CN1184002C - Prepn. method for producing titanium dioxide having visible light catalytic activation - Google Patents
Prepn. method for producing titanium dioxide having visible light catalytic activation Download PDFInfo
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- CN1184002C CN1184002C CN 02120037 CN02120037A CN1184002C CN 1184002 C CN1184002 C CN 1184002C CN 02120037 CN02120037 CN 02120037 CN 02120037 A CN02120037 A CN 02120037A CN 1184002 C CN1184002 C CN 1184002C
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Abstract
The present invention discloses a preparation method for an anatase type titanium dioxide catalyst with visible-light photocatalysis activity. The present invention is carried out according to the following steps: 5 to 10 wt% of, 1 to 20 wt% of hydrolyst and 70 to 90 wt% of diluting agents react for 10 to 50 hours in a reactor under the irradiation of an ultraviolet light source with a specific wavelength range; obtained titanium collosol is aged for 3 to 10 days at 20 to 30 DEG C; solvent is volatilized at 20 to 30 DEG C; titanium gelatin is calcined for 1 to 5 hours at the temperature below 150 DEG C to obtain target anatase type titanium dioxide powder. The target titanium dioxide catalyst obtained by using the preparation method of the present invention can absorb visual light; the titanium dioxide catalyst has photocatalytic activity under the irradiation of the visual light and can effectively catalyze and degrade organic pollutants; the titanium dioxide catalyst has the characteristics of small catalyst particle size, large specific surface area, etc.
Description
Technical field
The present invention relates to a kind of high catalytic activity anatase titanium dioxide Preparation of catalysts method, this catalyst can be activated in visible wavelength range, the catalytic degradation organic matter.
Background technology
Twentieth century second half, the energy crisis of outburst was not only brought developing rapidly of Optical Electro-Chemistry, and the Application and Development of catalysis material is also become an emerging problem day by day.Fujishima in 1972 and Honda reported first at TiO
2The photodissociation phenomenon of water on the semiconductor monocrystal electrode, the basis of having established heterogeneous conductor photocatalysis indicates the metal oxide photocatalyst beginning of a New Times.Titanium dioxide (TiO
2) as the highest the most active photochemical catalyst of research at present, it can absorb the sunshine of 4-5%, and has both had good stability, characteristics such as nontoxic, fast light corrosivity, cheapness; In handling the pollutant process, except that deriving from airborne oxygen, do not need to add any other chemicals just can catalytic degradation water in organic and inorganic pollutant; In addition, the bactericidal action of titanium dioxide also is the important step of photocatalysis technology.
Along with the develop rapidly of nanometer technology, also bring opportunity to develop for catalysis material.The preparation of nano material occupies very consequence in the present material scientific research, the new material preparation process and the research of process have material impact to the microstructure and the performance of control nano material.Preparation of nanomaterials has a variety of, but can be divided into physical method and chemical method generally, the key of preparation is the size of control particulate and obtains narrower particle diameter distribution, changes the surface electronic configuration and the distribution of particle, and then improve the photocatalytic activity of catalyst.Physical method comprises using vaporization condensation process, physical crushing method, mechanical metal method.Chemical method comprises vapour deposition process, the precipitation method, hydration established law, sol-gel process, solvent evaporated method and microemulsion method, and wherein sol-gel process is widely adopted owing to characteristics such as it prepare particle purity height, good dispersion, narrow diameter distribution.
Summary of the invention
Yet by the synthetic titanium dioxide of traditional sol-gel process, if without follow-up heat treatment process, what obtain is unformed titanium dioxide, and its catalytic activity is very little.Titanium dioxide has three kinds of crystal formations: anatase, and brockite and golden titanium ore, wherein the catalytic activity of anatase is the highest.The titanium dioxide powder synthetic by traditional sol-gel process must be through being higher than 300 ℃ temperature sintering, just can obtain the titanium dioxide of anatase phase, the object of the present invention is to provide a kind of ultraviolet lamp as light source of using specific wavelength, collosol-gelatum system is carried out radiation prepare the anatase titanium dioxide catalyst, adopt this method just to heat-treat at 100 ℃ and can obtain anatase titanium dioxide, its grain size is less than 5nm.
The method for preparing anatase titanium dioxide provided by the present invention follows these steps to carry out (mass percent):
Titanate esters with 5-10%, the hydrolyst of 1-20%, the diluent of 70-90% and the high purity water of 1-5%, place reactor, reaction is 10-50 hour under ultraviolet source irradiation, and the colloidal sol that obtains is in 25 ± 5 ℃ of aging 5-10 days, 25 ± 5 ℃ of solvent flashings, at 50-150 ℃ roasting temperature 1-5 hour, obtain anatase titanium dioxide powder catalyst.
The wave-length coverage of described light source is 200-600nm, and ultraviolet source can be basic, normal, high pressure mercury lamp, xenon lamp, halogen tungsten lamp, described ultraviolet source apart from reactor apart from 1-50cm.
Described titanate esters can be following any:
Butyl titanate [Ti (OC
4H
9)
4], titanium propanolate [Ti (OC
3H
7)
4], tetraethyl titanate [[Ti (OC
2H
5)
4]
Described hydrolyst can be following any:
Hydrochloric acid, nitric acid, sulfuric acid, glacial acetic acid, ammonium acetate, ammonium nitrate
Diluent can be selected for use following any:
Absolute ethyl alcohol, absolute methanol, isopropyl alcohol, n-butanol, normal propyl alcohol, the tert-butyl alcohol
Preferred version one:
Titanate esters with 5-10%, the hydrolyst of 1-10%, the diluent of 70-80% and the high purity water of 1-5%, place reactor, reaction is 20-30 hour under ultraviolet source irradiation, and the colloidal sol that obtains is in 25 ± 5 ℃ of aging 5-10 days, 25 ± 5 ℃ of solvent flashings, at 50-150 ℃ roasting temperature 2-4 hour, obtain anatase titanium dioxide powder catalyst.
Preferred version two:
Titanate esters with 5-8%, the hydrolyst of 1-5%, the diluent of 70-90% and the high purity water of 1-5%, place reactor, reaction is 30-50 hour under ultraviolet source irradiation, and the colloidal sol that obtains is in 25 ± 5 ℃ of aging 5-10 days, 25 ± 5 ℃ of solvent flashings, at 50-100 ℃ roasting temperature 2-3 hour, obtain anatase titanium dioxide powder catalyst.
One of advantage of the present invention is the ultraviolet light source of specific wavelength is introduced the colloidal sol preparation process, and 100 ℃ are carried out sintering and obtained the anatase titanium dioxide powder of particle size less than 5nm; And must just can obtain the anatase phase through sintering more than 300 ℃ by the titanium dioxide of traditional sol-gel process preparation, and such heat treatment will cause interparticle mutual gathering, the growth of particle size has reduced the specific area of catalyst thus, influences catalytic activity.
Preparation method provided by the present invention has solved this difficult problem well, obtains anatase phase titanium dioxide in lower temperature, has avoided the growth process that is gathered into of particle.Secondly, for the research of organic and inorganic pollutant in the photocatalytic degradation water, one of them important research field is to improve sunshine utilization rate and catalyst activity, and titanium dioxide is a catalyst (E that stable forbidden band is big
g=3.2ev), have only by UV-irradiation activity is just arranged, and sunshine middle ultraviolet band light intensity is less than 10% of whole sunshine light intensity, therefore the catalytic activity of semiconductor catalyst under solar radiation is not high, so how to improve broadband semiconductor just becomes current catalysis material research field in the catalytic activity of visible region heat subject.Two of advantage of the present invention is to utilize the ultraviolet light of particular range of wavelengths to do light source, the radiation wavelength that changes light source is regulated and control the configuration of surface and the band structure of particle, under exciting, visible light (400-800nm) just shows good catalytic activity, improved the utilization of catalyst to the sunshine energy, thereby improve the service efficiency of catalyst, the research and development of catalysis material is brought profound influence.
Utilize the present invention can also prepare other semiconductor catalysts, as ZrO
2, SnO
2, Al
2O
3, V
2O
5, MoO
3, WO
3, NiO etc.
The specific embodiment
The invention will be further described below in conjunction with embodiment.
Embodiment 1:
The preparation of 1# sample under the ultraviolet radiation.
The raw material proportioning (mass percent) of synthetic titanium sol-gel.
Isopropyl titanate (analyzing pure): 5%
Isopropyl alcohol (analyzing pure): 90%
Concentrated hydrochloric acid (36.5): 4%
High purity water: 1%
Ultraviolet wavelength: 254 ± 10nm
Light application time: 20 hours
According to the above ratio with isopropyl titanate, isopropyl alcohol and concentrated hydrochloric acid, high purity water places reactor, in 25 ± 2 ℃ of vigorous stirring, use simultaneously apart from the 500W high voltage mercury lamp radiation of reactor 10cm 20 hours, insert the narrow band pass filter of 254 ± 10nm in the light path, obtain titanium colloidal sol.Titanium colloidal sol in 25 ± 5 ℃ of slakings 3 days, is obtained gel, and gel makes the 1# sample 100 ℃ of calcinings 2 hours.
The 1# sample at x-ray diffractometer, is measured on the transmission electron microscope, can be learnt that sample is an anatase shape, particle diameter is less than 10nm, and is as Fig. 1, shown in Figure 2.
Comparative Examples 1:
Unglazed preparation according to 2# sample under the condition.
Isopropyl titanate (analyzing pure): 5%
Isopropyl alcohol (analyzing pure): 90%
Concentrated hydrochloric acid (36.5%): 4%
High purity water: 1%
According to the above ratio with isopropyl titanate, isopropyl alcohol and concentrated hydrochloric acid, high purity water places reactor, in 25 ± 2 ℃ of vigorous stirring, obtains titanium colloidal sol.Titanium colloidal sol in 25 ± 5 ℃ of slakings 3 days, is obtained gel, and gel makes the 2# sample 100 ℃ of calcinings 2 hours.
The 2# sample is measured on x-ray diffractometer, do not occurred any obvious diffraction peak on the collection of illustrative plates, the 2# sample is an amorphous state as can be known, as shown in Figure 3.
Embodiment 2:
The preparation of 3# sample under the ultraviolet radiation.
The raw material proportioning (mass percent) of synthetic titanium sol-gel.
Isopropyl titanate (analyzing pure): 8%
Isopropyl alcohol (analyzing pure): 88%
Concentrated hydrochloric acid (36.5%): 2.5%
High purity water: 1.5%
Ultraviolet wavelength: 300 ± 10nm
Light application time: 36 hours
According to the above ratio with isopropyl titanate, isopropyl alcohol and concentrated hydrochloric acid, high purity water places reactor, in 25 ± 2 ℃ of vigorous stirring, use simultaneously apart from the 500W high voltage mercury lamp radiation of reactor 10cm 36 hours, insert the narrow band pass filter of 300 ± 10nm in the light path, obtain titanium colloidal sol.Titanium colloidal sol in 25 ± 5 ℃ of slakings 3 days, is obtained gel, and gel makes the 3# sample 100 ℃ of calcinings 2 hours, and sample is pale brown look.
With 2#, the 3# sample is measured its absorption spectrum on the diffuse reflection ultraviolet-visible spectrophotometer, as seen from the figure, show the 3# sample visible region (＞400nm) have and absorb and the 2# sample does not absorb, as shown in Figure 4.
Embodiment 3:
Do the active testing test of visible light degradation of organic substances molecule.Rhodamine B is a kind of common dye molecule, often is used as the degraded target compound, because it has absorption at the 554nm place, therefore molecule itself has certain optical sensibilization, in this experiment, for fear of this optical sensibilization, we select the arrowband visible light less than 500nm for use, make the positive and negative 10nm of used excitation wavelength in selected centre wavelength, we have made the 3# sample at different wave length (420,450,470, under excited by visible light 500nm), the absorption spectrum of degraded rhodamine B.
Experimental results show that, the 3# sample is 420,450 and the excited by visible light of 470nm under the rhodamine B of degrading effectively, and the excited by visible light of 500nm does not almost have activity, therefore the visible light that the illumination sample that can judge us can the absorb 400-500nm organic molecule of degrading, as Fig. 5, Fig. 6, Fig. 7, shown in Figure 8.
Comparative Examples 2:
In order to detect the optical sensibilization of rhodamine B, we have done the blank assay that the light by rhodamine B and 420nm carries out.As seen from the figure, the rhodamine B molecule is very little under the experiment condition of the optical sensibilization under the radiation of visible light of 420nm at us, can ignore, as shown in Figure 9.
Comparative Examples 3:
The catalytic degradation experiment of 2# sample under the excited by visible light of 420nm, as seen from the figure, the 2# sample does not almost have catalytic activity under the excited by visible light of 420nm, as shown in figure 10.
Description of drawings:
Fig. 1: the XRD diffraction spectra of 1# sample.
Fig. 2: the TEM image of 1# sample.
Fig. 3: the XRD diffraction spectra of 2# sample.
Fig. 4: 2#, the diffuse reflection ultraviolet absorption spectrum of 3# sample.
Fig. 5: under the radiation of visible light of 420nm, the degrade uv-visible absorption spectra of rhodamine B of 3# sample.
Fig. 6: under the radiation of visible light of 450nm, the degrade uv-visible absorption spectra of rhodamine B of 3# sample.
Fig. 7: under the radiation of visible light of 470nm, the degrade uv-visible absorption spectra of rhodamine B of 3# sample.
Fig. 8: under the radiation of visible light of 500nm, the degrade uv-visible absorption spectra of rhodamine B of 3# sample.
Fig. 9: the blank assay of rhodamine B under the radiation of visible light of 420nm.
Figure 10: under the radiation of visible light of 420nm, the degrade uv-visible absorption spectra of rhodamine B of 2# sample.
Claims (6)
1. light helps synthetic preparation method with titanium dioxide powder of visible light catalysis activity, follow these steps to carry out (mass percent): with the titanate esters of 5-10%, the hydrolyst of 1-20%, the diluent of 70-90%, under the irradiation of the ultraviolet light source of particular range of wavelengths, reaction is 10-50 hour in reactor, the titanium colloidal sol that obtains was in 25 ± 5 ℃ of aging 3-10 days, 25 ± 5 ℃ of solvent flashings, the titanium gel was 50-150 ℃ roasting temperature 1-5 hour, obtain target anatase titanium dioxide powder catalyst, this catalyst can in visible wavelength range, be excited catalytic activity, catalyze and degrade organic pollutants effectively.
2. according to the preparation method of claim 1, it is characterized in that: the wave-length coverage of described ultraviolet light source is 200-600nm.
3. according to the preparation method of claim 1, it is characterized in that: effective visible wavelength range that this catalyst is suitable for is 400-800nm.
4. according to the preparation method of claim 1, it is characterized in that: described light source be in, low, high-pressure sodium lamp, xenon lamp, halogen tungsten lamp.
5. according to the preparation method of claim 1, it is characterized in that: described light source apart from reactor apart from 1-50cm.
6. according to the preparation method of claim 1, it is characterized in that: described titanate esters is butyl titanate, titanium propanolate and tetraethyl titanate.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100396372C (en) * | 2005-07-14 | 2008-06-25 | 天津大学 | Coating agent of photocatalysis with needle shape Tio2 anatase crystal grain and it preparation process |
| CN1317194C (en) * | 2005-11-17 | 2007-05-23 | 上海交通大学 | Process for preparing anatase type nano crystal TiO2 solar energy cell material |
| CN100404127C (en) * | 2006-06-23 | 2008-07-23 | 华中科技大学 | Artificial anitibody type composite photocatalyst and its prepn. method |
| FR2920762B1 (en) * | 2007-09-10 | 2009-10-23 | Saint Gobain | MATERIAL WITH PHOTOCATALYTIC PROPERTIES |
| CN102557126B (en) * | 2011-11-18 | 2014-01-29 | 浙江工业大学 | Sunlight-induced method for preparing fasciculate rutile titanium dioxide |
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