CN101518731A - Composite nanometer phosphotungstic acid-titanium dioxide photocatalysis material and preparation method thereof - Google Patents
Composite nanometer phosphotungstic acid-titanium dioxide photocatalysis material and preparation method thereof Download PDFInfo
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- CN101518731A CN101518731A CN200910106483A CN200910106483A CN101518731A CN 101518731 A CN101518731 A CN 101518731A CN 200910106483 A CN200910106483 A CN 200910106483A CN 200910106483 A CN200910106483 A CN 200910106483A CN 101518731 A CN101518731 A CN 101518731A
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Abstract
The invention discloses a composite nanometer phosphotungstic acid-titanium dioxide photocatalysis material and a preparation method thereof. The method includes the steps: firstly, titanium dioxide collosol, phosphotungstic acid and propylene glycol methyl ether, of which the mass ratio is 20 to 3 to 50, are uniformly mixed to form composite collosol; secondly, the composite collosol is heated for 30 minutes at the temperature of 300 DEG C to form dried gel; and finally, the dried gel is mechanically processed for two hours by ball milling so as to obtain phosphotungstic acid-titanium dioxide photorecombination photocatalyst materials. Compared with the prior art, the phosphotungstic acids of the invention are combined into a stable netty structure in the form of W-O-P molecular linkages, thereby reducing the oxidation-reduction potential, enabling a titanium dioxide composite membrane photoabsorption wavelength to generate redshift, and improving the utility ratio of titanium visible light; and further more, after the subsequent step of heating photocatalysis materials is accomplished, the keggin structure of the phosphotungstic acid is not affected, and high catalytic activity can still be maintained.
Description
Technical field:
The present invention relates to photocatalyst material, particularly a kind of composite nanometer phosphotungstic acid-titanium dioxide photocatalysis material that can be used for treating indoor air pollution the invention still further relates to a kind of method for preparing this material simultaneously.
Background technology:
In recent years, along with the raising of people's living standard, in the continuous inlet chamber of daily necessitiess such as modern furniture of a large amount of new decorative materials and luxurious fashion, the indoor environmental pollution that is caused also is on the rise thus.Volatile organic matter (voc) severe overweights such as present indoor major pollutants formaldehyde, benzene, toluene give that people are healthy to bring very big injury.
About the improvement of indoor pollutant, several different methods is arranged both at home and abroad, as: physics method, chemical method, bioanalysis, photocatalyst technology etc.That wherein the photocatalyst technology adopts is Nano titanium dioxide (TiO
2) by ultraviolet catalyzed, produce free electron and hole, and then produce active oxygen and hydroxyl radical free radical with extremely strong oxidation, and then airborne organic pollution is oxidized to carbon dioxide and water.Its advantage is that elimination speed is fast, and is effective, and longer duration does not produce secondary pollution substantially, and photocatalyst is not depleted as catalyst itself simultaneously; Shortcoming is to need ultraviolet excitation, and the visible light utilization rate is low, and indoor light is weak can to influence catalytic effect.In order to break through the bottleneck of photocatalysis oxidation technique, two technological approaches are arranged: the one, to TiO
2Carry out modification, keeping TiO
2On the basis of the advantage that is had itself, the excitation wavelength red shift that makes its photocatalytic effect is to visible light wave range; The 2nd, development is to visible light-responded novel photocatalysis agent.
No matter at present, emerge in an endless stream for the synthetic method report of nano titanium oxide, be to adopt gas-phase synthesizing method or employing liquid-phase synthesis process, and numerous researchers are devoted to prepare high dispersive, and particle is little, the nano-titania particle of better crystallinity degree.Since the saturated phosphotungstic acid of titanium dichloride load Keggin structure, silico-tungstic acid photochemical catalyst are synthesized, extensive not enough to its research with application, known research mainly concentrates on the degraded aspect to dyestuff, and uses more also photocatalyst of titanium dioxide material just aspect treating indoor air pollution.Polyacid compound of a great variety, but less relatively to the research of its application feature, different heteropoly acids is prepared into titanium dioxide composite film, to organic matter, and the degraded of organic pollutant has certain application value.Polyacid is as photochemical catalyst, and obtains extensive studies, is to be determined by it self advantage: the molecule of multi-metal oxygen cluster complex can be regarded the semiconductor substance of quantum stage as; Strong acid, strong oxidizing property and high photochemical activity; Toxicity is low, and is free from environmental pollution; Active high, reaction condition gentleness, not etching apparatus.
Summary of the invention:
For this reason, the object of the present invention is to provide a kind of composite nanometer phosphotungstic acid-titanium dioxide photocatalysis material and prepare the method for this material, to improve traditional photocatalyst of titanium dioxide material photocatalytic properties.
For achieving the above object, the present invention mainly adopts technical scheme as follows:
A kind of composite nanometer phosphotungstic acid photocatalysis material of titanium dioxide comprises TiO 2 sol, phosphotungstic acid and propylene glycol monomethyl ether, and the mass ratio of wherein said TiO 2 sol, phosphotungstic acid and propylene glycol monomethyl ether is 20:3:50.
The concentration of described TiO 2 sol is 1%.
The present invention also provides a kind of preparation method of composite nanometer phosphotungstic acid-titanium dioxide photocatalysis material in addition, wherein specifically comprises step:
B, get TiO 2 sol, phosphotungstic acid and propylene glycol monomethyl ether that mass ratio is 20:3:50 and mix and obtain complex sol;
C, above-mentioned complex sol is remained on 300 ℃ of temperature heating 30 minutes, obtain xerogel;
D, above-mentioned xerogel was obtained phosphotungstic acid-titanium dioxide composite photo catalyst material in two hours by mechanical ball milling.
The concentration of described TiO 2 sol is 1%.
Also comprise step before the step B:
A, preparation TiO 2 sol.
Steps A specifically comprises:
A1, inorganic titanium salt is obtained metatitanic acid solution by hydrolysis;
A2, above-mentioned metatitanic acid solution is settled out titanium dioxide granule by microwave, and precipitates washing;
Add additive and catalyst in a3, the solution after washing,, after the cooling, add precipitating reagent, be settled out the inorganic foreign material of non-titanium class, obtain the water-based titanium oxide sol through the Temperature Treatment of substep through precipitation.
Step B specifically comprises: phosphotungstic acid is dissolved in the propylene glycol monomethyl ether, slowly joins then in the TiO 2 sol, added thermal agitation 6 hours simultaneously under 60 ℃, up to forming phosphotungstic acid and titanium dioxide complex sol.
Compared with prior art, the present invention has following beneficial effect:
1, phosphotungstic acid is combined into stable network structure with W-O-P molecular link form among the present invention, this structure has reduced the oxidation-reduction potential of titanium, make the titanium dioxide composite film light absorption wavelength produce red shift, improve the visible light utilization rate of titanium, and after subsequent optical catalysis material heat treated, the keggin structure of phosphotungstic acid is unaffected, still keeps high catalytic activity.
2, phosphotungstic acid and Ti0 among the present invention
2There is certain chemical action between the network, makes the polyacid molecule be strapped in Ti0 securely
2The inside of network, thus make material of the present invention have high surface area and resistance to water.
The specific embodiment:
Core concept of the present invention is: get TiO 2 sol, phosphotungstic acid and propylene glycol monomethyl ether that mass ratio is 20:3:50 and mix and make complex sol; And this complex sol remained on 300 ℃ of temperature heating 30 minutes, obtain xerogel; Make phosphotungstic acid-titanium dioxide photoreactivation photocatalyst material by mechanical ball milling then.
Because phosphotungstic acid is combined into stable network structure with W-O-P molecular link form among the present invention, this structure has reduced the oxidation-reduction potential of titanium, make the titanium dioxide composite film light absorption wavelength produce red shift, improve the visible light utilization rate of titanium, and after subsequent optical catalysis material heat treated, the keggin structure of phosphotungstic acid is unaffected, still keeps high catalytic activity.
For setting forth thought of the present invention and purpose, the present invention is described further below in conjunction with specific embodiment.
The invention provides a kind of composite nanometer phosphotungstic acid-titanium dioxide photocatalysis material, comprise TiO 2 sol, phosphotungstic acid and propylene glycol monomethyl ether, the mass ratio of wherein said TiO 2 sol, phosphotungstic acid and propylene glycol monomethyl ether is 20:3:50, and wherein the concentration of TiO 2 sol is 1% here.
The present invention also provides a kind of preparation method of composite nanometer phosphotungstic acid-titanium dioxide photocatalysis material in addition, wherein specifically comprises step:
A, to produce concentration in advance be 1% TiO 2 sol;
Wherein detailed process comprises:
A1, inorganic titanium salt is obtained metatitanic acid solution by hydrolysis;
A2, above-mentioned metatitanic acid solution is settled out titanium dioxide granule by microwave, and precipitates washing;
Add additive and catalyst in a3, the solution after washing,, after the cooling, add precipitating reagent, be settled out the inorganic foreign material of non-titanium class, obtain the water-based titanium oxide sol through the Temperature Treatment of substep through precipitation.
B, get TiO 2 sol, phosphotungstic acid and propylene glycol monomethyl ether that mass ratio is 20:3:50 and mix and obtain complex sol;
Wherein at first phosphotungstic acid is dissolved in the propylene glycol monomethyl ether, slowly joins then in the TiO 2 sol, under 60 ℃, added thermal agitation 6 hours simultaneously, up to forming phosphotungstic acid and titanium dioxide complex sol.
C, above-mentioned complex sol is remained on 300 ℃ of temperature heating 30 minutes, obtain xerogel;
D, above-mentioned xerogel was obtained phosphotungstic acid titanium-dioxide photo composite photo catalyst material in two hours by mechanical ball milling.
The present invention will be further described with concrete experimental data below in conjunction with preferred embodiment.
Preferred embodiment one, at first inorganic titanium salt is calculated in molar ratio the quality of titanium dioxide, take by weighing the inorganic TiO 2 sol (1%) of 2 grams then, 0.3 gram phosphotungstic acid, 5 gram propylene glycol monomethyl ethers make complex sol by steps A, adopt spraying process that complex sol is formed film then on glass substrate, and with above-mentioned coating 300 ℃ of Temperature Treatment 30 minutes, obtain photocatalysis coating.
Photocatalysis coating to above-mentioned formation carries out degradation experiment: a closed room (in 2 * 1.5 * 1.5m), produce formaldehyde by the formaldehyde generator, utilizing fan to quicken air flows, adopting 4 200W uviol lamps simultaneously is that the photocatalysis coating of 1m * 1m excites 24 hours to the coating area, and the Degradation Formaldehyde rate is 63% afterwards.
Preferred embodiment two, at first inorganic titanium salt is calculated in molar ratio the quality of titanium dioxide, take by weighing the inorganic TiO 2 sol (1%) of 4 grams, 0.6 gram phosphotungstic acid, 10 gram propylene glycol monomethyl ethers mixing obtain complex sol, mixed sols 300 ℃ of Temperature Treatment 30 minutes, is obtained having the xerogel of photocatalysis performance, xerogel was obtained nanoscale phosphotungstic acid-titanium dioxide composite photo catalyst material in two hours by mechanical ball milling.
Photocatalyst material to above-mentioned formation carries out degradation experiment: a closed room (in 2 * 1.5 * 1.5m), produce formaldehyde by the formaldehyde generator, utilizing fan to quicken air flows, adopt 4 200W uviol lamps simultaneously, then the amount of one square metre of needed complex sol of spraying on glass was carried out illumination 24 hours, the Degradation Formaldehyde rate is 59%.
By above data as can be known, composite nanometer phosphotungstic acid-titanium dioxide photocatalysis material of the present invention can improve traditional photocatalyst of titanium dioxide material photocatalytic properties greatly.
More than be that a kind of composite Nano provided by the present invention-phosphotungstic acid photocatalysis material of titanium dioxide and preparation method are described in detail, used concrete data herein each composition and ratio thereof in the invention are set forth, above embodiment just is used for helping to understand method of the present invention and core concept thereof; Simultaneously, for one of ordinary skill in the art, according to thought of the present invention, the part that all can change in specific embodiments and applications, in sum, this description should not be construed as limitation of the present invention.
Claims (7)
1, a kind of composite nanometer phosphotungstic acid-titanium dioxide photocatalysis material is characterized in that comprising TiO 2 sol, phosphotungstic acid and propylene glycol monomethyl ether, and the mass ratio of wherein said TiO 2 sol, phosphotungstic acid and propylene glycol monomethyl ether is 20:3:50.
2, composite nanometer phosphotungstic acid-titanium dioxide photocatalysis material according to claim 1, the concentration that it is characterized in that described TiO 2 sol is 1%.
3, a kind of preparation method of composite nanometer phosphotungstic acid-titanium dioxide photocatalysis material is characterized in that comprising step:
B, get TiO 2 sol, phosphotungstic acid and propylene glycol monomethyl ether that mass ratio is 20:3:50 and mix and obtain complex sol;
C, above-mentioned complex sol is remained on 300 ℃ of temperature heating 30 minutes, obtain xerogel;
D, above-mentioned xerogel was obtained phosphotungstic acid-titanium dioxide composite photo catalyst material in two hours by mechanical ball milling.
4, the preparation method of composite nanometer phosphotungstic acid-titanium dioxide photocatalysis material according to claim 3 is characterized in that: the concentration of described TiO 2 sol is 1%.
5, the preparation method of composite nanometer phosphotungstic acid-titanium dioxide photocatalysis material according to claim 3 is characterized in that step B also comprises step before:
A, preparation TiO 2 sol.
6, the preparation method of composite nanometer phosphotungstic acid-titanium dioxide photocatalysis material according to claim 5 is characterized in that steps A specifically comprises:
A1, inorganic titanium salt is obtained metatitanic acid solution by hydrolysis;
A2, above-mentioned metatitanic acid solution is settled out titanium dioxide granule by microwave, and precipitates washing;
Add additive and catalyst in a3, the solution after washing,, after the cooling, add precipitating reagent, be settled out the inorganic foreign material of non-titanium class, obtain the water-based titanium oxide sol through the Temperature Treatment of substep through precipitation.
7, the preparation method of composite nanometer phosphotungstic acid-titanium dioxide photocatalysis material according to claim 3, it is characterized in that step B specifically comprises: phosphotungstic acid is dissolved in the propylene glycol monomethyl ether, slowly join in the TiO 2 sol then, simultaneously under 60 ℃, added thermal agitation 6 hours, up to forming phosphotungstic acid and titanium dioxide complex sol.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102698809A (en) * | 2012-05-11 | 2012-10-03 | 沈阳化工大学 | Preparation method of H3PW12O40/ nanometer TiO2 composite photocatalyst |
| CN102989515A (en) * | 2012-12-17 | 2013-03-27 | 江南大学 | Preparation method of titanium dioxide/heteropolyacid compound photo-catalyst |
| CN105013534A (en) * | 2015-06-24 | 2015-11-04 | 湖南师范大学 | Effective photocatalysis system for selective oxidation of hydrocarbon by N2O |
| CN106975503A (en) * | 2017-05-09 | 2017-07-25 | 东北师范大学 | A kind of preparation method of the modified phosphotungstic acid/titanium dioxide composite film catalyst of silver |
| CN109046411A (en) * | 2018-10-16 | 2018-12-21 | 九江学院 | A kind of visible light-responded high activity TiO2The preparation method of composite photo-catalyst |
-
2009
- 2009-04-01 CN CN2009101064832A patent/CN101518731B/en active Active
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102698809A (en) * | 2012-05-11 | 2012-10-03 | 沈阳化工大学 | Preparation method of H3PW12O40/ nanometer TiO2 composite photocatalyst |
| CN102989515A (en) * | 2012-12-17 | 2013-03-27 | 江南大学 | Preparation method of titanium dioxide/heteropolyacid compound photo-catalyst |
| CN105013534A (en) * | 2015-06-24 | 2015-11-04 | 湖南师范大学 | Effective photocatalysis system for selective oxidation of hydrocarbon by N2O |
| CN106975503A (en) * | 2017-05-09 | 2017-07-25 | 东北师范大学 | A kind of preparation method of the modified phosphotungstic acid/titanium dioxide composite film catalyst of silver |
| CN106975503B (en) * | 2017-05-09 | 2019-06-04 | 东北师范大学 | A kind of preparation method of the modified phosphotungstic acid/titanium dioxide composite film catalyst of silver |
| CN109046411A (en) * | 2018-10-16 | 2018-12-21 | 九江学院 | A kind of visible light-responded high activity TiO2The preparation method of composite photo-catalyst |
| CN109046411B (en) * | 2018-10-16 | 2021-05-14 | 九江学院 | Visible light response high-activity TiO2Preparation method of composite photocatalyst |
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