CN1623656A - Photocatalyst of high active nano magnetic compound and its preparation process - Google Patents

Photocatalyst of high active nano magnetic compound and its preparation process Download PDF

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CN1623656A
CN1623656A CN 200410072590 CN200410072590A CN1623656A CN 1623656 A CN1623656 A CN 1623656A CN 200410072590 CN200410072590 CN 200410072590 CN 200410072590 A CN200410072590 A CN 200410072590A CN 1623656 A CN1623656 A CN 1623656A
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absolute ethyl
ethyl alcohol
tin
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CN100355497C (en
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张昊
谭欣
赵林
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Tianjin University
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Abstract

A high-activity magnetic nano-class photocatalyst is composed of the core (organically modified Fe3O4) and the shell (composite SnO2-TiO2 semiconductor). Its preparing process includes such steps as preparing the magnetic alcohol-base fluid from FeCl2, FeCl3, and polyethanediol or diethanolamine by codeposition method, preparing SnO2 sol from SnCl2 or SnCl4 by sol-gel method, mixing them together, ultrasonic dispersing and heat treating. Its advantages are high catalytic activity and cyclic use.

Description

The photochemical catalyst of high active nano magnetic compound and preparation method
Technical field
The present invention relates to a kind of photochemical catalyst and preparation method of high active nano magnetic compound, belong to the magnetic photocatalyst technology.
Background technology
Relevant magnetic photocatalyst paper:
Li Xinjun etc. the preparation of magnetic nanometer photocatalyst and photocatalysis performance thereof [J]. China YouSe Acta Metallurgica Sinica, 2001,11 (6): 971-976
Article has been set forth and has been utilized the organic-inorganic nanometer composite technology, and phthalocyanine nickel and ferriferrous oxide nano-particle is compound, as magnetic nuclear, adopts colloidal sol-gel technique to prepare the nano magnetic compound photochemical catalyst.Its structure is a nucleocapsid structure, and shell is a titanium dioxide, examines to be phthalocyanine nickel and tri-iron tetroxide compound particle, in order to prevent contacting of magnetic nuclear and titanium dioxide, has also added the silica inert layer.
The prepared magnetic nuclear of the method disperses to be suspended state in ethanol, non-nano yardstick (colloidal state), and only adopted stirring in colloidal sol-gel process, be difficult to make magnetic nuclear to reach nano level dispersion.The heat treatment programming rate is not controlled, and causes sintering to subside seriously.
The nano magnetic compound photochemical catalyst long time without surface modification that above method is prepared, photocatalytic activity is lower.
Summary of the invention
The object of the present invention is to provide a kind of photochemical catalyst and preparation method of high active nano magnetic compound, this photocatalyst activity height, preparation process is simple.
The present invention is realized by following technical proposals.A kind of photochemical catalyst of high active nano magnetic compound is characterized in that this catalyst average grain diameter is 80nm～100nm; The nuclear material is organically-modified tri-iron tetroxide, and the shell material is the composite semiconductor of tin ash titanium dioxide, and titanium tin iron atom ratio is in the photochemical catalyst: (75～80): (10～15): (5～10).
Above-mentioned photochemical catalyst preparation method is characterized in that may further comprise the steps:
1, alcohol radical Fe 3O 4The magnetic fluid preparation
Prepare nanometer Fe with coprecipitation 3O 4Magnetic fluid: press Fe 2+, Fe 3+Mol ratio is 1: 2～2: 3, with the 0.25mol/L～0.5mol/L FeCl for preparing 2Solution and 0.25mol/L～0.5mol/L FeCl 3Solution and Macrogol 4000 solution or diethanolamine solution join and are equipped with in the churned mechanically four-hole boiling flask; wherein to account for the mass percent of reactant liquor be 1%～2% for Macrogol 4000 or diethanol amine; in 60 ℃～80 ℃ waters bath with thermostatic control, heat, feed nitrogen protected simultaneously.Slowly drip 1mol/L～2mol/L NaOH solution, treat pH value to 6～7, black Fe is arranged 3O 4Particle occurs, and continues to add alkali, and regulating the pH value is 11～12.Temperature rises to 80 ℃～90 ℃, ageing.Fe with preparation 3O 4Particle spends deionised water to neutral, uses absolute ethanol washing again, and after the magnetic force sedimentation, with the absolute ethyl alcohol dilution, alcohol radical Fe is made in ultrasonic dispersion 3O 4Magnetic fluid.
2, tin ash colloidal sol preparation
Adopting stannous chloride or butter of tin is raw material, joins in the absolute ethyl alcohol, is mixed with the solution of 0.2mol/L～0.5mol/L, under the magnetic agitation condition, refluxes, and obtains water white transparency colloidal sol.Ageing 12h～24h slowly drips 1mol/L～10mol/L NH 3H 2O forms the milky gel.Spend deionised water, alcohol is washed till no chlorion again.Filter the washing back, and filter cake is transferred in the absolute ethyl alcohol, and ultrasonic dispersion forms tin ash colloidal sol.
3, complex photochemical catalyst preparing gel
By titanium tin atom ratio is 8: 1～5: 1, and the ferrotianium atomic ratio is 7.5: 1～16: 1.Get above-mentioned tin ash colloidal sol, add butyl titanate, ultrasonic dispersion, ageing adds above-mentioned alcohol radical Fe again 3O 4Magnetic fluid, ultrasonic dispersion forms solution A.By sour titanium mol ratio (H +/ Ti) be 0.05: 1～0.2: 1, pure titanium mol ratio is 9: 1～18: 1, water titanium mol ratio is 2.8: 1～5.6: 1.Deionized water is joined in the absolute ethyl alcohol, drip nitric acid, ultrasonic dispersion is mixed with solution B, under the violent mechanical agitation, solution B is slowly splashed in the solution A, forms until gel.
4, the heat treatment of gel
Gel 70 ℃～90 ℃ following vacuum drying, is ground, under nitrogen atmosphere, through the heat treatment of temperature programmed control Muffle furnace.25 ℃～250 ℃ heat up with 1 ℃/min, heat up with 2 ℃/min more than 250 ℃, are warming up to 450 ℃～650 ℃, more than the insulation 1h, close nitrogen when being cooled to below 150 ℃.
Its advantage of above-mentioned photochemical catalyst and preparation method is:
Whole process of preparation is the liquid phase chemical approach, adopts nanometer/nanometer composite technology, can guarantee the rational in infrastructure of complex particles, and nanoscale mixes, and coats evenly.Magnetic nuclear can be colloidal state and disperse after the organic surface active agent modification in ethanol, guaranteed the nanoscale of magnetic nuclear.Surfactant not only plays the effect of antioxidant and dispersant, can also play the barrier film effect in heat treatment process, prevents the generation of ferrotitanium compound.Compound tin ash provides the transfer location of carrier, has improved the separation rate in light induced electron hole, thereby makes the activity of nano magnetic compound photochemical catalyst improve about 40%.Adopted ultrasonic dispersion in the preparation process in a large number, can guarantee that colloidal sol, colloid reach the dispersion of nanoscale after mixing.Controlled atmosphere temperature programmed control gel heat treatment technics can guarantee that material do not reunite substantially in heat treatment process, reduce sintering and subside.
This kind nano magnetic compound photochemical catalyst is convenient to separate and is reclaimed, and recycles.
Description of drawings
Fig. 1 is the B-H loop of high active nano magnetic compound catalysis material.By curve as can be seen, the coercivity of high active nano magnetic compound catalysis material is 17.77oe, and saturation magnetization is 3.145emu/g.
Fig. 2 composes entirely for the XPS of high active nano magnetic compound photochemical catalyst.By spectrogram as can be seen, elements such as catalyst surface aerobic, titanium, tin, iron.According to Ti2p, Sn3d, the spectrogram of Fe2p, the atomic ratio that obtains titanium tin iron after the normalized is: 79.2: 12.5: 8.3.
Fig. 3 is magnetic photocatalyst of the present invention and the Comparative Examples magnetic photocatalyst degradation rate curve to methyl orange.Among the figure, the TSF curve is the degradation rate curve of magnetic photocatalyst of the present invention to methyl orange, and the TF curve is the degradation rate curve of Comparative Examples magnetic photocatalyst to methyl orange.As seen from the figure, magnetic photocatalyst of the present invention to the photocatalytic degradation rate of methyl orange than the photocatalytic degradation rate high about 40% of Comparative Examples magnetic photocatalyst to methyl orange.
The specific embodiment
Embodiment 1
The experiment agents useful for same all is the A.R rank, and all solution are through 0.22 μ m filtering with microporous membrane, to remove corpuscular property impurity harmful in the solution.With the 0.25mol/L FeCl for preparing 2Solution 80mL and 0.25mol/L FeCl 3Solution 120mL and polyglycol solution 80mL (containing the 5g Macrogol 4000) join and have in the churned mechanically 500mL four-hole boiling flask, heat in 70 ℃ of waters bath with thermostatic control, feed high pure nitrogen protected simultaneously.Slowly drip 1mol/L NaOH solution, survey the pH value, treat pH value to 6～7, black Fe is arranged every 2min 3O 4Particle occurs, and continues to add alkali, and regulating the pH value is 11～12.Temperature rises to 80 ℃, ageing 2h.Fe with preparation 3O 4The nano particles by using deionized water washing is used absolute ethanol washing again to neutral, after the magnetic force sedimentation, with the dilution of 250mL absolute ethyl alcohol, in ultrasonic 5 cycles, makes alcohol radical Fe 3O 4Magnetic fluid is named F1.
Take by weighing 11.2815g SnCl 22H 2O is dissolved in the 100mL absolute ethyl alcohol, through 0.22 μ m filtering with microporous membrane, is mixed with the tin-salt solution of 0.5mol/L.Magnetic agitation, backflow 4h.Behind the ageing 24h, slowly drip 2mol/L NH 3H 2O is to neutrality, ageing 12h.Spend deionised water, alcohol is washed till no chlorion again.Washing is after 0.45 μ m filtering with microporous membrane is transferred to filter cake in the 200mL absolute ethyl alcohol, and ultrasonic dispersion forms tin ash colloidal sol, is named S1.
Get 20mL tin ash colloidal sol (S1), add the 8mL butyl titanate, in ultrasonic 4 cycles, ageing 0.5h adds 20mL alcohol radical Fe again 3O 4Magnetic fluid (F1) in ultrasonic 2 cycles, forms solution A.1.5mL deionized water joins in the 15mL absolute ethyl alcohol, drips 0.15mL nitric acid, ultrasonic dispersion is mixed with solution B.Under violent mechanical agitation, solution B is slowly splashed in the solution A, continue to stir, form until gel.
With gel 80 ℃ of following vacuum drying, pick up broken, under nitrogen atmosphere, through the heat treatment of temperature programmed control muffle furnace.25 ℃～250 ℃ heat up with 1 ℃/min, heat up with 2 ℃/min more than 250 ℃, are warming up to 450 ℃, and insulation 1h closes nitrogen when being cooled to below 150 ℃.Sample is named TSF1.
Embodiment 2
With the 0.5mol/L FeCl for preparing 2Solution 40mL and 0.5mol/L FeCl 3Solution 80mL and polyglycol solution 80mL (containing the 4.5g Macrogol 4000) join and are equipped with in the churned mechanically 500mL four-hole boiling flask, heat in 60 ℃ of waters bath with thermostatic control, feed high pure nitrogen protected simultaneously.Slowly drip 2mol/L NaOH solution, survey the pH value, treat pH value to 6～7, black Fe is arranged every 2min 3O 4Particle occurs, and continues to add alkali, and regulating the pH value is 11～12.Temperature rises to 90 ℃, ageing 2h.Fe with preparation 3O 4The nano particles by using deionized water washing is used absolute ethanol washing again to neutral, after the magnetic force sedimentation, with the dilution of 250mL absolute ethyl alcohol, in ultrasonic 5 cycles, makes alcohol radical Fe 3O 4Magnetic fluid is named F2.
Take by weighing 11.2815g SnCl 22H 2O is dissolved in the 125mL absolute ethyl alcohol, through 0.22 μ m filtering with microporous membrane, is mixed with the tin-salt solution of 0.4mol/L.Magnetic agitation, backflow 4h.Behind the ageing 24h, slowly drip 10mol/L NH 3H 2O is to neutrality, ageing 12h.Spend deionised water, alcohol is washed till no chlorion again.Washing is after 0.45 μ m filtering with microporous membrane is transferred to filter cake in the 200mL absolute ethyl alcohol, and ultrasonic dispersion forms tin ash colloidal sol, is named S2.
Get 18mL tin ash colloidal sol (S2), add the 9mL butyl titanate, in ultrasonic 4 cycles, ageing 0.5h adds 15mL alcohol radical Fe again 3O 4Magnetic fluid (F2) in ultrasonic 2 cycles, forms solution A.2.4mL deionized water joins in the 24mL absolute ethyl alcohol, drips 0.2mL nitric acid, ultrasonic dispersion is mixed with solution B.Under violent mechanical agitation, solution B is slowly splashed in the solution A, continue to stir, form until gel.
With gel 90 ℃ of following vacuum drying, pick up broken, under nitrogen atmosphere, through the heat treatment of temperature programmed control muffle furnace.25 ℃～250 ℃ heat up with 1 ℃/min, heat up with 2 ℃/min more than 250 ℃, are warming up to 650 ℃, and insulation 1h closes nitrogen when being cooled to below 150 ℃.Sample is named TSF2.
Embodiment 3, with the 0.4mol/L FeCl for preparing 2Solution 50mL and 0.4mol/L FeCl 3Solution 75mL and polyglycol solution 80mL (containing the 2.5g Macrogol 4000) join and are equipped with in the churned mechanically 500mL four-hole boiling flask, heat in 80 ℃ of waters bath with thermostatic control, feed high pure nitrogen protected simultaneously.Slowly drip 1.5mol/L NaOH solution, survey the pH value, treat pH value to 6～7, black Fe is arranged every 2min 3O 4Particle occurs, and continues to add alkali, and regulating the pH value is 11～12.Temperature rises to 85 ℃, ageing 2h.Fe with preparation 3O 4The nano particles by using deionized water washing is used absolute ethanol washing again to neutral, after the magnetic force sedimentation, with the dilution of 250mL absolute ethyl alcohol, in ultrasonic 5 cycles, makes alcohol radical Fe 3O 4Magnetic fluid is named F3.
Take by weighing 11.2815g SnCl 22H 2O is dissolved in the 250mL absolute ethyl alcohol, through 0.22 μ m filtering with microporous membrane, is mixed with the tin-salt solution of 0.2mol/L.Magnetic agitation, backflow 4h.Behind the ageing 24h, slowly drip 1mol/L NH 3H 2O is to neutrality, ageing 12h.Spend deionised water, alcohol is washed till no chlorion again.Washing is after 0.45 μ m filtering with microporous membrane is transferred to filter cake in the 200mL absolute ethyl alcohol, and ultrasonic dispersion forms tin ash colloidal sol, is named S3.
Get 15mL tin ash colloidal sol (S3), add the 7mL butyl titanate, in ultrasonic 4 cycles, ageing 0.5h adds 25mL alcohol radical Fe again 3O 4Magnetic fluid (F3) in ultrasonic 2 cycles, forms solution A.1.2mL deionized water joins in the 12mL absolute ethyl alcohol, drips 0.08mL nitric acid, ultrasonic dispersion is mixed with solution B.Under violent mechanical agitation, solution B is slowly splashed in the solution A, continue to stir, form until gel.
With gel 85 ℃ of following vacuum drying, pick up broken, under nitrogen atmosphere, through the heat treatment of temperature programmed control muffle furnace.25 ℃～250 ℃ heat up with 1 ℃/min, heat up with 2 ℃/min more than 250 ℃, are warming up to 500 ℃, and insulation 1h closes nitrogen when being cooled to below 150 ℃.Sample is named TSF3.
Embodiment 4
With the 0.25mol/L FeCl for preparing 2Solution 80mL and 0.25mol/L FeCl 3Solution 120mL and diethanolamine solution 80mL (containing the 5ml diethanol amine) join and have in the churned mechanically 500mL four-hole boiling flask, heat in 70 ℃ of waters bath with thermostatic control, feed high pure nitrogen protected simultaneously.Slowly drip 1mol/L NaOH solution, survey the pH value, treat pH value to 6～7, black Fe is arranged every 2min 3O 4Particle occurs, and continues to add alkali, and regulating the pH value is 11～12.Temperature rises to 80 ℃, ageing 2h.Fe with preparation 3O 4The nano particles by using deionized water washing is used absolute ethanol washing again to neutral, after the magnetic force sedimentation, with the dilution of 250mL absolute ethyl alcohol, in ultrasonic 5 cycles, makes alcohol radical Fe 3O 4Magnetic fluid is named F4.
Take by weighing 17.55g SnCl 22H 2O is dissolved in the 125mL absolute ethyl alcohol, through 0.22 μ m filtering with microporous membrane, is mixed with the tin-salt solution of 0.4mol/L.Magnetic agitation, backflow 4h.Behind the ageing 24h, slowly drip 10mol/L NH 3H 2O regulates pH value to 8～9, ageing 12h.Spend deionised water, alcohol is washed till no chlorion again.Washing is after 0.45 μ m filtering with microporous membrane is transferred to filter cake in the 200mL absolute ethyl alcohol, and ultrasonic dispersion forms tin ash colloidal sol, is named S4.
Get 20mL tin ash colloidal sol (S4), add the 8mL butyl titanate, in ultrasonic 4 cycles, ageing 0.5h adds 20mL alcohol radical Fe again 3O 4Magnetic fluid (F4) in ultrasonic 2 cycles, forms solution A.1.5mL deionized water joins in the 15mL absolute ethyl alcohol, drips 0.15mL nitric acid, ultrasonic dispersion is mixed with solution B.Under violent mechanical agitation, solution B is slowly splashed in the solution A, continue to stir, form until gel.
Other condition makes the nano magnetic compound photochemical catalyst at last and is named as TSF4 with embodiment 1.
Embodiment 5
With the 0.25mol/L FeCl for preparing 2Solution 80mL and 0.25mol/L FeCl 3Solution 120mL and diethanolamine solution 80mL (containing the 3ml diethanol amine) join and have in the churned mechanically 500mL four-hole boiling flask, heat in 70 ℃ of waters bath with thermostatic control, feed high pure nitrogen protected simultaneously.Slowly drip 1mol/L NaOH solution, survey the pH value, treat pH value to 6～7, black Fe is arranged every 2min 3O 4Particle occurs, and continues to add alkali, and regulating the pH value is 11～12.Temperature rises to 80 ℃, ageing 2h.Fe with preparation 3O 4The nano particles by using deionized water washing is used absolute ethanol washing again to neutral, after the magnetic force sedimentation, with the dilution of 250mL absolute ethyl alcohol, in ultrasonic 5 cycles, makes alcohol radical Fe 3O 4Magnetic fluid is named F5.
Take by weighing 17.55g SnCl 45H 2O is dissolved in the 250mL absolute ethyl alcohol, through 0.22 μ m filtering with microporous membrane, is mixed with the tin-salt solution of 0.2mol/L.Magnetic agitation, backflow 4h.Behind the ageing 24h, slowly drip 2mol/L NH 3H 2O regulates pH value to 8～9, ageing 12h.Spend deionised water, alcohol is washed till no chlorion again.Washing is after 0.45 μ m filtering with microporous membrane is transferred to filter cake in the 200mL absolute ethyl alcohol, and ultrasonic dispersion forms tin ash colloidal sol, is named S5.
Get 20mL tin ash colloidal sol (S5), add the 8mL butyl titanate, in ultrasonic 4 cycles, ageing 0.5h adds 20mL alcohol radical Fe again 3O 4Magnetic fluid (F5) in ultrasonic 2 cycles, forms solution A.1.5mL deionized water joins in the 15mL absolute ethyl alcohol, drips 0.15mL nitric acid, ultrasonic dispersion is mixed with solution B.Under violent mechanical agitation, solution B is slowly splashed in the solution A, continue to stir, form until gel.
Other condition makes the nano magnetic compound photochemical catalyst at last and is named as TSF5 with embodiment 1.
Embodiment 6
With the 0.25mol/L FeCl for preparing 2Solution 80mL and 0.25mol/L FeCl 3Solution 120mL and diethanolamine solution 80mL (containing the 6ml diethanol amine) join and have in the churned mechanically 500mL four-hole boiling flask, heat in 70 ℃ of waters bath with thermostatic control, feed high pure nitrogen protected simultaneously.Slowly drip 1mol/L NaOH solution, survey the pH value, treat pH value to 6～7, black Fe is arranged every 2min 3O 4Particle occurs, and continues to add alkali, and regulating the pH value is 11～12.Temperature rises to 80 ℃, ageing 2h.Fe with preparation 3O 4The nano particles by using deionized water washing is used absolute ethanol washing again to neutral, after the magnetic force sedimentation, with the dilution of 250mL absolute ethyl alcohol, in ultrasonic 5 cycles, makes alcohol radical Fe 3O 4Magnetic fluid is named F6.
Take by weighing 17.55g SnCl 45H 2O is dissolved in the 100mL absolute ethyl alcohol, through 0.22 μ m filtering with microporous membrane, is mixed with the tin-salt solution of 0.5mol/L.Magnetic agitation, backflow 4h.Behind the ageing 24h, slowly drip 1mol/L NH 3H 2O regulates pH value to 8～9, ageing 12h.Spend deionised water, alcohol is washed till no chlorion again.Washing is after 0.45 μ m filtering with microporous membrane is transferred to filter cake in the 200mL absolute ethyl alcohol, and ultrasonic dispersion forms tin ash colloidal sol, is named S6.
Get 20mL tin ash colloidal sol (S6), add the 8mL butyl titanate, in ultrasonic 4 cycles, ageing 0.5h adds 20mL alcohol radical Fe again 3O 4Magnetic fluid (F6) in ultrasonic 2 cycles, forms solution A.1.5mL deionized water joins in the 15mL absolute ethyl alcohol, drips 0.15mL nitric acid, ultrasonic dispersion is mixed with solution B.Under violent mechanical agitation, solution B is slowly splashed in the solution A, continue to stir, form until gel.
Other condition makes the nano magnetic compound photochemical catalyst at last and is named as TSF6 with embodiment 1.
Comparative Examples
To omit the preparation process of tin ash colloidal sol among the embodiment 1, and in complex photochemical catalyst gel preparation course, do not use tin ash colloidal sol, and use absolute ethyl alcohol, other condition obtains magnetic photocatalyst with embodiment 1, is named TF.Its photocatalytic degradation rate curve to methyl orange is the TF curve of Fig. 3.

Claims (2)

1, a kind of high active nano magnetic compound photochemical catalyst is characterized in that: this catalyst average grain diameter is 80nm～100nm; The nuclear material is organically-modified tri-iron tetroxide, and the shell material is the composite semiconductor of tin ash titanium dioxide, and titanium tin iron atom ratio is in the photochemical catalyst: (75～80): (10～15): (5～10).
2, the described high active nano magnetic compound photochemical catalyst of a kind of claim 1 preparation method is characterized in that may further comprise the steps:
(1) alcohol radical Fe 3O 4The magnetic fluid preparation
Prepare nanometer Fe with coprecipitation 3O 4Magnetic fluid: press Fe 2+, Fe 3+Mol ratio is 1: 2～2: 3, with the 0.25mol/L～0.5mol/L FeCl for preparing 2Solution and 0.25mol/L～0.5mol/L FeCl 3Solution and Macrogol 4000 solution or diethanolamine solution join and are equipped with in the churned mechanically four-hole boiling flask, and wherein to account for the mass percent of reactant liquor be 1%～2% for Macrogol 4000 or diethanol amine; In 60 ℃～80 ℃ waters bath with thermostatic control, heat, feed nitrogen protected simultaneously, slowly drip 1mol/L～2mol/L NaOH solution, treat pH value to 6～7, black Fe is arranged 3O 4Particle occurs, and continues to add alkali, and regulating the pH value is 11～12, and temperature rises to 80 ℃～90 ℃, ageing; Fe with preparation 3O 4Particle spends deionised water to neutral, uses absolute ethanol washing again, and after the magnetic force sedimentation, with the absolute ethyl alcohol dilution, alcohol radical Fe is made in ultrasonic dispersion 3O 4Magnetic fluid;
(2) tin ash colloidal sol preparation
Adopting stannous chloride or butter of tin is raw material, joins in the absolute ethyl alcohol, is mixed with the solution of 0.2mol/L～0.5mol/L, refluxes under the magnetic agitation condition, obtains water white transparency colloidal sol, and ageing 12h～24h slowly drips 1mol/L～10mol/L NH 3H 2O forms the milky gel, spends deionised water, and alcohol is washed till no chlorion again, and filter the washing back, and filter cake is transferred in the absolute ethyl alcohol, and ultrasonic dispersion forms tin ash colloidal sol;
(3) complex photochemical catalyst preparing gel
By titanium tin atom ratio is 8: 1～5: 1, and the ferrotianium atomic ratio is 7.5: 1～16: 1; Get above-mentioned tin ash colloidal sol, add butyl titanate, ultrasonic dispersion, ageing adds above-mentioned alcohol radical Fe again 3O 4Magnetic fluid, ultrasonic dispersion forms solution A; By sour titanium mol ratio (H +/ Ti) be 0.05: 1～0.2: 1, pure titanium mol ratio is 9: 1～18: 1, water titanium mol ratio is 2.8: 1～5.6: 1; Deionized water is joined in the absolute ethyl alcohol, drip nitric acid, ultrasonic dispersion is mixed with solution B; Under the violent mechanical agitation, solution B is slowly splashed in the solution A, form until gel;
(4) heat treatment of gel
Gel 70 ℃～90 ℃ following vacuum drying, is ground, under nitrogen atmosphere, through the heat treatment of temperature programmed control Muffle furnace, 25 ℃～250 ℃ heat up with 1 ℃/min, heat up with 2 ℃/min more than 250 ℃, be warming up to 450 ℃～650 ℃, more than the insulation 1h, close nitrogen when being cooled to below 150 ℃.
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CN100351011C (en) * 2005-10-10 2007-11-28 北京科技大学 Composite photo catalytic sewage treating material and its prepn
CN103773650A (en) * 2014-02-17 2014-05-07 江苏科技大学 Application of chitosan magnetic bead fixed yeast to brewing blueberry fruit wine
CN105198004A (en) * 2015-08-18 2015-12-30 西北大学 Fe3O4-SnO2 nanometer composite and preparation method thereof
CN106475039A (en) * 2016-10-09 2017-03-08 同济大学 A kind of sea urchin shape three-dimensional Fe3O4/SnO2Nanometer stick array and its synthetic method and application
CN106475039B (en) * 2016-10-09 2019-05-14 同济大学 A kind of sea urchin shape three-dimensional Fe3O4/SnO2Nanometer stick array and its synthetic method and application
CN108993473A (en) * 2018-08-25 2018-12-14 华北水利水电大学 A kind of compound catalysis material SnO2/TiO2Preparation method
CN108993473B (en) * 2018-08-25 2021-02-26 华北水利水电大学 Composite photocatalytic material SnO2/TiO2Preparation method of (1)
CN109530418A (en) * 2018-12-31 2019-03-29 南京格洛特环境工程股份有限公司 Heavy-metal contaminated soil restorative procedure
CN113745546A (en) * 2021-09-06 2021-12-03 南京理工大学 Dynamic SnO2Membrane electrode of-Sb catalyst layer, preparation method and application
CN113745546B (en) * 2021-09-06 2022-07-29 南京理工大学 Dynamic SnO 2 Membrane electrode of-Sb catalyst layer, preparation method and application

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