CN106552614A - The preparation method of hydrophobicity titanium dioxide/mesoporous silicon core shell composite photo-catalyst - Google Patents
The preparation method of hydrophobicity titanium dioxide/mesoporous silicon core shell composite photo-catalyst Download PDFInfo
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Abstract
This proposes a kind of preparation method of new hydrophobicity titanium dioxide/mesoporous silicon core shell composite photo-catalyst.First surfactant and the titanium dioxide with high catalytic activity are added into hot water, the pH11.0-12.0 of suspension are adjusted using strong aqua ammonia or highly basic, are added tetraethoxysilane under strong stirring（1.60-2.40g）With phenyl or fluorine-based silane reagent（0.8-1.6g）Dehydrated alcohol（6.0-10.0mL）Solution, ultrasonic 5-15min are stirred at room temperature hydrolysis 4-12h, filter, and with organic solvent and distilled water wash, 60-80 DEG C is vacuum dried, then is washed with backflow（50-100mL dehydrated alcohol and 80-90 DEG C of 0.15-0.5mol/L hydrochloric acid backflow 12-48h remove structure directing agent, after repeating 2-4 time, then with dehydrated alcohol and water washing 5-8 time）Or roasting（550-650 DEG C of roasting 6-3h）Mode remove template agent removing.
Description
Technical field
The invention belongs to semiconductor light-catalyst field, and in particular to a kind of preparation and use of hydrophobicity titanium dioxide/mesoporous silicon core shell composite photo-catalyst.
Background technology
Nano titanium oxide（TiO2）Because having catalysis activity high, physicochemical properties are stable, and low cost is widely used in the photocatalytic degradation of toxic organic pollutant the advantages of nontoxic, has broad application prospects.But routine TiO2There is following deficiency in photocatalytic degradation hydrophobic organic pollutant in nano-powder：（1）Because great amount of hydroxy group is contained on its surface, major surfaces are hydrophilic under the action of uv light, to the substantially no absorbability of hydrophobic organic pollutant, therefore low concentration, hydrophobic organic pollution are difficult to realize enrichment concentration on its surface, and numerous studies show that the pollutant of catalyst surface are the main of photocatalysis removal, therefore, when processing this pollutant, effect is poor.（2）Conventional TiO2There is nano-powder and be not easily recycled in nano-powder after the completion of photocatalytic degradation enforcement, easily cause waste, and use cost is high.
In order to solve these problems, often adsorption technology is combined with photocatalysis technology at present, composite catalyst is made while having absorbability and photocatalytic degradation efficiency.Conventional adsorbent has zeolite molecular sieve, mesoporous silicon oxide, carbonaceous material and natural minerals.Wherein mesoporous silicon oxide is because with specific surface area is big, photopermeability is good, easily modified and low cost and other advantages, often being combined with titanium dioxide, being prepared titanium dioxide/mesoporous silicon oxide composite photo-catalyst.
The combination of titanium dioxide/mesoporous silicon composite has two kinds at present：1. with mesoporous silicon as carrier, by the method carried titanium dioxide such as physics, chemistry, the composite photo-catalyst of mesoporous silicon carried titanium dioxide is obtained.Titanium dioxide in this composite is dispersed to mesoporous silicon face, and specific surface area is larger, and the free settling feature after the completion of catalytic process using silicon dioxide, realizes the recycling of photocatalyst.But the mesoporous silicon face in the composite that synthesizes in this way of profit still has substantial amounts of hydrophilic hydroxy group, weaker to hydrophobic organic pollutant absorbability, actual processing effect is not good.2. by various chemical methodes, it is obtained with titanium dioxide as core, core-shell material of the silicon dioxide for shell is spaced from each other TiO 2 particles using the silicon dioxide of cladding, reduces titanium dioxide reunion problem.The silica shell of preparation often has two types：（1）Silica shell does not have duct, is directly Nano particles of silicon dioxide.Such as Wang Sheng seminars[1]With commercial P25 as raw material, using hydro-thermal method and sol-gal process, it is prepared for TiO2For core, SiO2For the new type structure of hud nano-photocatalyst TiO of shell2@@SiO2, as silica shell does not have duct, so in titanium dioxide core and silica shell interlayer, having manufactured a ghost, having had the Transport And Transformation using contaminant molecule.And on this basis, which is modified to silica shell using C18 so as to hydrophobicity, and the photocatalytic degradation of dyestuff, percolate is applied to, achieves preferable effect.But this kind of material exists following not enough：1. the silica shell in composite is thicker, about 40nm, and no duct, even if with the presence of one layer of ghost between titanium dioxide core and silica shell, organic pollution in water body moves to that Titanium Dioxide avtive spot is more difficult, and photocatalysis efficiency is poor.2. modified C18 can be only present in the surface of silica shell, can play adsorption, but the target contaminant for adsorbing can only be migrated to silica shell layer surface, it is difficult to migrate to the avtive spot of catalyst.3. preparation process is more complicated, and first titanium dioxide is activated, then prepares one layer of charcoal and then its surface prepares layer of silicon dioxide again, and roasting removes layer of charcoal, recycles C18 organic functionals reagent to graft to silica surface in organic atmosphere.（2）Silica shell is to receive hole or the loose structure such as mesoporous, using the size of silica shell, realize degradation selectivity to small molecule, and to macromole because cannot passing hole channel enter to active catalyst sites and cannot be degraded, so as to realize degradation selectivity.For example,
Ikeda seminars[2]In the sharp titanium titanium dioxide of commercialization（ST-41）Surface, has been initially formed one layer of charcoal, and then its surface is prepared for layer of silicon dioxide again, and multiple titanium dioxide bags in a ghost, the composite of formation has nano pore structure, and degrading gaseous-phase organic pollutant acetone, with preferable effect.Kazuyuki
[3]Seminar is prepared for one layer of mesoporous silicon in commodity titanium dioxide surface, and is used for Photocatalytic Degradation of Phenol, nonyl phenol and octane, as a result shows the photocatalytic degradation effect of composite Pyrogentisinic Acid and nonyl phenol preferably, and to the substantially no effect of octane.However, the porous silicon surface in this kind of material has substantial amounts of hydrophilic group hydroxyl, to low concentration, the substantially no absorbability of hydrophobic pollutant, actual processing effect is not good.
Document
[1] Xu Zhanglian, Wang Sheng, king draw. SiO2-TiO2The preparation of hollow type interface optical catalyst and performance. catalysis journal, 9 (2008)
987-991
[2] S. Ikeda, H. Kobayashi, Y. Ikom. Et.al. Structural effects of titanium(IV)
oxide encapsulated in a hollow silica shell on photocatalytic
activity for gas-phase decomposition of organics. Applied Catalysis A: General
369 (2009) 113-118.
[3] K. J. Nakamura, Y. Ide, M. Ogawa.Molecular recognitive photocatalytic decomposition on mesoporous
silica coated TiO2 particle. Materials Letters, 65 (2011) 24-26。
The content of the invention
The problem that composite titania/silica photocatalyst agent for existing preparation is present, the present invention is prepared for a kind of brand-new with titanium dioxide as core, with the composite photo-catalyst that the atom modified mesoporous silicon of small molecule organo-functional group phenyl or inorganic fluorine is shell, so that low concentration present in water, hydrophobicity be strong, highly toxic incretion interferent as model pollutant, study its removal effect.Preparation process is simple, composite photo-catalyst is easily isolated recoverys, and with preferable pollutant removal.
Character：Described hydrophobicity titanium dioxide/mesoporous silicon core shell photocatalyst genus blastomyces powder, the proportion of mesoporous silicon oxide therein is 60-40%, and the proportion of titanium dioxide is 40-60%.Fig. 1 is the high explanation transmission electron microscope picture of hydrophobicity titanium dioxide/mesoporous silicon core shell photocatalyst prepared by the present invention（TEM）, the composite for preparing as we know from the figure is core shell composite photo-catalyst of the mesoporous silicon for shell with titanium dioxide as core, and the size of core is 20-30nm,
Size 2-4nm of shell.
Another object of the present invention is to provide the preparation method of the hydrophobicity titanium dioxide/mesoporous silicon composite, following steps are specifically included：
In the present invention, synthetic method includes following step：
（1）
The first step, the preparation of tio_2 suspension：With 15-28 g hot water（40-60℃）Dissolving 0.3-0.7 g surfactants, add 1.8-2.0g strong aqua ammonia after being cooled to room temperature（25%）, under strong stirring, addition given commodity titanium dioxide, ultrasonic 5-15min, the pH value that solution is adjusted with alkali is 11.00-12.00.
（2）
Second step, the another preparation with functionalized SiO 2 precursor body fluid：6.0-10.0mL dehydrated alcohol, 1.60-2.40g tetraethoxysilanes and 0.8-1.6g functional silanes are taken, 15-30min is placed in stirring.
（3）
3rd step, solgel reaction：Under strong stirring, the precursor body fluid of second step is added to the first step in the suspension prepared, ultrasonic 5-15
Min, is stirred at room temperature hydrolysis 4-12h, filters, with organic solvent and distilled water wash, 60-80 DEG C of vacuum drying.
（4）
4th step, the removal of template：Two kinds of A and B can be adopted to remove the 3rd step and to prepare the structure directing agent in material（Surfactant）.
A. backflow washing removes surfactant：For the composite that the preparation of precursor body fluid is turned to organic functionses, 50-100mL dehydrated alcohol and 0.15-0.5mol/L hydrochloric acid can be used
80-90 DEG C of backflow 12-48h removes structure directing agent, and after repeating 2-4 time, then with dehydrated alcohol and water washing 5-8 time, 50-80 DEG C is vacuum dried.
B. roasting removes surfactant：For the composite prepared with functional fluoropolymer SiClx alkane precursor body fluid, 550-650 DEG C of roasting 6-3h. is can select
Described functional silaneThere is reagent containing small molecule hydrophobic group for phenyl triethoxysilane, phenyl-trimethylsilicane, triethoxyfluorosilane, trimethoxyfluorosilane, 13 fluorine-based octyltri-ethoxysilanes, tetramethyl siloxanes and trim,ethylchlorosilane etc..
Described surfactantOptional cetyl trimethylammonium bromide and cetyl trimethyl ammonia chloride.
Described titanium dioxide is anatase titanium dioxide and anatase/rutile mixed crystal titanium dioxide（Such as commodity oxide/titanium dioxide P25, Degussa）Deng；
The organic solvent may be selected the small molecule solvents such as ethanol, acetone, butanol and propanol；
Described alkali is strong aqua ammonia（25%）、0.5mol/L
NaOH and KOH；
Step of the present invention（3）Described in strong stirring condition be mixing speed between 1200 ~ 2000rpm, the condition power of ultrasonic disperse is to disperse 5 ~ 15min in the ultrasonic cleaner of 240 ~ 700W.
Can be used for that absorption/photocatalysis collaboration removal low concentration, hydrophobicity under ultraviolet light be strong, highly toxic organic pollution the hydrophobicity titanium dioxide/mesoporous silicon composite is invented, with preferable clean-up effect, specifically include following steps：Hydrophobicity titanium dioxide/mesoporous silicon composite is added in the water containing target contaminant, is stirred in dark place0.5-3hAdsorption-desorption balance is reached, eliminating rate of absorption is obtained, the absorption property of evaluating combined material, being then turned on uviol lamp carries out photocatalytic degradation experiment1-3h, photocatalytic degradation clearance is obtained, total absorption/photocatalysis collaboration clearance is obtained, the absorption/photocatalysis collaboration for weighing composite removes the efficiency of target contaminant.
Described simulated target pollutant are bisphenol-A（BPA）With 17- α-ethinyl estradiol（EE2）Incretion interferent.
Advantages of the present invention and effect：
（1）Silica shell is made meso-hole structure, is had and is mutually migrated to Titanium Dioxide avtive spot from water using organic pollution；
（2）Using the modified mesoporous silicon of the silylating reagent containing small molecule phenyl or fluorine hydrophobic group, the patency in duct can be kept（Because if selecting the organo-functional group of long-chain easily to block duct）, and the hydroxyl of mesoporous silicon face can be replaced so as to hydrophobicity, there can be preferable absorbability to water phase or the low concentration in gas phase, hydrophobic organic pollutant, so as to realize enrichment concentration, accelerate catalytic efficiency；
（3）Preparation method is simple, environmental protection, only uses Small molecule organic solvents ethanol of nontoxic or low toxicity etc..
Description of the drawings
Fig. 1 is the high explanation transmission electron microscope picture of the hydrophobicity titanium dioxide/mesoporous silicon core shell photocatalyst of present invention synthesis（TEM）；
Fig. 2 is the titanium dioxide/phenyl mesoporous silicon of present invention synthesis（TiO2/Ph-MS）N2Adsorption isotherm（a）And graph of pore diameter distribution（b）；
Fig. 3 is the infrared spectrogram of the titanium dioxide/phenyl mesoporous silicon of present invention synthesis（IR）.
Specific embodiment
Embodiment 1
1. the first step, the preparation of tio_2 suspension：Use 28g hot water（50℃）Dissolving 0.6g CTABs（CTAB）, after being cooled to room temperature, add 1.8g strong aqua ammonia（25%）, with vigorous stirring, add 0.8g commodity titanium dioxide（P25）, ultrasonic 5min, with strong aqua ammonia adjust solution pH value be11.0；
2. second step, separately matches somebody with somebody the preparation of functionalized SiO 2 precursor body fluid：8.0mL dehydrated alcohol, 2.00g TEOS and1.10g
Phenyl triethoxysilane（ PhTES ）, strong stirring placement 30min；
3. the 3rd step, solgel reaction：With vigorous stirring, during the precursor body fluid of second step to be added to the first step suspension prepared, ultrasonic 10min is stirred at room temperature hydrolysis 6h, filters, with dehydrated alcohol and distilled water wash, 80 DEG C of vacuum drying；
4. the 4th step, the removal of template：Structure directing agent CTAB is removed with 80 DEG C of backflow 24h of 50 mL dehydrated alcohol and 0.15 mol/L HCl, after being repeated twice then multiple with dehydrated alcohol and water washing, 80 DEG C of vacuum drying are obtained titanium dioxide/phenyl mesoporous silicon composite photo-catalyst；
5. absorption/photocatalysis cooperative experiment：0.005g titanium dioxide/Linesless charcoal composite is weighed respectively in the quartz test tube of 50mL, the bisphenol-A solution of 50.00ml 3mg/L is pipetted with pipet, add magnetic stir bar, in dark place, stirring 2h reaches adsorption-desorption balance, composite is made to be uniformly dispersed and reach adsorption-desorption balance, eliminating rate of absorption is obtained, the uviol lamp for being then turned on 20W carries out photocatalytic degradation experiment, degrade 3h.Eliminating rate of absorption is 17.80%, and photocatalysis clearance is 42.14%, and total absorption/photocatalysis collaboration clearance is 59.94%.
Embodiment
2
1. the first step, the preparation of tio_2 suspension：Use 28g hot water（60℃）Dissolving 0.70g cetyl trimethyl ammonia chlorides（CTAB）, after being cooled to room temperature, add 2.0g strong aqua ammonia（25%）, with vigorous stirring, add 0.8g commodity titanium dioxide（P25）, ultrasonic 5min, with strong aqua ammonia adjust solution pH value be12.0；
2. second step, separately matches somebody with somebody the preparation of functionalized SiO 2 precursor body fluid：8.0mL dehydrated alcohol, 2.00g TEOS and1.50g
Phenyl triethoxysilane（ PhTES ）, place 30min；
3. the 3rd step, solgel reaction：With vigorous stirring, during the precursor body fluid of second step to be added to the first step suspension prepared, ultrasonic 10min is stirred at room temperature hydrolysis 4h, filters, with dehydrated alcohol and distilled water wash, 80 DEG C of vacuum drying；
4. the 4th step, the removal of template：Structure directing agent CTAB is removed with 80 DEG C of backflow 24h of 50 mL dehydrated alcohol and 0.15 mol/L HCl, after being repeated twice then multiple with dehydrated alcohol and water washing, 80 DEG C of vacuum drying are obtained titanium dioxide/phenyl mesoporous silicon composite photo-catalyst；
5. absorption/photocatalysis cooperative experiment：0.005g titanium dioxide/Linesless charcoal composite is weighed respectively in the quartz test tube of 50mL, the bisphenol-A solution of 50.00ml 3mg/L is pipetted with pipet, add magnetic stir bar, in dark place, stirring 2h reaches adsorption-desorption balance, composite is made to be uniformly dispersed and reach adsorption-desorption balance, eliminating rate of absorption is obtained, the uviol lamp for being then turned on 20W carries out photocatalytic degradation experiment, degrade 3h.Eliminating rate of absorption is 16.8%, and photocatalysis clearance is 40.48%, and total absorption/photocatalysis collaboration clearance is 57.28%.
Embodiment
3
1. the first step, the preparation of tio_2 suspension：Use 28g hot water（40℃）Dissolving 0.6g CTABs（CTAB）, after being cooled to room temperature, add 1.8g strong aqua ammonia（25%）, with vigorous stirring, add 0.8g commodity titanium dioxide（P25）, ultrasonic 5min, the pH value for adjusting solution with strong aqua ammonia are 11.0；
2. second step, separately matches somebody with somebody the preparation of functionalized SiO 2 precursor body fluid：6.0mL dehydrated alcohol,2.40g TEOSWith0.80g
Triethoxyfluorosilane（ TEFS ）, place 30min；
3. the 3rd step, solgel reaction：With vigorous stirring, during the precursor body fluid of second step to be added to the first step suspension prepared, ultrasonic 10min is stirred at room temperature hydrolysis 12h, filters, with dehydrated alcohol and distilled water wash, 80 DEG C of vacuum drying；
4. the 4th step, the removal of template：, 550 DEG C of roasting 4h are can select, titanium dioxide/fluorine-based mesoporous silicon is prepared；
5. absorption/photocatalysis cooperative experiment：0.005g titanium dioxide/Linesless charcoal composite is weighed respectively in the quartz test tube of 50mL, the bisphenol-A solution of 50.00ml 3mg/L is pipetted with pipet, add magnetic stir bar, in dark place, stirring 2h reaches adsorption-desorption balance, composite is made to be uniformly dispersed and reach adsorption-desorption balance, eliminating rate of absorption is obtained, the uviol lamp for being then turned on 20W carries out photocatalytic degradation experiment, degrade 3h.Eliminating rate of absorption is 10.20%, and photocatalysis clearance is 68.17%, and total absorption/photocatalysis collaboration clearance is 78.27%.
Embodiment
4
1. the first step, the preparation of tio_2 suspension：Use 28g hot water（50℃）Dissolving 0.6g CTABs（CTAB）, after being cooled to room temperature, add 1.8g strong aqua ammonia（25%）, with vigorous stirring, add 0.8g commodity titanium dioxide（P25）, ultrasonic 5min, the pH value for adjusting solution with strong aqua ammonia are 11.0；
2. second step, separately matches somebody with somebody the preparation of functionalized SiO 2 precursor body fluid：6.0 mL dehydrated alcohol, 2.00g TEOS and 0.8gTriethoxyfluorosilane（ TEFS ）, place 30min；
3. the 3rd step, solgel reaction：With vigorous stirring, during the precursor body fluid of second step to be added to the first step suspension prepared, ultrasonic 10min is stirred at room temperature 6 h of hydrolysis, filters, with dehydrated alcohol and distilled water wash, 80 DEG C of vacuum drying；
4. the 4th step, the removal of template：, 550 DEG C of roasting 4h are can select, titanium dioxide/fluorine-based mesoporous silicon is prepared；
5. absorption/photocatalysis cooperative experiment：0.005g titanium dioxide/Linesless charcoal composite is weighed respectively in the quartz test tube of 50mL, pipettes 50.00ml 3mg/L's with pipet17- α - Ethinyl estradiol（ EE2 ）Solution, adds magnetic stir bar, stirs in dark place0.5hAdsorption-desorption balance is reached, composite is uniformly dispersed and is reached adsorption-desorption balance, is obtained eliminating rate of absorption, the uviol lamp for being then turned on 20W carries out photocatalytic degradation experiment, and degrade 3h.Eliminating rate of absorption is 40.18%, and photocatalysis clearance is 58.17%, and total absorption/photocatalysis collaboration clearance is98.35%。
Embodiment
5
1. the first step, the preparation of tio_2 suspension：Use 28g hot water（60℃）Dissolving 0.6g CTABs（CTAB）, after being cooled to room temperature, add 1.8g strong aqua ammonia（25%）, with vigorous stirring, add 0.8g commodity titanium dioxide（P25）, ultrasonic 15min, the pH value for adjusting solution with strong aqua ammonia are 11.0；
2. second step, separately matches somebody with somebody the preparation of functionalized SiO 2 precursor body fluid：6.0 mL dehydrated alcohol, 2.00g TEOS and 0.80g13 fluorine-based octyltri-ethoxysilanes, place 30min；
3. the 3rd step, solgel reaction：With vigorous stirring, during the precursor body fluid of second step to be added to the first step suspension prepared, ultrasonic 10min is stirred at room temperature 4 h of hydrolysis, filters, with dehydrated alcohol and distilled water wash, 80 DEG C of vacuum drying；
4. the 4th step, the removal of template：, 550 DEG C of roasting 4h are can select, titanium dioxide/fluorine-based mesoporous silicon is prepared；
5. absorption/photocatalysis cooperative experiment：0.005g titanium dioxide/Linesless charcoal composite is weighed respectively in the quartz test tube of 50mL, pipettes 50.00ml with pipet3mg/L17- α-ethinyl estradiol（EE2）Solution, adds magnetic stir bar, stirs in dark place3.0hAdsorption-desorption balance is reached, composite is uniformly dispersed and is reached adsorption-desorption balance, is obtained eliminating rate of absorption, the uviol lamp for being then turned on 20W carries out photocatalytic degradation experiment, and degrade 3h.Eliminating rate of absorption is 20.45%, and photocatalysis clearance is 64.17%, and total absorption/photocatalysis collaboration clearance is 84.62%.
Embodiment
6
1. the first step, the preparation of tio_2 suspension：Use 28g hot water（50℃）Dissolving0.70 g Cetyl trimethyl ammonia chloride, after being cooled to room temperature, add 1.8g strong aqua ammonia（25%）, with vigorous stirring, add 0.6g commodity titanium dioxide（P25）, ultrasonic 5min, the pH value for adjusting solution with strong aqua ammonia are 12.0；
2. second step, separately matches somebody with somebody the preparation of functionalized SiO 2 precursor body fluid：6.0 mL dehydrated alcohol, 2.00g TEOS and 0.80g13 fluorine-based octyltri-ethoxysilanes, place 30min；
3. the 3rd step, solgel reaction：With vigorous stirring, during the precursor body fluid of second step to be added to the first step suspension prepared, ultrasonic 10min is stirred at room temperature hydrolysis 6h, filters, with dehydrated alcohol and distilled water wash, 80 DEG C of vacuum drying；
4. the 4th step, the removal of template：, 550 DEG C of roasting 4h are can select, titanium dioxide/fluorine-based mesoporous silicon is prepared；
5. absorption/photocatalysis cooperative experiment：0.005g titanium dioxide/Linesless charcoal composite is weighed respectively in the quartz test tube of 50mL, pipettes 50.00ml with pipet3mg/LBisphenol-A（BPA）Solution, adds magnetic stir bar, stirs in dark place2.0 hAdsorption-desorption balance is reached, composite is uniformly dispersed and is reached adsorption-desorption balance, is obtained eliminating rate of absorption, the uviol lamp for being then turned on 20W carries out photocatalytic degradation experiment, and degrade 3h.Eliminating rate of absorption is 18.36%, and photocatalysis clearance is 54.24%, and total absorption/photocatalysis collaboration clearance is 72.60%.
Embodiment
7
1. the first step, the preparation of tio_2 suspension：Use 28g hot water（40℃）Dissolving 0.6g CTABs（CTAB）, after being cooled to room temperature, add 1.8g strong aqua ammonia（25%）, with vigorous stirring, add 0.8g commodity titanium dioxide（P25）, ultrasonic 5min, with strong aqua ammonia adjust solution pH value be11.0；
2. second step, separately matches somebody with somebody the preparation of functionalized SiO 2 precursor body fluid：8.0mL dehydrated alcohol, 1.60g TEOS and1.40
g Phenyl-trimethylsilicane, place 30min；
3. the 3rd step, solgel reaction：With vigorous stirring, during the precursor body fluid of second step to be added to the first step suspension prepared, ultrasonic 5min is stirred at room temperature 12 h of hydrolysis, filters, with dehydrated alcohol and distilled water wash, 60 DEG C of vacuum drying；
4. the 4th step, the removal of template：Structure directing agent CTAB is removed with 80 DEG C of backflow 24h of 50 mL dehydrated alcohol and 0.15 mol/L HCl, after being repeated twice then multiple with dehydrated alcohol and water washing, 80 DEG C of vacuum drying are obtained titanium dioxide/phenyl mesoporous silicon composite photo-catalyst；
5. absorption/photocatalysis cooperative experiment：0.005g titanium dioxide/Linesless charcoal composite is weighed respectively in the quartz test tube of 50mL, the bisphenol-A solution of 50.00ml 3mg/L is pipetted with pipet, add magnetic stir bar, in dark place, stirring 2h reaches adsorption-desorption balance, composite is made to be uniformly dispersed and reach adsorption-desorption balance, eliminating rate of absorption is obtained, the uviol lamp for being then turned on 20W carries out photocatalytic degradation experiment, degrade 3h.Eliminating rate of absorption is 47.20%, and photocatalysis clearance is 45.40%, and total absorption/photocatalysis collaboration clearance is 92.60%.
Embodiment
8
1. the first step, the preparation of tio_2 suspension：Use 28g hot water（50℃）Dissolving 0.7g cetyl trimethyl ammonia chlorides, add 2.0g strong aqua ammonia after being cooled to room temperature（25%）, with vigorous stirring, add 0.8g commodity titanium dioxide（P25）, ultrasonic 5min, with strong aqua ammonia adjust solution pH value be12.0；
2. second step, separately matches somebody with somebody the preparation of functionalized SiO 2 precursor body fluid：10.0 mL dehydrated alcohol, 1.60g TEOS and1.60g Trim,ethylchlorosilane, place 30min；
3. the 3rd step, solgel reaction：With vigorous stirring, during the precursor body fluid of second step to be added to the first step suspension prepared, ultrasonic 5min is stirred at room temperature hydrolysis 6h, filters, with dehydrated alcohol and distilled water wash, 60 DEG C of vacuum drying；
4. the 4th step, the removal of template：Structure directing agent cetyl trimethyl ammonia chloride is removed with 80 DEG C of backflow 24h of 50 mL dehydrated alcohol and 0.15 mol/L HCl, after being repeated twice, dehydrated alcohol and water washing are used again repeatedly, and 80 DEG C of vacuum drying are obtained titanium dioxide/chloromethyl mesoporous silicon composite photo-catalyst；
5. absorption/photocatalysis cooperative experiment：0.005g titanium dioxide/Linesless charcoal composite is weighed respectively in the quartz test tube of 50mL, the bisphenol-A solution of 50.00ml 3mg/L is pipetted with pipet, add magnetic stir bar, in dark place, stirring 2h reaches adsorption-desorption balance, composite is made to be uniformly dispersed and reach adsorption-desorption balance, eliminating rate of absorption is obtained, the uviol lamp for being then turned on 20W carries out photocatalytic degradation experiment, degrade 3h.Eliminating rate of absorption is 42.55%, and photocatalysis clearance is 40.37%, and total absorption/photocatalysis collaboration clearance is 82.92%.
Embodiment
9
1. the first step, the preparation of tio_2 suspension：Use 15g hot water（60℃）Dissolving 0.3g CTABs, add 1.0g strong aqua ammonia after being cooled to room temperature（25%）, with vigorous stirring, add 0.6g commodity titanium dioxide（P25）, ultrasonic 5min, with strong aqua ammonia adjust solution pH value be11.0；
2. second step, separately matches somebody with somebody the preparation of functionalized SiO 2 precursor body fluid：10.0 mL dehydrated alcohol, 2.00g TEOS and1.60g Trim,ethylchlorosilane, place 30min；
3. the 3rd step, solgel reaction：With vigorous stirring, during the precursor body fluid of second step to be added to the first step suspension prepared, ultrasonic 5min is stirred at room temperature hydrolysis 4h, filters, with dehydrated alcohol and distilled water wash, 60 DEG C of vacuum drying；
4. the 4th step, the removal of template：Structure directing agent cetyl trimethyl ammonia chloride is removed with 80 DEG C of backflow 24h of 50 mL dehydrated alcohol and 0.15 mol/L HCl, after being repeated twice, dehydrated alcohol and water washing are used again repeatedly, and 80 DEG C of vacuum drying are obtained titanium dioxide/chloromethyl mesoporous silicon composite photo-catalyst；
5. absorption/photocatalysis cooperative experiment：0.005g titanium dioxide/Linesless charcoal composite is weighed respectively in the quartz test tube of 50mL, pipettes the 17- α-ethinyl estradiol of 50.00ml 3mg/L with pipet（EE2）Solution, adds magnetic stir bar, and in dark place, stirring 2h reaches adsorption-desorption balance, composite is uniformly dispersed and is reached adsorption-desorption balance, obtains eliminating rate of absorption, and the uviol lamp for being then turned on 20W carries out photocatalytic degradation experiment, and degrade 3h.Eliminating rate of absorption is 52.55%, and photocatalysis clearance is 43.30%, and total absorption/photocatalysis collaboration clearance is 95.98%.
Embodiment
10
6. the first step, the preparation of tio_2 suspension：Use 28g hot water（60℃）Dissolving 0.6g CTABs, add 1.8 g strong aqua ammonia after being cooled to room temperature（25%）, with vigorous stirring, add 0.6g commodity titanium dioxide（P25）, ultrasonic 5min, with strong aqua ammonia adjust solution pH value be11.0；
7. second step, separately matches somebody with somebody the preparation of functionalized SiO 2 precursor body fluid：10.0 mL dehydrated alcohol, 1.60g TEOS and1.6 g Phenyl-trimethylsilicane, place 30min；
8. the 3rd step, solgel reaction：With vigorous stirring, during the precursor body fluid of second step to be added to the first step suspension prepared, ultrasonic 5min is stirred at room temperature hydrolysis 4h, filters, with dehydrated alcohol and distilled water wash, 60 DEG C of vacuum drying；
9. the 4th step, the removal of template：Structure directing agent cetyl trimethyl ammonia chloride is removed with 80 DEG C of backflow 24h of 50 mL dehydrated alcohol and 0.15 mol/L HCl, after being repeated twice then multiple with dehydrated alcohol and water washing, 80 DEG C of vacuum drying are obtainedTitanium dioxide / Phenyl mesoporous siliconComposite photo-catalyst；
10. absorption/photocatalysis cooperative experiment：0.005g titanium dioxide/Linesless charcoal composite is weighed respectively in the quartz test tube of 50mL, the bisphenol-A solution of 50.00ml 3mg/L is pipetted with pipet, add magnetic stir bar, in dark place, stirring 2h reaches adsorption-desorption balance, composite is made to be uniformly dispersed and reach adsorption-desorption balance, eliminating rate of absorption is obtained, the uviol lamp for being then turned on 20W carries out photocatalytic degradation experiment, degrade 3h.Eliminating rate of absorption is 31.48%, and photocatalysis clearance is 45.20%, and total absorption/photocatalysis collaboration clearance is 76.68%.
Claims (2)
1. the preparation method of a kind of hydrophobicity titanium dioxide/mesoporous silicon core shell composite photo-catalyst, it is characterised in that comprise the steps：
The first step, the preparation of tio_2 suspension：With 15-28 g hot water（40-60℃）Dissolving 0.3-0.7 g surfactants, add 1.8-2.0g strong aqua ammonia after being cooled to room temperature（25%）, under strong stirring, addition given commodity titanium dioxide, ultrasonic 5-15min, the pH value that solution is adjusted with alkali is 11.00-12.00；
Second step, the another preparation with functionalized SiO 2 precursor body fluid：6.0-10.0mL dehydrated alcohol, 1.60-2.40g tetraethoxysilanes and 0.8-1.6g functional silanes are taken, 15-30min is placed；
3rd step, solgel reaction：Under strong stirring, the precursor body fluid of second step is added to the first step in the suspension prepared, ultrasonic 5-15 min are stirred at room temperature hydrolysis 4-12h, filtered, with organic solvent and distilled water wash, 60-80 DEG C of vacuum drying；
4th step, the removal of template：Two kinds of A and B can be adopted to remove the 3rd step and to prepare the structure directing agent in material（Surfactant）；
Backflow washing removes surfactant：For the composite that the preparation of precursor body fluid is turned to organic functionses, 80-90 DEG C of backflow 12-48h of available 50-100mL dehydrated alcohol and 0.15-0.5mol/L hydrochloric acid removes structure directing agent, after repeating 2-4 time, then with dehydrated alcohol and water washing 5-8 time, 50-80 DEG C is vacuum dried；
Roasting removes surfactant：For the composite prepared with functional fluoropolymer SiClx alkane precursor body fluid, 550-650 DEG C of roasting 6-3h is can select；
Described functional silane is that phenyl triethoxysilane, phenyl-trimethylsilicane, triethoxyfluorosilane, trimethoxyfluorosilane, 13 fluorine-based octyltri-ethoxysilanes, tetramethyl siloxanes and trim,ethylchlorosilane etc. have reagent containing small molecule hydrophobic group；
Described surfactant may be selected cetyl trimethylammonium bromide and cetyl trimethyl ammonia chloride；
Described titanium dioxide is anatase titanium dioxide and anatase/rutile mixed crystal titanium dioxide（Such as commodity oxide/titanium dioxide P25, Degussa）Deng；
The organic solvent may be selected the small molecule solvents such as ethanol, acetone, butanol and propanol；
Described alkali is strong aqua ammonia（25%）, 0.5mol/L NaOH and KOH.
2. hydrophobicity titanium dioxide/mesoporous silicon core shell composite photo-catalyst that prepared by the method for claim 1, it is characterised in that：Described hydrophobicity titanium dioxide/mesoporous silicon core shell photocatalyst genus blastomyces powder, the proportion of mesoporous silicon oxide therein is 60-40%, and the proportion of titanium dioxide is 40-60%；And composite is core shell composite photo-catalyst of the mesoporous silicon for shell with titanium dioxide as core, the size of core is 20-30nm, size 2-4nm of shell.
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