CN101537348A - Energy-converting photocatalysis nanophase material and preparation method thereof - Google Patents
Energy-converting photocatalysis nanophase material and preparation method thereof Download PDFInfo
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- CN101537348A CN101537348A CN200910031169A CN200910031169A CN101537348A CN 101537348 A CN101537348 A CN 101537348A CN 200910031169 A CN200910031169 A CN 200910031169A CN 200910031169 A CN200910031169 A CN 200910031169A CN 101537348 A CN101537348 A CN 101537348A
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Abstract
The invention discloses an energy-converting photocatalysis nano material and a preparation method thereof. Firstly, 0.02-3.5 mol.L<-1> titanium tetrachloride is used as the raw material, and one or two oxides of the rare earth elements of Yb, Er, Ho and Tm are mixed with the titanium tetrachloride. The mixed rare earth oxides account for 0.01-20 percent of the total weight. The mixed solution is subject to hydrolysis for 20-480 minutes at a temperature of 20-90 DEG C. Then, the mixed solution is extracted by means of an organic extraction method with organic amine so as to remove the Cl<-> in the solution and obtain anatase type nanometer titanium dioxide gel containing rare earth elements, and the titanium dioxide gel is aged for 2-48 hours. Finally, the titanium dioxide gel undergoes hydrothermal crystallization at a temperature of 120-240 DEG C so as to obtain the nano energy-converting photocatalysis material. In the invention, through energy conversion, part of the visible light, which is absorbed by the anatase type titanium dioxide, is converted into ultraviolet energy to be absorbed, without reducing forbidden gap, thereby improving the utilization rate of the visible light by a titanium dioxide photocatalyst, being capable of realizing the industrialization production of titanium tetrachloride hydrolysis and avoiding particle aggregation possibly generated by high-temperature calcining.
Description
Technical field
The present invention relates to a kind of preparation method who under visible light, has the anatase-type nanometer titanium dioxide of photocatalytic activity.
Background technology
With the titanium tetrachloride is the anatase titanium dioxide (TiO of the different-grain diameter of primary raw material preparation
2) have a photocatalysis performance, when titanium dioxide nanoparticle size during less than a certain critical dimension, the oxidability in light induced electron and hole is increased sharply, can the most of organic matters of oxidation.Simultaneously, titanium dioxide has stable, the nontoxic and free of contamination advantage of chemical property, is widely used in the harmless treatment of indoor air purification, natural water body and industrial wastewater.
In the preparation and use of anatase-type nanometer titanium dioxide as photochemical catalyst, two key technical problems are arranged: the one, the anatase titanium dioxide energy gap is 3.2ev, absorb the energy light wavelength that is complementary with energy gap be located at ultraviolet region (λ＜387nm), (sunlight wavelength is 460～500nm) to have reduced photocatalysis efficiency in natural daylight; The 2nd, in preparation anatase-type nanometer titanium dioxide method, be the sol-gel process of raw material if adopt the higher metatitanic acid fourth fat of cost, its gel needs to finish crystallization 500～600 ℃ of calcinings, produces the reunion of nano particle inevitably; If adopt the preparation of the lower-cost titanium tetrachloride hydrolysis method or the titanium sulfate precipitation method, need be to behind unbodied titanium dioxide (titanic acid-sol) cyclic washing, again at 500～600 ℃ of calcined crystallizations, except the reunion of nano particle, because unbodied titanium dioxide granule degree is very little, be close to colloid, washing is difficulty very, is difficult to promote in suitability for industrialized production.
At present, the method that improves the catalytic efficiency of anatase-type nanometer titanium dioxide in sunshine mainly is to reduce the titanium dioxide energy gap, increase blemish by metal ion or metal oxide, with light absorbing wave band red shift, for example: the patent No. is that 200410033800.x, name are called " having titanium deoxid film of high catalytic activity and preparation method thereof under visible light ", and doping lithium salts and antimonic salt have prepared the titanium deoxid film of high catalytic activity under the visible light.The patent No. is 03158740.2, name is called " having visible light-responded photochemical catalyst and its production and application ", has prepared by major element such as doped ferric oxide, rubidium oxide and nickel oxide and oxidation of interim metal to have the corresponding photochemical catalyst of visible light.The patent No. is 200410059680.0, name is called " preparation method of visible-light response type photocatalyst of titanium dioxide indoor air purification agent ", and metal oxide has mixed.Number of patent application is 200410022019.2, name is called " composite photocatalyst anti-biotic material of a kind of excited by visible light and preparation method thereof cerium oxide that mixed.Patent 200410066813.7, name are called " preparation method of visual responsing titania light catalyst ", and the nitrogen element that mixed has all prepared visible light-responded photochemical catalyst.Above-mentioned publication no doubt can reduce the titanium dioxide energy gap by mixing, make the absorption bands part red shift that is complementary to visible light wave range, but its defective is: the minimizing of energy gap will reduce the oxidation-reduction potential of titanium dioxide, weakens the organic ability of its oxidation Decomposition.
Summary of the invention
The present invention seeks to overcoming the deficiencies in the prior art, a kind of last switching energy effect that has is provided, can under visible light, have the anatase-type nanometer titanium dioxide catalysis material of photocatalytic activity.
Another object of the present invention provides to be had last switching energy effect, can have the preparation method of the anatase-type nanometer titanium dioxide catalysis material of photocatalytic activity under visible light.
For achieving the above object, the technical scheme that energy-converting photocatalysis nanophase material of the present invention adopts is: doped with rare-earth elements Yb in anatase-type nanometer titanium dioxide, Er, Ho, the percentage that one or both of the oxide of Tm, Doped Rare Earth oxide account for gross weight is 0.01～20%.
The preparation method of above-mentioned energy-converting photocatalysis nanophase material is: be 0.02～3.5mol.L with concentration earlier
-1Titanium tetrachloride is a raw material, doped with rare-earth elements Yb, Er, Ho, one or both in the oxide of Tm; With the hydrolysis 20～480 minutes under 20～90 ℃ temperature of above-mentioned mixed solution, with the organic extraction method that contains organic amine mixed solution is extracted again, remove the Cl in the solution
-, obtain containing the anatase-type nanometer titanium dioxide gel of rare earth element, ageing 2～48 hours; At last with titania gel at 120～240 ℃ of hydrothermal crystallizings, obtain nanometer energy-converting photocatalysis material.
After adopting technique scheme, the present invention compared with prior art has following advantage:
1, the rare earth element of transition effects combination on the present invention has mixed in anatase titania and had, on the titanium oxide matrix, absorb a plurality of energy photons (visible light wave range), emission high-energy photons (ultraviolet light wave band), making anatase titanium dioxide absorption portion visible light be converted to uv energy by power conversion is absorbed and does not lower its energy gap, improved the utilization ratio of titanium dioxide optical catalyst to visible light.
2, utilize organic amine extraction system extraction titanium tetrachloride hydrolysis to produce a large amount of hydrochloric acid, minimum can be with Cl in the solution
-Concentration be reduced to 10
-7Mol.L
-1, avoided aligning the washing of metatitanic acid colloid, realize the suitability for industrialized production of titanium tetrachloride hydrolysis method.
3, the gel that utilizes hydro-thermal reaction crystallization titanium tetrachloride hydrolysis to obtain, the preparation nano-anatase titanium oxide has been avoided the issuable particle aggregation of high-temperature calcination.
Description of drawings
The invention will be further described below in conjunction with the drawings and specific embodiments.
Fig. 1 is the uv-visible absorption spectra of not rare earth doped oxide anatase titania catalysis material.Ordinate among the figure is light transmittance (T/%), and abscissa is lambda1-wavelength (λ, nm);
Fig. 2 is the uv-visible absorption spectra of the energy-converting photocatalysis material of the embodiment of the invention 1, and the ordinate among the figure is light transmittance (T/%), and abscissa is lambda1-wavelength (λ, nm);
Fig. 3 is the power conversion nano-photocatalyst material stereoscan photograph of the embodiment of the invention 1 preparation.
The specific embodiment
In anatase-type nanometer titanium dioxide, be doped with the oxide of rare earth element, doped with rare-earth elements Yb, Er, Ho, one or both of the oxide of Tm, promptly the Doped Rare Earth element can be the oxide of Yb and Er, also can be the oxide of Yb and Ho, can also be the oxide of Yb and Tm, the percentage that the oxide weight of rare earth element accounts for whole mixed solution gross weight is 0.01～20%.During preparation, be 0.02～3.5mol.L with concentration earlier
-1Titanium tetrachloride is a raw material, doped with rare-earth elements Yb, and Er, Ho, one or both in the oxide of Tm, doping percentage by weight are 0.01～20%; With the hydrolysis 20～480 minutes under 20～90 ℃ temperature of above-mentioned mixed solution, with the organic extraction method that contains organic amine mixed solution is extracted again, organic amine wherein is the fat tertiary amine class, molecular weight is 200～600.The used diluent of extracting process is alkane or compound fragrant hydrocarbon; Back washing agent is the inorganic base that comprises ammoniacal liquor, NaOH and potassium hydroxide.Just can remove Cl in the solution after the extraction
-, Cl
-Content is 0.1～1 * 10
-7Mol.L
-1Obtain containing the anatase-type nanometer titanium dioxide gel of rare earth element, with this titania gel ageing 2～48 hours,, can obtain nanometer energy-converting photocatalysis material of the present invention at last with the crystallization after 120～240 ℃ of hydro-thermal reactions of the titania gel after the ageing.
Below in conjunction with accompanying drawing 1-3 and 4 embodiment the present invention is described:
Embodiment 1
Analytically pure titanium tetrachloride solution 112mL is put into there-necked flask, drip distilled water 388mL in ice bath, temperature is no more than 20 ℃.Obtaining concentration approximately is the titanium dioxide storing solution (solution I) of 2mol/L.Get solution I 20mL, take by weighing ytterbium oxide 0.0652 gram, erbium oxide 0.0652 gram after the stirring and dissolving, adds 100ml distilled water.50 ℃ of following constant temperature hydrolysis 4 hours, obtain clear solution.With toluene and trioctylamine (volume ratio is 2: the 1) clear solution that is extractant after normal temperature concussion extraction said hydrolyzed 15 minutes.Water phase separated and organic facies, organic facies is shaken back extraction with 10% NaOH 20mL at normal temperature, and the organic facies that obtains can be used repeatedly.Up to the pH of water value 6.5～7.Ageing 24 hours, obtain transparent anatase-type nanometer titanium dioxide gel, get about 50 grams of this titania gel, join in the hydrothermal reaction kettle, adding distil water is to reactor 70%, under 200 ℃, hydro-thermal reaction 6 hours, cool to room temperature, drive still, Solid-Liquid Separation after 100ml distilled water washing 3 times, is drying to obtain power conversion nano-titanium oxide catalysis material under 105 ℃.In the above-mentioned power conversion nano-titanium oxide catalysis material, the titanium dioxide percentage by weight is 97.8%, and the ytterbium oxide percentage by weight is 2%, and the erbium oxide percentage by weight is 0.2%.
Above-mentioned power conversion nano-titanium oxide catalysis material 1.5g is put in the 100ml methyl orange solution that concentration is 20mg/L, under solar light irradiation, stir about 6 hours, the methyl orange degradation rate reaches more than 99%.See that Fig. 1 is the uv-visible absorption spectra of not rare earth doped oxide anatase titania catalysis material, Fig. 2 is the uv-visible absorption spectra by the energy-converting photocatalysis nanophase material light of above-mentioned condition preparation, and Fig. 3 is the energy-converting photocatalysis nanophase material stereoscan photograph (SEM) by above-mentioned condition preparation.
Embodiment 2
Get the solution I 20mL among the embodiment 1, take by weighing ytterbium oxide 0.0652 gram, holimium oxide 0.0652 gram after the stirring and dissolving, adds 80ml distilled water.60 ℃ of following constant temperature hydrolysis 3 hours, obtain clear solution.With toluene and trioctylamine (volume ratio is 2: the 1) clear solution that is extractant after normal temperature concussion extraction said hydrolyzed 15 minutes.Water phase separated and organic facies, organic facies is shaken back extraction with 10% NaOH 20mL at normal temperature, and the organic facies that obtains can be used repeatedly.Up to the pH of water value 6.5～7.Ageing 24 hours, obtain transparent anatase-type nanometer titanium dioxide gel, get about 50 grams of this titania gel, join in the hydrothermal reaction kettle, adding distil water is to reactor 70%, under 200 ℃, hydro-thermal reaction 6 hours, cool to room temperature, drive still, Solid-Liquid Separation after 100ml distilled water washing 3 times, is drying to obtain power conversion nano-titanium oxide catalysis material under 105 ℃.In the above-mentioned power conversion nano-titanium oxide catalysis material, the titanium dioxide percentage by weight is 97.8%, and the ytterbium oxide percentage by weight is 2%, and the holimium oxide percentage by weight is 0.2%.
Above-mentioned power conversion nano-titanium oxide catalysis material 1.5g is put in the 100ml methyl orange solution that concentration is 20mg/L, under solar light irradiation, stir about 6 hours, the methyl orange degradation rate reaches more than 99%.
Embodiment 3
Get the solution I 20mL among the embodiment 1, take by weighing ytterbium oxide 0.0652 gram, thulium oxide 0.0652 gram after the stirring and dissolving, adds 80ml distilled water.50 ℃ of following constant temperature hydrolysis 4 hours, obtain clear solution.With toluene and trioctylamine (volume ratio is 2: the 1) clear solution that is extractant after normal temperature concussion extraction said hydrolyzed 15 minutes.Water phase separated and organic facies, organic facies is shaken back extraction with 10% NaOH 20mL at normal temperature, and the organic facies that obtains can be used repeatedly.Up to the pH of water value 6.5～7.Ageing 24 hours, obtain transparent anatase-type nanometer titanium dioxide gel, get about 50 grams of this titania gel, join in the hydrothermal reaction kettle, adding distil water is to reactor 70%, under 240 ℃, hydro-thermal reaction 3 hours, cool to room temperature, drive still, Solid-Liquid Separation after 100ml distilled water washing 3 times, is drying to obtain power conversion nano-titanium oxide catalysis material under 105 ℃.In the wherein above-mentioned power conversion nano-titanium oxide catalysis material, the titanium dioxide percentage by weight is 97.8%, and the ytterbium oxide percentage by weight is 2%, and the thulium oxide percentage by weight is 0.2%.
Above-mentioned power conversion nano-titanium oxide catalysis material 1.5g is put in the 100ml methyl orange solution that concentration is 20mg/L, under solar light irradiation, stir about 6 hours, the methyl orange degradation rate reaches more than 99%.
Embodiment 4
Get the solution I 20mL among the embodiment 1, erbium oxide 0.0652 gram after the stirring and dissolving, adds 80ml distilled water 40 ℃ of following constant temperature hydrolysis 5 hours, obtains clear solution.With toluene and trioctylamine (volume ratio is 2: the 1) clear solution that is extractant after normal temperature concussion extraction said hydrolyzed 15 minutes.Water phase separated and organic facies, organic facies is shaken back extraction with 10% NaOH20mL at normal temperature, and the organic facies that obtains can be used repeatedly.Up to the pH of water value 6.5～7.Ageing 24 hours, obtain transparent anatase-type nanometer titanium dioxide gel, get about 50 grams of this titania gel, join in the hydrothermal reaction kettle, adding distil water is to reactor 70%, under 160 ℃, hydro-thermal reaction 12 hours, cool to room temperature, drive still, Solid-Liquid Separation after 100ml distilled water washing 3 times, is drying to obtain power conversion nano-titanium oxide catalysis material under 105 ℃.In the above-mentioned power conversion nano-titanium oxide catalysis material, wherein the titanium dioxide percentage by weight is 98%, and the erbium oxide percentage by weight is 2%.
Above-mentioned power conversion nano-titanium oxide catalysis material 1.5g is put in the 100ml methyl orange solution that concentration is 20mg/L, under solar light irradiation, stir about 10 hours, the methyl orange degradation rate reaches more than 99%.
Claims (4)
1, a kind of energy-converting photocatalysis nanophase material, it is characterized in that: this photocatalysis nano material is doped with rare-earth elements Yb in anatase-type nanometer titanium dioxide, Er, Ho, the percentage that one or both of the oxide of Tm, Doped Rare Earth oxide account for gross weight is 0.01～20%.
2, a kind of preparation method of energy-converting photocatalysis nanophase material as claimed in claim 1 is characterized in that: be 0.02～3.5mol.L with concentration earlier
-1Titanium tetrachloride is a raw material, doped with rare-earth elements Yb, Er, Ho, one or both in the oxide of Tm; With the hydrolysis 20～480 minutes under 20～90 ℃ temperature of above-mentioned mixed solution, with the organic extraction method that contains organic amine mixed solution is extracted again, remove the Cl in the solution
-, obtain containing the anatase-type nanometer titanium dioxide gel of rare earth element, ageing 2～48 hours; At last this titania gel is got final product at 120～240 ℃ of hydrothermal crystallizings.
3, preparation method according to claim 2 is characterized in that: described organic amine is the fat tertiary amine class, and molecular weight is 200～600.
4, preparation method according to claim 2 is characterized in that: the used diluent of extracting process is alkane or compound fragrant hydrocarbon; Back washing agent is the inorganic base that comprises ammoniacal liquor, NaOH and potassium hydroxide.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101947469A (en) * | 2010-08-30 | 2011-01-19 | 浙江工业大学 | Novel visible light catalyst capable of promoting degradation of organic pollutants and use thereof |
| CN104275182A (en) * | 2014-09-19 | 2015-01-14 | 安徽工程大学 | Titanium dioxide/copper oxide nano composite material, as well as preparation method and application thereof |
| CN105688886A (en) * | 2016-03-07 | 2016-06-22 | 山东源根化学技术研发有限公司 | Preparing method of water-soluble visible-light response photocatalysis degradation agent |
| CN110314447A (en) * | 2019-08-07 | 2019-10-11 | 安徽元琛环保科技股份有限公司 | A kind of preparation method of automatically cleaning dust removal and filtration material and filtering material obtained |
-
2009
- 2009-04-24 CN CN200910031169A patent/CN101537348A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101947469A (en) * | 2010-08-30 | 2011-01-19 | 浙江工业大学 | Novel visible light catalyst capable of promoting degradation of organic pollutants and use thereof |
| CN101947469B (en) * | 2010-08-30 | 2012-01-18 | 浙江工业大学 | Novel visible light catalyst capable of promoting degradation of organic pollutants and use thereof |
| CN104275182A (en) * | 2014-09-19 | 2015-01-14 | 安徽工程大学 | Titanium dioxide/copper oxide nano composite material, as well as preparation method and application thereof |
| CN105688886A (en) * | 2016-03-07 | 2016-06-22 | 山东源根化学技术研发有限公司 | Preparing method of water-soluble visible-light response photocatalysis degradation agent |
| CN110314447A (en) * | 2019-08-07 | 2019-10-11 | 安徽元琛环保科技股份有限公司 | A kind of preparation method of automatically cleaning dust removal and filtration material and filtering material obtained |
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Open date: 20090923 |