CN107175112B - Micro-motor photocatalyst and preparation method and application thereof - Google Patents

Micro-motor photocatalyst and preparation method and application thereof Download PDF

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CN107175112B
CN107175112B CN201710321670.7A CN201710321670A CN107175112B CN 107175112 B CN107175112 B CN 107175112B CN 201710321670 A CN201710321670 A CN 201710321670A CN 107175112 B CN107175112 B CN 107175112B
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photocatalyst
znfe
micromotor
motor
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CN107175112A (en
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李嘉
徐超超
李红艳
宋鹏
杨萍
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University of Jinan
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/889—Manganese, technetium or rhenium
    • B01J23/8892—Manganese
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • B01J35/39—
    • B01J35/51—
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/30—Treatment of water, waste water, or sewage by irradiation
    • C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/722—Oxidation by peroxides
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
    • H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/308—Dyes; Colorants; Fluorescent agents
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2305/00—Use of specific compounds during water treatment
    • C02F2305/02—Specific form of oxidant
    • C02F2305/026—Fenton's reagent
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2305/00—Use of specific compounds during water treatment
    • C02F2305/10—Photocatalysts

Abstract

the invention discloses a micro-motor photocatalyst, which is used for synthesizing α -Fe by a solvothermal method 2O3‑ZnFe2O4Micromotor photocatalyst microspheres of ZnFe 2O4the diameter of the hollow microsphere is 0.4-0.8 μm, and the flake alpha-Fe 2O3And Mn 2O3Nanoparticles grown on ZnFe 2O4On the microspheres. The invention also discloses a preparation method and application thereof. The micromotor photocatalyst has a magnetic microsphere structure, is beneficial to recovery and magnetic control, and can catalyze H 2O2Generating bubbles to perform autonomous movement at H 2O2Has better degradation efficiency on organic pollutants in the dye wastewater under the participated UV-Fenton reaction, and can be used for the efficient treatment of the dye wastewater And (6) processing. In the reaction system H 2O2not only used as a reagent for UV-Fenton reaction, but also used for promoting alpha-Fe 2O3‑ZnFe2O4Fuel for the micro-motor.

Description

Micro-motor photocatalyst and preparation method and application thereof
Technical Field
The invention relates to a self-driven motor photocatalyst in the aspect of sewage treatment, in particular to a micro-motor photocatalyst and a preparation method and application thereof.
Background
In the current society, water pollution is more and more serious, dye wastewater is one of the most serious pollution in water pollution, and the treatment of the dye wastewater generally comprises methods such as an adsorption method, a catalytic method, a chemical method, a biological method and the like. The catalytic method can realize deep oxidation of refractory substances to obtain harmless inorganic substances, and the photocatalytic technology has no secondary pollution.
Fenton and its related reactions, are oxides (usually H) 2O2) Reaction with iron ions forms active oxygen species (. OH) that oxidize organic or inorganic compounds. The Fenton method is simple to operate, green and nontoxic, and deep oxidation of refractory substances can be realized through excellent oxidation performance. But the catalyst can effectively play a role in strong acid, secondary pollution caused by iron mud is generated, and the treatment cost is high, so that the problem can be solved by ultraviolet-assisted Fenton (UV-Fenton) combining a Fenton method and a photo-technology, and H is improved 2O2The utilization ratio of (2).
ZnFe2O4The material has narrow forbidden band width, can be used as a catalyst and a catalyst carrier, has magnetism, is beneficial to recovery, but has poor effect of degrading organic pollutants by photocatalysis, and ZnFe 2O4can react with α -Fe 2O3Is complexed with H 2O2The UV-Fenton reaction occurs to generate hydroxyl radicals to degrade organic pollutants. Micromotors are artificial devices that convert chemical or other forms of energy into mechanical energy on a micron scale. The driving method is chemical, magnetic field, light, ultrasonic wave, etc., and the driving method is usually The catalyst is used for reacting with hydrogen peroxide to generate bubbles as a drive. The invention uses ZnFe 2O4with alpha-Fe 2O3、Mn2O3Composite of Mn 2O3And H 2O2The reaction generates oxygen to drive the motor to move, ZnFe 2O4with alpha-Fe 2O3And H 2O2Hydroxyl radicals are generated by reaction to degrade organic pollutants, and the photo-Fenton technology is combined with a motor to degrade the organic pollutants. H 2O2As a reagent for the Fenton reaction and as a fuel to propel the micromotors. The importance of the motor of the present invention is to open up a method of manufacturing an autonomous microscopic cleaning system that can operate without external energy input and in a faster manner than its static counterpart.
Disclosure of Invention
The invention aims to provide a micro-motor photocatalyst.
The invention also provides a preparation method and application of the micro-motor photocatalyst.
The invention is realized by the following technical scheme:
A micro-motor photocatalyst is prepared by solvothermal synthesis of alpha-Fe 2O3-ZnFe2O4Micromotor photocatalyst microspheres of ZnFe 2O4the diameter of the hollow microsphere is 0.4-0.8 μm, and the flake alpha-Fe 2O3And Mn 2O3Nanoparticles grown on ZnFe 2O4On the microspheres.
said, α -Fe 2O3-ZnFe2O4The particle size of the micromotor photocatalyst microspheres is 0.5-1 mu m.
A preparation method of a micro-motor photocatalyst is prepared by the following steps:
1) Adding Zn (CH) 3COO)2·2H2O and Fe (NO) 3)3·9H2Adding O into the mixed solution, magnetically stirring for 10min, adding into a reaction kettle for reaction, cooling to room temperature after the reaction is finished, washing with distilled water for 3 times, and drying to obtain ZnFe 2O4Hollow microspheres A precursor of (a);
2) diluting 3-5m L50% manganese nitrate solution with distilled water to 15m L to obtain dilute manganese nitrate solution, and mixing with Fe (NO) 3)3·9H2Adding O into dilute manganese nitrate solution, mixing uniformly, and adding 0.5g ZnFe 2O4And (3) dipping, filtering, drying, calcining and cooling a precursor of the hollow microsphere to room temperature to obtain the micro-motor photocatalyst.
in the step 1), the mixed solution is prepared from 18m L glycerol and 60m L isopropanol, Zn (CH) 3COO)2·2H2The adding amount of O is 1 mmol; fe (NO) 3)3·9H2The addition amount of O is 2 mmol; the reaction temperature is 180 ℃, the reaction time is 12h, and the drying temperature is 80 ℃.
In the step 2), Fe (NO) 3)3·9H2The dosage of O is 200 mg; the dipping time is 2 h; the drying temperature is 80 ℃; the calcining temperature is 500 ℃, and the calcining time is 1 h.
The micro-motor photocatalyst is used for catalyzing and degrading dye wastewater; at H 2O2Under the participation, the ultraviolet irradiation condition is simulated to catalyze and degrade the dye wastewater.
the concentration of organic matters in the dye wastewater is 5 mg/L, the dosage of the micromotor photocatalyst is 1 g/L, and H is 2O2The volume ratio of the dye solution to the simulated ultraviolet light is 1:50, and the simulated ultraviolet light irradiation time is 1-45 min.
Said, H 2O2The concentration of (2) is 30%.
The invention has the beneficial effects that:
The micromotor photocatalyst has a magnetic microsphere structure, is beneficial to recovery and magnetic control, and can catalyze H 2O2Generating bubbles to perform autonomous movement at H 2O2Has better degradation efficiency on organic pollutants in the dye wastewater under the participated UV-Fenton reaction, and can be used for the high-efficiency treatment of the dye wastewater. In the reaction system H 2O2not only used as a reagent for UV-Fenton reaction, but also used for promoting alpha-Fe 2O3-ZnFe2O4Fuel for the micro-motor. The invention The preparation method has mild conditions, low energy consumption and easy operation of the preparation process.
Drawings
Figure 1 is a graph of the degradation of methylene blue by the micromotor photocatalyst prepared in examples 1-3 under simulated uv light.
FIG. 2 is an SEM, EDS, TEM, HRTEM, and mapping photograph of the micromotor photocatalyst prepared in example 3.
In the figure, (a), (b) and (c) are SEM images of the micromotor photocatalyst; (d) EDS spectra for the micromotor photocatalyst; (e) TEM images of the micromotor photocatalyst; (f) HRTEM photographs of the micromotor photocatalyst, and (g), (h), (i) and (j) are the corresponding micromotor photocatalyst mapping photographs.
Figure 3 is an XRD profile of the micromotor photocatalyst prepared in example 3.
FIG. 4 is the ZnFe prepared in example 3 2O4SEM image of hollow microspheres.
Fig. 5 is a hysteresis loop at room temperature for the micromotor photocatalyst prepared in example 3.
Fig. 6 is a graph of the uv-vis spectra of the micromotor photocatalyst prepared in example 3 for different catalytic times of methylene blue.
Detailed Description
The present invention will be further described with reference to the following examples.
Example 1
A micro-motor photocatalyst is prepared by solvothermal synthesis of alpha-Fe 2O3-ZnFe2O4Micromotor photocatalyst microspheres of ZnFe 2O4the diameter of the hollow microsphere is 0.4-0.8 μm, and the flake alpha-Fe 2O3And Mn 2O3Nanoparticles grown on ZnFe 2O4On the microspheres.
said, α -Fe 2O3-ZnFe2O4The particle size of the micromotor photocatalyst microspheres is 0.5-1 mu m.
A preparation method of a micro-motor photocatalyst is prepared by the following steps:
1) Adding Zn (CH) 3COO)2·2H2O and Fe (NO) 3)3·9H2Adding O into the mixed solution, magnetically stirring for 10min, adding into a reaction kettle for reaction, cooling to room temperature after the reaction is finished, washing with distilled water for 3 times, and drying to obtain ZnFe 2O4Precursors of hollow microspheres;
in the step 1), the mixed solution is prepared from 18m L glycerol and 60m L isopropanol, Zn (CH) 3COO)2·2H2The adding amount of O is 1 mmol; fe (NO) 3)3·9H2The addition amount of O is 2 mmol; the reaction temperature is 180 ℃, the reaction time is 12h, and the drying temperature is 80 ℃.
2) diluting 3m L50% manganese nitrate solution with distilled water to 15m L to obtain dilute manganese nitrate solution, and mixing with Fe (NO) 3)3·9H2Adding O into dilute manganese nitrate solution, mixing uniformly, and adding 0.5g ZnFe 2O4And (3) dipping, filtering, drying, calcining and cooling a precursor of the hollow microsphere to room temperature to obtain the micro-motor photocatalyst.
In the step 2), Fe (NO) 3)3·9H2The dosage of O is 200 mg; the dipping time is 2 h; the drying temperature is 80 ℃; the calcining temperature is 500 ℃, and the calcining time is 1 h.
The micro-motor photocatalyst is used for catalyzing and degrading dye wastewater; at H 2O2Under the participation, the ultraviolet irradiation condition is simulated to catalyze and degrade the dye wastewater.
the concentration of organic matters in the dye wastewater is 5 mg/L, the dosage of the micromotor photocatalyst is 1 g/L, and H is 2O2The volume ratio of the dye solution to the simulated ultraviolet light is 1:50, and the simulated ultraviolet light irradiation time is 1-45 min.
Said, H 2O2The concentration of (2) is 30%.
Example 2
A micro-motor photocatalyst is prepared by solvothermal synthesis of alpha-Fe 2O3-ZnFe2O4Micromotor photocatalyst microspheres of ZnFe 2O4the diameter of the hollow microsphere is 0.4-0.8 μm, and the flake alpha-Fe 2O3And Mn 2O3Nanoparticles grown on ZnFe 2O4On the microspheres.
said, α -Fe 2O3-ZnFe2O4The particle size of the micromotor photocatalyst microspheres is 0.5-1 mu m.
A preparation method of a micro-motor photocatalyst is prepared by the following steps:
1) Adding Zn (CH) 3COO)2·2H2O and Fe (NO) 3)3·9H2Adding O into the mixed solution, magnetically stirring for 10min, adding into a reaction kettle for reaction, cooling to room temperature after the reaction is finished, washing with distilled water for 3 times, and drying to obtain ZnFe 2O4Precursors of hollow microspheres;
2) diluting 4m L50% manganese nitrate solution with distilled water to 15m L to obtain diluted manganese nitrate solution, and mixing Fe (NO) 3)3·9H2Adding O into dilute manganese nitrate solution, mixing uniformly, and adding 0.5g ZnFe 2O4And (3) dipping, filtering, drying, calcining and cooling a precursor of the hollow microsphere to room temperature to obtain the micro-motor photocatalyst.
in the step 1), the mixed solution is prepared from 18m L glycerol and 60m L isopropanol, Zn (CH) 3COO)2·2H2The adding amount of O is 1 mmol; fe (NO) 3)3·9H2The addition amount of O is 2 mmol; the reaction temperature is 180 ℃, the reaction time is 12h, and the drying temperature is 80 ℃.
In the step 2), Fe (NO) 3)3·9H2The dosage of O is 200 mg; the dipping time is 2 h; the drying temperature is 80 ℃; the calcining temperature is 500 ℃, and the calcining time is 1 h.
The micro-motor photocatalyst is used for catalyzing and degrading dye wastewater; at H 2O2Under the participation, the ultraviolet irradiation condition is simulated to catalyze and degrade the dye wastewater.
the concentration of organic matters in the dye wastewater is 5 mg/L, the dosage of the micromotor photocatalyst is 1 g/L, and H is 2O2The volume ratio of the dye solution to the simulated ultraviolet light is 1:50, and the simulated ultraviolet light irradiation time is 1-45 min.
Said, H 2O2The concentration of (2) is 30%.
Example 3
A micro-motor photocatalyst is prepared by solvothermal synthesis of alpha-Fe 2O3-ZnFe2O4Micromotor photocatalyst microspheres of ZnFe 2O4the diameter of the hollow microsphere is 0.4-0.8 μm, and the flake alpha-Fe 2O3And Mn 2O3Nanoparticles grown on ZnFe 2O4On the microspheres.
said, α -Fe 2O3-ZnFe2O4The particle size of the micromotor photocatalyst microspheres is 0.5-1 mu m.
A preparation method of a micro-motor photocatalyst is prepared by the following steps:
1) Adding Zn (CH) 3COO)2·2H2O and Fe (NO) 3)3·9H2Adding O into the mixed solution, magnetically stirring for 10min, adding into a reaction kettle for reaction, cooling to room temperature after the reaction is finished, washing with distilled water for 3 times, and drying to obtain ZnFe 2O4Precursors of hollow microspheres;
2) diluting 5m L50% manganese nitrate solution with distilled water to 15m L to obtain dilute manganese nitrate solution, and mixing with Fe (NO) 3)3·9H2Adding O into dilute manganese nitrate solution, mixing uniformly, and adding 0.5g ZnFe 2O4And (3) dipping, filtering, drying, calcining and cooling a precursor of the hollow microsphere to room temperature to obtain the micro-motor photocatalyst.
in the step 1), the mixed solution is prepared from 18m L glycerol and 60m L isopropanol, Zn (CH) 3COO)2·2H2The adding amount of O is 1 mmol; fe (NO) 3)3·9H2The addition amount of O is 2 mmol; the reaction temperature is 180 ℃, the reaction time is 12h, and the drying temperature is 80 ℃.
In the step 2), Fe (NO) 3)3·9H2The dosage of O is 200 mg; the dipping time is 2 h; the drying temperature is 80 ℃; the calcining temperature is 500 ℃, and the calcining time is 1 h.
The micro-scale The motor photocatalyst is used for catalyzing and degrading the dye wastewater; at H 2O2Under the participation, the ultraviolet irradiation condition is simulated to catalyze and degrade the dye wastewater.
the concentration of organic matters in the dye wastewater is 5 mg/L, the dosage of the micromotor photocatalyst is 1 g/L, and H is 2O2The volume ratio of the dye solution to the simulated ultraviolet light is 1:50, and the simulated ultraviolet light irradiation time is 1-45 min.
Said, H 2O2The concentration of (2) is 30%.
Test example
FIG. 1 is a graph showing the degradation of methylene blue by the micro-motor photocatalyst prepared in examples 1 to 3 under simulated ultraviolet light, and the degradation effect of the micro-motor photocatalyst prepared in examples 1 to 3 under simulated ultraviolet light was tested by using a methylene blue solution to simulate organic contaminants in dye wastewater by placing 0.05g of the micro-motor photocatalyst into a methylene blue solution of 50m L5 mg/L, placing the solution in the dark for 30min until the adsorption was balanced, and adding 1m L30% of H into the methylene blue solution after the adsorption was saturated 2O2the UV-Fenton reaction is carried out under the irradiation of a 500W mercury lamp, 4m L methylene blue solution is taken out as a sample after 5, 15, 25, 35 and 45min of light irradiation, centrifugal separation is carried out for 5min at 4000r/min, and a spectrophotometer is used for testing the absorbance of the methylene blue solution under different catalytic time and converting the absorbance into concentration so as to represent the degradation effect, so that the graphs show that the degradation rates of the micro-motor photocatalyst prepared in the embodiments 1 to 3 on the methylene blue are 93.9%, 96.6% and 98.9% respectively at 45min, which shows that the micro-motor photocatalyst prepared in the embodiments 1 to 3 has high-efficiency catalytic effect on the methylene blue dye and can be used for high-efficiency treatment of dye wastewater.
FIG. 2 is an SEM photograph, an EDS spectrum, a TEM, an HRTEM and a mapping photograph of the micro-motor photocatalyst prepared in example 3, in which (a), (b) and (c) are SEM photographs of the micro-motor photocatalyst, and it can be seen from the SEM photographs that α -Fe was prepared 2O3-ZnFe2O4The micro-motor photocatalyst microspheres are uniformly dispersed, are in flower-like spheres and have the diameter of about 0.5-1 mu m. (d) Is an EDS spectrum of the micro-motor photocatalyst, and a sample contains Zn, Fe. Mn, O and other elements, and the molar ratio Zn: fe: mn: o = 5.19: 37.63: 7.94: 49.24, which corresponds to the expected stoichiometry. (e) For TEM image of the micromotor photocatalyst, ZnFe can be seen 2O4And Mn 2O3the nanoparticles correspond to the position of small black dots thereon, α -Fe 2O3Represented as nanosheets in the figure, which is consistent with the results obtained in SEM photographs, indirectly demonstrating the successful synthesis of the micromotor photocatalyst target material. (f) HRTEM photograph of the micromotor photocatalyst shows that 0.487nm and 0.298nm respectively correspond to ZnFe 2O4the (111) and (220) crystal planes of (A), 0.270nm corresponding to α -Fe 2O3Crystal face (104) of (1), 0.277nm corresponding to Mn 2O3(g-j) is a picture of the corresponding micromotor photocatalyst mapping, and proves that O, Zn, Fe and Mn coexist in α -Fe 2O3-ZnFe2O4Micro-motor photocatalyst microspheres.
Figure 3 is an XRD profile of the micromotor photocatalyst prepared in example 3. The XRD spectrogram shows that the sample is made of ZnFe 2O4、α-Fe2O3And Mn 2O3And (4) forming.
FIG. 4 is the ZnFe prepared in example 3 2O4SEM image of hollow microspheres. ZnFe can be seen from the figure 2O4The hollow microspheres are relatively dispersed and uniform in size. ZnFe thus prepared 2O4The diameter of the hollow microspheres is about 0.4-0.8um, and each hollow microsphere is assembled by nano particles.
FIG. 5 is a hysteresis loop at room temperature for the micromotor photocatalyst prepared in example 3, ranging from-10 KOe to 10KOe, with a saturation magnetization of 1.37emug -1the remanence is 1.72 × 10-3emug -1The coercive force was 0.62 Oe. From the figure, the hysteresis loop of the micromotor photocatalyst microspheres is a classic S-shaped curve and shows superparamagnetism.
Fig. 6 is a graph of the uv-vis spectra of the micromotor photocatalyst prepared in example 3 for different catalytic times of methylene blue. As can be seen, the peak maximum at 664nm was observed, and the peak of methylene blue was significantly reduced with the increase of the photo-Fenton time, and almost completely disappeared after 45 minutes.

Claims (5)

1. A micro-motor photocatalyst is characterized in that α -Fe is synthesized by a solvothermal method 2O3-ZnFe2O4Micromotor photocatalyst microspheres of ZnFe 2O4the diameter of the hollow microsphere is 0.4-0.8 μm, and the flake alpha-Fe 2O3And Mn 2O3Nanoparticles grown on ZnFe 2O4On the microspheres; the micromotor photocatalyst is prepared by the following steps:
1) Adding Zn (CH) 3COO)2·2H2O and Fe (NO) 3)3·9H2Adding O into the mixed solution, magnetically stirring for 10min, adding into a reaction kettle for reaction, cooling to room temperature after the reaction is finished, washing with distilled water for 3 times, and drying to obtain ZnFe 2O4Precursors of hollow microspheres;
2) diluting 3-5m L50% manganese nitrate solution with distilled water to 15m L to obtain dilute manganese nitrate solution, and mixing with Fe (NO) 3)3·9H2Adding O into dilute manganese nitrate solution, mixing uniformly, and adding 0.5g ZnFe 2O4Dipping, filtering, drying, calcining and cooling a precursor of the hollow microsphere to room temperature to obtain the micro-motor photocatalyst;
in the step 1), the mixed solution is prepared from 18m L glycerol and 60m L isopropanol, Zn (CH) 3COO)2·2H2The adding amount of O is 1 mmol; fe (NO) 3)3·9H2The addition amount of O is 2 mmol; the reaction temperature is 180 ℃, the reaction time is 12h, and the drying temperature is 80 ℃;
In the step 2), Fe (NO) 3)3·9H2The dosage of O is 200 mg; the dipping time is 2 h; the drying temperature is 80 ℃; the calcining temperature is 500 ℃, and the calcining time is 1 h.
2. the micromotor photocatalyst of claim 1, wherein the α -Fe is 2O3-ZnFe2O4The particle size of the micromotor photocatalyst microspheres is 0.5-1 mu m.
3. Use of the micro-motor photocatalyst of claim 1 for the catalytic degradation of dye wastewater; at H 2O2Under the participation, the ultraviolet irradiation condition is simulated to catalyze and degrade the dye wastewater.
4. the application of claim 3, wherein the concentration of organic matters in the dye wastewater is 5 mg/L, the dosage of the micromotor photocatalyst is 1 g/L, and H is 2O2The volume ratio of the dye solution to the simulated ultraviolet light is 1:50, and the simulated ultraviolet light irradiation time is 1-45 min.
5. Use according to claim 3, wherein H is 2O2The concentration of (2) is 30%.
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CN109580740B (en) * 2018-12-19 2019-10-11 南京工业大学 High-ratio surface hollow tubular micron motor, preparation method and application
CN109594326B (en) * 2018-12-21 2021-06-29 福建工程学院 Based on gamma-Fe2O3/MnO2Magnetic conduction self-propelled micro-nano motor and preparation method thereof
US10934175B1 (en) * 2019-12-02 2021-03-02 King Saud University Method of making zinc oxide nanoparticles using red sand
CN111001419A (en) * 2019-12-25 2020-04-14 陕西国防工业职业技术学院 Preparation method of silver-modified magnetic separable photocatalyst
CN111762937B (en) * 2020-06-19 2021-10-29 昆明理工大学 Preparation method and application of composite photocatalytic nano motor
CN112427009B (en) * 2020-11-18 2023-02-28 昆明理工大学 Preparation method and application of nano motor adsorption material
CN115180678B (en) * 2022-06-24 2023-12-12 浙江工业大学 Method for enhancing performance of degrading typical PPCPs by using magnetic zinc ferrite nanorods and using UV-LED/chlorine system

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1454851A (en) * 2002-04-17 2003-11-12 国际商业机器公司 Synthesizing of magnetite nano particles and method for forming iron-base nano material
CN106140173A (en) * 2015-04-14 2016-11-23 中国科学院大连化学物理研究所 A kind of ferrite/metal oxide materials and its preparation method and application
CN106268830A (en) * 2016-08-08 2017-01-04 辽宁大学 A kind of Fe2o3/ ZnFe2o4composite photo-catalyst and its preparation method and application

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1454851A (en) * 2002-04-17 2003-11-12 国际商业机器公司 Synthesizing of magnetite nano particles and method for forming iron-base nano material
CN106140173A (en) * 2015-04-14 2016-11-23 中国科学院大连化学物理研究所 A kind of ferrite/metal oxide materials and its preparation method and application
CN106268830A (en) * 2016-08-08 2017-01-04 辽宁大学 A kind of Fe2o3/ ZnFe2o4composite photo-catalyst and its preparation method and application

Non-Patent Citations (7)

* Cited by examiner, † Cited by third party
Title
Decomposition of hydrogen peroxide over pure and mixed copper oxide and manganese oxide prepared from carbonates;N.A.Youssef et al.;《Commun.Fac.Univ.Ank.Series B》;19930228;第39页最后一段 *
Effect of surfactant amount on the morphology and magnetic properties of monodisperse ZnFe2O4 nanoparticles;Haitao Zhao et al.;《Materials Research Bulletin》;20151130;第172-177页 *
Facile synthesis and characterization of ZnFe2O4/a-Fe2O3 composite hollow nanospheres;Yu Shen et al.;《Materials Research Bulletin》;20110910;第4节第一句、最后一句、图3、第2.1节 *
Lluı＇s Soler et al..Self-Propelled Micromotors for Cleaning Polluted Water.《ACS nano》.2013, *
Nanosheet-Assembled ZnFe2O4 Hollow Microspheres for High-Sensitive Acetone Sensor;Xin Zhou et al.;《ACS Applied Materials & Interfaces》;20150623;第2.1节 *
Synthesis and photocatalytic activity of cobalt oxide doped ZnFe2O4-Fe2O3-ZnO mixed oxides;Jiahai Bai;《Materials Letters》;20090401;第1485-1488页 *
化学驱动微纳米马达运动规律及应用研究;王林;《中国博士学位论文全文数据库 工程科技I辑》;20170215(第2期);第B020-140页 *

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