CN1194813C - Method of preparing SnO2 cladded Tio2 nano particle photocatalyst - Google Patents

Method of preparing SnO2 cladded Tio2 nano particle photocatalyst Download PDF

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CN1194813C
CN1194813C CNB03105160XA CN03105160A CN1194813C CN 1194813 C CN1194813 C CN 1194813C CN B03105160X A CNB03105160X A CN B03105160XA CN 03105160 A CN03105160 A CN 03105160A CN 1194813 C CN1194813 C CN 1194813C
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nano particle
photochemical catalyst
filter cake
reactant liquor
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CN1454709A (en
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徐明霞
鄂磊
汪成建
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Tianjin University
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Tianjin University
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Abstract

The present invention discloses a method for preparing SnO2 cladded TiO2 nanometer particle photocatalyst. The aim of the present invention is to provide a method for preparing SnO2 cladded TiO2 nanometer particle photocatalyst with low cost and short technical cycle. The present invention adopts TiOSO4 inorganic salts and SnCl2 inorganic salts as raw materials, aqueous ammonia with different concentrations is successively adopted as a precipitating agent, a non-ionic dispersing agent and an anionic dispersing agent are respectively added in the precipitation process, a proper quantity of macromolecular surface active agents is added into obtained products before the obtained products are dried, and the obtained products are treated by thermal treatment and ball milling to obtain composite powder. The obtained composite powder of the present invention has primary particle size smaller than 20 nanometers, good dispersivity, high activity, obvious photocatalytic degradation effect on common organic substances in water and air, high ultraviolet screening capability and capability of being used for preparing weathering self-cleaning high-performance nanometer paint, and is suitable for preparing nanometer multifunctional ceramic powder.

Description

Preparation SnO 2Coat TiO 2The method of nano particle photochemical catalyst
Technical field
The present invention relates to a kind of preparation method of nano particle photochemical catalyst, relate to a kind of single dispersion of step-by-step precipitation method preparation, high activity SnO of utilizing in particular 2Coat TiO 2The method of nano particle photochemical catalyst.
Background technology
SnO 2Coat TiO 2Sol-gel technology and coprecipitation technology are used in the preparation of composite granule usually.Sol-gel technology, its expensive raw material price is difficult for obtaining; And the distribution of particles of coprecipitation technology gained powder is inhomogeneous, and powder particle particle diameter broad, makes powder active lower.
Summary of the invention
The present invention is in order to overcome weak point of the prior art, provides that a kind of preparation cost is low, process cycle short, the preparation SnO that its lytic activity is high 2Coat TiO 2The method of nano particle photochemical catalyst.
The present invention is achieved by following technical proposals: the non-ionic dispersing agent that adds 2-5wt% in distilled water; Be heated to 38～45 ℃, drip the TiOSO of 0.5-0.8mol/L simultaneously 4With the ammoniacal liquor of 6N, stirring and adjusting also keeps pH 4.8～5.5; Dropwising the back continues to stir and be incubated 0.5～1 hour down at 38～45 ℃; Continuation adds the anionic dispersing agent of 0.5～2.0wt% in reactant liquor, drip 0.5～1.0N ammoniacal liquor and 0.5-1.5mol/L SnCl simultaneously 2, regulate rate of addition and make pH 4.8～5.5; 38～45 ℃ of insulations 1 hour; Reactant liquor is carried out decompress filter, and the filter cake that obtains is washed with deionized water; In filter cake, add the 2-5wt% molecules surfactant; Then that filter cake is following dry 3～5 hours at 80～100 ℃; The product of drying was dry grinded 0.5～1 hour; The ball milling product was calcined 0.5～1 hour at 380～700 ℃, obtained SnO 2Coat TiO 2Nano particle photochemical catalyst powder.
Described non-ionic dispersing agent is PEG1000 or PEG1540, and described anionic dispersing agent is PAA1000 or PAA2000, and described molecules surfactant is O ∏-10 or PVA, uses the particle sphere grinding machine when described desciccate is dry grinded.
Technology novelty of the present invention, raw material sources are wide, product cost is low, powder primary particle size is less than 20 nanometers, and good dispersion is active high, obvious to organic matter photocatalytic degradation effect common in the water and air, have high ultraviolet screener ability, can be used for the preparation of weather-proof, self-cleaning high-performance nano coating, be suitable for preparing the multifunctional nano ceramic powder.
Technology novelty of the present invention, raw material sources are wide, product cost is low, powder primary particle size is less than 20 nanometers, and good dispersion is active high, obvious to organic matter photocatalytic degradation effect common in the water and air, have high ultraviolet screener ability, can be used for the preparation of weather-proof, self-cleaning high-performance nano coating, be suitable for preparing the multifunctional nano ceramic powder.
Fig. 1 shows 400 ℃ of following SnO 2/ TiO 2The compound particle principal crystalline phase is a rutile, all is the rutile phase in the time of 700 ℃; Common pure TiO 2Need just to occur more than 750 ℃ the rutile phase, and the SnO of other method preparation 2/ TiO 2Compound particle generally the rutile phase need just occur more than 600 ℃, this proves absolutely gained powder active height of the present invention, and crystal phase transition temperature reduces by 200～300 ℃.
Can know from Fig. 2 and see the powder good combination property that utilizes the present invention to produce, particle is nanometer not only, and size is very even, i.e. Unusually narrow particle size distribution.
Description of drawings
Fig. 1: SnO 2/ TiO 2The XRD figure of composite particles;
Fig. 2: SnO 2/ TiO 2The TEM figure of composite particles (600 ℃ are amplified 100,000 times).
The specific embodiment
The invention will be further described below in conjunction with embodiment.
At first in beaker, add 100ml distilled water, add 2～5wt% again and (account for product SnO 2/ TiO 2Middle TiO 2) non-ionic dispersing agent, thermometer bulb is heated to 38～45 ℃, drips the TiOSO of 0.5～0.8mol/L simultaneously 4With the ammoniacal liquor of 6N, stirring also keeps PH between 4.8～5.5, makes TiOSO 4Hydrolysis generates the hydrate of titanium; Dropwise the back and continue stirring and be incubated 0.5-1 hour, react fully and finish at 38～45 ℃.In reactant liquor, drip 0.5～2.0wt% and (account for product SnO 2/ TiO 2Middle SnO 2) anionic dispersing agent, drip 0.5～1.0N ammoniacal liquor and 0.5～1.5mol/L SnCl then simultaneously 2, regulate rate of addition and make PH between 4.8～5.5, dropwise the back 38～45 ℃ of insulations 0.5～1 hour, keep stirring to make SnCl 2Fully reaction; Decompress filter is used deionized water rinsing 4～7 times, and each water consumption is approximately 1/2nd of reactant liquor; In filter cake, add 2～5wt% molecules surfactant and (account for product SnO 2/ TiO 2), the filter cake that will have activating agent then is following dry 3～5 hours at 80～100 ℃; The product of drying is used particle sphere grinding machine dry grinding 0.5～1 hour; The product of will dry grinding was calcined 0.5～1 hour at 380～700 ℃, obtained SnO 2Coat TiO 2Nano particle photochemical catalyst powder.
Be preparation SnO below 2Coat TiO 2The embodiment of nano particle photochemical catalyst powder.
Embodiment 1:
Add 100ml distilled water in beaker, add the dispersant PEG1540 of 80mg again, thermometer bulb is heated to 40 ℃, drips 100ml simultaneously, the TiOSO of 0.5mol/L 4With the ammoniacal liquor of 6N, stir and maintenance PH=5, make TiOSO 4Hydrolysis generates the hydrate of titanium; Dropwise the back and continue stirring and be incubated 0.7 hour, react fully and finish at 40 ℃.In reactant liquor, add the aqueous solution 2ml that contains 8mg dispersant PAA2000, drip 0.8N ammoniacal liquor and 11ml simultaneously, 0.5mol/L SnCl 2, regulate rate of addition and make PH=5, dropwise the back 40 ℃ of insulations 1 hour, keep stirring to make SnCl 2Fully reaction; Decompress filter is used deionized water rinsing 5 times, and each water consumption is approximately 120～130ml; In filter cake, add 96mg dispersant O ∏-10, then that filter cake is following dry 5 hours at 80 ℃; The product of drying is used particle sphere grinding machine dry grinding 0.7 hour; The product of will dry grinding was calcined 0.8 hour at 450 ℃, obtained SnO 2Coat TiO 2Nano particle photochemical catalyst powder.
Embodiment 2:
Add 100ml distilled water in beaker, add the dispersant PEG1540 of 170mg again, thermometer bulb is heated to 38 ℃, drips 100ml simultaneously, the TiOSO of 0.7mol/L 4With the ammoniacal liquor of 6N, stir and maintenance PH=4.8, make TiOSO 4Hydrolysis generates the hydrate of titanium; Dropwise the back and continue stirring and be incubated 0.7 hour, react fully and finish at 38 ℃.In reactant liquor, drip the aqueous solution 2ml that contains 8mg dispersant PAA2000, drip 0.5N ammoniacal liquor and 15ml then simultaneously, 0.5mol/L SnCl 2, regulate rate of addition and make PH=4.8, dropwise the back 38 ℃ of insulations 1 hour, keep stirring to make SnCl 2Fully reaction; Decompress filter is used deionized water rinsing 4 times, and each water consumption is approximately 120～130ml; In filter cake, add 200mg dispersant PVA, then that filter cake is following dry 3 hours at 90 ℃; The product of drying is used particle sphere grinding machine dry grinding 0.5 hour; The product of will dry grinding was calcined 0.5 hour at 500 ℃, obtained SnO 2Coat TiO 2Nano particle photochemical catalyst powder.
Embodiment 3:
Add 100ml distilled water in beaker, add the dispersant PEG1000 of 280mg again, thermometer bulb is heated to 45 ℃, drips 100ml simultaneously, the TiOSO of 0.7mol/L 4With the ammoniacal liquor of 6N, stir and maintenance PH=5.5, make TiOSO 4Hydrolysis generates the hydrate of titanium; Dropwise the back and continue stirring and be incubated 1 hour, react fully and finish at 45 ℃.In reactant liquor, drip the aqueous solution 2ml that contains 17mg dispersant PAA1000, drip 1.0N ammoniacal liquor and 7.5ml then simultaneously, 1.0mol/L SnCl 2, regulate rate of addition and make PH=5.5, dropwise the back 45 ℃ of insulations 1 hour, keep stirring to make SnCl 2Fully reaction; Decompress filter is used deionized water rinsing 6 times, and each water consumption is approximately 120～130ml; In filter cake, add 330mg dispersant O ∏-10, then that filter cake is following dry 3 hours at 100 ℃; The product of drying is used particle sphere grinding machine dry grinding 1 hour; The product of will dry grinding was calcined 1 hour at 500 ℃, obtained SnO 2Coat TiO 2Nano particle photochemical catalyst powder.
Embodiment 4:
Add 100ml distilled water in beaker, add the dispersant PEG1540 of 200mg again, thermometer bulb is heated to 42 ℃, drips 100ml simultaneously, the TiOSO of 0.8mol/L 4With the ammoniacal liquor of 6N, stir and maintenance PH=5, make TiOSO 4Hydrolysis generates the hydrate of titanium; Dropwise the back and continue stirring and be incubated 1 hour, react fully and finish at 42 ℃.In reactant liquor, drip the aqueous solution 2ml that contains 17mg dispersant PAA2000, drip 0.7N ammoniacal liquor and 7ml then simultaneously, 1.2mol/L SnCl 2, regulate rate of addition and make PH=5, dropwise the back 42 ℃ of insulations 1 hour, keep stirring to make SnCl 2Fully reaction; Decompress filter is used deionized water rinsing 7 times, and each water consumption is approximately 120～130ml; In filter cake, add 300mg dispersant O ∏-10, then that filter cake is following dry 4 hours at 100 ℃; The product of drying is used particle sphere grinding machine dry grinding 1 hour; The product of will dry grinding was calcined 0.5 hour at 700 ℃, obtained SnO 2Coat TiO 2Nano particle photochemical catalyst powder.
Embodiment 5:
Add 100ml distilled water in beaker, add the dispersant PEG1540 of 200mg again, thermometer bulb is heated to 45 ℃, drips 100ml simultaneously, the TiOSO of 0.8mol/L 4With the ammoniacal liquor of 6N, stir and maintenance PH=5.2, make TiOSO 4Hydrolysis generates the hydrate of titanium; Dropwise the back and continue stirring and be incubated 0.5 hour, react fully and finish at 40 ℃.In reactant liquor, drip the aqueous solution 2ml that contains 20mg dispersant PAA1000, drip 1.0N ammoniacal liquor and 10.5ml then simultaneously, 0.8mol/L SnCl 2, regulate rate of addition and make PH=5.2, dropwise the back 45 ℃ of insulations 1 hour, keep stirring to make SnCl 2Fully reaction; Decompress filter is used deionized water rinsing five times, and each water consumption is approximately 120～130ml; In filter cake, add 400mg dispersant PVA, then that filter cake is following dry 3 hours at 100 ℃; The product of drying is used particle sphere grinding machine dry grinding 0.8 hour; The product of will dry grinding was calcined 1 hour at 380 ℃, obtained SnO 2Coat TiO 2Nano particle photochemical catalyst powder.
Embodiment 6:
Add 100ml distilled water in beaker, add the dispersant PEG2000 of 200mg again, thermometer bulb is heated to 40 ℃, drips 100ml simultaneously, the TiOSO of 0.6mol/L 4With the ammoniacal liquor of 6N, stir and maintenance PH=5, make TiOSO 4Hydrolysis generates the hydrate of titanium; Dropwise the back and continue stirring and be incubated 0.7 hour, react fully and finish at 40 ℃.In reactant liquor, drip the aqueous solution 2ml that contains 12mg dispersant PAA2000, drip 0.8N ammoniacal liquor and 7ml then simultaneously, 0.9mol/L SnCl 2, regulate rate of addition and make PH=5, dropwise the back 40 ℃ of insulations 1 hour, keep stirring to make SnCl 2Fully reaction; Decompress filter is used deionized water rinsing 5 times, and each water consumption is approximately 120～130ml; In filter cake, add 170mg dispersant O ∏-10, then that filter cake is following dry 4 hours at 80 ℃; The product of drying is used particle sphere mushroom machine dry grinding 0.6 hour; The product of will dry grinding was calcined 0.5～1 hour at 550 ℃, obtained SnO 2Coat TiO 2Nano particle photochemical catalyst powder.
Embodiment 7:
Add 100ml distilled water in beaker, add the dispersant PEG1000 of 200mg again, thermometer bulb is heated to 38 ℃, drips 100ml simultaneously, the TiOSO of 0.5mol/L 4With the ammoniacal liquor of 6N, stir and maintenance PH=5, make TiOSO 4Hydrolysis generates the hydrate of titanium; Dropwise the back and continue stirring and be incubated 0.9 hour, react fully and finish at 40 ℃.In reactant liquor, drip the aqueous solution 2ml that contains 12mg dispersant PAA1000, drip 1.0N ammoniacal liquor and 9ml then simultaneously, 0.6mol/L SnCl 2, regulate rate of addition and make PH=5, dropwise the back 42 ℃ of insulations 1 hour, keep stirring to make SnCl 2Fully reaction; Decompress filter is used deionized water rinsing 5 times, and each water consumption is approximately 120～130ml; In filter cake, add 170mg dispersant O ∏-10, then that filter cake is following dry 4.5 hours at 80 ℃; The product of drying is used particle sphere grinding machine dry grinding 1 hour; The product of will dry grinding was calcined 0.8 hour at 650 ℃, obtained SnO 2Coat TiO 2Nano particle photochemical catalyst powder.
Embodiment 8:
Add 100ml distilled water in beaker, add the dispersant PEG1540 of 200mg again, thermometer bulb is heated to 45 ℃, drips 100ml simultaneously, the TiOSO of 0.7mol/L 4With the ammoniacal liquor of 6N, stir and maintenance PH=5, make TiOSO 4Hydrolysis generates the hydrate of titanium; Dropwise the back and continue stirring and be incubated 1 hour, react fully and finish at 40 ℃.In reactant liquor, drip the aqueous solution 2ml that contains 22mg dispersant PAA2000, drip 1.0N ammoniacal liquor and 5ml then simultaneously, 1.5mol/L SnCl 2, regulate rate of addition and make PH=5, dropwise the back 45 ℃ of insulations 1 hour, keep stirring to make SnCl 2Fully reaction; Decompress filter is used deionized water rinsing 5 times, and each water consumption is approximately 120～130ml; In filter cake, add 330mg dispersant O ∏-10, then that filter cake is following dry 4 hours at 90 ℃; The product of drying is used particle sphere grinding machine dry grinding 0.8 hour; The product of will dry grinding was calcined 1 hour at 600 ℃, obtained SnO 2Coat TiO 2Nano particle photochemical catalyst powder.

Claims (5)

1. one kind prepares SnO 2Coat TiO 2The method of nano particle photochemical catalyst is characterized in that, comprises the steps:
(1) non-ionic dispersing agent of adding 2-5wt% in distilled water;
(2) reactant liquor is heated to 38～45 ℃, in this reactant liquor, drips the TiOSO of 0.5-0.8mol/L simultaneously 4Regulate with the ammoniacal liquor of 6N and keep the pH of this reactant liquor to remain on 4.8～5.5;
(3) dropwising the back continues to stir and be incubated 0.5～1 hour down at 38～45 ℃;
(4) continuation adds the anionic dispersing agent of 0.5～2.0wt% in above-mentioned reactant liquor, drips 0.5～1.0N ammoniacal liquor and 0.5-1.5mol/L SnCl simultaneously 2, regulate rate of addition and make this reactant liquor pH remain on 4.8～5.5;
(5) 38～45 ℃ of insulations 0.5～1 hour; Reactant liquor is carried out decompress filter, obtain filter cake, and the filter cake that obtains is washed with deionized water;
(6) in above-mentioned filter cake, add the 2-5wt% molecules surfactant; The filter cake that will have activating agent then descended dry 3-5 hour at 80～100 ℃;
(7) product of drying was dry grinded 0.5～1 hour;
(8) product of will dry grinding was calcined 0.5～1 hour at 380～700 ℃, obtained SnO 2Coat TiO 2Nano particle photochemical catalyst powder.
2. preparation SnO according to claim 1 2Coat TiO 2The method of nano particle photochemical catalyst is characterized in that, described non-ionic dispersing agent is PEG1000 or PEG1540.
3. preparation SnO according to claim 1 2Coat TiO 2The method of nano particle photochemical catalyst is characterized in that, described anionic dispersing agent is PAA1000 or PAA2000.
4. preparation SnO according to claim 1 2Coat TiO 2The method of nano particle photochemical catalyst is characterized in that, described molecules surfactant is O ∏-10 or PVA.
5. preparation SnO according to claim 1 2Coat TiO 2The method of nano particle photochemical catalyst is characterized in that, the particle sphere grinding machine is used in described dry grinding.
CNB03105160XA 2003-03-06 2003-03-06 Method of preparing SnO2 cladded Tio2 nano particle photocatalyst Expired - Fee Related CN1194813C (en)

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Publication number Priority date Publication date Assignee Title
CN1319642C (en) * 2004-08-11 2007-06-06 天津大学 Method for preparing peroxo-titanic acid photocatalytic coating agent
CN100402467C (en) * 2005-06-03 2008-07-16 中南大学 Method for preparing Nano composite material of stannic oxide / titanium dioxide
CN100345764C (en) * 2005-08-23 2007-10-31 浙江大学 Two-step method for preparing stannic oxide nano material
CN100436375C (en) * 2006-02-09 2008-11-26 武汉理工大学 Process for preparing coated ZrB2 composite powder
CN101733133B (en) * 2009-12-10 2013-03-13 浙江大学 Titanium dioxide photocatalyst with coating layer coated on surface and preparation method thereof
CN116274330B (en) * 2023-03-22 2023-09-22 江苏暨之阳环保科技有限公司 Method for repairing organic pollutant polluted soil

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