CN103657628B - A kind of SnO 2-TiO 2the preparation method of compound nanometer photocatalyst - Google Patents
A kind of SnO 2-TiO 2the preparation method of compound nanometer photocatalyst Download PDFInfo
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- CN103657628B CN103657628B CN201310694832.3A CN201310694832A CN103657628B CN 103657628 B CN103657628 B CN 103657628B CN 201310694832 A CN201310694832 A CN 201310694832A CN 103657628 B CN103657628 B CN 103657628B
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Abstract
A kind of SnO
2-TiO
2the preparation method of compound nanometer photocatalyst, operating procedure is: (1), by butyl titanate, absolute ethyl alcohol, glacial acetic acid mixing, adds dust technology adjust ph, stirs, and add water; (to be 3 ︰ 1 An Tai ︰ tin mol ratio add SnCl to solution after mixing to 2)
45H
2o solution, stirs, ageing 22 ~ 26h; (3) material after ageing is put into autoclave and keep 175 ~ 185 DEG C of process 22 ~ 25h, make material in autoclave be cooled to room temperature; (4) by product centrifugation, dry at 95 ~ 110 DEG C, roasting 2 ~ 6h, obtains product.SnO prepared by the present invention
2-TiO
2compound nanometer photocatalyst purity, activity are higher, good dispersion, and heat endurance is strong, reproducible; The present invention does not need to add surfactant etc. in addition, makes cost lower, greatly reduces production cost; Production time shortens to 2 ~ 3d simultaneously, and simple to operate, safety.
Description
Technical field
The invention belongs to nano material and photocatalysis technology field, relate to a kind of SnO
2-TiO
2the preparation method of compound nanometer photocatalyst.
Background technology
TiO
2being commonly called as titanium dioxide, is a kind of semi-conducting material of N-shaped, and energy gap is 3.2eV.Because it has high-specific surface area, inexpensive nontoxic, photoelectric properties are strong, and catalytic activity advantages of higher, therefore becomes the current photochemical catalyst having application potential most.But, TiO
2inherent physical characteristic determine that it is very low to solar energy utilization ratio, electron-hole recombination rate is high, causes photocatalytic activity greatly to reduce.Therefore, by TiO
2carry out the wavelength that modification makes it excite to expand to visible ray from ultraviolet, the compound of the electron-hole that slows down, increase photocatalysis efficiency, become the research emphasis of scientist.At present, in order to realize this goal, adopt multiple different technologies to TiO
2carry out modification or doping, to improve its photocatalytic activity.As at TiO
2metal surface containing transition metal, nonmetal, surface deposition noble metal, surface sensitization process and semiconductors coupling etc.Semiconductors coupling mainly utilizes two kinds of semiconductors coupling that bandwidth is different but close, photo-generated carrier so not only can be made to transport between different energy level carrier, and extend the life-span of carrier, avoid the compound of carrier to a great extent, improve the separation rate of carrier, thus improve the photocatalytic activity of system.
SnO
2also be a kind of typical n-type semiconductor, its energy gap 3.5 ~ 3.6eV, stable chemical nature, its energy level and semiconductor TiO
2match, and SnO
2with TiO
2conduction level between difference cause SnO
2and TiO
2after compound, light induced electron is from TiO
2surface transfer and at SnO
2upper enrichment, correspondingly decreases TiO
2the density of surface electronic, light induced electron can effectively be separated with hole, also just decreases the right recombination probability of photo-generate electron-hole, greatly can improve TiO
2photocatalytic activity, for this reason we wish by research nano-TiO
2with SnO
2the composite formed effectively reduces the right compound of photo-generate electron-hole, thus improves quantum yield, widens ultraviolet-visible absorption spectroscopy simultaneously, reaches the object improving photocatalytic activity.
Nano-photocatalyst is the jinx of pollutant, its mechanism of action is: it is right that nano-photocatalyst is excited to generate " electron-hole " under the irradiation of special wavelength light, this " electron-hole " is to after having an effect with the water of surrounding, oxygen, there is extremely strong oxidationreduction ability, the pollutant such as formaldehyde in air, benzene Direct Resolution can be become harmless tasteless material.Under light illumination, if the energy of photon is greater than semiconductor energy gap, the electronics (e in its valence band
-) will be excited on conduction band, in valence band, produce hole (h simultaneously
+).Photohole has very strong oxidability, and light induced electron has very strong reducing power, and they can move to the diverse location of semiconductor surface, with the pollutant generation redox reaction of adsorption.
At present, SnO is made
2and TiO
2the technological means of compound has a variety of, coprecipitation wherein, sol-gal process, hydro-thermal method are all very typical conventional methods, the preparation of many nano materials be all prepared by these methods or by these methods prolong Shen or combine method preparation, therefore, they play a very important role in the preparation and research of solid catalysis agent material.
Sol-gel process is that the slaine of some facile hydrolysis is obtained colloidal sol through chemical reactions such as hydrolysis and polycondensations, then colloidal sol is converted into gel, then obtains the method for nano-powder by roasting.The method synthesis temperature is low, and process is easy to control; Technique is simply beneficial to batch production, and obtained powder has the chemical composition uniformity, Gao Chunxing, ultra-fine property etc. of height.
The hot method of sol-solvent is transferred directly in autoclave carries out solvent thermal reaction by forming the colloidal sol before gel in sol-gal process.
The precipitation method are classical and a kind of method preparing solid catalyst of extensive use, nearly all solid catalyst has at least a part to be prepared by the precipitation method, coprecipitation is the method two or more components needed for catalyst simultaneously precipitated under the effect of precipitating reagent, be characterized in once can obtaining several component simultaneously, and the distribution of each component is more even, if can solid solution be formed between each component, so better to the absorbability of light.
Co-precipitation-hydro-thermal method the component forming precipitation is transferred directly in autoclave to carry out hydro-thermal reaction.
Hydro-thermal method is in sealed reactor, using the aqueous solution as reaction medium, heating reaction vessel, create reaction under high pressure environment, at normal temperatures and pressures, material not easily oxidized in solution or the material not easily synthesized, to get off a kind of material preparation method of carrying out of accelerated reaction by system being placed in closed high-temperature and high-pressure conditions.The technology and equipment of hydro-thermal method is simple, and be easy to control, without the need to high temperature sintering process, product is directly crystalline state.
Existing these methods of bibliographical information prepare SnO
2-TiO
2compound nanometer photocatalyst, but the catalyst activity that these methods prepare is not high, makes reaction effect bad; When the independent precipitation method or hydro-thermal method Kaolinite Preparation of Catalyst, the presoma used is titanium tetrachloride, and during the decomposes of titanium tetrachloride, reaction is violent, occurs a large amount of dense smoke, makes course of reaction more dangerous; Prior art prepares SnO
2-TiO
2need during composite catalyst to add the materials such as surfactant, cause production cost higher, meanwhile, general 4 ~ 5d consuming time in this catalyst process of preparation, the time is oversize.
Summary of the invention
The present invention is directed to the deficiencies in the prior art, invention one prepares SnO
2-TiO
2the method of compound nanometer photocatalyst, makes obtained catalyst have high activity, high stability; Meanwhile, the inventive method reaction time is short, catalyst is reproducible; Further, present invention reduces production cost, make simple to operate, safety.
For solving the problems of the technologies described above, technical scheme of the present invention is:
A kind of SnO
2-TiO
2the preparation method of compound nanometer photocatalyst, comprises following operating procedure:
(1) by butyl titanate, absolute ethyl alcohol, glacial acetic acid mixing, then adding dust technology adjust ph is 2 ~ 4, stirs 10 ~ 20min, adds water and stir, and leaves standstill;
(2) are that the rear solution of 3 ︰ 1 mixing in step (1) adds SnCl An Tai ︰ tin mol ratio
45H
2o solution, stirs, then ageing 22 ~ 26h;
(3) material after ageing in step (2) is put into autoclave and keep 175 ~ 185 DEG C of constant temperature process 22 ~ 25h, then make material in autoclave be cooled to room temperature;
(4) by products therefrom centrifugation in step (3), dry at 95 ~ 110 DEG C, then roasting 2 ~ 6h at 500 ~ 600 DEG C, obtains product.
A kind of SnO
2-TiO
2the preparation method of compound nanometer photocatalyst, its more detailed step is as follows:
(1) butyl titanate, absolute ethyl alcohol, glacial acetic acid are mixed, under continuous stirring state, dropwise add dust technology adjust ph is 2 ~ 4, stirs 10 ~ 20min, adds water and then continues to stir, leave standstill;
(2) are that the rear solution of 3 ︰ 1 mixing in step (1) adds SnCl An Tai ︰ tin mol ratio
45H
2o solution, stirs, then ageing 22 ~ 26h;
(3) material after ageing in step (2) is put into autoclave and keep 175 ~ 185 DEG C of constant temperature process 22 ~ 25h, then make material in autoclave be cooled to room temperature;
(4) by products therefrom centrifugation after ageing 22 ~ 25h in step (3), dry at 95 ~ 110 DEG C, then roasting 2 ~ 6h at 500 ~ 600 DEG C, obtains product.
Preferably, the volume ratio of the butyl titanate added in step (1), absolute ethyl alcohol, glacial acetic acid, dust technology, water is 3 ~ 5 ︰ 14 ~ 21 ︰ 1 ︰ 1 ~ 3 ︰ 1 ~ 3.
Preferably, the volume ratio of the butyl titanate added in step (1), absolute ethyl alcohol, glacial acetic acid, dust technology, water is 4 ︰ 17 ︰ 1 ︰ 2 ︰ 2.
Preferably, the diluted nitric acid aqueous solution of to be nitric acid and water volume ratio be 1 ︰ 10 of the dust technology described in step (1).
Preferably, described water is deionized water or distilled water.
Preferably, SnCl used in step (2)
45H
2the molar concentration of O solution is 1.4mol/L.
Preferably, the also mixing time that adds water in step (1) is 10min, and time of repose is 30min.
Preferably, after drying at 95 ~ 110 DEG C in step (4), after being pulverized by product, then roasting is carried out.
The present invention is the SnO prepared under sol-gel process and solvent-thermal method compound action
2-TiO
2compound nanometer photocatalyst, make the degree of polymerization between colloidal sol good, obtained catalyst purity, activity are higher, good dispersion, and heat endurance is strong, reproducible; Further the present invention does not need to add the activating substances such as surfactant in addition, makes cost lower, greatly reduces production cost; Production time shortens to 2 ~ 3d simultaneously, and simple to operate, safety; Further the presoma of the inventive method use is for comparatively gentle when butyl titanate reacts, and makes danger in production process lower, is of value to expansion suitability for industrialized production.
Accompanying drawing explanation
Accompanying drawing 1 is SnO prepared by 5 kinds of distinct methods
2-TiO
2compound nanometer photocatalyst XRD collection of illustrative plates.
Accompanying drawing 2 is the SnO of sol-solvent hot preparation
2-TiO
2the scanning electron microscope diagram sheet of compound nanometer photocatalyst.
Accompanying drawing 3 is SnO prepared by 5 kinds of distinct methods
2-TiO
2the photocatalytic degradation effect figure of compound nanometer photocatalyst.
Detailed description of the invention
Further describe the present invention referring to detailed description of the invention, to make those skilled in the art can implement according to this with reference to description word, scope is not limited by embodiments of the present invention.In an embodiment, experiment component is three groups to carry out, and is respectively embodiment 1, embodiment 2, embodiment 3; Contrast test is divided into two groups, is respectively embodiment 4, embodiment 5.Wherein s-g represents sol-gel process, and s-hyth is the hot method of sol-solvent (methods for sol-gel process and solvent-thermal method two kinds of compounds), and cop is coprecipitation, and cop-hyth is co-precipitation-hydro-thermal method, and hyth is hydro-thermal method.
Embodiment 1
6ml tetra-n-butyl titanate, 25ml absolute ethyl alcohol, 1.5ml glacial acetic acid are mixed, under constantly stirring, dropwise adding 3ml dust technology (Xiao Suan ︰ water=1 ︰ 10) adjust ph is 3, after continuing to stir 15min, add 3ml deionized water, stir 10min again, then leaving standstill 30min, is the SnCl that 3 ︰ 1 add that 4ml molar concentration is 1.4mol/L again An Tai ︰ tin mol ratio
45H
2o solution, stirs, ageing 24h, makes slowly to be polymerized between colloidal sol.Transferred to by colloidal sol after ageing at 180 DEG C of constant temperature process 24h in autoclave, then make product in autoclave be cooled to room temperature, products therefrom is carried out centrifugation, dry at 100 DEG C after separation, then grind into powder, identified as samples is designated as s-hyth.By powder 550 DEG C of roasting 4h in Muffle furnace, obtain SnO
2-TiO
2solid solution.
Embodiment 2
6ml tetra-n-butyl titanate, 28ml absolute ethyl alcohol, 2.0ml glacial acetic acid are mixed, under constantly stirring, dropwise adding 3ml dust technology (Xiao Suan ︰ water=1 ︰ 10) adjust ph is 2, after continuing to stir 15min, add 1ml deionized water, stir 10min again, then leave standstill 30min, by titanium: tin mol ratio is the SnCl that 3 ︰ 1 add that 4ml molar concentration is 1.4mol/L again
45H
2o solution, stirs, ageing 22h, makes slowly to be polymerized between colloidal sol.Colloidal sol after ageing to be transferred in autoclave at 175 DEG C of constant temperature process 22h, then make product in autoclave be cooled to room temperature, products therefrom is carried out centrifugation, dry at 95 DEG C after separation, then grind into powder, by powder 500 DEG C of roasting 6h in Muffle furnace, obtains SnO
2-TiO
2solid solution.
Embodiment 3
12.5ml tetra-n-butyl titanate, 52.5ml absolute ethyl alcohol, 2.5ml glacial acetic acid are mixed, under constantly stirring, dropwise adding 2.5ml dust technology (nitric acid: water=1 ︰ 10) adjust ph is 4, after continuing to stir 15min, add 7.5ml distilled water, stir 10min again, then leave standstill 30min, by titanium: tin mol ratio is the SnCl that 3 ︰ 1 add that 4ml molar concentration is 1.4mol/L again
45H
2o solution, stirs, ageing 26h, makes slowly to be polymerized between colloidal sol.Colloidal sol after ageing to be transferred in autoclave at 185 DEG C of constant temperature process 25h, then make product in autoclave be cooled to room temperature, products therefrom is carried out centrifugation, dry at 110 DEG C after separation, then grind into powder, by powder 600 DEG C of roasting 2h in Muffle furnace, obtains SnO
2-TiO
2solid solution.
Embodiment 4
6ml tetra-n-butyl titanate, 25ml absolute ethyl alcohol, 1.5ml glacial acetic acid are mixed, under constantly stirring, dropwise add 3ml dust technology (Xiao Suan ︰ water=1 ︰ 10) to pH=3, after continuing to stir 15min, then after stirring, 3ml deionized water is added in mixed liquor, stir 10min, leave standstill 30min, then add the SnCl that 4ml molar concentration is 1.4mol/L
45H
2o solution, stirs, and stirs, then ageing 24h, makes slowly to be polymerized between colloidal sol.Dried in 100 DEG C of baking ovens by ready colloidal sol, then by drying and grinding into powder, identified as samples is designated as s-g.By gained powder 550 DEG C of roasting 4h in Muffle furnace, obtain SnO
2-TiO
2solid solution.
Embodiment 5
The following three parts of identical mixed solutions of preparation: by each material mol ratio Wei Tai ︰ Xi ︰ urea=3 ︰ 1 ︰ 60, be the TiCl of 2mol/L by 8ml concentration
4solution and 4ml concentration are 1.4mol/LSnCl
45H
2o solution mixes, and stirs 30min, then adds the urea liquid that 75ml concentration is 6mol/L, stirs 1h.Above-mentioned three parts of identical mixed solutions are labeled as cop, cop-hyth, hyth respectively, and by under the condition of cop, cop-hyth two parts of mixed solutions in Keep agitation 80 DEG C of oil bath pans, isothermal reaction 8h, makes mixed solution precipitate completely; Then the cop precipitated completely is put and at room temperature cool, ageing 24h, by products therefrom washing, centrifugal, oven dry at 60 DEG C, material grind into powder after then drying, for subsequent use; The turbid solution being masked as cop-hyth is put into autoclave in 180 DEG C of constant temperature process 24h, then makes product in autoclave be cooled to room temperature, by products therefrom wash, centrifugal, at 60 DEG C dry, then grind into powder, for subsequent use; The mixed solution being masked as hyth is directly put into autoclave, constant temperature process 24h at 180 DEG C, then makes product in autoclave be cooled to room temperature, products therefrom is washed, centrifugal, dry at 60 DEG C, then will dry afterwards material grind into powder, for subsequent use; Each for above-mentioned gained powder is placed on respectively 550 DEG C of roasting 4h in Muffle furnace, obtains mark and be respectively: the SnO of cop, cop-hyth, hyth
2-TiO
2solid solution.
Be catalyst crystalline phases variation diagram at accompanying drawing 1, as can be seen from the figure the crystal formation of obtained catalyst is pure rutile type; Can find out in fig 2, the comparatively unification of sol-solvent hot gained catalyst form, each molecular distribution is good; Can find out in fig. 3, gained catalyst is prepared by above-mentioned 5 kinds of methods, in the reaction applying to catalytic degradation methyl blue under ultraviolet light, all show activity, especially best with the catalyst activity prepared by the hot method of sol-solvent, due to the preparation by this method, make the polymerization between colloidal sol relatively good, obtain the particle that particle diameter is less, there is larger specific area, more adsorption site.Higher photocatalytic activity may be by changing its electronic structure, improves Surface Oxygen hole number and surface hydroxyl number.Thus make obtained catalyst activity better, prepare gained SnO higher than conventional method far away
2-TiO
2compound nanometer photocatalyst.
The present invention is the SnO prepared under sol-gel process and solvent-thermal method compound action
2-TiO
2compound nanometer photocatalyst, make the degree of polymerization between colloidal sol good, obtained catalyst purity, activity are higher, good dispersion, and heat endurance is strong, reproducible; Further the present invention does not need to add the activating substances such as surfactant in addition, makes cost lower, greatly reduces production cost; Production time shortens to 2 ~ 3d simultaneously, and simple to operate, safety; Further the presoma of the inventive method use is for comparatively gentle when butyl titanate reacts, and makes danger in production process lower, is of value to expansion suitability for industrialized production.
Claims (8)
1. a SnO
2-TiO
2the preparation method of compound nanometer photocatalyst, is characterized in that, comprises following operating procedure:
(1) by butyl titanate, absolute ethyl alcohol, glacial acetic acid mixing, then adding dust technology adjust ph is 2 ~ 4, stirs 10 ~ 20min, adds water and stir, and leaves standstill;
(2) are that the rear solution of 3 ︰ 1 mixing in step (1) adds SnCl An Tai ︰ tin mol ratio
45H
2o solution, stirs, then ageing 22 ~ 26h;
(3) material after ageing in step (2) is put into autoclave and keep 175 ~ 185 DEG C of constant temperature process 22 ~ 25h, then make material in autoclave be cooled to room temperature;
(4) by products therefrom centrifugation in step (3), dry at 95 ~ 110 DEG C, then roasting 2 ~ 6h at 500 ~ 600 DEG C, obtains product.
2. SnO according to claim 1
2-TiO
2the preparation method of compound nanometer photocatalyst, is characterized in that: the volume ratio of the butyl titanate added in step (1), absolute ethyl alcohol, glacial acetic acid, dust technology, water is 3 ~ 5 ︰ 14 ~ 21 ︰ 1 ︰ 1 ~ 3 ︰ 1 ~ 3.
3. SnO according to claim 1
2-TiO
2the preparation method of compound nanometer photocatalyst, is characterized in that: the volume ratio of the butyl titanate added in step (1), absolute ethyl alcohol, glacial acetic acid, dust technology, water is 4 ︰ 17 ︰ 1 ︰ 2 ︰ 2.
4. SnO according to claim 1
2-TiO
2the preparation method of compound nanometer photocatalyst, is characterized in that: the dust technology described in step (1) is nitric acid and water volume ratio is 1 ︰ 10.
5. SnO according to claim 1
2-TiO
2the preparation method of compound nanometer photocatalyst, is characterized in that: described water is deionized water or distilled water.
6. SnO according to claim 1
2-TiO
2the preparation method of compound nanometer photocatalyst, is characterized in that: SnCl used in step (2)
45H
2the molar concentration of O solution is 1.4mol/L.
7. SnO according to claim 1
2-TiO
2the preparation method of compound nanometer photocatalyst, is characterized in that: the also mixing time that adds water in step (1) is 10min, and time of repose is 30min.
8. SnO according to claim 1
2-TiO
2the preparation method of compound nanometer photocatalyst, is characterized in that: after drying at 95 ~ 110 DEG C in step (4), after being pulverized by product, then carry out roasting.
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| CN105086305A (en) * | 2015-08-31 | 2015-11-25 | 南宁市聚祥塑料制品有限责任公司 | Antibacterial preservative film |
| CN107952367A (en) * | 2016-10-17 | 2018-04-24 | 秦素洁 | A kind of porous material for high-efficient purification formaldehyde and preparation method thereof |
| CN107952289A (en) * | 2016-10-17 | 2018-04-24 | 秦素洁 | A kind of filter screen with purifying formaldehyde and preparation method thereof |
| CN111617792B (en) * | 2020-04-26 | 2021-08-03 | 中国科学院化学研究所 | B, N codoped SnO responding to visible light2/TiO2Precursor and preparation method and application thereof |
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