CN101264449B - Preparation of TiO2/ZnFe2O4 magnetic composite photocatalyst - Google Patents
Preparation of TiO2/ZnFe2O4 magnetic composite photocatalyst Download PDFInfo
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- CN101264449B CN101264449B CN2008101061420A CN200810106142A CN101264449B CN 101264449 B CN101264449 B CN 101264449B CN 2008101061420 A CN2008101061420 A CN 2008101061420A CN 200810106142 A CN200810106142 A CN 200810106142A CN 101264449 B CN101264449 B CN 101264449B
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Abstract
The invention relates to a preparation method for TiO2/ZnFe2O4 magnetic complex photocatalyst, belonging to the technical field of nanometer photocatalyst material preparation, which adopts magnetic material ZnFe2O4 as carrier, requires no organic compounds or middle-tier; the magnetic material ZnFe2O4 is assembled into magnetic photocatalyst of complex nanometer grain through the method of sol-gel. The preparation method has the advantages of retaining perfect suspension property and high photocatalyst activity, and conveniently and rapidly recovering magnetic photocatalyst by means of magnetism separation technology, so as to reach the purpose of repeated recycle and utilization.
Description
Technical field
TiO
2/ ZnFe
2O
4The preparation method of magnetic composite photocatalyst belongs to the preparing technical field of nano-photo catalytic agent material.
Background technology
Since Japanese Fujishima and Honda discovery in 1970 TiO
2The monocrystalline electrode can photocatalytic hydrogen production by water decomposition since, the conductor photocatalysis technology has caused people's great interest and extensive concern.Because the environmental crisis that global industrialization brings is serious day by day; the survival and development of human society are faced with grave danger; environmental protection and sustainable development become the matter of utmost importance that human society must be considered, this makes photocatalytic degradation green, environmental protection handle the research focus that the organic pollution technology becomes the environment researcher.
TiO
2Nontoxic, stable performance, have anti-chemistry and anti-photoetch, photocatalytic activity height, water is polluted in organic matter degradation non-selectivity, mineralising thoroughly, advantage such as non-secondary pollution, be the most valued current photocatalyst oxidizes agent, have broad application prospects.TiO
2Photocatalysis performance be subjected to the influence of many-sided factor, such as density of degree of crystallinity, purity, surface area and surface hydroxyl etc., yet most important factor is the influence of crystal structure and surface area.TiO
2There are two kinds of crystal structures to be often used as photochemical catalyst most: Detitanium-ore-type and rutile-type.Detitanium-ore-type TiO
2Energy gap be 3.3eV, greater than rutile TiO
2Energy gap (3.1eV), therefore, Detitanium-ore-type TiO
2Conduction band potential more negative than rutile, easier absorption O
2, H
2Material such as O and on its surface and light induced electron or cavitation, and light induced electron or hole are more easily separated, and these factors have caused Detitanium-ore-type TiO
2Photocatalytic activity be higher than rutile TiO
2Catalytic activity.Yet, the TiO of reaction back suspended state
2With shipwreck to separate, make TiO
2Application still be restricted.Having report to adopt glass marble or glass plate is that carrier formation solid-carrying type photochemical catalyst overcomes this defective, but because TiO
2Stationarity the catalytic performance of catalyst is reduced greatly.
With TiO
2Well be assembled into the magnetic photocatalyst of composite nanometer particle with magnetisable material, both can keep good suspension property and have higher photocatalytic activity, can utilize magnetic separation technique conveniently to reclaim magnetic photocatalyst rapidly again, reach the purpose of repeatedly regeneration.Since Chen etc. has reported a kind of photochemical catalyst TiO that can separate rapidly briefly under the externally-applied magnetic field effect
2/ SiO
2/ γ-Fe
2O
3After, so far, existing Fe
3O
4, Fe
2O
3, MFe
2O
4(M=Ni, Co, Mn) and carbuncle type MFe
12O
19(M=Ba, Sr) ferrite is a magnetic nuclear, thereon or directly depositing Ti O
2, or coat behind the intermediate layer depositing Ti O again
2Report.But synthetic at present magnetic photocatalyst needs the protection in intermediate layer (as silica) usually or adds organic substance such as polymine etc.This makes synthesis technique complicated to a certain extent, has increased cost, and organic adding also causes certain harm to environment.
Summary of the invention
Purpose of the present invention just is to overcome above defective, adopts magnetic material ZnFe
2O
4Make carrier, provide a kind of sol-gel process for preparing to synthesize TiO
2/ ZnFe
2O
4Magnetic composite photocatalyst, and do not need to add any organic substance or intermediate layer.The composite photo-catalyst that this method makes both can keep good suspension property and have higher photocatalytic activity, can utilize the convenient recovery rapidly of magnetic separation technique again.
TiO of the present invention
2/ ZnFe
2O
4The sol-gel process for preparing of magnetic composite photocatalyst is characterized in that, comprises following processing step:
(1) is to add pH at 1: 2 fully to stir in 10 the NaOH aqueous solution to make 180 ℃ of its dissolvings reaction 24 hours down in molar ratio with zinc acetate and ferric nitrate, obtains ZnFe
2O
4Precipitation.
(2) ZnFe that step 1 is obtained
2O
4Precipitation 2.41 grams are scattered in 200 milliliters V
Water: V
EthanolUltrasonic dispersion was stirred 2 hours after 30 minutes in=1: 8 the ethanol water, with glacial acetic acid regulator solution pH to 5, obtained solution A.
(3) get 3.4-20.4 milliliter butyl titanate respectively and join in 20 milliliters of ethanol, stir and obtained solution B in 30 minutes.
(4) dropwise whole of the solution B that obtains in the step 3 are splashed in the solution A that step 2 obtains, fully stir 10 hours after, obtain red precipitate C through centrifugation and deionized water washing.
(5) the red precipitate C that step 4 is obtained calcines down at 200-800 ℃ and obtained required product in 4 hours.
Advantage of the present invention and effect are that raw material are cheap, are easy to get, nothing or low toxicity are pollution-free, production technology is simplified, equipment is simple relatively, and reaction temperature and energy consumption are lower, and the whole production cost is also low, be easy to carry out industrial large-scale production, and its product size is evenly distributed, good dispersion, the higher and easy recovery of photocatalysis performance.The NEW TYPE OF COMPOSITE catalysis material superior performance, the steady quality that adopt the method to make are reliable.
Description of drawings
Powder x-ray diffraction (XRD) collection of illustrative plates of Fig. 1-embodiment of the invention 1-4 products therefrom.
Fig. 2-embodiment of the invention 1,5-7 products therefrom powder x-ray diffraction (XRD) collection of illustrative plates.
The TiO that Fig. 3-embodiment of the invention 2 is prepared
2/ ZnFe
2O
4The transmission electron microscope picture of nanometer powder product.
The TiO that Fig. 4-embodiment of the invention 3 is prepared
2/ ZnFe
2O
4The transmission electron microscope picture of nanometer powder product.
Fig. 5-example 3 of the present invention (a), the prepared TiO of 7 (b)
2/ ZnFe
2O
4Nanometer powder product, and P25 (the mixed crystal type TiO that 30% rutile and 70% anatase are formed
2) (c) degradation of methylene blue curve map.
The specific embodiment
Below by embodiment the present invention is specifically described.Be necessary to be pointed out that at this present embodiment only is used for the present invention is further specified; can not be interpreted as limiting the scope of the invention, the person skilled in the art of this area can make some nonessential improvement and adjustment to the present invention according to the content of the invention described above.
Embodiment 1
(1) be to add pH at 1: 2 fully to stir in 10 the NaOH aqueous solution to make its dissolving in molar ratio with zinc acetate and ferric nitrate, 180 ℃ of reactions 24 hours down obtain ZnFe
2O
4Precipitation.
(2) ZnFe that step 1 is obtained
2O
4Precipitation 2.41 grams are scattered in 200 milliliters V
Water: V
EthanolIn=1: 8 the ethanol water, stirred 2 hours after ultrasonic 30 minutes,, obtain solution A with glacial acetic acid regulator solution pH to 5.
(3) get 3.4 milliliters of butyl titanates and join in 20 milliliters of ethanol, stir and obtained solution B in 30 minutes.
(4) dropwise whole of the solution B that obtains in the step 3 are splashed in the solution A that step 2 obtains, fully stir 10 hours after, obtain red precipitate C through centrifugation and deionized water washing.
(5) the red precipitate C that step 4 is obtained calcines down at 800 ℃ and obtained required product in 4 hours.The x-ray diffractogram of powder of product is seen Fig. 1.
Embodiment 2
(1) be to add pH at 1: 2 fully to stir in 10 the NaOH aqueous solution to make its dissolving in molar ratio with zinc acetate and ferric nitrate, 180 ℃ of reactions 24 hours down obtain ZnFe
2O
4Precipitation.
(2) ZnFe that step 1 is obtained
2O
4Precipitation 2.41 grams are scattered in 200 milliliters V
Water: V
EthanolIn=1: 8 the ethanol water, stirred 2 hours after ultrasonic 30 minutes,, obtain solution A with glacial acetic acid regulator solution pH to 5.
(3) get 6.8 milliliters of butyl titanates and join in 20 milliliters of ethanol, stir and obtained solution B in 30 minutes.
(4) dropwise whole of the solution B that obtains in the step 3 are splashed in the solution A that step 2 obtains, fully stir 10 hours after, obtain red precipitate C through centrifugation and deionized water washing.
(5) the red precipitate C that step 4 is obtained calcines down at 800 ℃ and obtained required product in 4 hours.
As Fig. 1, shown in Figure 3, products obtained therefrom is TiO
2And ZnFe
2O
4The mixing phase, and have good dispersion, the granule-morphology of particle diameter narrow distribution.The particle of about 10 nanometers of particle diameter is ZnFe
2O
4Mutually and the particle of about 30 nanometers of particle diameter is TiO
2Phase.
Embodiment 3
(1) be to add pH at 1: 2 fully to stir in 10 the NaOH aqueous solution to make its dissolving in molar ratio with zinc acetate and ferric nitrate, 180 ℃ of reactions 24 hours down obtain ZnFe
2O
4Precipitation.
(2) ZnFe that step 1 is obtained
2O
4Precipitation 2.41 grams are scattered in 200 milliliters V
Water: V
EthanolIn=1: 8 the ethanol water, stirred 2 hours after ultrasonic 30 minutes,, obtain solution A with glacial acetic acid regulator solution pH to 5.
(3) get 12.6 milliliters of butyl titanates and join in 20 milliliters of ethanol, stir and obtained solution B in 30 minutes.
(4) dropwise whole of the solution B that obtains in the step 3 are splashed in the solution A that step 2 obtains, fully stir 10 hours after, obtain red precipitate C through centrifugation and deionized water washing.
(5) the red precipitate C that step 4 is obtained calcines down at 800 ℃ and obtained required product in 4 hours.
Shown in Fig. 1,4, products obtained therefrom is rutile phase TiO
2And ZnFe
2O
4The mixing phase, and along with the increase of butyl titanate consumption, TiO in the products obtained therefrom
2Content also increase to some extent, show as TiO in the XRD figure
2The peak grow.Product has good dispersion, the granule-morphology of particle diameter narrow distribution.The particle of about 10 nanometers of particle diameter is ZnFe
2O
4Mutually and the particle of about 30 nanometers of particle diameter is TiO
2Phase.As shown in Figure 5, the photocatalysis performance of the photocatalysis performance of embodiment 3 products obtained therefroms and P25 is basic identical.
Embodiment 4
(1) be to add pH at 1: 2 fully to stir in 10 the NaOH aqueous solution to make its dissolving in molar ratio with zinc acetate and ferric nitrate, 180 ℃ of reactions 24 hours down obtain ZnFe
2O
4Precipitation.
(2) ZnFe that step 1 is obtained
2O
4Precipitation 2.41 grams are scattered in 200 milliliters V
Water: V
EthanolIn=1: 8 the ethanol water, stirred 2 hours after ultrasonic 30 minutes,, obtain solution A with glacial acetic acid regulator solution pH to 5.
(3) get 20.4 milliliters of butyl titanates and join in 20 milliliters of ethanol, stir and obtained solution B in 30 minutes.
(4) dropwise whole of the solution B that obtains in the step 3 are splashed in the solution A that step 2 obtains, fully stir 10 hours after, obtain red precipitate C through centrifugation and deionized water washing.
(5) the red precipitate C that step 4 is obtained calcines down at 800 ℃ and obtained required product in 4 hours.The x-ray diffractogram of powder of product is seen Fig. 1.
Embodiment 5
(1) be to add pH at 1: 2 fully to stir in 10 the NaOH aqueous solution to make its dissolving in molar ratio with zinc acetate and ferric nitrate, 180 ℃ of reactions 24 hours down obtain ZnFe
2O
4Precipitation.
(2) ZnFe that step 1 is obtained
2O
4Precipitation 2.41 grams are scattered in 200 milliliters V
Water: V
EthanolIn=1: 8 the ethanol water, stirred 2 hours after ultrasonic 30 minutes,, obtain solution A with glacial acetic acid regulator solution pH to 5.
(3) get 12.6 milliliters of butyl titanates and join in 20 milliliters of ethanol, stir and obtained solution B in 30 minutes.
(4) dropwise whole of the solution B that obtains in the step 3 are splashed in the solution A that step 2 obtains, fully stir 10 hours after, obtain red precipitate C through centrifugation and deionized water washing.
(5) the red precipitate C that step 4 is obtained calcines down at 200 ℃ and obtained required product in 4 hours.The x-ray diffractogram of powder of product is seen Fig. 2.
Embodiment 6
(1) be to add pH at 1: 2 fully to stir in 10 the NaOH aqueous solution to make its dissolving in molar ratio with zinc acetate and ferric nitrate, 180 ℃ of reactions 24 hours down obtain ZnFe
2O
4Precipitation.
(2) ZnFe that step 1 is obtained
2O
4Precipitation 2.41 grams are scattered in 200 milliliters V
Water: V
EthanolIn=1: 8 the ethanol water, stirred 2 hours after ultrasonic 30 minutes,, obtain solution A with glacial acetic acid regulator solution pH to 5.
(3) get 12.6 milliliters of butyl titanates and join in 20 milliliters of ethanol, stir and obtained solution B in 30 minutes.
(4) dropwise whole of the solution B that obtains in the step 3 are splashed in the solution A that step 2 obtains, fully stir 10 hours after, obtain red precipitate C through centrifugation and deionized water washing.
(5) the red precipitate C that step 4 is obtained calcines down at 400 ℃ and obtained required product in 4 hours.The x-ray diffractogram of powder of product is seen Fig. 2.
Embodiment 7
(1) be to add pH at 1: 2 fully to stir in 10 the NaOH aqueous solution to make its dissolving in molar ratio with zinc acetate and ferric nitrate, 180 ℃ of reactions 24 hours down obtain ZnFe
2O
4Precipitation.
(2) ZnFe that step 1 is obtained
2O
4Precipitation 2.41 grams are scattered in 200 milliliters V
Water: V
EthanolIn=1: 8 the ethanol water, stirred 2 hours after ultrasonic 30 minutes,, obtain solution A with glacial acetic acid regulator solution pH to 5.
(3) get 12.6 milliliters of butyl titanates and join in 20 milliliters of ethanol, stir and obtained solution B in 30 minutes.
(4) dropwise whole of the solution B that obtains in the step 3 are splashed in the solution A that step 2 obtains, fully stir 10 hours after, obtain red precipitate C through centrifugation and deionized water washing.
(5) the red precipitate C that step 4 is obtained calcines down at 600 ℃ and obtained required product in 4 hours.All the other conditions are with embodiment 1.
As Fig. 2, shown in 5, products obtained therefrom is anatase phase TiO
2And ZnFe
2O
4The mixing phase, and the photocatalysis performance of its photocatalysis performance and P25 and embodiment 3 products obtained therefroms is all basic identical.According to result of study as can be known: the TiO that nano-scale, particle size range are evenly distributed
2/ ZnFe
2O
4Powder has excellent photocatalytic performance, belongs to high-quality nanometer and closes catalyst material.
Obviously, learn from above-mentioned implementation step, data, graphic analyses, the present invention have raw material cheap, be easy to get, do not have or low toxicity pollution-free, production technology is simplified, the process conditions claimed range is wide, and reaction temperature and energy consumption are lower, and the whole production cost is also low, be easy to carry out industrial large-scale production, and its product is that nano-scale and particle diameter are evenly distributed, and does not have other organic matter and metal ion pollution, and photocatalysis performance is basic identical with P25 and can recycling use.
Claims (1)
1. TiO
2/ ZnFe
2O
4The preparation method of magnetic composite photocatalyst is characterized in that, may further comprise the steps:
(1) is to add pH at 1: 2 fully to stir in 10 the NaOH aqueous solution to make 180 ℃ of its dissolvings reaction 24 hours down in molar ratio with zinc acetate and ferric nitrate, obtains ZnFe
2O
4Precipitation;
(2) ZnFe that step 1 is obtained
2O
4Precipitation 2.41 grams are scattered in 200 milliliters V
Water: V
EthanolUltrasonic dispersion was stirred 2 hours after 30 minutes in=1: 8 the ethanol water, with glacial acetic acid regulator solution pH to 5, obtained solution A;
(3) get 3.4-20.4 milliliter butyl titanate respectively and join in 20 milliliters of ethanol, stir and obtained solution B in 30 minutes;
(4) dropwise whole of the solution B that obtains in the step 3 are splashed in the solution A that step 2 obtains, fully stir 10 hours after, obtain red precipitate C through centrifugation and deionized water washing;
(5) the red precipitate C that step 4 is obtained calcines down at 200-800 ℃ and obtained required product in 4 hours.
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