor with titanium adds in the alcohol earlier, is mixed with the alcoholic solution that concentration is 0.1～0.5mol/L.Presoma is titanium tetrachloride or titanium sulfate, titanyl sulfate, butyl titanate, isopropyl titanate.Can use ethanol, isopropyl alcohol during dissolving titanium precursor body.(b) get 10～50ml alcoholic solution, under room temperature (20～25 ℃) condition, slowly splash in 5～20ml water while stir, warming-in-water to 25 after dropwising～100 ℃ continues to stir 30～100 minutes under this temperature.During hydrolysis solvent can water, ammoniacal liquor, ethanolamines or diluted acid.(c) add 0.01～0.1mol/L acid solution, seal bottleneck, 25-100 ℃ is continued to stir 2～8 hours, promptly obtains even, transparent TiO
2Liquid.Acid is hydrochloric acid, sulfuric acid, acetic acid or nitric acid.The rotating speed that stirs in the entire reaction course is 50～2000 rev/mins.(d) with the nano-TiO of the photocatalytic activity that makes
2Stoste is diluted 5～50 times with redistilled water, and in this solution, dropwise add the NaOH aqueous solution of a certain amount of 2mol/L, regulate the pH value 4.0-7.0 of liquid, can obtain the photocatalytic activity nano-TiO that is directly used in air cleaning in the daily life, environmental contaminants degraded and has bacteriostasis
2Colloidal sol (nano-TiO
2Photocatalyst solution).The nano-TiO that the present invention obtains
2The colloidal sol catalytic property is very stable, can be used for the degradation treatment of a large amount of organic pollutions for a long time.
The present invention is directed to powder TiO in the prior art
2Or TiO
2Film disperses inhomogeneous, and light utilization efficiency is low excessively, the not high major defect of photocatalytic activity, and the fresh water hydrolysis products that dissolves presoma with diluted acid makes TiO
2Colloidal sol.Adopt the present invention, materials safety is easy to get, and is cheap, operate fast and conveniently, do not need the experiment condition of harshness, makes laboratory mass preparation and even suitability for industrialized production become possibility.Transmission electron microscope results proves, product homogeneous and good dispersiveness is arranged, stability, the TiO that ultra-violet absorption spectrum explanation the present invention makes
2Liquid has good absorption in the ultra-violet (UV) band, can be applicable to remove in the environment toxic organic compound, administer waste water, purify air and aspect such as bacteria growing inhibiting, and the light degradation of dyestuff, formaldehyde and toluene etc. experimental results show that its photocatalytic activity obviously is better than powder TiO
2Or TiO
2Film.Adopt the colloidal sol of equal volume to make TiO
2Film, the methyl orange of degraded same amount, required time is 7 times of this product.
Description of drawings
Fig. 1 is a nano-TiO of the present invention
2The ultra-violet absorption spectrum of photocatalyst solution;
Fig. 2 is a nano-TiO of the present invention
2The TEM image of photocatalyst solution;
Fig. 3 is a nano-TiO of the present invention
2Photocatalyst solution is to saccharomycetic inhibition effect;
Wherein left culture dish: add TiO2 of the present invention, right no TiO2, bacteriostasis rate surpasses 99%.
The specific embodiment
A kind of preparation photocatalytic activity nano-TiO
2The method of colloidal sol, synthetic example one:
1. get the 3ml butyl titanate, earlier it is dissolved in the absolute ethyl alcohol, be mixed with the ethanolic solution that concentration is 0.35mol/L;
2. get the ethanolic solution of 25ml butyl titanate, stir down and slowly splashes in the 10ml redistilled water of room temperature, dropwise back warming-in-water to 70 ℃, stirred 40 minutes at this temperature lower opening;
3. add the 0.04mol/LHCl aqueous solution then, seal bottleneck, 70 ℃ continue to be stirred 4 hours, promptly obtained homogeneous, transparent TiO
2Colloidal sol stoste;
4. with the TiO of above-mentioned gained
2Colloidal sol stoste is diluted 10 times with redistilled water, and adds the NaOH aqueous solution of a certain amount of 2mol/L in this solution, and the pH value of regulating liquid is 5, can obtain being directly used in the nano-TiO of degraded of daily life environmental contaminants and bacteriostasis
2Photocatalyst solution.
Synthetic example two:
1. get the 3ml butyl titanate, earlier it is dissolved in the absolute ethyl alcohol, be mixed with the ethanolic solution that concentration is 0.35mol/L;
2. get the ethanolic solution of 25ml butyl titanate, stir down and slowly splashes in the 10ml redistilled water of room temperature, dropwise back warming-in-water to 70 ℃, stirred 40 minutes at this temperature lower open mouth;
3. add 0.04mol/LHNO then
3The aqueous solution is sealed bottleneck, and constant temperature continues to stir 4 hours, promptly obtains even, transparent TiO
2Colloidal sol stoste;
4. with the TiO of above-mentioned gained
2Colloidal sol stoste is diluted 10 times with redistilled water, and adds the NaOH aqueous solution of a certain amount of 2mol/L in this solution, and the pH value of regulating liquid is 5.1, can obtain being directly used in the nano-TiO of degraded of daily life environmental contaminants and bacteriostasis
2Photocatalyst solution.
The photocatalytic activity nano-TiO
2The photocatalytic activity example of colloidal sol:
1. get nano-TiO
2Photocatalyst solution 5ml adds methyl orange, methyl blue or the acridine orange aqueous solution of 50 μ l 0.2%, is statically placed in the uviol lamp irradiation down of 125W, observes its degraded situation (seeing Table 1).Find that methyl orange, methyl blue or the complete degradation time of acridine orange are no more than 2 hours.
2. get nano-TiO
2Photocatalyst solution 40ml adds the formalin of 8 μ l 36%, in the ultra violet lamp of 100W, calculates its degradation rate and degradation time (seeing Table 2) according to the variation of TOC in the reactant liquor (total content of organic carbon) value under the stirring state.Find to degrade fully within one day.
3. get nano-TiO
2Photocatalyst solution 20ml adds the pure toluene of 1 μ l, in the ultra violet lamp of 100W, calculates its degradation rate and degradation time (seeing Table 3) according to the variation of TOC in the reactant liquor (total content of organic carbon) value under the stirring state.Find to degrade fully in about 25 hours.
4. get nano-TiO
2Photocatalyst solution 20ml in the ultra violet lamp of 100W, calculates ethanol degradation rate and degradation time (seeing Table 4) in matchmaker's solution according to the variation of TOC in the reactant liquor (total content of organic carbon) value under the stirring state.Find to degrade fully within one day.
5. get nano-TiO
2Photocatalyst solution 5ml adds 30ml yeast cells culture medium, and the irradiation of 30W fluorescent lamp is total to overnight incubation down, calculates its antibacterial efficient by the count plate method.Find to add TiO
2Bacteriostasis rate surpasses 99%.
Table 1
| Dyestuff | Complete degradation time |
| Methyl orange | ????20min |
| Methyl blue | ????115min |
| Acridine orange | ????74min |
Table 2
| The Degradation Formaldehyde time | The HCl system | ????HNO 3System |
| ????6.5h | ????61.0％ | ????41.4％ |
| ????11.5h | ????78.2％ | ????80.8％ |
| ????15.5h | ????94.7％ | ????88.3％ |
| ????＜23.5h | ????100％ | ????100％ |
Table 3
| The toluene degradation time | The HCl system | ????HNO 3System |
| ????10h | ????25.3％ | ????54.0％ |
| ????18h | ????80.4％ | ????71.7％ |
| ????25h | ????100％ | ????100％ |
Table 4
| The ethanol degradation time | The HCl system | ????HNO 3System |
| ????5.5h | ????41.4％ | ????50.1％ |
| ????12h | ????58.1％ | ????68.3％ |
| ????23.5h | ????100％ | ????100％ |
Product side effect example:
In the domestic environment, nano-TiO
2Metope (coating, wallpaper), cloth art (sofa, carpet, curtain, clothing), woodwork (floor, furniture) that photocatalyst solution may relate in handling, product detects very important to the security of these relative articles.
1, fabric experiment
Experiment product: fabrics such as the chemical fibre that varies in color, cotton textiles.
Experimental project: product is sprayed on the various fabrics respectively at uviol lamp, and irradiation is observed its color with the variation of light application time and to the erosion of fabric under the incandescent lamp.
| Light application time | The situation of fading | Erosion condition | The spraying number of times | |
| Ultraviolet | 20 hours | Basic no change | Do not have | 8 times |
| As seen | 18 days | Basic no change | Do not have | 4 times |
2, coating experiment
Experiment product: the plasterboard model that scribbles different colours coating.
Experimental project: product is sprayed on the various gypsum respectively at uviol lamp, and irradiation is observed its color and is decomposed situation with the variation and the painting color of light application time under the incandescent lamp.
| Light application time | The situation of fading | Coating decomposes | The spraying number of times | |
| Ultraviolet | 20 hours | Basic no change | Do not have | 8 times |
| As seen | 18 days | Basic no change | Do not have | 4 times |
3, wallpaper experiment
Experiment product: wallpapers such as the pure paper that varies in color, synthetic fibers.
Experimental project: product is sprayed on the various wallpapers respectively at uviol lamp, and irradiation is observed its color with the variation of light application time and to the erosion condition of wallpaper under the incandescent lamp.
| Light application time | The situation of fading | Erosion condition | The spraying number of times | |
| Ultraviolet | 20 hours | Basic no change | Do not have | 8 times |
| As seen | 18 days | Basic no change | Do not have | 4 times |
4, woodwork experiment
Experimental project: product is sprayed on the woodwork respectively at uviol lamp, and variation and the erosion condition of its color with light application time observed in irradiation under the incandescent lamp.
| Light application time | The situation of fading | Erosion condition | The spraying number of times | |
| Ultraviolet | 20 hours | Basic no change | Do not have | 8 times |
| As seen | 18 days | Basic no change | Do not have | 4 times |
Claims (6)
1. photocatalytic activity nano-TiO
2The preparation method of colloidal sol, it comprises the following steps:
(a) the inorganic or organic precursor with titanium adds in the alcohol, is mixed with the alcoholic solution that concentration is 0.1～0.5mol/L;
(b) get 10～50ml alcoholic solution, at ambient temperature, in the 5～20ml water that splashes into while stirring, warming-in-water to 25 after dropwising～100 ℃, continue to stir 30～100 minutes under this temperature:
(c) add 0.01～0.1mol/L acid solution, seal bottleneck, 25-100 ℃ is continued to stir 2～8 hours, promptly gets the nano-TiO of photocatalytic activity
2Stoste;
(d) with the nano-TiO of the photocatalytic activity that makes
2Stoste is diluted 5～50 times with redistilled water, and is added dropwise to the NaOH aqueous solution of 2mol/L in this solution, and regulator solution pH value is 4.0～7.0, can obtain nano-TiO
2Colloidal sol.
2. a kind of photocatalytic activity nano-TiO according to claim 1
2The preparation method of colloidal sol is characterized in that: presoma is titanium tetrachloride or titanium sulfate, titanyl sulfate, butyl titanate, isopropyl titanate.
3. a kind of photocatalytic activity nano-TiO according to claim 1
2The preparation method of colloidal sol is characterized in that: can use ethanol, isopropyl alcohol during dissolving titanium precursor body.
4. a kind of photocatalytic activity nano-TiO according to claim 1
2The preparation method of colloidal sol is characterized in that: solvent can water or ammoniacal liquor, ethanolamines, diluted acid during hydrolysis.
5. a kind of photocatalytic activity nano-TiO according to claim 1
2The preparation method of colloidal sol is characterized in that: the rotating speed that stirs in the entire reaction course is 50～2000 rev/mins.
6. a kind of TiO according to claim 1
2The photocatalytic activity nano-TiO
2The method of colloidal sol is characterized in that: acid is hydrochloric acid, sulfuric acid, acetic acid or nitric acid.
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| CN1304107C CN1304107C (en) | 2007-03-14 |
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100593524C (en) * | 2007-02-07 | 2010-03-10 | 中国科学院山西煤炭化学研究所 | Method of preparing high refractive index nanocrystalline TiO2 collosol-gel film |
| CN101119933B (en) * | 2005-12-20 | 2011-04-20 | Lg化学株式会社 | Titania sol, method of preparing the same, and coating composition comprising the same |
| CN102658103A (en) * | 2012-04-17 | 2012-09-12 | 太原理工大学 | Preparation method and application of high-active-dispersibility nanometer titanium dioxide |
| CN103657622A (en) * | 2013-12-04 | 2014-03-26 | 上海纳米技术及应用国家工程研究中心有限公司 | Efficient titanium dioxide photocatalyst, preparation thereof and applications thereof |
| CN103831078A (en) * | 2012-11-27 | 2014-06-04 | 张加艳 | Preparation method of heavy metal ion adsorbent |
| CN104150531A (en) * | 2014-06-27 | 2014-11-19 | 仙桃市中星电子材料有限公司 | Preparation method of titanium dioxide with high specific surface area |
| CN104761931A (en) * | 2008-02-14 | 2015-07-08 | 水晶美国股份公司 | Colloidal titanium dioxide sols |
| CN105537614A (en) * | 2015-12-28 | 2016-05-04 | 重庆文理学院 | Method for preparing hollow precious metal nano material with cuprous oxide as template |
| CN106914236A (en) * | 2017-03-20 | 2017-07-04 | 福州名谷纳米科技有限公司 | The amorphous state plasma hetero-junctions nano-TiO of efficient visible light response2Colloidal sol |
| CN107986327A (en) * | 2017-12-18 | 2018-05-04 | 苏州中科纳福材料科技有限公司 | The preparation method of titanium dioxide nano-film |
| CN109133164A (en) * | 2018-11-15 | 2019-01-04 | 湖北天瓷电子材料有限公司 | A kind of high dispersiveness spherical titanium dioxide process |
| CN109179495A (en) * | 2018-08-28 | 2019-01-11 | 绍兴文理学院 | A kind of preparation method of high-dispersion nano titanium dioxide |
| CN111569832A (en) * | 2020-05-19 | 2020-08-25 | 西南科技大学 | Method for preparing hypha/molybdenum sulfide adsorption-catalysis material by utilizing biological enrichment |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3777931D1 (en) * | 1986-09-22 | 1992-05-07 | Ishihara Sangyo Kaisha | TITANIUM DIOXYDSOL AND METHOD FOR THE PRODUCTION THEREOF. |
| JP3080162B2 (en) * | 1998-01-27 | 2000-08-21 | 日本パーカライジング株式会社 | Titanium oxide sol and method for producing the same |
| KR100374478B1 (en) * | 1999-09-20 | 2003-03-03 | 엘지전자 주식회사 | Method for Preparing an Anatase Typed-Titanium Dioxide Photocatalyst and Photocatalyst Produced by the same |
| CN1295977A (en) * | 2000-12-19 | 2001-05-23 | 中国科学院上海硅酸盐研究所 | Simple method for preparing titanium dioxide collosol |
-
2004
- 2004-10-22 CN CNB2004100609942A patent/CN1304107C/en not_active Expired - Fee Related
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101119933B (en) * | 2005-12-20 | 2011-04-20 | Lg化学株式会社 | Titania sol, method of preparing the same, and coating composition comprising the same |
| US7935329B2 (en) | 2005-12-20 | 2011-05-03 | Lg Chem, Ltd. | Titania sol, method of preparing the same, and coating composition comprising the same |
| CN100593524C (en) * | 2007-02-07 | 2010-03-10 | 中国科学院山西煤炭化学研究所 | Method of preparing high refractive index nanocrystalline TiO2 collosol-gel film |
| CN104761931A (en) * | 2008-02-14 | 2015-07-08 | 水晶美国股份公司 | Colloidal titanium dioxide sols |
| CN102658103A (en) * | 2012-04-17 | 2012-09-12 | 太原理工大学 | Preparation method and application of high-active-dispersibility nanometer titanium dioxide |
| CN103831078A (en) * | 2012-11-27 | 2014-06-04 | 张加艳 | Preparation method of heavy metal ion adsorbent |
| CN103657622A (en) * | 2013-12-04 | 2014-03-26 | 上海纳米技术及应用国家工程研究中心有限公司 | Efficient titanium dioxide photocatalyst, preparation thereof and applications thereof |
| CN104150531A (en) * | 2014-06-27 | 2014-11-19 | 仙桃市中星电子材料有限公司 | Preparation method of titanium dioxide with high specific surface area |
| CN105537614A (en) * | 2015-12-28 | 2016-05-04 | 重庆文理学院 | Method for preparing hollow precious metal nano material with cuprous oxide as template |
| CN106914236A (en) * | 2017-03-20 | 2017-07-04 | 福州名谷纳米科技有限公司 | The amorphous state plasma hetero-junctions nano-TiO of efficient visible light response2Colloidal sol |
| CN107986327A (en) * | 2017-12-18 | 2018-05-04 | 苏州中科纳福材料科技有限公司 | The preparation method of titanium dioxide nano-film |
| CN107986327B (en) * | 2017-12-18 | 2019-11-15 | 苏州中科纳福材料科技有限公司 | The preparation method of titanium dioxide nano-film |
| CN109179495A (en) * | 2018-08-28 | 2019-01-11 | 绍兴文理学院 | A kind of preparation method of high-dispersion nano titanium dioxide |
| CN109133164A (en) * | 2018-11-15 | 2019-01-04 | 湖北天瓷电子材料有限公司 | A kind of high dispersiveness spherical titanium dioxide process |
| CN111569832A (en) * | 2020-05-19 | 2020-08-25 | 西南科技大学 | Method for preparing hypha/molybdenum sulfide adsorption-catalysis material by utilizing biological enrichment |
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