CN103721700B - A kind of high activity SnO 2-TiO 2the preparation method of composite photo-catalyst - Google Patents
A kind of high activity SnO 2-TiO 2the preparation method of composite photo-catalyst Download PDFInfo
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 38
- QHGNHLZPVBIIPX-UHFFFAOYSA-N tin(II) oxide Inorganic materials [Sn]=O QHGNHLZPVBIIPX-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 230000000694 effects Effects 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000002131 composite material Substances 0.000 title description 15
- OGIDPMRJRNCKJF-UHFFFAOYSA-N TiO Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 title description 2
- 229910010413 TiO 2 Inorganic materials 0.000 claims abstract description 48
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 36
- 230000032683 aging Effects 0.000 claims abstract description 31
- 238000005516 engineering process Methods 0.000 claims abstract description 24
- 239000000243 solution Substances 0.000 claims abstract description 24
- 239000000428 dust Substances 0.000 claims abstract description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229960000583 Acetic Acid Drugs 0.000 claims abstract description 19
- QTBSBXVTEAMEQO-UHFFFAOYSA-N acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000012362 glacial acetic acid Substances 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 19
- 238000005119 centrifugation Methods 0.000 claims abstract description 18
- 229910052718 tin Inorganic materials 0.000 claims abstract description 18
- ATJFFYVFTNAWJD-UHFFFAOYSA-N tin hydride Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 18
- 150000001875 compounds Chemical class 0.000 claims abstract description 17
- 238000001816 cooling Methods 0.000 claims abstract description 16
- 238000005406 washing Methods 0.000 claims abstract description 16
- 239000000463 material Substances 0.000 claims abstract description 11
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000011017 operating method Methods 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 238000000227 grinding Methods 0.000 claims abstract description 3
- 239000011259 mixed solution Substances 0.000 claims abstract description 3
- 238000003756 stirring Methods 0.000 claims description 39
- 239000006227 byproduct Substances 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 12
- GRYLNZFGIOXLOG-UHFFFAOYSA-N nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- 239000012153 distilled water Substances 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 230000029087 digestion Effects 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 19
- 239000002904 solvent Substances 0.000 abstract description 5
- 230000035484 reaction time Effects 0.000 abstract description 4
- 239000006185 dispersion Substances 0.000 abstract description 3
- 239000000047 product Substances 0.000 description 26
- 230000001699 photocatalysis Effects 0.000 description 11
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 10
- -1 titanium tin Chemical compound 0.000 description 10
- 229910006404 SnO 2 Inorganic materials 0.000 description 8
- 239000004065 semiconductor Substances 0.000 description 8
- 239000000969 carrier Substances 0.000 description 5
- 230000015556 catabolic process Effects 0.000 description 4
- 230000004059 degradation Effects 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
- 239000003344 environmental pollutant Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 231100000719 pollutant Toxicity 0.000 description 4
- 238000007796 conventional method Methods 0.000 description 3
- 230000001808 coupling Effects 0.000 description 3
- 238000010168 coupling process Methods 0.000 description 3
- 238000005859 coupling reaction Methods 0.000 description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N oxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000006011 modification reaction Methods 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- MCPLVIGCWWTHFH-UHFFFAOYSA-L Methyl blue Chemical compound [Na+].[Na+].C1=CC(S(=O)(=O)[O-])=CC=C1NC1=CC=C(C(=C2C=CC(C=C2)=[NH+]C=2C=CC(=CC=2)S([O-])(=O)=O)C=2C=CC(NC=3C=CC(=CC=3)S([O-])(=O)=O)=CC=2)C=C1 MCPLVIGCWWTHFH-UHFFFAOYSA-L 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N Tin dioxide Chemical group O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 238000004847 absorption spectroscopy Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000003197 catalytic Effects 0.000 description 1
- 230000024881 catalytic activity Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 238000005755 formation reaction Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 238000009114 investigational therapy Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 150000002843 nonmetals Chemical class 0.000 description 1
- 230000003000 nontoxic Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 230000001235 sensitizing Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000001340 slower Effects 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
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- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
Abstract
The present invention is a kind of high activity 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, adds dust technology, water, stirs, leave standstill; (2) are add SnCl in the mixed solution of 10 ~ 80 ︰ 1 An Tai ︰ tin mol ratio
45H
2o solution, stirs, then ageing; (3) material after ageing is put into autoclave constant temperature process 22 ~ 27h, be cooled to room temperature; (4) products therefrom absolute ethyl alcohol cyclic washing after cooling, then carries out centrifugation, and be separated afterproduct and dry, grinding, obtains product.The present invention is that the method for sol-solvent heat prepares SnO
2-TiO
2compound nanometer photocatalyst, obtained catalyst has high activity, simultaneously higher, the good dispersion of purity; Operating procedure of the present invention is obviously less, foreshortens to 2 ~ 3d, even shorter, and make simpler and more direct, safety, reaction time is shorter, and operating parameter is easily controlled.
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.But these methods all exist many weak points, cause preparation-obtained photocatalyst activity not satisfactory, the most basic dyestuff methyl blue of photocatalytic degradation all needs several hours.For the method for this type of compound between two, unfixing operating condition, scope used is also comparatively limited to; Catalyst activity simultaneously obtained by complex method is unstable, and dispersive property is also bad, and consuming time longer during preparation, general manufacturing cycle is 4 ~ 5d, thus makes the scope of application still wideless.
Therefore, how to develop the activity that a kind of method can improve composite photo-catalyst activity, can reduce again preparation the production time become a problem demanding prompt solution.
Summary of the invention
The present invention is directed to above-mentioned technical problem, invention one has high activity, can reduce costs, simple to operate, safety, and reaction time is short, reproducible, the SnO that Operating parameters is easily controlled
2-TiO
2the preparation method of composite photo-catalyst, thus be expected to be applied in the practical application of investigation of materials and photocatalytic pollutant degradation.
For solving the problem of prior art, technical solution of the present invention is as follows:
A kind of high activity SnO
2-TiO
2the preparation method of compound nanometer photocatalyst, operating procedure is as follows:
(1) butyl titanate, absolute ethyl alcohol, glacial acetic acid are uniformly mixed, add dust technology, add water, stir, leave standstill;
(2) are that 10 ~ 80 ︰ 1 add SnCl in step (1) mixed solution An Tai ︰ tin mol ratio
45H
2o solution, stirs, then ageing;
(3) material after ageing in step (2) is put into autoclave constant temperature process 22 ~ 27h, then make material in autoclave be cooled to room temperature;
(4) by products therefrom absolute ethyl alcohol cyclic washing after cooling in step (3), then carry out centrifugation, be separated afterproduct and dry, grinding, obtains SnO
2-TiO
2compound nanometer photocatalyst.
A kind of high activity 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 3, stirs 10 ~ 20min, adds water and then continues to stir, leave standstill;
(2) are that the rear solution of 10 ~ 80 ︰ 1 mixing in step (1) adds SnCl An Tai ︰ tin mol ratio
45H
2o solution, stirs, then ageing;
(3) material after ageing in step (2) is put into autoclave constant temperature process 22 ~ 27h, then make material in autoclave be cooled to room temperature;
(4) by products therefrom absolute ethyl alcohol cyclic washing after cooling in step (3), then carry out centrifugation, be separated afterproduct and dry, products therefrom after oven dry is ground, obtains SnO
2-TiO
2compound nanometer photocatalyst.
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 ~ 3 ︰ 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, step (2) is middle is that the rear solution of 60 ︰ 1 mixing in step (1) adds SnCl An Tai ︰ tin mol ratio
45H
2o solution
Preferably, adding nitric acid adjust ph in step (1) is 3.
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, SnCl used in step (2)
45H
2the molar concentration of O solution is 1.4mol/L, and digestion time is 20 ~ 28h.
Preferably, in step (3), material after ageing in step (2) is put into autoclave 180 DEG C of constant temperature process.
Preferably, dry at 55 ~ 65 DEG C after centrifugation in step (4).
Preferably, described water is deionized water or distilled water.
Compared with prior art, beneficial effect of the present invention is:
The present invention is that sol-solvent heat and sol-gel process and solvent heat composite algorithm prepare SnO
2-TiO
2compound nanometer photocatalyst, obtained catalyst has high activity, simultaneously higher, the good dispersion of purity; By adding the ratio of suitable titanium tin, making the polymerization between colloidal sol relatively good, obtaining the particle that particle diameter is less, there is larger specific area, more adsorption site; In addition, the titanium tin ratio in the present invention, can obtain the composite oxides that a certain proportion of anatase titanium dioxide and rutile-type coexist, the synergy between them, makes the composite oxides of acquisition have less with gap, is beneficial to light absorption to produce more polyelectron-hole pair; Higher photocatalytic activity may be by changing its electronic structure, improves Surface Oxygen hole number and surface hydroxyl number, thus makes obtained catalyst activity better, prepares gained SnO far away higher than conventional method
2-TiO
2compound nanometer photocatalyst; Further, operating procedure of the present invention is obviously less, foreshortens to 2 ~ 3d, even shorter, and make simpler and more direct, safety, reaction time is shorter, and operating parameter is easily controlled.
Accompanying drawing explanation
Accompanying drawing 1 is a series of SnO
2-TiO
2compound nanometer photocatalyst XRD collection of illustrative plates.
Accompanying drawing 2 is a series of SnO
2-TiO
2compound nanometer photocatalyst photocatalytic degradation effect figure.
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.Before embodiment, active testing is carried out to commercial photochemical catalyst P25.In the embodiment of the present invention, experimental group has 10 groups, is respectively embodiment 1,2,3,4,5,6,7, in balanced range, wherein choose 5 embodiments: embodiment 1,4,5,6,7 makes active testing respectively; Contrast test has 5 groups, is respectively embodiment 8,9,10,11,12, does active testing respectively to catalyst obtained in each embodiment;
Embodiment 1
60ml tetra-n-butyl titanate, 255ml absolute ethyl alcohol, 30ml glacial acetic acid are mixed, under constantly stirring, dropwise adding 30ml dust technology (Xiao Suan ︰ water=1 ︰ 10) adjust ph is 3, after continuing to stir 15min, add 30ml deionized water, stir 10min again, then leaving standstill 30min, is the SnCl that 60 ︰ 1 add that molar concentration is 1.4mol/L An Tai ︰ tin mol ratio
45H
2o solution, stirs, ageing 24h, makes slowly to be polymerized between colloidal sol.Colloidal sol after ageing is transferred in autoclave at 180 DEG C of constant temperature process 24h, then product in autoclave is made to be cooled to room temperature, products therefrom absolute ethyl alcohol cyclic washing after cooling, then centrifugation is carried out, be separated afterproduct to dry, bake out temperature is 60 DEG C, is ground by products therefrom after oven dry, obtains SnO
2-TiO
2compound nanometer photocatalyst, is masked as T60S1, does active testing.
Embodiment 2
57ml tetra-n-butyl titanate, 266ml absolute ethyl alcohol, 19ml glacial acetic acid are mixed, under constantly stirring, dropwise adding 57ml dust technology (Xiao Suan ︰ water=1 ︰ 10) adjust ph is 3, after continuing to stir 15min, add 30ml deionized water, stir 10min again, then leaving standstill 30min, is the SnCl that 55 ︰ 1 add that molar concentration is 1.4mol/L An Tai ︰ tin mol ratio
45H
2o solution, stirs, ageing 20h, makes slowly to be polymerized between colloidal sol.Colloidal sol after ageing is transferred in autoclave at 180 DEG C of constant temperature process 22h, then product in autoclave is made to be cooled to room temperature, products therefrom absolute ethyl alcohol cyclic washing after cooling, then centrifugation is carried out, be separated afterproduct to dry, bake out temperature is 55 DEG C, is ground by products therefrom after oven dry, obtains SnO
2-TiO
2compound nanometer photocatalyst.
Embodiment 3
65ml tetra-n-butyl titanate, 273ml absolute ethyl alcohol, 39ml glacial acetic acid are mixed, under constantly stirring, dropwise adding 13ml dust technology (Xiao Suan ︰ water=1 ︰ 10) adjust ph is 3, after continuing to stir 15min, add 30ml and remove distilled water, stir 10min again, then leaving standstill 30min, is the SnCl that 65 ︰ 1 add that molar concentration is 1.4mol/L An Tai ︰ tin mol ratio
45H
2o solution, stirs, ageing 28h, makes slowly to be polymerized between colloidal sol.Colloidal sol after ageing is transferred in autoclave at 180 DEG C of constant temperature process 27h, then product in autoclave is made to be cooled to room temperature, products therefrom absolute ethyl alcohol cyclic washing after cooling, then centrifugation is carried out, be separated afterproduct to dry, bake out temperature is 65 DEG C, is ground by products therefrom after oven dry, obtains SnO
2-TiO
2compound nanometer photocatalyst.
Embodiment 4
10ml tetra-n-butyl titanate, 42.5ml absolute ethyl alcohol, 5ml glacial acetic acid are mixed, under constantly stirring, dropwise adding 5ml dust technology (Xiao Suan ︰ water=1 ︰ 10) adjust ph is 3, after continuing to stir 15min, add 5ml deionized water, stir 10min again, then leaving standstill 30min, is the SnCl that 10 ︰ 1 add that molar concentration is 1.4mol/L An Tai ︰ tin mol ratio
45H
2o solution, stirs, ageing 24h, makes slowly to be polymerized between colloidal sol.Colloidal sol after ageing is transferred in autoclave at 180 DEG C of constant temperature process 24h, then product in autoclave is made to be cooled to room temperature, products therefrom absolute ethyl alcohol cyclic washing after cooling, then centrifugation is carried out, be separated afterproduct to dry, bake out temperature is 60 DEG C, is ground by products therefrom after oven dry, obtains SnO
2-TiO
2compound nanometer photocatalyst, is masked as T10S1, does active testing.
Embodiment 5
20ml tetra-n-butyl titanate, 85ml absolute ethyl alcohol, 10ml glacial acetic acid are mixed, under constantly stirring, dropwise adding 10ml dust technology (Xiao Suan ︰ water=1 ︰ 10) adjust ph is 3, after continuing to stir 15min, add 10ml deionized water, stir 10min again, then leaving standstill 30min, is the SnCl that 20 ︰ 1 add that molar concentration is 1.4mol/L An Tai ︰ tin mol ratio
45H
2o solution, stirs, ageing 24h, makes slowly to be polymerized between colloidal sol.Colloidal sol after ageing is transferred in autoclave at 180 DEG C of constant temperature process 24h, then product in autoclave is made to be cooled to room temperature, products therefrom absolute ethyl alcohol cyclic washing after cooling, then centrifugation is carried out, be separated afterproduct to dry, bake out temperature is 60 DEG C, is ground by products therefrom after oven dry, obtains SnO
2-TiO
2compound nanometer photocatalyst, is masked as T20S1, does active testing.
Embodiment 6
40ml tetra-n-butyl titanate, 170ml absolute ethyl alcohol, 20ml glacial acetic acid are mixed, under constantly stirring, dropwise adding 20ml dust technology (Xiao Suan ︰ water=1 ︰ 10) adjust ph is 3, after continuing to stir 15min, add 20ml deionized water, stir 10min again, then leaving standstill 30min, is the SnCl that 40 ︰ 1 add that molar concentration is 1.4mol/L An Tai ︰ tin mol ratio
45H
2o solution, stirs, ageing 24h, makes slowly to be polymerized between colloidal sol.Colloidal sol after ageing is transferred in autoclave at 180 DEG C of constant temperature process 24h, then product in autoclave is made to be cooled to room temperature, products therefrom absolute ethyl alcohol cyclic washing after cooling, then centrifugation is carried out, be separated afterproduct to dry, bake out temperature is 60 DEG C, is ground by products therefrom after oven dry, obtains SnO
2-TiO
2compound nanometer photocatalyst, is masked as T40S1, does active testing.
Embodiment 7
80ml tetra-n-butyl titanate, 272ml absolute ethyl alcohol, 32ml glacial acetic acid are mixed, under constantly stirring, dropwise adding 32ml dust technology (Xiao Suan ︰ water=1 ︰ 10) adjust ph is 3, after continuing to stir 15min, add 32ml deionized water, stir 10min again, then leaving standstill 30min, is the SnCl that 80 ︰ 1 add that molar concentration is 1.4mol/L An Tai ︰ tin mol ratio
45H
2o solution, stirs, ageing 24h, makes slowly to be polymerized between colloidal sol.Colloidal sol after ageing is transferred in autoclave at 180 DEG C of constant temperature process 24h, then product in autoclave is made to be cooled to room temperature, products therefrom absolute ethyl alcohol cyclic washing after cooling, then centrifugation is carried out, be separated afterproduct to dry, bake out temperature is 60 DEG C, is ground by products therefrom after oven dry, obtains SnO
2-TiO
2compound nanometer photocatalyst, is masked as T80S1, does active testing.
Embodiment 8
10ml tetra-n-butyl titanate, 42.5ml absolute ethyl alcohol, 5ml glacial acetic acid are mixed, under constantly stirring, dropwise adding 5ml dust technology (Xiao Suan ︰ water=1 ︰ 10) adjust ph is 3, after continuing to stir 15min, add 5ml deionized water, stir 10min again, then leaving standstill 30min, is the SnCl that 1 ︰ 1 adds that molar concentration is 1.4mol/L An Tai ︰ tin mol ratio
45H
2o solution, stirs, ageing 24h, makes slowly to be polymerized between colloidal sol.Colloidal sol after ageing is transferred in autoclave at 180 DEG C of constant temperature process 24h, then product in autoclave is made to be cooled to room temperature, products therefrom absolute ethyl alcohol cyclic washing after cooling, then centrifugation is carried out, be separated afterproduct to dry, bake out temperature is 60 DEG C, is ground by products therefrom after oven dry, obtains SnO
2-TiO
2compound nanometer photocatalyst, is masked as T1S1, does active testing.
Embodiment 9
10ml tetra-n-butyl titanate, 42.5ml absolute ethyl alcohol, 5ml glacial acetic acid are mixed, under constantly stirring, dropwise adding 5ml dust technology (Xiao Suan ︰ water=1 ︰ 10) adjust ph is 3, after continuing to stir 15min, add 5ml deionized water, stir 10min again, then leaving standstill 30min, is the SnCl that 1 ︰ 3 adds that molar concentration is 1.4mol/L An Tai ︰ tin mol ratio
45H
2o solution, stirs, ageing 24h, makes slowly to be polymerized between colloidal sol.Colloidal sol after ageing is transferred in autoclave at 180 DEG C of constant temperature process 24h, then product in autoclave is made to be cooled to room temperature, products therefrom absolute ethyl alcohol cyclic washing after cooling, then centrifugation is carried out, be separated afterproduct to dry, bake out temperature is 60 DEG C, is ground by products therefrom after oven dry, obtains SnO
2-TiO
2compound nanometer photocatalyst, is masked as T1S3, does active testing.
Embodiment 10
10ml tetra-n-butyl titanate, 42.5ml absolute ethyl alcohol, 5ml glacial acetic acid are mixed, under constantly stirring, dropwise adding 5ml dust technology (Xiao Suan ︰ water=1 ︰ 10) adjust ph is 3, after continuing to stir 15min, add 5ml deionized water, stir 10min again, then leaving standstill 30min, is the SnCl that 3 ︰ 1 add that molar concentration is 1.4mol/L An Tai ︰ tin mol ratio
45H
2o solution, stirs, ageing 24h, makes slowly to be polymerized between colloidal sol.Colloidal sol after ageing is transferred in autoclave at 180 DEG C of constant temperature process 24h, then product in autoclave is made to be cooled to room temperature, products therefrom absolute ethyl alcohol cyclic washing after cooling, then centrifugation is carried out, be separated afterproduct to dry, bake out temperature is 60 DEG C, is ground by products therefrom after oven dry, obtains SnO
2-TiO
2compound nanometer photocatalyst, is masked as T3S1, does active testing.
Embodiment 11
Pure TiO
2the preparation of catalyst: 10ml tetra-n-butyl titanate, 42.5ml absolute ethyl alcohol, 5ml glacial acetic acid are mixed, under constantly stirring, dropwise adding 5ml dust technology (Xiao Suan ︰ water=1 ︰ 10) adjust ph is 3, after continuing to stir 15min, add 5ml deionized water, then stir 10min, then leave standstill 30min, ageing 24h, makes slowly to be polymerized between colloidal sol.Colloidal sol after ageing is transferred in autoclave at 180 DEG C of constant temperature process 24h, then product in autoclave is made to be cooled to room temperature, products therefrom absolute ethyl alcohol cyclic washing after cooling, then centrifugation is carried out, be separated afterproduct to dry, bake out temperature is 60 DEG C, is ground by products therefrom after oven dry, obtains pure TiO
2catalyst, is masked as TiO
2, do active testing.
Embodiment 12
Pure SnO
2the preparation of catalyst: make solvent with absolute ethyl alcohol is that the ratio of 35 ︰ 1 is by SnCl in Chun ︰ tin mol ratio
45H
2o is dissolved in ethanol, stir, leave standstill 24h, directly putting into autoclave 180 DEG C of constant temperature process 24h by leaving standstill rear solution, then making product in autoclave be cooled to room temperature, products therefrom absolute ethyl alcohol cyclic washing after cooling, then carry out centrifugation, be separated afterproduct and dry, bake out temperature is 60 DEG C, products therefrom after oven dry is ground, obtains pure SnO
2catalyst, is masked as SnO
2, do active testing.
Change in conjunction with above-described embodiment and as can be seen from the crystalline phase of catalyst in accompanying drawing 1, each catalyst defines titanium tin composite oxides, as can be seen from the XRD result of catalyst in accompanying drawing 1, when titanium tin mol ratio is 1:3 and 1:1, there is the SnO belonging to cassiterite structure
2with the characteristic diffraction peak of rutile type titanium tin composite oxides.When titanium tin mol ratio is 3:1, only there is the characteristic diffraction peak of rutile type titanium tin composite oxides.As titanium tin mol ratio >3:1, observe the composite oxides that anatase titanium dioxide and rutile-type coexist.What these results illustrated the tin of seldom amount adds the structure that just can change titanium dioxide, the composite oxides of formation different proportion anatase titanium dioxide and rutile-type.As can be seen from accompanying drawing 2, catalyst activity prepared by the present invention is very high, particularly T10S1, T20S1, T40S1, T60S1, the activity of T80S1 is all higher than commercial photochemical catalyst P25, wherein the catalyst activity of T60S1 is best, and illumination about 30min degradation rate reaches 100%.In sum, the present invention is that the method for sol-solvent heat prepares SnO
2-TiO
2compound nanometer photocatalyst, obtained catalyst has high activity, simultaneously higher, the good dispersion of purity; The ratio of the titanium tin wherein added, makes the polymerization between colloidal sol relatively good, obtains the particle that particle diameter is less, has larger specific area, more adsorption site; In addition, the titanium tin ratio in the present invention, can obtain the composite oxides that a certain proportion of anatase titanium dioxide and rutile-type coexist, the synergy between them, makes the composite oxides of acquisition have less with gap, is beneficial to light absorption to produce more polyelectron-hole pair; Higher photocatalytic activity may be by changing its electronic structure, improves Surface Oxygen hole number and surface hydroxyl number, thus makes obtained catalyst activity better, prepares gained SnO far away higher than conventional method
2-TiO
2compound nanometer photocatalyst; Further, operating procedure of the present invention is obviously less, and make simpler and more direct, safety, reaction time is shorter, and operating parameter is easily controlled.
Claims (7)
1. a high activity SnO
2-TiO
2the preparation method of compound nanometer photocatalyst, is characterized in that, comprises following operating procedure:
(1) butyl titanate, absolute ethyl alcohol, glacial acetic acid are uniformly mixed, add dust technology, add water, stir, leave standstill, wherein, adding dust technology adjust ph is 3, and the volume ratio of the butyl titanate added, absolute ethyl alcohol, glacial acetic acid, dust technology, water is 3 ~ 5 ︰ 14 ~ 21 ︰ 1 ~ 3 ︰ 1 ~ 3 ︰ 1 ~ 3;
(2) are that 10 ~ 80 ︰ 1 add SnCl in step (1) mixed solution An Tai ︰ tin mol ratio
45H
2o solution, stir, then ageing, wherein, digestion time is 20 ~ 28h;
(3) material after ageing in step (2) is put into 180 DEG C of autoclave constant temperature process 22 ~ 27h, then make material in autoclave be cooled to room temperature;
(4) by products therefrom absolute ethyl alcohol cyclic washing after cooling in step (3), then carry out centrifugation, be separated afterproduct and dry, grinding, obtains SnO
2-TiO
2compound nanometer photocatalyst.
2. high activity 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.
3. high activity SnO according to claim 1
2-TiO
2the preparation method of compound nanometer photocatalyst, is characterized in that: step (2) is middle is that the rear solution of 60 ︰ 1 mixing in step (1) adds SnCl An Tai ︰ tin mol ratio
45H
2o solution.
4. high activity SnO according to claim 1
2-TiO
2the preparation method of compound nanometer photocatalyst, is characterized in that: 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).
5. high activity 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.
6. high activity SnO according to claim 1
2-TiO
2the preparation method of compound nanometer photocatalyst, is characterized in that: dry at 55 ~ 65 DEG C after centrifugation in step (4).
7. high activity 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.
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