CN101792117B - Method for preparing tungsten-doped anatase type nano titanium dioxide composite powder - Google Patents

Method for preparing tungsten-doped anatase type nano titanium dioxide composite powder Download PDF

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CN101792117B
CN101792117B CN 201010115236 CN201010115236A CN101792117B CN 101792117 B CN101792117 B CN 101792117B CN 201010115236 CN201010115236 CN 201010115236 CN 201010115236 A CN201010115236 A CN 201010115236A CN 101792117 B CN101792117 B CN 101792117B
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deionized water
titanium dioxide
composite powder
tungsten
tio
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CN101792117A (en
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史晓亮
杨行勇
王书伟
秦海波
彭美超
章桥新
王玉伏
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Wuhan University of Technology WUT
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Abstract

The invention relates to a method for preparing tungsten-doped anatase type nano titanium dioxide composite powder. The method for preparing the tungsten-doped anatase type nano titanium dioxide composite powder is characterized by comprising the following steps: 1) hydrolyzing TiCl4, namely selecting TiCl4, anhydrous ethanol and deionized water in a ratio of 20ml to 200ml to 80ml, putting the anhydrous ethanol into an ice-water bath, dripping the TiCl4 into the ice-water bath to obtain light yellow solution, violently stirring the light yellow solution in the ice-water bath for 2 hours, then adding the deionized water into the solution, stirring the solution to obtain colorless transparent solution, and placing the solution; 2) preparing a titanium dioxide precursor; 3) performing hydro-thermal treatment to obtain yellow sol; 4) adding the deionized water into the yellow sol obtained in the step 3) to dilute the yellow sol, then adding (NH4)6W7O24.6H2O into the diluted yellow sol, and ultrasonically dispersing the diluted yellow sol to obtain mixed sol; and 5) hydro-thermally treating the mixed sol, and drying the mixed sol under vacuum to obtain the tungsten-doped anatase type nano titanium dioxide composite powder. The method has the characteristics of low cost, high purity and simple process; and the powder has high visible light catalysis activity.

Description

The preparation method of tungsten-doped anatase type nano titanium dioxide composite powder
Technical field
The present invention relates to a kind of preparation method of tungsten-doped anatase type nano titanium dioxide composite powder.
Background technology
Along with science and technology development, earth environment pollutes serious day by day.Every days such as factory, people's life, the vehicles are all at a large amount of toxic and harmful and the pollutant of discharging, use the water that flows out after the field irrigation of chemical substance etc. in a large number, severe contamination around living environment.The earth environment pollution problem is one of the most scabrous problem in the world.
D.F.Ollis (D.F.Ollis, et al.Environ.Sci.Technol., 19 (1985) 4480-484.) sets forth the application prospect of photocatalysis in organic wastewater, has caused the climax of photocatalysis research in the world wide.So far, people have found many semi-conducting material (TiO 2, ZnO, Fe 2O 3, SrTiO 3, CdS, CdSe etc.) have and be suitable for light-catalysed band structure.Because of the restriction of energy gap, photocatalysis efficiency, photoetch phenomenon, chemical stability, price and factor such as nontoxic, TiO 2Be still of greatest concern, use the most extensively, most possibly realize the catalysis material of practicability.TiO 2Photocatalysis has been widely applied to fields such as deodorizing antibiotic, air cleaning, water treatment, automatically cleaning, and meaning is huge aspect the solar energy utilization and the depollution of environment, and development prospect is wide.Yet, TiO 2The band gap of broad causes it low to solar energy utilization rate, and the energy of absorption edge of titanium dioxide is at 388nm, can only utilize the ultraviolet portion (it is about 4% that the solar spectral middle-ultraviolet lamp only accounts for, and visible light accounts for about 48%) of solar spectral, has greatly limited practical application.
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 effectively realize the regulation and control to the catalysis material band structure, reduce band gap, strengthen the response to visible light.
Most metal ions is mixed, and helps at TiO 2Produce impurity energy level in the band gap, realize visible light-responded.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 the doping content scope is narrow simultaneously, and back TiO mixes 2Poor heat stability, some needs expensive ion implantation equipment.
At TiO 2An amount of noble metal of surface deposition helps light induced electron and the effective of hole separates, thereby improves activity of such catalysts.The noble metal loading amount is for TiO 2Activity influence very big, the deposition form then influences lessly, deposition is crossed the complex centre that may well make metal become electronics and hole, is unfavorable for TiO 2Photocatalysis, the noble metal cost (Shi Jianwen that compares in addition.China University Of Petroleum Beijing's Doctor of engineering academic dissertation, in April, 2007.)。
Nonmetal doping can improve the ability of visible light-responded scope and absorption degradation thing, carries out thereby help light-catalyzed reaction, and common nonmetal doping has activated carbon doped and nitrogen doping etc.But the high temperature solid-phase sintering that nonmetal doping generally adopts can cause the reduction (R.Ashi, et al.Science, 293 (2001) 269-271.) of powder specific area, thereby influences catalytic effect, and doped chemical is also wayward simultaneously.
The dyestuff optical active substance is adsorbed in TiO 2Photocatalyst surface can be expanded excitation wavelength range, improve reaction efficiency.But most of sensitizers are a little less than the near infrared region absorbs very, can not well matched with solar spectrum, often there is absorption competition between sensitizer and the pollutant in addition, and the light degradation reaction also possibly take place and constantly consume in sensitizer self.Therefore, in course of reaction, need to add more sensitizer (Fan Xiaojiang etc.Use chemical industry, 37 (2008) 1221-1225.)。
TiO 2Photocatalyst surface reduction, chelating, derive or super-strong acidified etc. also can improve its photocatalytic activity to a certain extent.TiO 2The surface has the titanium hydroxyl structure, and it is the shallow potential well of catching light induced electron and hole, compares Ti with the titanium hydroxyl 3+It is a kind of more effective light induced electron interfacial migration position.Reducibility gas is to TiO 2Heat-treat and to produce more Ti on its surface 3+The position is at TiO 2The surface forms suitable titanium hydroxyl and Ti 3+Proportion structure, promote shift effective separation the in electronics and hole with interface charge, thus raising photocatalytic activity (Liu Shouxin etc.Northeast Forestry University's journal, 31 (2003) 53-56.); At TiO 2Middle chelating agent or the derivating agent of adding like some metal oxides, makes TiO 2Part surface is chelated or derives.Through at TiO 2The chelating or the derivatization on surface can increase the speed that conduction band electron is transferred to acceptor in the solution, and make the absorbing wavelength red shift, respond near ultraviolet and visual field, improve the utilization rate to light; Excellent properties such as solid super acid catalyst has the active height of photochemical catalytic oxidation, the deep oxidation ability is strong, activity stabilized, anti humility performance is good.So strengthen the surface acidity of catalyst is to improve TiO 2A kind of new way (Chen Ying etc. of photocatalysis efficiency.Petrochemical technology and application, 26 (2008) 76-85.)。
Adopt narrower semiconductor and the TiO of energy gap 2Compound, 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, and common complex has TiO 2/ WO 3, TiO 2/ SnO 2, TiO 2/ CdS, TiO 2/ V 2O 5Deng.
Patent CN1775349 is an initiation material with ammonium tungstate and butyl titanate, with simple deposition and hydro-thermal method, has synthesized WO 3The nano-titanium oxide semiconductor light-catalyst of modifying.WO in the composite semiconductor powder 3The weight content percentage composition be 0.37～0.52% (high Lian, Yang Songwang.Open (bulletin) number: CN1775349 discloses the date: in May, 2006.)。
D.N.Ke etc. are with Ti (SO 4) 2Be dissolved in the deionized water, under magnetic agitation, add CTAB, drip Na then 2WO 4Solution, through 100 ℃-96h hydro-thermal reaction, product obtains WO through centrifugation, cleaning, 450～900 ℃ of calcinings 3/ TiO 2Composite powder.WO 3With TiO 2Mol ratio is for being 4～1: 1～6 respectively, wherein WO 3With TiO 2Mol ratio is 1: 3 a composite powder photocatalysis performance better (D.N.Ke, et al.Mater.Lett., 62 (2008) 447-450.).
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.).
Spraying prepares WO to the presoma of dissolving tungsten such as K.K.Akurati and titanium through oxyacetylene torch in suitable solvent 3/ TiO 2Composite powder, 3.6mol%WO 3/ TiO 2Has photocatalysis effect preferably (K.K.Akurati, et al.Appl.Catal.B:Environ., 79 (2008) 53-62.).
C.F.Lin etc. are with H 2WO 4And TiO 2Be raw material, in ammonium salt solution, mix, obtain TiO through 400 ℃-2h calcining 2/ WO 3Composite powder has photocatalysis effect preferably (C.F.Lin, et al.J.Hazard.Mater., 154 (2008) 1033-1039.).
These are reported in synthetic method, reaction scheme and tungsten and TiO 2The ratio aspect is all different with the present invention.
Summary of the invention
The preparation method who the purpose of this invention is to provide the high tungsten-doped anatase type nano titanium dioxide composite powder of a kind of visible light photocatalysis active, this method technology is simple.
In order to realize the object of the invention, the technical scheme that the present invention taked is: the preparation method of tungsten-doped anatase type nano titanium dioxide composite powder is characterized in that it comprises the steps:
1) TiCl 4Hydrolysis: press TiCl 4: absolute ethyl alcohol: deionized water=20mL: 200mL: 80mL, choose TiCl 4, absolute ethyl alcohol and deionized water, subsequent use;
Absolute ethyl alcohol is put into ice-water bath, drip TiCl 4, obtain pale yellow solution; Pale yellow solution is strong agitation 2h in ice-water bath, adds deionized water then, continues strong agitation 4h, gets colourless transparent solution, places 12 hours;
2) preparation of TiO 2 precursor: drip mass concentration ρ=0.91 * 10 in the colourless transparent solution after placing 12 hours 3Kg/m 3Ammonia spirit to pH=8, obtain white solid (white precipitate), use the deionized water filtration washing to pH=7 again, obtain TiO 2 precursor;
3) hydrothermal treatment consists: press TiCl 4: H 2O 2=20mL: (100～200) mL, choose mass concentration ρ=1.11 * 10 3Kg/m 3H 2O 2To step 2) add ρ=1.11 * 10 in the TiO 2 precursor that obtains 3Kg/m 3H 2O 2, stir 2h down at 60 ℃, obtain yellow sol;
4) by (NH 4) 6W 7O 246H 2O and TiCl 4Mol ratio=0.05～0.08, choose (NH 4) 6W 7O 246H 2O (ammonium tungstate); Press TiCl 4: deionized water=20mL: 80mL, choose deionized water; After adding the deionized water dilution in the yellow sol that step 3) obtains, add (NH again 4) 6W 7O 246H 2O, ultrasonic dispersion, stirring obtain mixed sols;
5) mixed sols is changed in the band teflon-lined agitated reactor carry out hydrothermal treatment consists then, the temperature of hydrothermal treatment consists is 140～160 ℃, and the time is 2～4h; Product after the hydrothermal treatment consists directly through 60～85 ℃ of vacuum drying, obtains yellow, has the tungsten-doped anatase type nano titanium dioxide composite powder of high visible photocatalytic activity.
Strong agitation of the present invention is meant that speed of agitator is more than 400 rev/mins.
The power of described ultrasonic dispersion is 60～100W, and frequency of ultrasonic is 20 kilo hertzs～40 kilo hertzs, and the time is 10～30min.
The invention has the beneficial effects as follows:
1, preparation condition gentle, can obtain high activity, visible light-responded tungsten-doped anatase type nano titanium dioxide composite powder without high-temperature heat treatment; The even particle size distribution of the tungsten-doped anatase type nano titanium dioxide composite powder of preparing, good dispersion, purity height (are not introduced other foreign ion; Guaranteed the high-purity and the high activity of later stage powder), have the high visible photocatalytic activity.
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 is simple.
The present invention can be widely used in fields such as sewage disposal, air cleaning, sterilization, clean surfaces and photolysis water hydrogens.
TiO with prepared tungsten-doped anatase type nano titanium dioxide composite powder and Degussa company 2(trade names P25, anatase phase and rutile are in a ratio of 4: 1, specific area 55m 2/ g) in cutoff wavelength the photocatalytic activity of measuring the red B dyestuff of its degraded Luo Ming under the light source irradiation of 400nm filter plate as photochemical catalyst respectively.The result shows: the tungsten-doped anatase type nano titanium dioxide composite powder of the present invention's preparation demonstrates very high visible light photocatalysis active, and experimental result is as shown in Figure 4.
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 tungsten-doped anatase type nano titanium dioxide composite powder;
Fig. 3 a is the field transmission Electronic Speculum figure that instance 1 of the present invention makes tungsten-doped anatase type nano titanium dioxide composite powder;
Fig. 3 b is the enlarged drawing of Fig. 3 a;
Fig. 4 is the red B effect contrast figure of Photocatalytic Activity for Degradation Luo Ming (the tungsten-doped anatase type nano titanium dioxide powder and the P25 of instance 1 preparation compare);
Fig. 5 is the photo in kind of visible light photocatalysis active.
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:
Like Fig. 1 institute, the preparation method of tungsten-doped anatase type nano titanium dioxide composite powder, it comprises the steps:
1) the 200mL absolute ethyl alcohol is put into ice-water bath, drip the TiCl of 20mL 4, obtain pale yellow solution; Pale yellow solution is strong agitation 2h in ice-water bath, adds the deionized water of 80mL then, continues strong agitation 4h, gets colourless transparent solution, places 12 hours;
2) preparation of TiO 2 precursor: drip mass concentration ρ=0.91 * 10 in the colourless transparent solution after placing 12 hours 3Kg/m 3Ammonia spirit to pH=8, obtain white solid (white precipitate), use the deionized water filtration washing to pH=7 again, obtain TiO 2 precursor;
3) ρ=1.11 * 10 that add 200mL in the TiO 2 precursor that hydrothermal treatment consists: to step 2) obtains 3Kg/m 3H 2O 2, stir 2h down at 60 ℃, obtain yellow sol;
4) by (NH 4) 6W 7O 246H 2O and TiCl 4Mol ratio=0.065, choose (NH 4) 6W 7O 246H 2O (ammonium tungstate); After adding the deionized water dilution of 80mL in the yellow sol that step 3) obtains, add (NH again 4) 6W 7O 246H 2O, ultrasonic dispersion, stirring (also needing magnetic agitation after the ultrasonic dispersion) obtain mixed sols;
5) mixed sols is changed in the band teflon-lined agitated reactor carry out hydrothermal treatment consists then, the temperature of hydrothermal treatment consists is 140 ℃, and the time is 2h; Product after the hydrothermal treatment consists directly through 60 ℃ of vacuum drying, obtains yellow, has the tungsten-doped anatase type nano titanium dioxide composite powder of high visible photocatalytic activity.
Fig. 2 is the XRD figure spectrum of tungsten-doped anatase type nano titanium dioxide composite powder.Fig. 3 a is the field transmission Electronic Speculum figure of tungsten-doped anatase type nano titanium dioxide composite powder; The nano composite powder even particle size distribution that shows preparation; The crystallization of Fig. 3 b explanation particle is more complete; Lattice fringe is high-visible, and anatase-type nanometer titanium dioxide is dispersed between amorphous wolframic acid ammonia.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, tungsten-doped anatase type nano titanium dioxide composite powder shows good visible light photocatalysis effect.Through 3 hours, the photochemical catalyst of this method preparation made 77% the red B degraded of Luo Ming, and contrast P25 only degrades 40%.The photo in kind of visible light photocatalysis active is seen Fig. 5, and Fig. 5 a is that photo, Fig. 5 b before the catalysis is 5 hours photos behind the visible light photocatalysis.
Embodiment 2:
The preparation method of tungsten-doped anatase type nano titanium dioxide composite powder, it comprises the steps:
1) the 200mL absolute ethyl alcohol is put into ice-water bath, drip the TiCl of 20mL 4, obtain pale yellow solution; Pale yellow solution is strong agitation 2h in ice-water bath, adds the deionized water of 80mL then, continues strong agitation 4h, gets colourless transparent solution, places 12 hours;
2) preparation of TiO 2 precursor: drip mass concentration ρ=0.91 * 10 in the colourless transparent solution after placing 12 hours 3Kg/m 3Ammonia spirit to pH=8, obtain white solid (white precipitate), use the deionized water filtration washing to pH=7 again, obtain TiO 2 precursor;
3) ρ=1.11 * 10 that add 200mL in the TiO 2 precursor that hydrothermal treatment consists: to step 2) obtains 3Kg/m 3H 2O 2, stir 2h down at 60 ℃, obtain yellow sol;
4) by (NH 4) 6W 7O 246H 2O and TiCl 4Mol ratio=0.05, choose (NH 4) 6W 7O 246H 2O (ammonium tungstate); After adding the deionized water dilution of 80mL in the yellow sol that step 3) obtains, add (NH again 4) 6W 7O 246H 2O, ultrasonic dispersion, stirring obtain mixed sols;
5) mixed sols is changed in the band teflon-lined agitated reactor carry out hydrothermal treatment consists then, the temperature of hydrothermal treatment consists is 140 ℃, and the time is 2h; Product after the hydrothermal treatment consists directly through 60 ℃ of vacuum drying, obtains yellow, has the tungsten-doped anatase type nano titanium dioxide composite powder of high visible photocatalytic activity.
Fig. 2 is the XRD figure spectrum of tungsten-doped anatase type nano titanium dioxide composite powder.
Embodiment 3:
The preparation method of tungsten-doped anatase type nano titanium dioxide composite powder, it comprises the steps:
1) the 200mL absolute ethyl alcohol is put into ice-water bath, drip the TiCl of 20mL 4, obtain pale yellow solution; Pale yellow solution is strong agitation 2h in ice-water bath, adds the deionized water of 80mL then, continues strong agitation 4h, gets colourless transparent solution, places 12 hours;
2) preparation of TiO 2 precursor: drip mass concentration ρ=0.91 * 10 in the colourless transparent solution after placing 12 hours 3Kg/m 3Ammonia spirit to pH=8, obtain white solid (white precipitate), use the deionized water filtration washing to pH=7 again, obtain TiO 2 precursor;
3) ρ=1.11 * 10 that add 100mL in the TiO 2 precursor that hydrothermal treatment consists: to step 2) obtains 3Kg/m 3H 2O 2, stir 2h down at 60 ℃, obtain yellow sol;
4) by (NH 4) 6W 7O 246H 2O and TiCl 4Mol ratio=0.08, choose (NH 4) 6W 7O 246H 2O (ammonium tungstate); After adding the deionized water dilution of 80mL in the yellow sol that step 3) obtains, add (NH again 4) 6W 7O 246H 2O, ultrasonic dispersion, stirring obtain mixed sols;
5) mixed sols is changed in the band teflon-lined agitated reactor carry out hydrothermal treatment consists then, the temperature of hydrothermal treatment consists is 160 ℃, and the time is 4h; Product after the hydrothermal treatment consists directly through 85 ℃ of vacuum drying, obtains yellow, has the tungsten-doped anatase type nano titanium dioxide composite powder of high visible photocatalytic activity.
Fig. 2 is the XRD figure spectrum of tungsten-doped anatase type nano titanium dioxide composite powder.

Claims (1)

1. the preparation method of tungsten-doped anatase type nano titanium dioxide composite powder is characterized in that it comprises the steps:
1) TiCl 4Hydrolysis: press TiCl 4: absolute ethyl alcohol: deionized water=20mL: 200mL: 80mL, choose TiCl 4, absolute ethyl alcohol and deionized water, subsequent use;
Absolute ethyl alcohol is put into ice-water bath, drip TiCl 4, obtain pale yellow solution; Pale yellow solution is strong agitation 2h in ice-water bath, adds deionized water then, continues strong agitation 4h, gets colourless transparent solution, places 12 hours;
Described strong agitation is meant that speed of agitator is more than 400 rev/mins;
2) preparation of TiO 2 precursor: drip mass concentration ρ=0.91 * 10 in the colourless transparent solution after placing 12 hours 3Kg/m 3Ammonia spirit to pH=8, obtain white solid, use the deionized water filtration washing to pH=7 again, obtain TiO 2 precursor;
3) hydrothermal treatment consists: press TiCl 4: H 2O 2=20mL: (100～200) mL, choose mass concentration ρ=1.11 * 10 3Kg/m 3H 2O 2To step 2) add ρ=1.11 * 10 in the TiO 2 precursor that obtains 3Kg/m 3H 2O 2, stir 2h down at 60 ℃, obtain yellow sol;
4) by (NH 4) 6W 7O 246H 2O and TiCl 4Mol ratio=0.05～0.08, choose (NH 4) 6W 7O 246H 2O; Press TiCl 4: deionized water=20mL: 80mL, choose deionized water; After adding the deionized water dilution in the yellow sol that step 3) obtains, add (NH again 4) 6W 7O 246H 2O, ultrasonic dispersion, stirring obtain mixed sols;
The power of described ultrasonic dispersion is 60～100W, and frequency of ultrasonic is 20 kilo hertzs～40 kilo hertzs, and the time is 10～30min;
5) mixed sols is changed in the band teflon-lined agitated reactor carry out hydrothermal treatment consists then, the temperature of hydrothermal treatment consists is 140～160 ℃, and the time is 2～4h; Product after the hydrothermal treatment consists directly through 60～85 ℃ of vacuum drying, obtains tungsten-doped anatase type nano titanium dioxide composite powder.
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