CN102120182B - Method for preparing fluorine and tungste co-doped anatase type nano titanium dioxide composite powder - Google Patents
Method for preparing fluorine and tungste co-doped anatase type nano titanium dioxide composite powder Download PDFInfo
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- CN102120182B CN102120182B CN2011100364076A CN201110036407A CN102120182B CN 102120182 B CN102120182 B CN 102120182B CN 2011100364076 A CN2011100364076 A CN 2011100364076A CN 201110036407 A CN201110036407 A CN 201110036407A CN 102120182 B CN102120182 B CN 102120182B
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Abstract
The invention relates to a method for preparing fluorine and tungste co-doped anatase type nano titanium dioxide composite powder, which is characterized by comprising the following steps: 1) preparing butyl titanate, absolute ethanol, acetic acid, HF, deionized water and ammonium tungstate according to a ratio of 20mL:200mL:5mL:(0.1 to 0.15mL):5mL:(85-340g), mixing and uniformly stirring the absolute ethanol and the acetic acid to obtain mixed liquid and dripping the butyl titanate into the mixed liquid to obtain yellowish sol; 2) preparing solution of fluorine and tungsten; 3) adding F-W-H2O into the yellowish sol to obtain milky sol, and standing the milky sol for 2 to 3 days; and 4) washing the milky sol which is stood for 2 to 3 days with deionized water till the pH value is 7, filtering to obtain a precipitate and drying to obtain the fluorine and tungste co-doped anatase type nano titanium dioxide composite powder. The method has the characteristics of low cost and simple preparation process and can realize batch production, and the prepared fluorine and tungste co-doped anatase type nano titanium dioxide composite powder has the characteristics of high catalytic activity and the like.
Description
Technical field
The present invention relates to a kind of preparation method of fluorine tungsten codope anatase type nano titanium dioxide composite powder.
Background technology
TiO
2Be widely used in handling various sewage as durable photochemical catalyst, its degraded object relates to multiple organic compound and part inorganic matters such as phenols, dyestuff.(K.Harada such as Harada Keni; Et al.Water Res.; 24 (1990) 1415-1417.) photocatalytic degradation to 34 kinds of organic pollutions in the water has carried out systematic research, show photocatalysis can with the hydro carbons in the water, halides, surfactant, dyestuff, itrogenous organic substance and phosphorous agrochemical quickly complete oxidation be CO
2, H
2Innocuous substances such as O.In addition, nano titanium dioxide photocatalyst is being handled aspect inorganic pollution, the air cleaning and antibiosis all has application.Along with the catalytic capability of nano titanium oxide under visible light constantly by people's development and utilization; The appearance in succession of antibiotic light modulation, anti-bacterial fibre, antibiotic building materials, antibiotic paint and anti-bacteria ceramic sanitary installation is along with the science and technology development nano titanium oxide will be more widely used.
Yet TiO
2Also there are some problem demanding prompt solutions in practical application: (1) nano-TiO
2Solar energy utilization ratio lower because TiO
2The limitation of himself is arranged, and energy gap is about 3.2ev, excites the generation electron-hole pair to need ultraviolet light or black light, and corresponding light absorbing threshold values is 387.5nm, and ultraviolet part only accounts for about 5%; (2) recombination rate of electric charge carrier is very fast, and quantum yield is very low, is about 4.Therefore, the key for preparing highly active photochemical catalyst is how to reduce the recombination probability and the expansion TiO in light induced electron and hole
2To the absorption of visible light scope.
At present, the band structure design is TiO
2The main means that the photoresponse wavelength is expanded, modes such as, noble metal loading compound through metal/non-metal ion doping, semiconductor, dye sensitization can reduce the band gap of band structure to a certain extent, strengthen the response to visible light.Most metal ions is doped with and is beneficial at TiO
2Produce impurity energy level in the band gap, realize visible light-respondedly, but impurity energy level also can become the carrier complex centre, reduces quantum efficiency (A.Kudo, et al.Chem.Lett., 33 (2004) 1534-1539.), and back TiO simultaneously mixes
2Poor heat stability, some needs expensive ion implantation equipment.Nonmetal doping mainly is for ability that improves catalyst absorption degradation thing and the recombination probability that reduces electronics-hole; Thereby impel the carrying out of light-catalyzed reaction; Common nonmetal doping has activated carbon, fluorine, nitrogen doping etc., but the high temperature solid-phase sintering that traditional nonmetal doping generally adopts can cause reduction (R.Ashi, the et al.Science of powder specific area; 293 (2001) 269-271.), thus influence catalytic effect.
At TiO
2The doped with fluorine ion has plurality of advantages in the crystal, as stoping TiO
2The Detitanium-ore-type phase rutile type of growing up, suppress of crystal grain changes (J.J.Xu; Et al.Appl.Surf.Sci.; 254 (2008) 3033-3038.), strengthen catalyst surface acidity (Chen Ying etc. petrochemical technology and application, 26 (2008) 76-85.), can also replenish TiO through electronics
2Ti in the lattice
4+Change Ti into
3+(C.Jimmy, et al.Chem.Mater., 14 (2004) 3808-3816.).Compare Ti with the titanium hydroxyl that the surface has
3+It is a kind of more effective light induced electron interfacial migration position.Therefore need not reducibility gas to TiO through the doped with fluorine ion
2Just heat-treat and to produce more Ti on its surface
3+The position promotes shift effective the separation with interface charge in electronics and hole, thereby the raising photocatalytic activity (Liu Shouxin etc. Northeast Forestry University's journal, 31 (2003) 53-56.).TiO
2/ WO
3Composite semiconductor has splendid visible light catalysis activity; Two kinds of semi-conductive conduction bands, valence band, energy gap is inconsistent and make the two that crossover take place; Between the semiconductor conveying of photo-generated carrier with separate, not only can suppress right compound in light induced electron-hole, also can be with TiO
2The photoresponse district expands to visible region, thereby has the photocatalytic activity higher than single semiconductor.
Adopt codoping technology between the different elements not only can fully utilize the advantage of each doped chemical, also possibly offset the weak point of each doped chemical simultaneously, thereby prepare codope TiO more efficiently
2Photochemical catalyst.
D.G.Huang etc. are presoma with the butyl titanate, and ammonium fluoride is nitrogen, fluorine source, have prepared N-F codope TiO
2, N/Ti=F/Ti ≈ 7% (D.G.Huang, et al.J.Photochem.Photobiol., A, 184 (2006) 282-288.).
Employing two-step methods such as V.Daniela have been synthesized Fe-N codope TiO
2Nanometer powder, wherein the optimum mole ratio of iron and titanium is 1.2～1.4 (V.Daniela, et al.J.Hazard.Mater., 179 (2010) 49-56.).
High Lians etc. are initiation material with ammonium tungstate and butyl titanate, with simple deposition and hydro-thermal method, have synthesized WO
3The nano-titanium oxide semiconductor light-catalyst of modifying.WO
3Shared mass percent is 0.37～0.52% (open (bulletin) number: CN1775349 discloses the date: in May, 2006).
H.Tian etc. are with Ti (SO
4)
2And Na
2WO
42H
2O is dissolved in the deionized water, stirs, hydrothermal treatment consists under 120～210 ℃, 3h then, and reactant obtains the titania powder that 0.5～4.0mol% tungsten mixes, wherein 2.0mol% tungsten doped Ti O after centrifugation, filtration, cleaning, drying
2Composite powder photocatalysis effect best (H.Tian, et al.Mater.Chem.Phys., 112 (2008) 47-51.).
Y.F.Shen etc. also successfully synthesize W-N codope TiO through a kind of simple two-step method
2: at first with butyl titanate and sodium tungstate (Na
2WO
4) prepare W-TiO for presoma
2Be nitrogenous source then with urea, adopt mechanical ball milling and calcination method to realize the introducing of nitrogen.Wherein tungsten and Ti mol ratio are about 10%, nitrogen and TiO
2Best in quality percentage be 3.0% (Y.F.Shen, et al.Appl.Catal., B, 83 (2008) 177-185.).
But up to the present, also do not report about the preparation method and the performance study of fluorine tungsten codope anatase-type nanometer titanium dioxide.
Summary of the invention
The purpose of this invention is to provide a kind of preparation method of fluorine tungsten codope anatase type nano titanium dioxide composite powder of high catalytic activity, this method technology is simple.
In order to realize the object of the invention, the technical scheme that the present invention taked is following: the preparation method of fluorine tungsten codope anatase type nano titanium dioxide composite powder is characterized in that it comprises the steps:
1) presses butyl titanate: absolute ethyl alcohol: acetate: HF: deionized water: the proportioning=20mL of ammonium tungstate: 200mL: 5mL: 0.1～0.15mL: 5mL: 85～340mg; Choose butyl titanate, absolute ethyl alcohol, acetate, HF, deionized water and ammonium tungstate, subsequent use;
With stirring after absolute ethyl alcohol and the acetate mixing, obtain mixed liquor earlier; Get butyl titanate and splash in the above-mentioned mixed liquor, continue in this process to stir 30～60 minutes, obtain light yellow colloidal sol;
2) preparation of fluorine tungsten solution: earlier HF is dissolved in the deionized water, processes the HF aqueous solution, then ammonium tungstate is dissolved in the above-mentioned HF aqueous solution, stirring makes the ammonium tungstate and the HF aqueous solution fully react (can suitably heat, heating-up temperature is 45～70 ℃), is designated as F-W-H
2O;
3) after obtaining light yellow colloidal sol, with F-W-H
2O is added dropwise in the light yellow colloidal sol, and strong agitation 10～15 hours obtains milky colloidal sol; The leucosol that obtains was placed 2～3 days;
4) will place leucosol after 2～3 days with washed with de-ionized water to pH=7, filter the back and obtain sediment; The sediment that obtains directly through 60～80 ℃ of vacuum drying, is obtained fluorine tungsten codope anatase type nano titanium dioxide composite powder.
Used chemicals is analyzes pure rank, butyl titanate Ti (OC
4H
9)
4Purity be 98～99.9wt.%, the concentration of acetate is 98～99.5wt.%, the concentration of HF is 40wt.%, ammonium tungstate ((NH
4)
6W
7O
246H
2O) purity is 85～98wt.%.
Described strong agitation is meant that rotating speed is more than 500 rev/mins.
The invention has the beneficial effects as follows:
1, preparation condition gentleness, the simple easy operating of equipment,, high-temperature heat treatment synthetic without hydro-thermal; Can obtain having the fluorine tungsten codope anatase type nano titanium dioxide composite powder of high catalytic activity at normal temperatures, the controllable granularity of the fluorine tungsten codope anatase type nano titanium dioxide composite powder of preparing within 10nm and good dispersion, purity high, active high.
2, the raw material component of using in its preparation process is few, and cost is low, and does not introduce other metal impurities ion, has guaranteed the high-purity of later stage powder.
3, preparation technology's simple possible is easy to mass production.
4, more significance and discovery be; With fluorine tungsten codope anatase type nano titanium dioxide photocatalyst and rhodamine B organic dyestuff in sonicated under the natural daylight, mix after; Under the condition of unglazed photograph, preserved 25 hours, the degradation rate of the rhodamine B of being surveyed reaches as high as more than 94.0%; And the mixed solution of P25 and rhodamine B organic dyestuff was preserved 25 hours under the condition of unglazed photograph; The degradation rate of the rhodamine B of being surveyed has only about 5.0%; And this rhodamine B degradation rate of about 5.0% is also only given the credit to the suction-operated of P25 nanometer grade powder, so the catalytic activity of the fluorine tungsten codope anatase type nano titanium dioxide photocatalyst prepared of this method is higher than P25's far away.The present invention has the characteristics of high catalytic activity.
The present invention can be in sewage disposal, air cleaning, sterilization, clean surfaces field such as clean and photolysis water hydrogen be widely used.TiO with Degussa company
2(trade names P25, anatase phase and rutile are in a ratio of 4: 1, specific area 55m to powder
2/ g) contrast, uses prepared fluorine tungsten codope anatase type nano titanium dioxide composite powder cutoff wavelength as the light source irradiation of 400nm filter plate under degraded Luo Ming pellet B dyestuff.The catalytic degradation data of being measured show: the fluorine tungsten codope anatase type nano titanium dioxide composite powder of the present invention preparation demonstrates very high visible light photocatalysis active, is higher than P25 far away, and its experimental result is as shown in Figure 4.And the fluorine tungsten codope anatase type nano titanium dioxide composite powder that this method is prepared also has very high catalytic degradation under the condition of unglazed photograph active, is that P25 nanometer powder institute can not match in excellence or beauty, and it is as shown in Figure 5 that it tests effect comparison.
Description of drawings
Fig. 1 is preparation technology's flow chart of the present invention;
Fig. 2 is the X ray diffracting spectrum that the embodiment of the invention 1,2,3 makes fluorine tungsten codope anatase type nano titanium dioxide composite powder;
Fig. 3 a is the field transmission Electronic Speculum figure that the embodiment of the invention 1 makes fluorine tungsten codope anatase type nano titanium dioxide composite powder;
Fig. 3 b is the enlarged drawing of Fig. 3 a;
Fig. 4 is that cutoff wavelength is the effect comparison diagram (the fluorine tungsten codope anatase type nano titanium dioxide composite powder and the P25 of embodiment 1,2,3 preparations compare) of the red B of its degraded Luo Ming under the light source irradiation of 400nm filter plate;
Fig. 5 is under the condition of unglazed photograph, the red B effect contrast figure of degraded Luo Ming (the fluorine tungsten codope anatase type nano titanium dioxide composite powder and the P25 of instance 1,2,3 preparations compare);
Fig. 6 is the photo in kind of visible light photocatalysis active, and a is that b is 2 hours photos behind the visible light photocatalysis among the preceding photo of catalysis, Fig. 6 among Fig. 6.
The specific embodiment
Further the present invention will be described below in conjunction with accompanying drawing and embodiment, but content of the present invention not only is confined to following embodiment.
Embodiment 1:
As shown in Figure 1, the preparation method of fluorine tungsten codope anatase type nano titanium dioxide composite powder, it comprises the steps:
1) earlier with stirring (obtain mixed liquor, be colourless solution) after 200mL absolute ethyl alcohol and 5mL acetate (concentration the is 99.5wt.%) mixing; Get the butyl titanate Ti (OC of 20mL
4H
9)
4(content is 99.9wt.%) slowly splashes in the above-mentioned mixed liquor, continues in this process to stir 60 minutes, obtains light yellow colloidal sol;
2) preparation of fluorine tungsten solution: the HF (concentration is 40wt.%) with 0.1mL is dissolved in the 5ml deionized water earlier, processes the HF aqueous solution, takes by weighing the ammonium tungstate [(NH of 85mg then
4)
6W
7O
246H
2O, content are 98wt.%], ammonium tungstate is dissolved in the above-mentioned HF aqueous solution, stirring makes itself and the HF aqueous solution fully react (heating-up temperature is 70 ℃), is designated as F-W-H
2O;
3) after obtaining light yellow colloidal sol, with F-W-H
2O dropwise adds in the light yellow colloidal sol, and strong agitation 15 hours obtains milky colloidal sol; The leucosol that obtains is placed 3 days (ageing);
4) will place leucosol after 3 days with a large amount of washed with de-ionized water to pH=7, filter the back and obtain the substantial white sediment; The white depositions that obtains directly through 80 ℃ of vacuum drying, can be obtained white, has the fluorine tungsten codope anatase type nano titanium dioxide composite powder of high catalytic activity.
Fig. 2 (a) is the XRD figure spectrum of the fluorine tungsten codope anatase type nano titanium dioxide composite powder of embodiment 1 preparation.
Fig. 3 a is the field transmission Electronic Speculum figure of the fluorine tungsten codope anatase type nano titanium dioxide composite powder of embodiment 1 preparation, and the even particle size distribution of demonstration fluorine tungsten codope anatase type nano titanium dioxide composite powder, granularity are less than 10nm.Fig. 4 for cutoff wavelength be the red B of its degraded Luo Ming under the light source irradiation of 400nm filter plate effect relatively, fluorine tungsten codope anatase type nano titanium dioxide composite powder shows good visible light photocatalysis effect.Through 1 hour, the fluorine tungsten codope anatase type nano titanium dioxide composite powder (photochemical catalyst) of embodiment 1 method preparation made 92.20% the red B degraded of Luo Ming, and contrast P25 only degrades 15.73%.Through 2 hours, the photochemical catalyst of embodiment 1 method preparation made 98.67% the red B degraded of Luo Ming, and contrast P25 only degrades 24.27%.Fig. 5 is under the condition of unglazed photograph, and 100% the red B degraded of Luo Ming is degraded, can be made after 49 hours to the fluorine tungsten codope anatase type nano titanium dioxide photocatalyst of embodiment 1 method preparation through making 94.67% the red B of Luo Ming after 25 hours; And under the condition of unglazed photograph; P25 made the degraded of 4.6% rhodamine B after 25 hours; The red B degradation rate of Luo Ming is merely 6.6% after 49 hours; And this rhodamine B degradation rate of 6.6% is also only given the credit to the suction-operated of P25 nanometer grade powder, and promptly P25 has the catalytic degradation activity hardly under the condition of unglazed photograph.The photo in kind of visible light photocatalysis active is seen Fig. 6, and wherein a is that b is 2.0 hours photos behind the visible light photocatalysis among the preceding photo of catalysis, Fig. 6 among Fig. 6.Fig. 4, Fig. 5, Fig. 6 explain that the fluorine tungsten codope anatase type nano titanium dioxide composite powder of the embodiment of the invention 1 preparation has high catalytic activity.
Embodiment 2:
The preparation method of fluorine tungsten codope anatase type nano titanium dioxide composite powder, it comprises the steps:
1) earlier with stirring (obtain mixed liquor, be colourless solution) after 200mL absolute ethyl alcohol and 5mL acetate (concentration the is 98wt.%) mixing; Get the butyl titanate Ti (OC of 20mL
4H
9)
4(content is 98wt.%) slowly splashes in the above-mentioned mixed liquor, continues in this process to stir 30 minutes, obtains light yellow colloidal sol;
2) preparation of fluorine tungsten solution: the HF (concentration is 40wt.%) with 0.15mL is dissolved in the 5mL deionized water earlier, processes the HF aqueous solution, takes by weighing the ammonium tungstate [(NH of 170mg then
4)
6W
7O
246H
2O, content are 85wt.%], it is dissolved in the above-mentioned HF aqueous solution, stirring makes itself and the HF aqueous solution fully react (heating-up temperature is 45 ℃), is designated as F-W-H
2O;
3) after obtaining light yellow colloidal sol, with F-W-H
2O dropwise adds in the light yellow colloidal sol, and strong agitation 12 hours obtains milky colloidal sol; The leucosol that obtains is placed 2.5 days (ageing).
4) will place leucosol after 2.5 days with a large amount of washed with de-ionized water to pH=7, filter the back and obtain the substantial white sediment; The white depositions that obtains directly through 70 ℃ of vacuum drying, can be obtained white, has the fluorine tungsten codope anatase type nano titanium dioxide composite powder of high catalytic activity.
Fig. 2 (b) is the XRD figure spectrum of the fluorine tungsten codope anatase type nano titanium dioxide composite powder of embodiment 2 preparations.
Fig. 4 for cutoff wavelength be the red B of its degraded Luo Ming under the light source irradiation of 400nm filter plate effect relatively, the fluorine tungsten codope anatase type nano titanium dioxide composite powder of embodiment 2 preparations shows good visible light photocatalysis effect.Through 1 hour, the fluorine tungsten codope anatase type nano titanium dioxide composite powder (photochemical catalyst) of embodiment 2 preparations made 75.73% the red B degraded of Luo Ming, and contrast P25 only degrades 15.73%.Through 2 hours, the photochemical catalyst of embodiment 2 preparations made 96.73% the red B degraded of Luo Ming, and contrast P25 only degrades 24.27%.Fig. 5 is under the condition of unglazed photograph, and 98.33% the red B degraded of Luo Ming is degraded, can be made after 49 hours to the fluorine tungsten codope anatase type nano titanium dioxide photocatalyst of embodiment 2 preparations through making 86.80% the red B of Luo Ming after 25 hours; And under the condition of unglazed photograph; P25 made the degraded of 4.6% rhodamine B after 25 hours; The red B degradation rate of Luo Ming is merely 6.6% after 49 hours; And this rhodamine B degradation rate of 6.6% is also only given the credit to the suction-operated of P25 nanometer grade powder, and promptly P25 has the catalytic degradation activity hardly under the condition of unglazed photograph.Fig. 4, Fig. 5 explain that the fluorine tungsten codope anatase type nano titanium dioxide composite powder of the embodiment of the invention 2 preparations has high catalytic activity.
Embodiment 3:
The preparation method of fluorine tungsten codope anatase type nano titanium dioxide composite powder, it comprises the steps:
1) earlier with stirring (obtain mixed liquor, be colourless solution) after 200mL absolute ethyl alcohol and 5mL acetate (concentration the is 99wt.%) mixing; Get the butyl titanate Ti (OC of 20mL
4H
9)
4Slowly splash in the above-mentioned mixed liquor, continue in this process to stir 40 minutes, obtain light yellow colloidal sol;
2) preparation of fluorine tungsten solution: the HF (concentration is 40wt.%) with 0.1mL is dissolved in the 5mL deionized water earlier, processes the HF aqueous solution, takes by weighing the ammonium tungstate ((NH of 340mg then
4)
6W
7O
246H
2O), ammonium tungstate is dissolved in the above-mentioned HF aqueous solution, stirring makes itself and the HF aqueous solution fully react (heating-up temperature is 60 ℃), is designated as F-W-H
2O;
3) after obtaining light yellow colloidal sol, with F-W-H
2O dropwise adds in the light yellow colloidal sol, and strong agitation 15 hours obtains milky colloidal sol; The leucosol that obtains is placed 2 days (ageing); Described strong agitation is meant that rotating speed is more than 500 rev/mins;
4) will place leucosol after 2 days with a large amount of washed with de-ionized water to pH=7, filter the back and obtain the substantial white sediment; The white depositions that obtains directly through 60 ℃ of vacuum drying, can be obtained white, has the fluorine tungsten codope anatase type nano titanium dioxide composite powder of high catalytic activity.
Fig. 2 (c) is the XRD figure spectrum of the fluorine tungsten codope anatase type nano titanium dioxide composite powder of embodiment 3 preparations.
Fig. 4 for cutoff wavelength be the red B of its degraded Luo Ming under the light source irradiation of 400nm filter plate effect relatively.The fluorine tungsten codope anatase type nano titanium dioxide composite powder of embodiment 3 preparations shows good visible light photocatalysis effect.Through 1 hour, the fluorine tungsten codope anatase type nano titanium dioxide composite powder (photochemical catalyst) of embodiment 3 preparations made 57.00% the red B degraded of Luo Ming, and contrast P25 only degrades 15.73%.Through 2 hours, the photochemical catalyst of embodiment 3 preparations made 97.73% the red B degraded of Luo Ming, and contrast P25 only degrades 24.27%.Fig. 5 be illumination 30 minutes under the visible light, back under the condition of unglazed photograph, the fluorine tungsten codope anatase type nano titanium dioxide photocatalyst of embodiment 3 preparation is through making 79.27% the red B degraded of Luo Ming, 97.93% the red B of Luo Ming being degraded after 25 hours; And under the condition of unglazed photograph; P25 made the degraded of 4.6% rhodamine B after 25 hours; The red B degradation rate of Luo Ming is merely 6.6% after 49 hours; And this rhodamine B degradation rate of 6.6% is also only given the credit to the suction-operated of P25 nanometer grade powder, and promptly P25 has the catalytic degradation activity hardly under the condition of unglazed photograph.Fig. 4, Fig. 5 explain that the fluorine tungsten codope anatase type nano titanium dioxide composite powder of the embodiment of the invention 3 preparations has high catalytic activity.
Claims (3)
1. the preparation method of fluorine tungsten codope anatase type nano titanium dioxide composite powder is characterized in that it comprises the steps:
1) presses butyl titanate: absolute ethyl alcohol: acetate: HF: deionized water: the proportioning=20mL of ammonium tungstate: 200mL: 5mL: 0.1～0.15mL: 5mL: 85～340mg; Choose butyl titanate, absolute ethyl alcohol, acetate, HF, deionized water and ammonium tungstate, subsequent use;
With stirring after absolute ethyl alcohol and the acetate mixing, obtain mixed liquor earlier; Get butyl titanate and splash in the above-mentioned mixed liquor, continue in this process to stir 30～60 minutes, obtain light yellow colloidal sol;
2) preparation of fluorine tungsten solution: earlier HF is dissolved in the deionized water, processes the HF aqueous solution, then ammonium tungstate is dissolved in the above-mentioned HF aqueous solution, stirring is fully reacted the ammonium tungstate and the HF aqueous solution, is designated as F-W-H
2O;
3) after obtaining light yellow colloidal sol, with F-W-H
2O is added dropwise in the light yellow colloidal sol, and strong agitation 10～15 hours obtains milky colloidal sol; The milky colloidal sol that obtains was placed 2～3 days;
4) will place milky colloidal sol after 2～3 days with washed with de-ionized water to pH=7, filter the back and obtain sediment; The sediment that obtains directly through 60～80 ℃ of vacuum drying, is obtained fluorine tungsten codope anatase type nano titanium dioxide composite powder.
2. the preparation method of fluorine tungsten codope anatase type nano titanium dioxide composite powder according to claim 1 is characterized in that: the concentration of acetate is 98～99.5wt%.
3. the preparation method of fluorine tungsten codope anatase type nano titanium dioxide composite powder according to claim 1 is characterized in that: the concentration of HF is 40wt%.
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|---|
| Anna Kubacka et al..Doping level effect on sunlight-driven W,N-co-doped TiO2-anatase photo-catalysts for aromatic hydrocarbon partial oxidation.《Applied Catalysis B: Environmental》.2009,第93卷274-281. * |
| AnnaKubackaetal..Dopingleveleffectonsunlight-drivenW N-co-doped TiO2-anatase photo-catalysts for aromatic hydrocarbon partial oxidation.《Applied Catalysis B: Environmental》.2009 |
| Jingjing Xu et al..Low-temperature preparation of F-doped TiO2 film and its photocatalytic activity under solar light.《Applied Surface Science》.2007,第254卷3033-3038. * |
| 刘奎仁 等.光降解用WO3-TiO2复合光催化剂.《东北大学学报( 自然科学版)》.2003,第24卷(第11期),1064-1066. * |
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