CN108686655B - Preparation method of dynamic Fenton-titanium dioxide coupling photocatalyst for environmental remediation - Google Patents

Preparation method of dynamic Fenton-titanium dioxide coupling photocatalyst for environmental remediation Download PDF

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CN108686655B
CN108686655B CN201810380964.1A CN201810380964A CN108686655B CN 108686655 B CN108686655 B CN 108686655B CN 201810380964 A CN201810380964 A CN 201810380964A CN 108686655 B CN108686655 B CN 108686655B
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hollow microspheres
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刘超
林阳
董雨菲
鲍艳
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Shaanxi University of Science and Technology
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    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/39—Photocatalytic properties
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    • B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
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    • B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
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    • B01J37/342—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electric, magnetic or electromagnetic fields, e.g. for magnetic separation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract

A process for preparing the dynamic Fenton-TiO 2 coupled photocatalyst used for restoring environment features that TiO is used2Adding the hollow microspheres into a mixed solvent of anhydrous ethanol containing ferric salt and deionized water, adding a reducing agent, continuing stirring, reacting at room temperature until the solution is black, collecting the product by magnetic decantation, washing for multiple times, and drying by nitrogen to obtain Fe0Supported TiO2Compounding hollow microspheres; mixing Fe0Supported TiO2Placing the composite hollow microspheres on the surface of an aluminum foil, and depositing a metal layer on the hemispherical surface of each microsphere; the prepared microspheres are peeled off from the surface of the aluminum foil by the ultrasonic action and collected by magnetic induction. The preparation method is simple to operate and low in cost, the prepared coupling photocatalyst has extremely strong photodegradation capability, the coupling photocatalyst can realize self-driving, the function of dynamic environment restoration is realized under the action of no mechanical stirring, and the catalyst can be recovered by magnetic induction.

Description

Preparation method of dynamic Fenton-titanium dioxide coupling photocatalyst for environmental remediation
Technical Field
The invention particularly relates to the technical field of inorganic functional materials and photocatalytic wastewater treatment, and particularly relates to a preparation method of a dynamic Fenton-titanium dioxide coupling photocatalyst for environmental remediation.
Background
With the rapid development of the dye chemical industry, synthetic dyes are increasingly applied in the production of industries such as textile, printing and dyeing, leather, food, daily chemical industry and the like, and dye wastewater becomes a non-negligible water pollution source. As about 10 to 15 percent of dye is discharged into the environment along with waste water in the using process, the dye has various varieties and poor biodegradability, and most of the dye and intermediate products thereof have carcinogenicity, Kawasaki and mutagenicity, thereby forming great threat to the environment and human health, and the treatment of the dye waste water becomes one of the important concerns of people.
In recent years, ozone and TiO have been used2Ultraviolet light and Fenton reagent (Fe)2+/H2O2) The advanced oxidation technology for treating the printing and dyeing wastewater is widely concerned. Wherein, the Fenton reagent and TiO2The Ultraviolet (UV) catalytic oxidation method for treating organic dyes has the characteristics of strong mineralization capability, simple and convenient operation, low cost and the like, is regarded as the water treatment technology with the most development potential and application prospect at present, and is valued by environmental scientists. However, H can also occur when the Fenton technology is improperly adjusted2O2The large Fe input amount causes the problems of large generation amount of iron sludge, high chroma, increased subsequent treatment cost and the like; and TiO 22Due to the limitation of the self forbidden bandwidth (anatase, 3.2eV), the solar cell can only be excited by UV to generate electrons and holes, and the utilization rate of sunlight is low. In addition, photo-generated electrons and holes are easily recombined, resulting in low photon efficiency, which is to TiO2Has caused great limitations in practical application. Currently, studies have demonstrated that the combination of Fenton reagent and TiO compounds2The composite system has a synergistic effect between the two, thereby obviously improving the catalytic efficiency. However, the existing composite systems are usually blended by simple solution (adding TiO into solution containing Fenton reagent)2Or in the presence of TiO2Adding Fe into the solution0、Fe2+Or Fe3+And H2O2) Although the iron salt or H can be reduced2O2The amount of iron sludge produced and TiO still cannot be solved2Problem of excitation by ultraviolet light only (reference: Filesonin, et al. zero-valent iron (Fe. 0))2Research on photocatalytic degradation characteristics, environmental pollution and control 2014,36(11): 46-49). Meanwhile, the existing catalysts are all 'static' particles, and a stirring device is required to be introduced to improve the catalysis of the catalystsEfficiency. For the treatment of large-area waste water such as dye waste water, a larger stirring device is required to be introduced for providing power, which inevitably increases the cost of waste water treatment.
Disclosure of Invention
To improve TiO2The invention aims to provide a preparation method of a dynamic Fenton-titanium dioxide coupling photocatalyst for environment restoration, the photocatalyst integrates the characteristics of simple preparation method, light drive, high action efficiency and the like, can realize the rapid and efficient degradation of printing and dyeing wastewater without introducing stirring equipment, and the existence of Fe in the structure enables the photocatalyst to be recycled through magnetic induction, so that the photocatalyst has potential application value in the restoration aspect of actual polluted water environment.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a preparation method of a dynamic Fenton-titanium dioxide coupled photocatalyst for environmental remediation specifically comprises the following steps:
(1) adding TiO into the mixture2Adding hollow microspheres into a mixed solvent of anhydrous ethanol containing ferric salt and deionized water, introducing nitrogen for protection, performing ultrasonic treatment, adding a reducing agent, continuously stirring and reacting at room temperature until the solution is black, collecting the product by magnetic decantation, washing for multiple times, and drying with nitrogen to obtain Fe0Supported TiO2Compounding hollow microspheres; wherein, Fe0In TiO2The mass loading amount of the surface is 0.5-10%;
(2) the prepared Fe0Supported TiO2Placing the composite hollow microspheres on the surface of an aluminum foil, and depositing a metal layer on the hemispherical surface of each microsphere; the prepared microspheres fall off from the surface of the aluminum foil through the ultrasonic action and are collected through magnetic induction to obtain the asymmetric spherical dynamic Fenton-TiO2The photocatalyst is coupled.
In a further development of the invention, the TiO is2The particle size of the hollow microsphere is 50 nm-10 mu m.
The invention has the further improvement that the volume ratio of the deionized water to the absolute ethyl alcohol is 1 (1-10).
In a further development of the invention, the TiO is2The mass ratio of the hollow microspheres to the mixed solvent is 1 (20-1000).
The invention is further improved in that the reducing agent is hydrazine hydrate, potassium borohydride, sodium citrate or ascorbic acid.
The further improvement of the invention is that the molar ratio of the reducing agent to the iron salt is 1 (5-150).
A further improvement of the invention is that the iron salt is a divalent or trivalent iron salt.
In a further development of the invention, the ferrous salt is FeCl2·4H2O、FeSO4·7H2O、Fe(NO3)26H2O or (NH)4)2Fe(SO4)2·6H2O; the trivalent iron salt being Fe2(SO4)3·9H2O、Fe(NO3)39H2O or FeCl3·6H2O。
In a further development of the invention, the metal layer is gold, silver, copper, iron, nickel or tungsten; and depositing a metal layer on the hemispherical surface of the microsphere by using an electron beam evaporation, spraying or electrochemical deposition method.
The further improvement of the invention is that the mass of the metal layer accounts for 2-30% of the total mass of the asymmetric spherical dynamic coupling photocatalyst.
Compared with the prior art, the invention has the beneficial effects that: the invention provides a dynamic Fenton-TiO for environmental remediation2The preparation method of the coupling photocatalyst has simple operation and low cost, and the prepared Fenton-TiO is2The coupled photocatalyst is compounded with Fenton reagent and TiO2The photocatalyst has the advantages of two advanced oxidation technologies, the capability of degrading organic dye is greatly improved, and compared with the traditional 'static' catalyst, the coupled photocatalyst can realize self-driving, the function of 'dynamic' environmental remediation is realized under the action of no mechanical stirring, and the catalyst can be recovered by magnetic induction. Therefore, the method has potential in the aspect of restoring the actual polluted water environmentThe application value of the method is high.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes and modifications can be made by one skilled in the art after reading the disclosure set forth herein, and equivalents may fall within the scope of the invention as defined by the claims appended hereto.
The invention comprises the following steps:
(1) commercial TiO with the grain diameter of 50 nm-10 mu m2Adding hollow microspheres into a mixed solvent of anhydrous ethanol containing ferric salt and deionized water, introducing nitrogen for protection, performing ultrasonic treatment, adding a reducing agent, continuously stirring and reacting at room temperature until the solution is black, collecting the product by magnetic decantation, washing for multiple times, and drying with nitrogen to obtain Fe0Supported TiO2Compounding hollow microspheres; wherein, Fe0In TiO2The mass loading amount of the surface is 0.5-10%; TiO 22The mass ratio of the hollow microspheres to the mixed solvent is 1 (20-1000), and the volume ratio of the deionized water to the absolute ethyl alcohol is 1 (1-10).
(2) The prepared Fe0Supported TiO2Placing the composite hollow microspheres on the surface of an aluminum foil, and depositing an upper metal layer on the hemispherical surfaces of the microspheres by using an electron beam evaporation, spraying or electrochemical deposition method; the prepared microspheres fall off from the surface of the aluminum foil through the ultrasonic action and are collected through magnetic induction to obtain the asymmetric spherical dynamic Fenton-TiO2The photocatalyst is coupled.
The molar ratio of the reducing agent to the iron salt is 1 (5-150). The reducing agent is hydrazine hydrate (with the mass concentration of 80 percent) and potassium borohydride KBH4Sodium borohydride NaBH4Sodium citrate or ascorbic acid.
The iron salt is a divalent or trivalent iron salt. The ferrous salt being FeCl2·4H2O、FeSO4·7H2O、Fe(NO3)26H2O or (NH)4)2Fe(SO4)2·6H2O; the trivalent iron salt being Fe2(SO4)3·9H2O、Fe(NO3)39H2O or FeCl3·6H2O。
The metal layer is gold, silver, copper, iron, nickel or tungsten; asymmetric spherical dynamic Fenton-TiO metal layer mass22-30% of the total mass of the coupling photocatalyst.
Example 1
To commercialize TiO2Hollow microspheres (particle size-500 nm) are dispersed in FeSO 0.55g4·7H2Adding 0.01mol NaBH into solution with the volume ratio of O being 1 (deionized water) to 1 (absolute ethyl alcohol), introducing nitrogen for protection and carrying out ultrasonic treatment for 30min, and then adding 0.01mol NaBH4Reacting at room temperature for 4h, collecting the product by magnetic decantation, washing the product with deionized water and absolute ethyl alcohol for three times, and blowing and drying the product by nitrogen to obtain gray black solid Fe0Supported TiO2Composite hollow microspheres, noted: fe0-TiO2Composite hollow microsphere (Fe)0The mass loading is about 3%), and the mixture is placed in a vacuum drying device for standby. Wherein, TiO2The mass ratio of the hollow microspheres to the mixed solvent is 1: 20.
Mixing Fe0-TiO2Placing the composite hollow microspheres on the surface of an aluminum foil, placing the aluminum foil in a magnetron sputtering coating machine, depositing the composite hollow microspheres on the hemispherical surface of the microspheres by using a Fe target, placing the composite hollow microspheres in deionized water in a dark place for ultrasonic treatment to separate the prepared composite photocatalyst, and collecting the composite photocatalyst by adopting magnetic decantation to obtain Fe/Fe0-TiO2The composite photocatalyst (the Fe layer accounts for 20% of the total mass of the composite photocatalyst).
The study found that for 300mL of acid red B dye wastewater with an initial concentration of 100mg/L, in TiO2Hollow microspheres (particle size 500nm) and Fe/Fe0-TiO2The adding amount of the composite photocatalyst is 1g/L, the pH is 3, and H is2O21mmol/L, and TiO when irradiated with 300W ultraviolet light for 60 minutes without stirring2Hollow microspheres (particle size 500nm) and Fe/Fe0-TiO2The degradation rate of the composite photocatalyst to the dye wastewater is respectively 19% and 75%; under the stirring condition of 500 revolutions per minute and the ultraviolet irradiation of 300W for 60 minutes, TiO is added2Hollow microsphere (particle size 5 ~ C)00nm) and Fe/Fe0-TiO2The degradation rate of the composite photocatalyst to the dye wastewater is 61% and 92% respectively.
Example 2
To commercialize TiO2Hollow microspheres (particle size-800 nm) are dispersed in FeCl containing 0.5g2·4H2Introducing nitrogen into a solution with the volume ratio of O being 1 (deionized water) to 3 (absolute ethyl alcohol), carrying out ultrasonic treatment for 30min, adding 2.5g of trisodium citrate, carrying out room-temperature reaction for 2h, carrying out magnetic decantation and collection on products, washing the products with deionized water and absolute ethyl alcohol for three times, and carrying out nitrogen purging and drying to obtain gray black solid Fe0-TiO2Composite hollow microsphere (Fe)0The mass loading is about 5%), and the mixture is placed in a vacuum drying device for standby. Wherein, TiO2The mass ratio of the hollow microspheres to the mixed solvent is 1: 1000.
Mixing Fe0-TiO2Placing the composite hollow microspheres on the surface of an aluminum foil, placing the aluminum foil in a magnetron sputtering coating machine, depositing the composite hollow microspheres on the hemispherical surface of the microspheres by using an Au target, placing the microspheres in deionized water in a dark place, carrying out ultrasonic treatment to separate the prepared composite photocatalyst, and collecting the composite photocatalyst by adopting magnetic decantation to obtain Au/Fe0-TiO2The composite photocatalyst (the Au layer accounts for 2% of the total mass of the composite photocatalyst).
The study found that 300mL of methylene blue dye wastewater with initial concentration of 100mg/L is treated in TiO2Hollow microspheres (particle size-800 nm) and Au/Fe0-TiO2The adding amount of the composite photocatalyst is 1g/L, the pH is 3.5, and H is2O21mmol/L, and TiO when irradiated with 300W ultraviolet light for 60 minutes without stirring2Hollow microspheres (particle size-800 nm) and Au/Fe0-TiO2The degradation rates of the composite photocatalyst to the dye wastewater are respectively 19% and 53%; under the stirring condition of 500 revolutions per minute and the ultraviolet irradiation of 300W for 60 minutes, TiO is added2Hollow microspheres (particle size 500nm) and Fe/Fe0-TiO2The degradation rate of the composite photocatalyst to the dye wastewater is 57% and 94% respectively.
Example 3
To commercialize TiO2Hollow microspheres (particle size: 10 μm) dispersed in a dispersion medium containing 3.2gFeCl3·6H2Introducing nitrogen into a solution with the volume ratio of O being 1 (deionized water) to 5 (absolute ethyl alcohol), carrying out ultrasonic treatment for 30min, adding 10mL hydrazine hydrate (80%), reacting at room temperature for 2h, carrying out magnetic decantation and collection on products, washing the products with deionized water and absolute ethyl alcohol for three times, and carrying out nitrogen purging and drying to obtain gray black solid Fe0-TiO2Composite hollow microsphere (Fe)0The mass loading is about 10%), and the mixture is placed in a vacuum drying device for standby. Wherein, TiO2The mass ratio of the hollow microspheres to the mixed solvent is 1: 500.
Mixing Fe0-TiO2Placing the composite hollow microspheres on the surface of an aluminum foil, placing the aluminum foil in a magnetron sputtering coating machine to deposit an Ag target on the hemispherical surface of the microspheres, placing the aluminum foil in deionized water in a dark place for ultrasonic treatment to separate the prepared composite photocatalyst, and collecting the composite photocatalyst by magnetic decantation to obtain Ag/Fe0-TiO2The composite photocatalyst (the Ag layer accounts for 10% of the total mass of the composite photocatalyst).
The research finds that 300mL of disperse red 3B (R60#) dye wastewater with the initial concentration of 100mg/L is treated in TiO2Hollow microspheres (particle size 10 mu m) and Ag/Fe0-TiO2The adding amount of the composite photocatalyst is 1g/L, the pH is 3.5, and H is2O21mmol/L, and TiO when irradiated with 300W ultraviolet light for 60 minutes without stirring2Hollow microspheres (particle size 10 μm) and Au/Fe0-TiO2The degradation rates of the composite photocatalyst to the dye wastewater are respectively 15% and 47%; under the stirring condition of 500 revolutions per minute and the ultraviolet irradiation of 300W for 60 minutes, TiO is added2Hollow microspheres (particle size 10 μm) and Fe/Fe0-TiO2The degradation rate of the composite photocatalyst to the dye wastewater is 68% and 97% respectively.
Example 4
TiO to be purchased2Hollow microspheres (particle size 50nm) dispersed in a dispersion containing 0.08g Fe2(SO4)3·9H2Introducing nitrogen gas to protect and ultrasonically treat for 30min in a solution with the volume ratio of O being 1 (deionized water) to 10 (absolute ethyl alcohol), adding 1g of ascorbic acid, reacting at room temperature for 2h, collecting a product by magnetic decantation, and adopting deionized water and absolute ethyl alcohol successivelyWashing for three times respectively, blowing and drying by nitrogen to obtain gray black solid Fe0-TiO2Composite hollow microsphere (Fe)0The mass loading is about 0.5%), and the mixture is placed in a vacuum drying device for standby. Wherein, TiO2The mass ratio of the hollow microspheres to the mixed solvent is 1: 800.
Mixing Fe0-TiO2Placing the composite hollow microspheres on the surface of an aluminum foil, placing the aluminum foil in a magnetron sputtering coating machine to deposit Ni targets on the hemispherical surfaces of the microspheres, placing the aluminum foil in deionized water in a dark place for ultrasonic treatment to separate the prepared composite photocatalyst, and collecting the composite photocatalyst by magnetic decantation to obtain Ni/Fe0-TiO2The composite photocatalyst (the Ni layer accounts for 30% of the total mass of the composite photocatalyst).
Studies have found that 300mL of Sudan III dye wastewater with an initial concentration of 100mg/L is treated with a catalyst in TiO2Hollow microspheres (particle size 50nm) and Ni/Fe0-TiO2The adding amount of the composite photocatalyst is 1g/L, the pH is 3.5, and H is2O21mmol/L, and TiO when irradiated with 300W ultraviolet light for 60 minutes without stirring2Hollow microspheres (particle size 50nm) and Ni/Fe0-TiO2The degradation rates of the composite photocatalyst to the dye wastewater are respectively 45% and 77%; under the stirring condition of 500 revolutions per minute and the ultraviolet irradiation of 300W for 60 minutes, TiO is added2Hollow microspheres (particle size 50nm) and Ni/Fe0-TiO2The degradation rate of the composite photocatalyst to the dye wastewater is 79 percent and 99 percent respectively.
Example 5
(1) TiO with the grain diameter of 50 nm-10 mu m2Adding hollow microspheres into a mixed solvent of anhydrous ethanol containing ferric salt and deionized water, introducing nitrogen for protection, performing ultrasonic treatment, adding sodium borohydride, continuously stirring, reacting at room temperature until the solution is black, collecting the product by magnetic decantation, washing for multiple times, and drying with nitrogen to obtain Fe0Supported TiO2Compounding hollow microspheres; wherein, Fe0In TiO2The mass loading of the surface was 7%; wherein, TiO2The mass ratio of the hollow microspheres to the mixed solvent is 1:700, and the volume ratio of the deionized water to the absolute ethyl alcohol is 1: 5. The molar ratio of sodium borohydride to iron salt is 1:150, and iron saltIs (NH)4)2Fe(SO4)2·6H2O；
(2) The prepared Fe0Supported TiO2Placing the composite hollow microspheres on the surface of an aluminum foil, depositing a nickel layer on the hemispherical surface of the microspheres by a spraying method, enabling the prepared microspheres to fall off from the surface of the aluminum foil by ultrasonic action and collecting by magnetic induction to obtain asymmetric spherical dynamic Fenton-TiO2The photocatalyst is coupled. Wherein the mass of the nickel layer accounts for the asymmetric spherical dynamic Fenton-TiO27 percent of the total mass of the coupling photocatalyst.
Example 6
(1) TiO with the grain diameter of 50 nm-10 mu m2Adding hollow microspheres into a mixed solvent of anhydrous ethanol containing ferric salt and deionized water, introducing nitrogen for protection, performing ultrasonic treatment, adding ascorbic acid, continuously stirring, reacting at room temperature until the solution is black, collecting the product by magnetic decantation, washing for multiple times, and drying with nitrogen to obtain Fe0Supported TiO2Compounding hollow microspheres; wherein, Fe0In TiO2The mass loading of the surface was 1%; wherein, TiO2The mass ratio of the hollow microspheres to the mixed solvent is 1:200, and the volume ratio of the deionized water to the absolute ethyl alcohol is 1: 8. The molar ratio of ascorbic acid to iron salt is 1:5, and the iron salt is Fe (NO)3)3·9H2O；
(2) The prepared Fe0Supported TiO2Placing the composite hollow microspheres on the surface of an aluminum foil, depositing a tungsten layer on the hemispherical surface of the microspheres through electron beam evaporation, enabling the prepared microspheres to fall off from the surface of the aluminum foil through ultrasonic action, and collecting through magnetic induction to obtain asymmetric spherical dynamic Fenton-TiO2The photocatalyst is coupled. Wherein the mass of the tungsten layer accounts for the asymmetrical spherical dynamic Fenton-TiO215% of the total mass of the coupled photocatalyst.
Repeated intensive studies have found that2O2In the acidic aqueous system of (3), Fe0With TiO2The TiO can be effectively improved by compounding2And a synergistic effect exists between the two. Meanwhile, the composite photocatalyst can be realized through certain structural design and processingIs self-driven, thereby preparing the dynamic Fenton-TiO2The photocatalyst is coupled. The dynamic Fenton-TiO2The coupling photocatalyst shows excellent degradation efficiency to dye wastewater under the condition of no need of stirring, and can greatly reduce the wastewater treatment cost, so that the coupling photocatalyst has great potential practical application value in the field of wastewater treatment. The catalyst of the invention can realize self-driving under the photocatalysis, and can also realize self-driving under the induction of a magnetic field or an electric field.

Claims (7)

1. A preparation method of a dynamic Fenton-titanium dioxide coupled photocatalyst for environmental remediation is characterized by comprising the following steps:
(1) adding TiO into the mixture2Adding hollow microspheres into a mixed solvent of anhydrous ethanol containing ferric salt and deionized water, introducing nitrogen for protection, performing ultrasonic treatment, adding a reducing agent, continuously stirring and reacting at room temperature until the solution is black, collecting the product by magnetic decantation, washing for multiple times, and drying with nitrogen to obtain Fe0Supported TiO2Compounding hollow microspheres; wherein, Fe0In TiO2The mass loading amount of the surface is 0.5-10%;
(2) the prepared Fe0Supported TiO2Placing the composite hollow microspheres on the surface of an aluminum foil, and depositing a metal layer on the hemispherical surface of each microsphere; the prepared microspheres fall off from the surface of the aluminum foil through the ultrasonic action and are collected through magnetic induction to obtain the asymmetric spherical dynamic Fenton-TiO2Coupling a photocatalyst;
wherein, TiO2The particle size of the hollow microsphere is 50 nm-10 mu m;
the iron salt is a divalent or trivalent iron salt;
the ferrous salt being FeCl2·4H2O、FeSO4·7H2O、Fe(NO3)2·6H2O or (NH)4)2Fe(SO4)2·6H2O; the trivalent iron salt being Fe2(SO4)3·9H2O、Fe(NO3)3·9H2O or FeCl3·6H2O。
2. The preparation method of the dynamic Fenton-titanium dioxide coupled photocatalyst for environmental remediation as claimed in claim 1, wherein the volume ratio of the deionized water to the absolute ethyl alcohol is 1 (1-10).
3. The method for preparing a dynamic Fenton-titanium dioxide coupled photocatalyst for environmental remediation as claimed in claim 1, wherein the TiO is2The mass ratio of the hollow microspheres to the mixed solvent is 1 (20-1000).
4. The method for preparing a dynamic Fenton-titanium dioxide coupled photocatalyst for environmental remediation as claimed in claim 1, wherein the reducing agent is hydrazine hydrate, potassium borohydride, sodium citrate or ascorbic acid.
5. The preparation method of the dynamic Fenton-titanium dioxide coupled photocatalyst for environmental remediation is characterized in that the molar ratio of the reducing agent to the iron salt is 1 (5-150).
6. The method for preparing a dynamic Fenton-titanium dioxide coupled photocatalyst for environmental remediation as claimed in claim 1, wherein the metal layer is gold, silver, copper, iron, nickel or tungsten; and depositing a metal layer on the hemispherical surface of the microsphere by using an electron beam evaporation, spraying or electrochemical deposition method.
7. The method for preparing a dynamic Fenton-titanium dioxide coupled photocatalyst for environmental remediation as claimed in claim 1, wherein the mass of the metal layer accounts for 2-30% of the total mass of the asymmetric spherical dynamic Fenton-titanium dioxide coupled photocatalyst.
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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101077478A (en) * 2006-05-24 2007-11-28 深圳成霖洁具股份有限公司 Photocatalyst compound structures body and preparation method thereof
BRPI1002600A2 (en) * 2010-06-14 2012-02-07 Univ Minas Gerais transition metal or transition metal oxide catalyst supported on autoclaved cellular concrete
CN103803695A (en) * 2014-02-25 2014-05-21 天津城建大学 Method for Fenton-like light-catalyzed reaction system for zero-valent iron and TiO2 photocatalytic coupling
CN104525201A (en) * 2015-01-05 2015-04-22 华东理工大学 Non-homogeneous-phase Fenton catalyst with magnetism and preparing method and application thereof
CN105776783A (en) * 2016-04-12 2016-07-20 浙江奇彩环境科技股份有限公司 Method for recycling Fenton iron mud through membrane technology
CN106732691A (en) * 2017-01-20 2017-05-31 四川师范大学 A kind of composite catalyst for organochlorine pollutant of degrading and preparation method thereof

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101077478A (en) * 2006-05-24 2007-11-28 深圳成霖洁具股份有限公司 Photocatalyst compound structures body and preparation method thereof
BRPI1002600A2 (en) * 2010-06-14 2012-02-07 Univ Minas Gerais transition metal or transition metal oxide catalyst supported on autoclaved cellular concrete
CN103803695A (en) * 2014-02-25 2014-05-21 天津城建大学 Method for Fenton-like light-catalyzed reaction system for zero-valent iron and TiO2 photocatalytic coupling
CN104525201A (en) * 2015-01-05 2015-04-22 华东理工大学 Non-homogeneous-phase Fenton catalyst with magnetism and preparing method and application thereof
CN105776783A (en) * 2016-04-12 2016-07-20 浙江奇彩环境科技股份有限公司 Method for recycling Fenton iron mud through membrane technology
CN106732691A (en) * 2017-01-20 2017-05-31 四川师范大学 A kind of composite catalyst for organochlorine pollutant of degrading and preparation method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
"Photodegradation of thiacloprid using Fe/TiO2 as a heterogeneous photo-Fenton catalyst";Banic, Nemanja et al.,;《APPLIED CATALYSIS B-ENVIRONMENTAL》;20110803;第107卷(第3期);第363-371页 *

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