CN100581649C - Compounding photocatalyst containing doped-cerium titanium dioxide/silica gel and its preparing method - Google Patents
Compounding photocatalyst containing doped-cerium titanium dioxide/silica gel and its preparing method Download PDFInfo
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- CN100581649C CN100581649C CN200710027809A CN200710027809A CN100581649C CN 100581649 C CN100581649 C CN 100581649C CN 200710027809 A CN200710027809 A CN 200710027809A CN 200710027809 A CN200710027809 A CN 200710027809A CN 100581649 C CN100581649 C CN 100581649C
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- titanium dioxide
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Abstract
A Ce doped TiO2/silica gel compound as composite photocatalyst used for the pollutant control of water and air, medical purpose and chemical synthesis contains Ce (0.01-1 mole%) and TiO2 (99-99.99 mole%), and has high degradation speed of pollutants. It is prepared by sol-gel method.
Description
Technical field
The present invention relates to a kind of photochemical catalyst, specifically, relate to a kind of cerium doped titanium dioxide/silica gel composite photo-catalyst and preparation method thereof.
Background technology
Poisonous persistent organic pollutants are pollution problems that the current whole world is the most general, be difficult to administer most.Sanitary sewage can be handled effectively with traditional biological treatment, but the compound of hundreds of high malicious difficult degradations can not must be sought out suitable, effective processing method with biological treatment.Studies show that in a large number photocatalytic method can be effectively with main organic pollutant degradation such as hydro carbons, halogenated organic matters, surfactant, dyestuff, agricultural chemicals, phenols, aromatic hydrocarbons, final mineralising is CO
2, H
2O, the halogen atom that contains in the organic pollution, sulphur atom, phosphorus atoms and nitrogen-atoms etc. then are separately converted to X
-, SO
4 2-, PO
4 3-, NH
4 +, NO
3 -Plasma reaches the purpose of eliminating organic pollution fully.
In all semiconductor light-catalysts, TiO
2Be proved to be and be suitable for environmental applications widely most.TiO
2Photoetch and chemical attack can not take place in good stability, and cost is low, and harmless.But, there are two basic problems the most tangible in the optically catalytic TiO 2 technology: the one, and the band-gap energy broad, be 3.2eV, therefore titanium dioxide can only be excited by the light that wavelength is equal to or less than the near ultraviolet part of 387.5 nanometers, and this part light only accounts for the sub-fraction (less than 5%) of sunshine, thereby can not make full use of sunshine.Moreover the light induced electron hole is to compound easily, and photoproduction electron hole pair compound is less than 10 on titanium dioxide surface
-9Finish in the time of second, the outstanding problem that therefore prepares high-activity photocatalyst is how to reduce the recombination probability in light induced electron and hole.In addition, the photocatalysis treatment organic pollutant wastewater adopts nano-TiO mostly at present
2There is nano-TiO in powder suspension system
2Powder particle is easily reunited and is made its active reduction, and is difficult to separate problems such as recovery, recycling.
At above-mentioned three problems, existing a large amount of document has proposed solution.Can reduce the compound of electron hole pair, the raising quantum yield as having reported people such as Choi proposition titanium dioxide Q-particle is mixed on " Journalof Physics Chemistry ".The binary metal oxide that forms with conductor oxidates such as tungstic acid, molybdenum trioxides also can impel separating of electron hole pair and improve quantum yield.In addition, the method that the titanium dioxide response wave length is moved to visible region that also had a large amount of bibliographical informations.As Cr
3+, Rh
3+, pb
2+Deng doping, sensitising agents such as surface absorption erythrosine, thionine.Chinese invention patent 97181439.2 discloses the method for load TiC raising TiO 2 visible light absorbability.Yet these methods are difficult to both improve the TiO 2 visible light absorbability simultaneously, reduce the right recombination rate in light induced electron hole again.In addition, reclaim, reuse for the ease of the separation of catalyst, many researchers are fixed on titanium dioxide on the suitable carriers, studies show that TiO
2Photocatalytic activity and its surface nature and used carrier closely related, as employing have high surface area, as carrier, effect is better for porous inert adsorbent (active carbon, silica, diatomite etc.).But these methods are difficult to both improve simultaneously the TiO 2 visible light absorbability, reduce the right recombination rate in light induced electron hole, and the separation of being convenient to catalyst is again reclaimed, recycling.
Summary of the invention
The object of the present invention is to provide a kind of absorbability to visible light strong, the light induced electron hole is low to recombination rate, separates the cerium doped titanium dioxide/silica gel composite photo-catalyst that reclaims and reuse easily.
Another object of the present invention provides the preparation method of above-mentioned cerium doped titanium dioxide/silica gel composite photo-catalyst.
Cerium doped titanium dioxide of the present invention/silica gel composite photo-catalyst, wherein the molar percentage of cerium is 0.01～1%, and the molar percentage of titanium dioxide is 99～99.99%, and the cerium doped titanium dioxide back loading forms composite photo-catalyst on silica gel.This composite photo-catalyst has visible light activity, can be by the excited by visible light of wavelength 387～500 nanometers.Trivalent cerium and quadrivalent cerium exist simultaneously, and this variable valence state makes cerium have good electronics transfer characteristic, optical excitation TiO in composite catalyst
2The e that forms
-The Ce that is easy to be doped
4+Catch and generate Ce
3+, Ce
4+Play e
-The effect of trapping agent: Ce
4++ e
-→ Ce
3+e
-By Ce
4+After catching, difficulty and h
+Compound, thus e promoted effectively
-With h
+Separation, improved TiO
2Photocatalytic activity.Cerium doped titanium dioxide is fixed on the recycling of being convenient to photochemical catalyst on the silica-gel carrier.
The preparation method of above-mentioned cerium doped titanium dioxide/silica gel composite photo-catalyst comprises the steps:
(1) absolute ethyl alcohol and diethanol amine are added in positive four butyl esters of metatitanic acid, stir, form light yellow or colourless solution, slowly splash into redistilled water, add ammonium ceric nitrate, stir, obtain colloidal sol; Add polyethylene glycol, keep 35～45 ℃ of dissolvings down of temperature, continue to stir, obtain yellowish or reddish colloidal sol;
(2) add silica gel, stir, suction filtration, 55～70 ℃ of oven dry obtain the Ce-TiO of load one deck doped with cerium titanium dioxide
2/ material silica gel composite;
(3) 400～500 ℃ of roastings of gained composite, make cerium doped titanium dioxide/silica gel composite photo-catalyst.
In above-mentioned preparation method, step (2) gained composite can be joined in the colloidal sol, stir, suction filtration, 60 ℃ of oven dry obtain the Ce-TiO of the two-layer doped with cerium titanium dioxide of load
2/ material silica gel composite is carried out step (3) again, thereby obtains cerium doped titanium dioxide/silica gel composite photo-catalyst.Perhaps with the Ce-TiO of the two-layer doped with cerium titanium dioxide of load
2/ material silica gel composite joins in the colloidal sol, stirs, and suction filtration, 60 ℃ of oven dry obtain the Ce-TiO of three layers of doped with cerium titanium dioxide of load
2/ material silica gel composite is carried out step (3) again, thereby obtains cerium doped titanium dioxide/silica gel composite photo-catalyst.
Compared with prior art, the present invention has following beneficial effect.
Support type cerium doped titanium dioxide provided by the invention/silica gel composite photo-catalyst, adopt the sol-gel manufactured, the visible absorption ability that it has improved titanium dioxide has reduced the right recombination rate in light induced electron hole, thereby improves the speed of photocatalysis degradation organic contaminant.In addition, this photochemical catalyst also separates recovery, recycling easily.The aspects such as improvement, medical and health and chemical synthesis that can be used for organic pollution in the water and air.
Description of drawings
Fig. 1 is the Ce 3d energy level spectrogram of 1% cerium doped titanium dioxide/silica gel composite photo-catalyst;
Fig. 2 is the reflectance spectrum figure of different cerium doped titanium dioxides/silica gel photochemical catalyst;
Fig. 3 is the influence of calcining heat PARA FORMALDEHYDE PRILLS(91,95) photocatalytic degradation;
Fig. 4 is the influence of cerium doping PARA FORMALDEHYDE PRILLS(91,95) photocatalytic degradation.
Wherein, among Fig. 1, abscissa is binding energy/electron-volt, and ordinate is a spectral strength; As can be seen from Figure 1, Ce 3d energy level spectrum is very complicated, and cerium is mainly with Ce
4+Exist, and a small amount of Ce is arranged
3+, have Ce in this explanation composite photo-catalyst
3+And Ce
4+Since signal too a little less than, can't accurately measure the cerium content of different valence state.
Among Fig. 2, abscissa is wavelength/nanometer, and ordinate is reflectivity/R%;
A:TiO
2, B:0.01%, C:0.1%; Curve A, B, C represent photochemical catalyst sample A (pure TiO respectively
2), the reflectance spectrum of B (0.01%), C (0.1%), represent the ultraviolet-visible spectrum absorbability of photochemical catalyst.
Among Fig. 3, abscissa be time/minute, ordinate is ln (c
0/ c);
C：-●-500℃，D：-▲-600℃，B：-□-400℃
Curve B, C, D represent the 0.1% cerium doped titanium dioxide/silica gel photocatalyst of 400 ℃, 500 ℃, 600 ℃ calcinings respectively;
Among Fig. 4, abscissa be time/minute, ordinate is ln (c
0/ c);
F：-○-0.1％，G：-■-1％，E：-△-0.01％，A：-
-TiO
2，
Curve A is represented pure TiO
2, E, F, G represent the molar percentage 0.01%, 0.1%, 1% of cerium respectively;
The specific embodiment
Embodiment 1
39mL absolute ethyl alcohol and 2.04g diethanol amine are added in positive four butyl esters of 8.51g metatitanic acid, stir, form light yellow or colourless solution, slowly splash into the 0.5mL redistilled water, add the 13.7mg ammonium ceric nitrate, stir 1h, obtain colloidal sol, add 0.25g polyethylene glycol (PEG4000), keep 40 ℃ of dissolvings down of temperature, continue to stir 30min, stablized, even, as clear as crystal yellowish or reddish colloidal sol.Add the silica gel of 10g through 180 ℃ of following vacuum drying 2h, stir 30min, suction filtration puts it into drying box, in 60 ℃ of oven dry, obtains the Ce-TiO of load one deck doped with cerium titanium dioxide
2/ material silica gel composite.The gained composite is joined in the colloidal sol, stir 30min, suction filtration in 60 ℃ of oven dry, obtains the Ce-TiO of the two-layer doped with cerium titanium dioxide of load
2/ material silica gel composite.Above-mentioned material is put into muffle furnace,, make different calcining heat 0.1% cerium doped titanium dioxides/silica gel composite photo-catalyst respectively at 400 ℃, 500 ℃, 600 ℃ roasting 1h.
Test the influence of different calcining heat PARA FORMALDEHYDE PRILLS(91,95) photocatalytic degradations; As shown in Figure 3, calcining heat is 500 ℃, and 0.1% cerium doped titanium dioxide/silica gel photocatalytic activity is the highest.
Embodiment 2
39mL absolute ethyl alcohol and 2.04g diethanol amine are added in positive four butyl esters of 8.51g metatitanic acid, stir, form light yellow or colourless solution, slowly splash into the 0.5mL redistilled water, be 0.01,0.1,1.0 according to molar content respectively, add 1.4mg, 13.7mg, 138.4mg ammonium ceric nitrate respectively, stir 1h, obtain colloidal sol, add 0.25g polyethylene glycol (PEG4000), keep 40 ℃ of dissolvings down of temperature, continue to stir 30min, stablized, even, as clear as crystal yellowish or reddish colloidal sol.Add 10g through 180 ℃ of following vacuum drying 2h silica gel, stir 30min, suction filtration puts it into drying box, in 60 ℃ of oven dry, obtains the Ce-TiO of load one deck doped with cerium titanium dioxide
2/ material silica gel composite.The gained composite is joined in the colloidal sol, stir 30min, suction filtration in 60 ℃ of oven dry, obtains the Ce-TiO of the two-layer doped with cerium titanium dioxide of load
2/ material silica gel composite.Above-mentioned material is put into muffle furnace,, make the cerium doped titanium dioxide/silica gel composite photo-catalyst of different cerium contents in 500 ℃ of roasting 1h.
Test the reflectance spectrum figure of different cerium doped titanium dioxides/silica gel photochemical catalyst, as shown in Figure 2.As shown in Figure 2, after the titanium dioxide doped with cerium, the cerium doped titanium dioxide/reflectivity of silica gel composite photo-catalyst in 360～500 nanometer range reduced significantly.Reflectivity reduces to illustrate that the absorbing properties of cerium doped titanium dioxide/silica gel composite photo-catalyst has improved, and has strengthened the absorption to visible light, the corresponding raising of photocatalytic activity.0.1%Ce-TiO
2/ silica gel absorbs the obvious red shift of sideband, and absorption spectrum and sunshine comparatively mate, and can utilize solar energy better, and this practical application for photocatalytic method is very important.
Embodiment 3
The employing volume is that 800 milliliters cylinder glass infuser is a reactor, adds the formalin that the 400mL initial concentration is 5ppm therein, adds the 0.50g photochemical catalyst, charges into air and stirs, and constitutes uniform suspension system.A luminous stable high-pressure sodium lamp of 250 watts (Asia, Beijing is bright) is inserted the reactor centre, fixing.Again reactor is placed in the condensation pond.Pick up counting then and carry out photocatalytic degradation, every the 10min sample analysis.Sample is through centrifugation, and concentration of formaldehyde is measured and adopted the acetylacetone,2,4-pentanedione photometry.At 721 type spectrophotometers is that its absorbance is measured in reference at wavelength 414nm place with water, and concentration of formaldehyde c is directly proportional with the absorbance A value.According to ln (c
0/ c) come the activity of more different photochemical catalysts with the change curve of light application time.
As shown in Figure 4, the cerium doping is when 0.01～1% (molar content) scope, and the cerium doped titanium dioxide/activity of silica gel composite photo-catalyst all is higher than the activity of pure titinium dioxide/silica gel.But photocatalytic activity is not directly proportional with the cerium doping, and photocatalytic activity increases with the cerium doping and improves, and along with the further increase of cerium doping, photocatalytic activity reduces on the contrary, and best cerium doping is 0.1%.
Claims (4)
1. the preparation method of cerium doped titanium dioxide/silica gel composite photo-catalyst, described composite photo-catalyst is that the cerium doped titanium dioxide back loading forms composite photo-catalyst on silica gel, wherein the molar percentage of cerium is 0.01～1%, and the molar percentage of titanium dioxide is 99～99.99%; It is characterized in that described preparation method comprises the steps:
(1) absolute ethyl alcohol and diethanol amine are added in positive four butyl esters of metatitanic acid, stir, form light yellow or colourless solution, slowly splash into redistilled water, add ammonium ceric nitrate, stir, obtain colloidal sol; Add polyethylene glycol, keep 35～45 ℃ of dissolvings down of temperature, continue to stir, obtain yellowish or reddish colloidal sol;
(2) add silica gel, stir, suction filtration, 55～70 ℃ of oven dry obtain the Ce-TiO of load one deck doped with cerium titanium dioxide
2/ material silica gel composite;
(3) 400～500 ℃ of roastings of gained composite, make cerium doped titanium dioxide/silica gel composite photo-catalyst.
2. preparation method as claimed in claim 1 is characterized in that step (2) gained composite is joined in the colloidal sol, stirs, and suction filtration, 60 ℃ of oven dry obtain the Ce-TiO of the two-layer doped with cerium titanium dioxide of load
2/ material silica gel composite.
3. preparation method as claimed in claim 2 is characterized in that the Ce-TiO with the two-layer doped with cerium titanium dioxide of the load that makes
2/ material silica gel composite joins in the colloidal sol, stirs, and suction filtration, 60 ℃ of oven dry obtain the Ce-TiO of three layers of doped with cerium titanium dioxide of load
2/ material silica gel composite.
4. cerium doped titanium dioxide/silica gel composite photo-catalyst that the described preparation method of claim 1 makes.
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| CN102641731B (en) * | 2011-02-22 | 2014-04-02 | 上海华明高技术（集团）有限公司 | Active carbon fiber load calcium-doping titanium dioxide (TiO2) photocatalyst and preparation method of photocatalyst |
| CN102716735B (en) * | 2012-06-25 | 2014-04-30 | 常州大学 | Preparation method of ATP/ Ce-Ti sold soluble oxide composite material |
| CN104941407A (en) * | 2015-06-04 | 2015-09-30 | 李雪涛 | Composite formaldehyde absorption remover |
| CN108854516A (en) * | 2018-05-31 | 2018-11-23 | 安徽科浦环保科技有限公司 | A kind of preparation method of indoor highly effective formaldehyde scavenger |
| CN110548500A (en) * | 2019-09-05 | 2019-12-10 | 刘美端 | Photocatalyst, preparation method thereof and air purifying agent |
| CN111589438B (en) * | 2020-06-29 | 2023-06-02 | 沈阳三聚凯特催化剂有限公司 | Catalyst carrier and preparation method and application thereof |
| CN112844436B (en) * | 2021-01-27 | 2022-05-17 | 宁波方太厨具有限公司 | Catalyst for removing formaldehyde and carbon monoxide by catalysis and preparation method thereof |
| CN114570348B (en) * | 2022-03-02 | 2024-03-12 | 济南大学 | Titanium dioxide-based nano composite photocatalyst for photocatalytic degradation by irradiation of visible light and application thereof |
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Non-Patent Citations (4)
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| Ce2O-TiO2 /SiO2的制备及除氟性能研究. 颜秀如等.中国稀土学报，第16卷第2期. 1998 |
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