CN101411991A - Heteropoly acid-titanic oxide composite photocatalyst and preparation method thereof - Google Patents
Heteropoly acid-titanic oxide composite photocatalyst and preparation method thereof Download PDFInfo
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- CN101411991A CN101411991A CNA2008102038192A CN200810203819A CN101411991A CN 101411991 A CN101411991 A CN 101411991A CN A2008102038192 A CNA2008102038192 A CN A2008102038192A CN 200810203819 A CN200810203819 A CN 200810203819A CN 101411991 A CN101411991 A CN 101411991A
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- heteropoly acid
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- mesoporous material
- composite photocatalyst
- titanic oxide
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Abstract
The invention discloses a heteropolyacid-titania composite photocatalyst and a preparation method thereof. An ordered mesoporous material is used as a carrier; heteropolyacid and titania are simultaneously loaded in the ordered mesoporous material to prepare the composite photocatalyst, wherein the load amount of the heteropolyacid in the ordered mesoporous material is between 0 and 50 percent; and the load amount of the titania is between 0 and 50 percent. The composite photocatalyst has stable performance, has good crystallization of TiO2, and high photocatalytic activity, solves the problem that the heteropolyacid is easy to fall off, and is convenient to recycle.
Description
Technical field
The present invention relates to a kind of heteropoly acid-titanic oxide composite photocatalyst and preparation method thereof.
Background technology
Be accompanied by the progress of science and technology and the continuous development of industry, increasing pollutant enters environment, has caused great harm for human beings'health and existence.Problem of environmental pollution has become one of the severeest problem that we faced.Photocatalysis oxidation technique can transform organic pollution up hill and dale and be decomposed into CO
2, H
2O and other little molecules are having broad application prospects aspect the organic pollution of handling difficult for biological degradation.The heterogeneous photocatalytic advanced oxidation technology of semiconductor, because of its have energy consumption low (can utilize sunshine to do the energy, inexhaustible), reaction condition gentleness (not needing conditions such as high temperature, high pressure), easy and simple to handle, safe in utilization, can make outstanding features such as permineralization of organic pollution non-selectivity and catalyst self nontoxic pollution-free and get most of the attention.In numerous semiconductor light-catalysts, TiO
2Advantages such as, highlight catalytic active moderate, photostability and chemical stability and extremely people's favor with band-gap energy, become the maximum photochemical catalyst of present research, but also have such as light induced electron and photohole is compound easily, quantum yield is low and use back separation difficulty, problems such as loss, so the high efficiency photocatalyst of development of new easily or improve TiO by various means
2Semi-conductive performance is the focus of current photocatalysis basic research with the efficient that improves photochemical catalyst.In recent years, TiO
2Photochemical catalyst improves TiO by methods such as modification such as noble metal loading, metal ion mixing, binary or polynary semiconductor are compound
2Photocatalytic activity.Heteropoly acid has similar conductor oxidate band structure, and its photocatalysis performance obtains extensive concern.If heteropoly acid is directly added the people to TiO
2In the light-catalyzed reaction system, though can improve TiO
2Photocatalytic activity, but heteropoly acid exists with homogeneous phase in this system, is unfavorable for the recycling of catalyst.If heteropoly acid is directly loaded on TiO
2On, in use heteropoly acid comes off again easily.
Summary of the invention
The purpose of this invention is to provide a kind of heteropoly acid-titanic oxide composite photocatalyst and preparation method thereof.
The technical solution used in the present invention
A kind of heteropoly acid-titanic oxide composite photocatalyst, it promptly is carrier with the ordered mesoporous material, heteropoly acid and titanium dioxide is carried on simultaneously prepares composite photo-catalyst in the ordered mesoporous material, wherein the load capacity of heteropoly acid in ordered mesoporous material is 0%～50%, and the titanium dichloride load amount is 0%～50%; Load capacity is the weight ratio of loaded article and carrier.
Wherein heteropoly acid is that one or several of phosphotungstic acid, silico-tungstic acid, phosphomolybdic acid, germanotungstic acid, germanium molybdic acid, phosphorus Vanadotungstic acid is compound;
TiO 2 precursor is that one or several of butyl titanate, isopropyl titanate, tetraethyl titanate, titanium tetrachloride, Titanium Nitrate is compound;
Ordered mesoporous material is the mesoporous silicon oxide of MCM series, SBA series or HMS series, and the aperture of mesoporous material is between 2～50nm.
The preparation process of heteropoly acid-titanic oxide composite photocatalyst is as follows:
(1) heteropoly acid and TiO 2 precursor are dissolved in organic solvent: in ethanol, isopropyl alcohol or the butanols;
(2) order mesoporous material is added in the described solution of step (1), at 20～50KHz, ultrasonic 20-60min under 50～300W is uniformly dispersed powder;
(3) under 30 ℃～80 ℃, 50～150r/min, rotary evaporation in vacuo 0.5～3h removes organic solvent, and complete when the solution evaporation, product is drying regime, closes Rotary Evaporators;
(4) at 20～50KHz, ultrasonic under 50～300W the product on bottle wall is come off automatically, be collected in the culture dish;
(5) with the gleanings heteropoly acid-titanic oxide in the step (4)/mesoporous carrier dry 6～12h in 110-150 ℃ of baking oven, in air atmosphere, can obtain heteropoly acid-titanic oxide composite photocatalyst then in 400～600 ℃ of calcining 2～6h.
Beneficial effect of the present invention
With order mesoporous material is carrier, heteropoly acid and titanium dioxide directly is carried on prepare composite photo-catalyst in the mesoporous material, and its stability is high, and TiO
2Crystallization degree is good, has higher photocatalytic activity, has not only solved the problem that heteropoly acid comes off easily, and is convenient to reclaim.
The specific embodiment:
With embodiment the present invention is specified, but do not limit the present invention.
Embodiment 1:
0.025g phosphotungstic acid and 0.31g butyl titanate are dissolved in the butanols, add the SBA-15 powder of 0.5g, at 20kHz, ultrasonic dispersion is 30 minutes under the 200W condition, and powder is uniformly dispersed; 80 ℃ of temperature, rotating speed 70r/min rotary evaporation in vacuo are removed butanols, when product all is bonded on bottle wall and is drying regime, when also not having butanols and oozing, can close Rotary Evaporators; The pyriform bottle is ultrasonic, the product on bottle wall is come off automatically, be collected in the culture dish, with TiO
2-HPW/SBA-15 in 140 ℃ of baking ovens dry 12 hours, 400 ℃ of calcinings of high temperature are 3 hours in the air atmosphere.
Embodiment 2:
0.075g phosphomolybdic acid and 0.11g isopropyl titanate are dissolved in the isopropyl alcohol, add the MCM-41 powder of 0.5g, at 20kHz, ultrasonic dispersion is 30 minutes under the 200W condition, and powder is uniformly dispersed; 50 ℃ of temperature, rotating speed 70r/min rotary evaporation in vacuo are removed isopropyl alcohol, when product all is bonded on bottle wall and is drying regime, when also no isopropanol oozes, can close Rotary Evaporators; The pyriform bottle is ultrasonic, the product on bottle wall is come off automatically, be collected in the culture dish, with TiO
2-HPMo/MCM-41 is in 130 ℃ of dryings 8 hours, and 600 ℃ of high-temperature calcinations are 5 hours in the air atmosphere.
Embodiment 3:
0.05g phosphotungstic acid and 0.21g butyl titanate are dissolved in the absolute ethyl alcohol, add the SBA-15 powder of 0.5g, at 20kHz, ultrasonic dispersion is 30 minutes under the 200W condition, and powder is uniformly dispersed; 40 ℃ of temperature, rotating speed 70r/min rotary evaporation in vacuo are removed ethanol, when product all is bonded on bottle wall and is drying regime, when also not having ethanol and oozing, can close Rotary Evaporators; The pyriform bottle is ultrasonic, the product on bottle wall is come off automatically, be collected in the culture dish, with TiO
2-HPW/SBA-15 in 120 ℃ of baking ovens dry 6 hours, 500 ℃ of calcinings of high temperature are 3 hours in the air atmosphere.
Embodiment 4:
0.075g silico-tungstic acid and 0.1059g tetraethyl titanate are dissolved in the absolute ethyl alcohol, add the HMS of 0.5g, at 20kHz, ultrasonic dispersion is 30 minutes under the 200W condition, and powder is uniformly dispersed; 40 ℃ of temperature, rotating speed 70r/min rotary evaporation in vacuo are removed ethanol, when product all is bonded on bottle wall and is drying regime, when also not having ethanol and oozing, can close Rotary Evaporators; The pyriform bottle is ultrasonic, the product on bottle wall is come off automatically, be collected in the culture dish, with TiO
2-HSiW/HMS is dried overnight in 110 ℃ of baking ovens, and 450 ℃ of high-temperature calcinations are 3 hours in the air atmosphere.
Embodiment 5:
0.1g germanotungstic acid and 0.2g Titanium Nitrate are dissolved in the absolute ethyl alcohol, add the SBA-15 of 0.5g, at 20kHz, ultrasonic dispersion is 30 minutes under the 200W condition, and powder is uniformly dispersed; 40 ℃ of temperature, rotating speed 70r/min rotary evaporation in vacuo are removed ethanol, when product all is bonded on bottle wall and is drying regime, when also not having ethanol and oozing, can close Rotary Evaporators; The pyriform bottle is ultrasonic, the product on bottle wall is come off automatically, be collected in the culture dish, with TiO
2-HGeW/SBA15 in 110 ℃ of baking ovens dry 8 hours, 450 ℃ of high-temperature calcinations are 3 hours in the air atmosphere.
The degradation capability test of embodiment of the invention gained heteropoly acid-titanic oxide composite photocatalyst:
Get 0.05g sample catalyst (phosphotungstic acid load capacity 10%, titanium dichloride load amount 50%) and 50mL dyestuff and add in the reaction vessel, ultrasonic 10 minutes, catalyst powder is spread in dyestuff, evenly distribute.Investigation is the catalytic degradation effect of dyestuff with methyl orange under ultraviolet light.Experimental result shows that degradation efficiency can reach more than 95%.
Get 0.05g sample catalyst (phosphotungstic acid load capacity 0%, titanium dichloride load amount 50%) and 50mL dyestuff and add in the reaction vessel, ultrasonic 10 minutes, catalyst powder is spread in dyestuff, evenly distribute.Investigation is the catalytic degradation effect of dyestuff with methyl orange under ultraviolet light.Experimental result shows that degradation efficiency is 35%.
Get 0.05g sample catalyst (phosphotungstic acid load capacity 20%, titanium dichloride load amount 0%) and 50mL dyestuff and add in the reaction vessel, ultrasonic 10 minutes, catalyst powder is spread in dyestuff, evenly distribute.Investigation is the catalytic degradation effect of dyestuff with methyl orange under ultraviolet light.Experimental result shows that degradation efficiency is 5%.
Further specify carried heteropoly acid-titanium dioxide composite photocatalyst by above degradation property test and have better catalytic activity and degradation efficiency than simple heteropoly acid of load or simple titanium dioxide.
Claims (4)
1, a kind of heteropoly acid-titanic oxide composite photocatalyst, it is characterized in that: be carrier with the ordered mesoporous material, heteropoly acid and titanium dioxide is carried on simultaneously prepares composite photo-catalyst in the ordered mesoporous material, the load capacity of heteropoly acid in ordered mesoporous material is 0%～50%, and the titanium dichloride load amount is 0%～50%;
Wherein heteropoly acid is that one or several of phosphotungstic acid, silico-tungstic acid, phosphomolybdic acid, germanotungstic acid, germanium molybdic acid, phosphorus Vanadotungstic acid is compound;
TiO 2 precursor is that one or several of butyl titanate, isopropyl titanate, tetraethyl titanate, titanium tetrachloride, Titanium Nitrate is compound;
Ordered mesoporous material is the mesoporous silicon oxide of MCM series, SBA series or HMS series.
2, as claims 1 described heteropoly acid-titanic oxide composite photocatalyst, it is characterized in that the load capacity of described heteropoly acid in ordered mesoporous material is preferably 5%～15%, the titanium dichloride load amount is preferably 40%～50%.
3, as claims 1 described heteropoly acid-titanic oxide composite photocatalyst, the aperture that it is characterized in that described ordered mesoporous material is between 2～50nm.
4, as claims 1 described heteropoly acid-titanic oxide composite photocatalyst, it is characterized in that preparation process is as follows:
(1) heteropoly acid and TiO 2 precursor are dissolved in organic solvent: in ethanol, isopropyl alcohol or the butanols;
(2) order mesoporous material is added in the described solution of step (1), at 20～50KHz, ultrasonic 20-60min under 50～300W is uniformly dispersed powder;
(3) under 30 ℃～80 ℃, 50～150r/min, rotary evaporation in vacuo 0.5～3h removes organic solvent, and complete when the solution evaporation, product is drying regime, closes Rotary Evaporators;
(4) at 20～50KHz, ultrasonic under 50～300W the product on bottle wall is come off automatically, be collected in the culture dish;
(5) with the gleanings heteropoly acid-titanic oxide in the step (4)/mesoporous carrier dry 6～12h in 110-150 ℃ of baking oven, in air atmosphere, can obtain heteropoly acid-titanic oxide composite photocatalyst then in 400～600 ℃ of calcining 2～6h.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102989515A (en) * | 2012-12-17 | 2013-03-27 | 江南大学 | Preparation method of titanium dioxide/heteropolyacid compound photo-catalyst |
| CN103203253A (en) * | 2013-04-08 | 2013-07-17 | 黄河三角洲京博化工研究院有限公司 | Method for synthesizing polyoxometalates/titanium dioxide catalyst |
| CN105126817A (en) * | 2015-07-07 | 2015-12-09 | 湖北师范学院 | Preparation method of catalyst H4GeW20O40/TiO2, and preparation method of butylparaben |
| CN106925252A (en) * | 2017-04-07 | 2017-07-07 | 中国矿业大学(北京) | A kind of metal doping nano TiO2/ sepiolite composite and preparation method |
| CN107597156A (en) * | 2017-09-19 | 2018-01-19 | 常州大学 | A kind of preparation method of phosphomolybdic acid Mn catalyst |
| CN110394198A (en) * | 2019-07-25 | 2019-11-01 | 长春工业大学 | A kind of structurally ordered phosphotungstic acid titanium-silicone metapore composite material and preparation method |
| CN110803745A (en) * | 2019-12-16 | 2020-02-18 | 嘉兴市众盛环保科技有限公司 | Polyoxometallate composite particle electrode and preparation method and application thereof |
| CN113042103A (en) * | 2021-03-26 | 2021-06-29 | 东阳久泰科技有限公司 | Method for modifying photocatalytic activity of titanium dioxide nanotube based on heteropoly acid |
-
2008
- 2008-12-02 CN CNA2008102038192A patent/CN101411991A/en active Pending
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102989515A (en) * | 2012-12-17 | 2013-03-27 | 江南大学 | Preparation method of titanium dioxide/heteropolyacid compound photo-catalyst |
| CN103203253A (en) * | 2013-04-08 | 2013-07-17 | 黄河三角洲京博化工研究院有限公司 | Method for synthesizing polyoxometalates/titanium dioxide catalyst |
| CN105126817A (en) * | 2015-07-07 | 2015-12-09 | 湖北师范学院 | Preparation method of catalyst H4GeW20O40/TiO2, and preparation method of butylparaben |
| CN106925252A (en) * | 2017-04-07 | 2017-07-07 | 中国矿业大学(北京) | A kind of metal doping nano TiO2/ sepiolite composite and preparation method |
| CN107597156A (en) * | 2017-09-19 | 2018-01-19 | 常州大学 | A kind of preparation method of phosphomolybdic acid Mn catalyst |
| CN110394198A (en) * | 2019-07-25 | 2019-11-01 | 长春工业大学 | A kind of structurally ordered phosphotungstic acid titanium-silicone metapore composite material and preparation method |
| CN110394198B (en) * | 2019-07-25 | 2022-05-10 | 长春工业大学 | Titanium silicon phosphotungstate mesoporous composite material with ordered structure and preparation method thereof |
| CN110803745A (en) * | 2019-12-16 | 2020-02-18 | 嘉兴市众盛环保科技有限公司 | Polyoxometallate composite particle electrode and preparation method and application thereof |
| CN110803745B (en) * | 2019-12-16 | 2022-04-01 | 嘉兴市众盛环保科技有限公司 | Polyoxometallate composite particle electrode and preparation method and application thereof |
| CN113042103A (en) * | 2021-03-26 | 2021-06-29 | 东阳久泰科技有限公司 | Method for modifying photocatalytic activity of titanium dioxide nanotube based on heteropoly acid |
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Open date: 20090422 |