CN102350354B - Magnetically supported titanium dioxide photocatalyst and preparation method thereof - Google Patents
Magnetically supported titanium dioxide photocatalyst and preparation method thereof Download PDFInfo
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- CN102350354B CN102350354B CN2011102458468A CN201110245846A CN102350354B CN 102350354 B CN102350354 B CN 102350354B CN 2011102458468 A CN2011102458468 A CN 2011102458468A CN 201110245846 A CN201110245846 A CN 201110245846A CN 102350354 B CN102350354 B CN 102350354B
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Abstract
The invention discloses a magnetically supported titanium dioxide photocatalyst and a preparation method thereof, belonging to the technical field of material preparation. A solvothermal process is used for obtaining a dimension-adjustable ferroferric oxide spherical particles, and the pH value, reaction temperature, reaction time and other experimental parameters are regulated to control the hydrolysis of tetrabutyl titanate, so that the tetrabutyl titanate is uniformly supported on the surface of the ferroferric oxide magnetic nucleus, thereby preparing the hexagonal crystal form magnetically supported titanium dioxide photocatalyst. The magnetically supported titanium dioxide photocatalyst has the advantages of controllable preparation technique, high safety and reliability and high yield, can be used for quickly catalyzing the degradation of pollutants, and can be easy in industrialization production.
Description
Technical field:
The invention belongs to technical field of material, particularly relate to a kind of magnetic carrying of titanium dioxide photocatalyst and preparation method thereof.
Background technology:
In recent years; Conductor photocatalysis oxidative degradation organic pollution has become a focus of environmental pollution improvement; Wherein titanium dioxide is with advantages such as its active high, nontoxic, Heat stability is good, longer duration, cheap, non-secondary pollution, extremely people's attention.In order to improve the photocatalytic activity of titanium dioxide; Usually utilize the small-size effect of catalyst; This just requires TiO 2 particles must be nanoscale, has so just formed the contradiction that activity of such catalysts and catalyst are prone to loss, Separation and Recovery difficulty, thereby has limited its industrialization promotion application.On the one hand, catalyst will have enough small particle diameter, guarantees activity of such catalysts; On the other hand, need to solve the Separation and Recovery problem behind catalyst and the pollutant reaction.Therefore, catalyst be fixed into new research focus, but after catalyst fixed, catalytic efficiency often was lower than the catalyst of suspended state, thereby has limited the practical application of photochemical catalyst.
Have based on this, make the present invention.
Summary of the invention:
First aspect of the present invention provides a kind of magnetic carrying of titanium dioxide photocatalyst, it is characterized in that: said catalyst is a carrier with the tri-iron tetroxide spheroidal particle, at the area load of tri-iron tetroxide spheroidal particle titanium dioxide is arranged.
Said titanium dioxide is hexagonal structure titanium dioxide, is coated on the surface of tri-iron tetroxide spheroidal particle.
Second aspect of the present invention provides a kind of preparation method of magnetic carrying of titanium dioxide photocatalyst, may further comprise the steps:
(1), be source of iron with the Iron(III) chloride hexahydrate, anhydrous sodium acetate and Macrogol 200 are additive, ethylene glycol is solvent, under the normal temperature and pressure, magnetic agitation obtains settled solution; The sealing of this settled solution is placed agitated reactor, and this agitated reactor is placed baking oven, be warming up to 180 ℃ with the rate of heat addition of 5 ℃/min, and under this temperature reaction 8 h (hour); After reaction finished, the mixture that reaction is obtained centrifugalized, and the black solid that obtains is after absolute ethanol washing is clean, and oven dry 8 h get the tri-iron tetroxide spheroidal particle in 80 ℃ baking oven;
(2), the tri-iron tetroxide spheroidal particle of step (1) preparation is placed round-bottomed flask, add absolute ethyl alcohol, ultrasonic disperse black suspension;
(3), under mechanical agitation; In the black suspension that step (2) makes, add octadecyl trimethylammonium bromide and Macrogol 200 successively; After fully mixing, mixed liquor is warming up to 60～80 ℃ under mechanical agitation, and under this temperature, continues to stir 1～2 h;
(4), in the mixed solution that step (3) makes, slowly add dilute sulfuric acid, and the pH value of regulator solution is 3～4, to wherein slowly dripping butyl titanate, after dropwising, continues to stir 2h again, adds distilled water again, continues stirring 6～10h; Stop after reaction finishes stirring, naturally cool to after the room temperature and filter behind ageing 12 h, product washs with ethanol, distilled water successively, and 80 ℃ of following vacuum drying 12h make magnetic carrying of titanium dioxide photocatalyst then.
In the described step 1, described agitated reactor is preferably the teflon-lined stainless steel cauldron.
In the described step 4, dilute sulfuric acid is meant 1～2 molL
-1The sulfuric acid solution of concentration.Reaction temperature in the butyl titanate hydrolytic process is 60～80 ℃.
Beneficial effect of the present invention is following:
1, magnetic carrying of titanium dioxide photocatalyst of the present invention; With the tri-iron tetroxide spheroidal particle is carrier; Area load at the tri-iron tetroxide spheroidal particle has titanium dioxide, and the tri-iron tetroxide spheroidal particle is a kind of magnetic material, can be adsorbed by magnet; On the tri-iron tetroxide surface, can it be separated coated by titanium dioxide from waste water fast with the method that adds permanent magnet.
2, the present invention adopts the tri-iron tetroxide magnetic nuclear of the synthetic size adjustable of solvent-thermal method, adopts sol-gel process to make its carried titanium dioxide again, thus the preparation magnetic carrying of titanium dioxide photocatalyst.This synthetic method is simple, cost is low, photocatalytic activity is high, catalytic degradation speed is fast.
The micro Fe of 3, in the preparation process, infiltrating
3+Can reduce the energy gap of titanium dioxide, absorbing wavelength is moved to visible region, improve photocatalysis efficiency.Therefore, magnetic carrying of titanium dioxide photocatalyst, magnetic separation technique not only capable of using is convenient to reclaim magnet carried photocatalyst fastly, makes it can keep good photocatalyst activity, again repeatedly regeneration.
4, preparation method of the present invention, the raw material of use is easy to get, technology is simple, pollution-free, productive rate is high, the easily separated recovery of catalyst, can be efficiently, various organic pollutions in catalytic degradation industry and the sanitary wastewater apace.
Below in conjunction with the accompanying drawing and the specific embodiment the present invention is described further.
Description of drawings:
Fig. 1 is SEM (SEM) photo (SEM, JEOL JSM-6360LV, accelerating potential are 10 kV) of the tri-iron tetroxide of the embodiment of the invention one preparation.
Fig. 2 is X-ray diffraction (XRD) figure (XRD, Shimadzu X-6000, Cu K α λ=0.15406 nm) of the tri-iron tetroxide of the embodiment of the invention one (a) and embodiment two (b) preparation.
Fig. 3 is X-ray diffraction (XRD) figure (XRD, Shimadzu X-6000, Cu K α λ=0.15406 nm) of the magnetic carrying of titanium dioxide photocatalyst of the embodiment of the invention one (a) and embodiment two (b) preparation.
Fig. 4 is that the magnetic carrying of titanium dioxide photocatalyst of the embodiment of the invention one preparation is handled the reactive orange degradation curve.
Fig. 5 is SEM (SEM) photo (SEM, JEOL JSM-6360LV, accelerating potential are 15 kV) of the tri-iron tetroxide of the embodiment of the invention two preparations.
Fig. 6 is that the magnetic carrying of titanium dioxide photocatalyst of the embodiment of the invention two preparations is handled the reactive orange degradation curve.
The specific embodiment:
Embodiment 1:
At normal temperatures and pressures with 1 * 10
-3Mol FeCl
36H
2O, 1.44 g anhydrous sodium acetates and 0.4 g Macrogol 200 are dissolved in respectively in the 20 mL ethylene glycol, under the magnetic agitation effect, make its fully mix settled solution.The sealing of this settled solution is positioned in the teflon-lined stainless steel cauldron that volume is 22 mL, and this agitated reactor is placed baking oven, be warming up to 180 ℃ with the rate of heat addition of 5 ℃/min, and under this temperature reaction 8 h.After question response finishes; The mixture that reaction is obtained carries out centrifuge and under 12000 r/min speed, separates 2 min; The black solid that obtains is cleaned more than 8 times with absolute ethyl alcohol, and the solid that obtains is dried 8 h in 80 ℃ baking oven, get final product tri-iron tetroxide.SEM (SEM) characterizes, and can know that like Fig. 1 product is the spheroidal particle of favorable dispersibility, about 200 nm of diameter; X-ray diffraction (XRD) characterizes, and can know like Fig. 2 (a), and near the diffraction maximum that 18.4,30.1,35.4,43.1,53.4,57.0,62.6,70.9,74.0 and 75.0, occurs is corresponding face-centered cubic Fe respectively
3O
4(111), the crystal face peak of (220), (311), (400), (422), (333), (440), (620), (533) and (622), other peak does not appear, explain that product is a tri-iron tetroxide.
Take by weighing dried tri-iron tetroxide 60 mg and place round-bottomed flask, again to wherein adding 50 mL absolute ethyl alcohols, ultrasonic disperse black suspension.Under mechanical agitation, in black suspension, add 40 mg octadecyl trimethylammonium bromides and 20 mL Macrogol 200s successively, after treating fully to mix, this mixed liquor is warming up to 60 ℃ with the speed of 3 ℃/min, and under this temperature, continues to stir 1 h.After stirring end, in this mixed liquor, slowly add 1 molL
-1Dilute sulfuric acid, and the pH value of regulator solution is 3, to wherein slowly dripping butyl titanate 6 mL, after dropwising, continues to stir 2 h again, and to wherein adding 10 mL distilled water, continues to stir 6 h.After reaction finishes, stop to stir, naturally cool to room temperature, ageing 12 h.Product is filtered, washs with ethanol, distilled water successively, and solid is put into 80 ℃ of vacuum drying chambers, dry 12 h, get final product magnetic carrying of titanium dioxide.X-ray diffraction (XRD) characterizes, and can know like Fig. 3 (a), and near the diffraction maximum that 35.4,43.1,56.9 and 62.5, occurs is corresponding face-centered cubic Fe respectively
3O
4(311), the crystal face peak of (400), (333) and (440), near the diffraction maximum that 17.9 and 24.4, occurs is six side TiO
2(220) and the crystal face peak of (411), show that product is the compound of tri-iron tetroxide and hexagonal structure titanium dioxide.
With hexagonal structure magnetic carrying of titanium dioxide photocatalyst 50 mg of above-mentioned preparation, put into the good 50mL100 mgL of device
-1In the quartz container of reactive orange solution, again this quartz container is placed illumination under the uviol lamp, illumination is 3 min only, and the degradation rate of reactive orange just surpasses 90 %, and the curve of degrading activity orange is as shown in Figure 4.
Embodiment 2:
At normal temperatures and pressures with 2 * 10
-3Mol FeCl
36H
2O, 1.44 g anhydrous sodium acetates and 0.4 g Macrogol 200 are dissolved in respectively in the 20 mL ethylene glycol, under the magnetic agitation effect, make its fully mix settled solution.The sealing of this settled solution is positioned in the teflon-lined stainless steel cauldron that volume is 22 mL, and this agitated reactor is placed baking oven, be warming up to 180 ℃ with the rate of heat addition of 5 ℃/min, and under this temperature reaction 8 h.After question response finishes; The mixture that reaction is obtained carries out centrifuge and under 12000 r/min speed, separates 2 min; The black solid that obtains is cleaned more than 8 times with absolute ethyl alcohol, and the solid that obtains is dried 8 h in 80 ℃ baking oven, get final product tri-iron tetroxide.SEM (SEM) characterizes, and can know that like Fig. 5 product is the spheroidal particle of favorable dispersibility, about 400 nm of diameter; X-ray diffraction (XRD) characterizes, and can know like Fig. 2 (b), and near the diffraction maximum that 18.2,30.1,35.6,43.1,53.4,57.0,62.5,70.9,73.9 and 74.9, occurs is corresponding face-centered cubic Fe respectively
3O
4(111), the crystal face peak of (220), (311), (400), (422), (333), (440), (620), (533) and (622), other peak does not appear, explain that product is a tri-iron tetroxide.
Take by weighing dried tri-iron tetroxide 60 mg and place round-bottomed flask, again to wherein adding 50 mL absolute ethyl alcohols, ultrasonic disperse black suspension.Under mechanical agitation, in black suspension, add 40 mg octadecyl trimethylammonium bromides and 20 mL Macrogol 200s successively, after treating fully to mix, this mixed liquor is warming up to 80 ℃ with the speed of 3 ℃/min, and under this temperature, continues to stir 2 h.After stirring end, in this mixed liquor, slowly add 2 molL
-1Dilute sulfuric acid, and the pH value of regulator solution is 4, to wherein slowly dripping butyl titanate 6 mL, after dropwising, continues to stir 2 h again, and to wherein adding 20 mL distilled water, continues to stir 10 h.After reaction finishes, stop to stir, naturally cool to room temperature, ageing 12 h.Product is filtered, washs with ethanol, distilled water successively, and solid is put into 80 ℃ of vacuum drying chambers, dry 12 h, get final product magnetic carrying of titanium dioxide.X-ray diffraction (XRD) characterizes, and can know like Fig. 3 (b), and near the diffraction maximum that 35.6,43.1,56.9 and 62.6, occurs is corresponding face-centered cubic Fe respectively
3O
4(311), the crystal face peak of (400), (333) and (440), near the diffraction maximum that 17.8 and 24.4, occurs is six side TiO
2(220) and the crystal face peak of (411), surperficial product is the compound of tri-iron tetroxide and hexagonal structure titanium dioxide.
With hexagonal structure magnetic carrying of titanium dioxide photocatalyst 50 mg of above-mentioned preparation, put into the good 50mL100 mgL of device
-1In the quartz container of reactive orange solution, again this quartz container is placed illumination under the uviol lamp, illumination is 2 min only, and the degradation rate of reactive orange just surpasses 90 %, and the curve of degrading activity orange is as shown in Figure 6.
Claims (4)
1. the preparation method of a magnetic carrying of titanium dioxide photocatalyst is characterized in that, may further comprise the steps:
(1), be source of iron with the Iron(III) chloride hexahydrate, anhydrous sodium acetate and Macrogol 200 are additive, ethylene glycol is solvent, under the normal temperature and pressure, magnetic agitation obtains settled solution; The sealing of this settled solution is placed agitated reactor, and this agitated reactor is placed baking oven, be warming up to 180 ℃ with the rate of heat addition of 5 ℃/min, and reaction 8 hours under this temperature; After reaction finished, the mixture that reaction is obtained centrifugalized, and the black solid that obtains is after absolute ethanol washing is clean, and oven dry is 8 hours in 80 ℃ baking oven, gets the tri-iron tetroxide spheroidal particle;
(2), the tri-iron tetroxide spheroidal particle of step (1) preparation is placed round-bottomed flask, add absolute ethyl alcohol, ultrasonic disperse black suspension;
(3), under mechanical agitation; In the black suspension that step (2) makes, add octadecyl trimethylammonium bromide and Macrogol 200 successively; After fully mixing, mixed liquor is warming up to 60～80 ℃ under mechanical agitation, and under this temperature, continues to stir 1～2 hour;
(4), in the mixed solution that step (3) makes, slowly add dilute sulfuric acid, and the pH value of regulator solution is 3～4, to wherein slowly dripping butyl titanate, after dropwising, continues to stir 2 hours again, adds distilled water again, continues stirring 6～10 hours; Stop after reaction finishes stirring, naturally cool to room temperature after ageing filters after 12 hours, product washs with ethanol, distilled water successively, 80 ℃ of following vacuum drying are 12 hours then, make the hexagonal structure magnetic carrying of titanium dioxide photocatalyst.
2. the preparation method of a kind of magnetic carrying of titanium dioxide photocatalyst according to claim 1, it is characterized in that: in the described step 1, agitated reactor is the teflon-lined stainless steel cauldron.
3. the preparation method of a kind of magnetic carrying of titanium dioxide photocatalyst according to claim 1, it is characterized in that: in the described step 4, dilute sulfuric acid is 1～2 molL
-1The sulfuric acid solution of concentration.
4. the preparation method of a kind of magnetic carrying of titanium dioxide photocatalyst according to claim 1, it is characterized in that: in the described step 4, the reaction temperature in the butyl titanate hydrolytic process is 60～80 ℃.
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| CN105301057B (en) * | 2015-10-20 | 2018-03-02 | 江苏宏远药业有限公司 | A kind of method that on-line monitoring prepares titanium dioxide |
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| CN107311235B (en) * | 2017-08-21 | 2019-02-22 | 南京师范大学 | A kind of preparation method and applications of ferrotitanium composite material |
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| CN113578366A (en) * | 2021-08-13 | 2021-11-02 | 南京信息工程大学 | OCN-TiO2@Fe3O4Magnetic photocatalytic material, preparation method and application thereof |
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