CN110339843B - Preparation method of magnetic bismuth oxide/bismuth vanadate composite photocatalyst - Google Patents

Preparation method of magnetic bismuth oxide/bismuth vanadate composite photocatalyst Download PDF

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CN110339843B
CN110339843B CN201910729540.6A CN201910729540A CN110339843B CN 110339843 B CN110339843 B CN 110339843B CN 201910729540 A CN201910729540 A CN 201910729540A CN 110339843 B CN110339843 B CN 110339843B
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徐龙君
杨雅寒
刘成伦
吴廷增
王海龙
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Chongqing University
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Abstract

Magnetic composite photocatalyst MnxZn1‑xFe2O4/β‑Bi2O3/BiVO4Belonging to the field of inorganic catalytic materials. The invention firstly prepares Mn by a hydrothermal methodxZn1‑xFe2O4Then preparing Mn by coprecipitation-roasting methodxZn1‑xFe2O4/BiVO4The magnetic composite photocatalyst Mn is prepared by adopting a precipitation-roasting methodxZn1‑xFe2O4/β‑Bi2O3/BiVO4. The method has the advantages of simple preparation process, less used equipment cost and less energy consumption. Prepared MnxZn1‑xFe2O4/β‑Bi2O3/BiVO4The composite photocatalytic material prepared by 0.1g is large in specific surface area, strong in stability and high in photocatalytic activity, 50mL of 10mg/L rhodamine B solution is degraded under the irradiation of a simulated sunlight xenon lamp, the degradation rate reaches 92.8% after 3 hours of illumination, the recovery rate after 3 times of repeated use is more than 89.7%, and the degradation rate of 3 times of repeated use on rhodamine B is still more than 84.9%. The product prepared by the invention can be widely used in the field of photocatalytic degradation of organic pollutants.

Description

Preparation method of magnetic bismuth oxide/bismuth vanadate composite photocatalyst
Technical Field
The invention relates to a magnetic bismuth oxide/bismuth vanadate composite photocatalyst MnxZn1-xFe2O4/β-Bi2O3/BiVO4Belonging to the technical field of inorganic catalytic materials.
Background
Semiconductor photocatalytic technology is a new technology to deal with environmental issues because of traditional photocatalysts (e.g. alumina, silica, etc.)TiO2And ZnO) has a large energy gap, and can only utilize 3% -5% of the ultraviolet light in solar energy, and people are making efforts to research and develop novel semiconductor photocatalysts at the present stage. Found that Bi2O3BiOBr, BiOI and BiVO4The bismuth-based visible light catalyst has the advantages of low cost, high efficiency and the like, and is widely applied to the degradation of organic pollutants in wastewater and the preparation of H2And CO2And (4) reduction. Besides, many scholars prove that the bismuth-based semiconductor photocatalyst has certain photocatalytic activity under the irradiation of visible light, so that the research of bismuth-based visible light materials becomes a hotspot. In the development of novel bismuth-based photocatalysts, beta-Bi2O3The band gap of the material is 2.58eV, the material can absorb visible light with the wavelength of more than 400nm, and the preparation method mainly comprises a chemical precipitation method, a sol-gel method, a microemulsion method, a hydrothermal synthesis method, a solid phase room temperature method and the like. BiVO4The bismuth vanadate has various structures, wherein monoclinic scheelite type, tetragonal zirconium silicate type and tetragonal scheelite (high-temperature phase) type are common, the forbidden band width is 2.3-2.4 eV, the bismuth vanadate can respond to a visible light region, and the photocatalysis effect is good. BiVO4The preparation method mainly comprises a chemical precipitation method, a roasting method, a hydrothermal method and the like. The photocatalyst is mostly in a suspension state in a photocatalytic reaction system, is in a slurry state after the photocatalytic reaction, and is difficult to separate, recycle and reuse, which is a main factor for restricting the application process of the photocatalyst. The magnetic composite photocatalyst is recycled through an external magnetic field, and the defect that the suspended photocatalyst is not easy to recycle is overcome. MnxZn1-xFe2O4(manganese-zinc-ferrite) with conventional metallic soft magnetic materials such as Fe3O4Compared with ferroferric oxide, the ferroferric oxide has the characteristics of high saturation magnetization, high magnetic conductivity and the like, and has the advantages of high production efficiency, low cost, stable product performance and the like. Therefore, with MnxZn1-xFe2O4The composite photocatalyst prepared from the magnetic matrix has strong magnetism and is convenient to separate and recycle.
At the present stage, research on the magnetic composite catalyst mainly focuses on improving the catalytic activity of the magnetic composite catalyst, and reports on how to prepare the magnetic composite catalyst with high catalytic activity and high recovery rate are relatively highLess. For example, in the invention patent "a method for preparing a manganese-zinc-ferrite-bismuth oxide magnetic photocatalyst" (publication No. CN104437536A) (reference 1), the disclosed method is: firstly, Mn is prepared by a roasting methodxZn1-xFe2O4And then preparing Mn by using a dipping roasting methodxZn1-xFe2O4/β-Bi2O3A magnetic composite photocatalyst. The main disadvantages of this method are: (1) preparation of manganese zinc ferrite (Mn) by roasting methodxZn1-xFe2O4) The temperature of the reaction is 1200 ℃, the energy consumption is high, and the prepared sample has larger particle size and smaller specific surface area, which is not beneficial to MnxZn1-xFe2O4And beta-Bi2O3The stability of the compound cannot be ensured due to the sufficient combination of the components; (2) composite beta-Bi prepared by roasting method2O3/MnxZn1-xFe2O4The specific surface area is small, which is not beneficial to the full contact and reaction between the catalyst and organic pollutants in the photocatalytic degradation process; (3) mn prepared by roasting methodxZn1-xFe2O4Small coercive force, limited magnetic retention capacity and no contribution to MnxZn1-xFe2O4/β-Bi2O3And (4) recycling. Also for example, "chemical research and application" 2010 05 th stage "magnetic photocatalyst BiVO4/Fe3O4Study on the degradation of methylene blue "(reference 2), the magnetic matrix Fe was sonicated3O4And BiVO4Compounding to prepare the magnetic visible-light-driven photocatalyst BiVO easy for solid-liquid separation4/Fe3O4. The method has the following defects: (1) the magnetic composite photocatalyst has low efficiency and BiVO (BiVO) under simulated sunlight4/Fe3O4The degradation rate of the magnetic composite photocatalyst to methylene blue within 5h is 96.2%, and the recycled BiVO4/Fe3O4The degradation rate of methyl orange is more than 80 percent, and the effect on dye which is difficult to degrade, such as rhodamine B, is not investigated; (2) the recovery rate of the magnetic composite photocatalyst is not high and is only 84%; (3) the preparation process has more impurities and is difficult to ensureThe organic silicon and the organic silicon are uniformly and firmly combined, the production cost is higher, and a large amount of volatile organic compounds are discharged in the subsequent drying and heat treatment processes, so that the pollution to the atmospheric environment is caused.
Mn prepared by hydrothermal methodxZn1-xFe2O4The composite photocatalyst has better magnetic stability, is more beneficial to magnetic recovery and has no secondary pollution to the environment; compared with a product prepared by a roasting method, the hydrothermal method has smaller particle size and larger specific surface area, and can better ensure firm combination between the catalytic matrix and the magnetic matrix, so that the combination has better stability. Thus, the hydrothermal method is used for preparing MnxZn1-xFe2O4Then with beta-Bi2O3、BiVO4Composite improvement of beta-Bi2O3And BiVO4The catalytic effect, recovery rate and magnetic stability of the catalyst are necessary.
Disclosure of Invention
The invention aims at the beta-Bi prepared by the roasting method2O3、MnxZn1-xFe2O4The problems of high energy consumption, unstable photocatalytic activity of the compound, limited magnetic retention capacity and the like exist, and the hydrothermal method is adopted to prepare MnxZn1-xFe2O4And hydrothermal-coprecipitation-roasting method for preparing MnxZn1-xFe2O4/β-Bi2O3/BiVO4A new method of a magnetic composite photocatalyst, which not only solves the problem of beta-Bi2O3/BiVO4The preparation method is simple, the production cost is low, the period is short, the catalytic activity is high, the magnetic composite photocatalyst is convenient to separate and recover from a liquid phase suspension system through an external magnetic field, the recovered catalyst still has high catalytic activity, the resource recycling is simply and efficiently realized, and the possible secondary pollution caused by the catalyst is avoided.
The magnetic composite photocatalyst Mn of the inventionxZn1-xFe2O4/β-Bi2O3/BiVO4The preparation method comprises the following steps:
(1)MnxZn1-xFe2O4preparation of
ZnO according to a molar ratio: MnO: fe2O313.3: 32.8: 53.9, respectively weighing a proper amount of zinc sulfate, ferric sulfate and manganese sulfate, adding 25mL of deionized water, and dissolving by ultrasonic oscillation to obtain a mixed solution; under the action of magnetic stirring, dropwise adding a NaOH solution with a certain concentration into the mixed solution, adjusting the pH of the solution to 13, and continuously stirring for 15 min; transferring the stirred solution into a 100mL reaction kettle, and reacting for 5h at 200 ℃; after the reaction is finished, cooling and suction filtering are carried out, filter cakes are respectively washed for 5 times by distilled water and ethanol, the filter cakes are dried for 12 hours at the temperature of 80 ℃, and Mn is obtained by grindingxZn1-xFe2O4。
(2)MnxZn1-xFe2O4/BiVO4Preparation of
Weighing a certain amount of bismuth nitrate pentahydrate, and adding HNO with the concentration of 2mol/L3In the solution, ultrasonic oscillation is carried out to dissolve the solution to obtain a solution A; according to Bi (NO)3)3·5H2Weighing tartaric acid according to different proportions, and dissolving the tartaric acid in hot water at the temperature of 80 ℃ to obtain a solution B; in a molar ratio of Bi (NO)3)3·5H2O:NH4VO3Weighing ammonium metavanadate at the ratio of 1:1, and dissolving the ammonium metavanadate in hot water at the temperature of 80 ℃ to obtain a solution C; dripping the solution B into the solution C to obtain a mixed solution D; then adding the solution A into the mixed solution D, cooling the solution, and adjusting the pH of the solution to 7.5 by using ammonia water to obtain BiVO4A precursor of (a); according to Mn1-xZnxFe2O4:BiVO4The mass ratio is 10:100 weighing the Mn obtained above1-xZnxFe2O4Adding into BiVO4Performing water bath reaction on the precursor at 80 ℃ for 30min, filtering, drying, grinding, placing in a muffle furnace at 450 ℃ for reaction for 3h, taking out, and cooling to room temperature to obtain MnxZn1-xFe2O4/BiVO4。
(3)MnxZn1-xFe2O4/β-Bi2O3/BiVO4Preparation of
Weighing a proper amount of bismuth nitrate, adding the bismuth nitrate into 10mL of 2mol/L HNO3Dissolving with ultrasound to obtain clear solution, and adding into 40mL of 0.6mol/L Na2CO3In the solution, mechanically stirring for 2h to obtain beta-Bi2O3Precursor solution; in the form of beta-Bi2O3:MnxZn1-xFe2O4/BiVO4Weighing Mn according to the mass ratio of 5-15: 100xZn1-xFe2O4/BiVO4To beta-Bi2O3Mechanically stirring the precursor solution for 2 hours, filtering, washing a filter cake with distilled water, then placing the filter cake in a drying oven at 60 ℃ for drying for 12 hours, and grinding to obtain composite precursor powder; putting the precursor powder into a muffle furnace, roasting at 380 ℃ for 10min, then quickly taking out the precursor powder from the muffle furnace, and naturally cooling to obtain Mn with different mass ratiosxZn1-xFe2O4/β-Bi2O3/BiVO4. By adopting the technical scheme, the invention mainly has the following effects:
(1) the magnetic composite photocatalyst Mn prepared by the methodxZn1-xFe2O4/β-Bi2O3/BiVO4Has high photocatalytic activity, and 0.1g of Mn is prepared under the irradiation of a xenon lamp simulating sunlightxZn1-xFe2O4/β-Bi2O3/BiVO4The magnetic composite photocatalyst is dispersed in 50mL of rhodamine B solution with the concentration of 10mg/L, and the degradation rate reaches 92.8 percent after illumination for 3 hours.
(2) The magnetic composite photocatalyst Mn prepared by the methodxZn1-xFe2O4/β-Bi2O3/BiVO4Under the action of an external magnetic field, the recovery rate after 3 times of repeated use is more than 89.7%, and the degradation rate of 3 times of repeated use on rhodamine B still reaches more than 84.9%.
(3) The invention is prepared by a hydrothermal-coprecipitation-roasting method, and the specific surface area of the magnetic composite photocatalyst reaches 17.8m2Perg, strong stability and simple preparation operationThe required equipment is less and the energy consumption is low.
Drawings
FIG. 1 is BiVO4、β-Bi2O3/MnxZn1-xFe2O4And beta-Bi2O3/BiVO4/MnxZn1-xFe2O4X-ray diffraction pattern of (a).
FIG. 2 shows beta-Bi2O3/BiVO4And beta-Bi2O3/BiVO4/MnxZn1-xFe2O4An infrared spectrum of (1).
Fig. 3 is a hysteresis chart of a magnetic sample.
Detailed Description
The present invention will be further described with reference to the following specific embodiments.
Example 1
Preparation of magnetic composite photocatalyst MnxZn1-xFe2O4/β-Bi2O3/BiVO4The method comprises the following specific steps:
(1)MnxZn1-xFe2O4preparation of
ZnO according to a molar ratio: MnO: fe2O313.3: 32.8: 53.9, respectively weighing a proper amount of zinc sulfate, ferric sulfate and manganese sulfate, adding 25mL of deionized water, and dissolving by ultrasonic oscillation to obtain a mixed solution; under the action of magnetic stirring, dropwise adding a NaOH solution with a certain concentration into the mixed solution, adjusting the pH of the solution to 13, and continuously stirring for 15 min; transferring the stirred solution into a 100mL reaction kettle, and reacting for 5h at 200 ℃; after the reaction is finished, cooling and suction filtering are carried out, filter cakes are respectively washed for 5 times by distilled water and ethanol, the filter cakes are dried for 12 hours at the temperature of 80 ℃, and Mn is obtained by grindingxZn1-xFe2O4。
(2)MnxZn1-xFe2O4/BiVO4Preparation of
Weighing a certain amount of bismuth nitrate pentahydrate, and adding HNO with the concentration of 2mol/L3Dissolving in solution by ultrasonic oscillationSolution A; according to Bi (NO)3)3·5H2Weighing tartaric acid according to different proportions, and dissolving the tartaric acid in hot water at the temperature of 80 ℃ to obtain a solution B; in a molar ratio of Bi (NO)3)3·5H2O:NH4VO3Weighing ammonium metavanadate at the ratio of 1:1, and dissolving the ammonium metavanadate in hot water at the temperature of 80 ℃ to obtain a solution C; dripping the solution B into the solution C to obtain a mixed solution D; then adding the solution A into the mixed solution D, cooling the solution, and adjusting the pH of the solution to 7.5 by using ammonia water to obtain BiVO4A precursor of (a); according to Mn1-xZnxFe2O4:BiVO4The mass ratio is 10:100 weighing the Mn obtained above1-xZnxFe2O4Adding into BiVO4Performing water bath reaction on the precursor at 80 ℃ for 30min, filtering, drying, grinding, placing in a muffle furnace at 450 ℃ for reaction for 3h, taking out, and cooling to room temperature to obtain BiVO4/Mn1-xZnxFe2O4。
(3)MnxZn1-xFe2O4/β-Bi2O3/BiVO4Preparation of
Weighing a proper amount of bismuth nitrate, adding the bismuth nitrate into 10mL of 2mol/L HNO3Dissolving in solution with ultrasound to obtain clear solution, and adding into 40mL of 0.6mol/L Na at a certain speed2CO3In the solution, mechanically stirring for 2h to obtain beta-Bi2O3Precursor solution; in the form of beta-Bi2O3:BiVO4/MnxZn1-xFe2O4Weighing Mn according to the mass ratio of 5:100xZn1-xFe2O4/BiVO4To beta-Bi2O3Mechanically stirring the precursor solution for 2 hours, filtering, washing a filter cake with distilled water, then placing the filter cake in a drying oven at 60 ℃ for drying for 12 hours, and grinding to obtain composite precursor powder; putting the precursor powder into a muffle furnace, roasting at 380 ℃ for 10min, then quickly taking out the precursor powder from the muffle furnace, and naturally cooling to obtain Mn with different mass ratiosxZn1-xFe2O4/β-Bi2O3/BiVO4。
Example 2
Preparation of magnetic composite photocatalyst MnxZn1-xFe2O4/β-Bi2O3/BiVO4The method comprises the following specific steps:
(1) the same as in (1) in example 1.
(2) Same as example 1 (2)
(3)β-Bi2O3/BiVO4/MnxZn1-xFe2O4Preparation of
Weighing a proper amount of bismuth nitrate, adding the bismuth nitrate into 10mL of 2mol/L HNO3Dissolving in solution with ultrasound to obtain clear solution, and adding into 40mL of 0.6mol/L Na at a certain speed2CO3In the solution, mechanically stirring for 2h to obtain beta-Bi2O3Precursor solution; in the form of beta-Bi2O3:BiVO4/MnxZn1-xFe2O4Weighing Mn according to the mass ratio of 10:100xZn1-xFe2O4/BiVO4To beta-Bi2O3Mechanically stirring the precursor solution for 2 hours, filtering, washing a filter cake with distilled water, then placing the filter cake in a drying oven at 60 ℃ for drying for 12 hours, and grinding to obtain composite precursor powder; putting the precursor powder into a muffle furnace, roasting at 380 ℃ for 10min, then quickly taking out the precursor powder from the muffle furnace, and naturally cooling to obtain Mn with different mass ratiosxZn1-xFe2O4/β-Bi2O3/BiVO4。
Example 3
Preparation of magnetic composite photocatalyst MnxZn1-xFe2O4/β-Bi2O3/BiVO4The method comprises the following specific steps:
(1) the same as in (1) in example 1.
(2) Same as example 1 (2)
(3)MnxZn1-xFe2O4/β-Bi2O3/BiVO4Preparation of
Weighing a proper amount of bismuth nitrate, adding the bismuth nitrate into 10mL of bismuth nitrate with the volume of 2mol/L HNO3Dissolving in solution with ultrasound to obtain clear solution, and adding into 40mL of 0.6mol/L Na at a certain speed2CO3In the solution, mechanically stirring for 2h to obtain beta-Bi2O3Precursor solution; in the form of beta-Bi2O3:BiVO4/MnxZn1-xFe2O4Weighing Mn according to the mass ratio of 15:100xZn1-xFe2O4/BiVO4To beta-Bi2O3Mechanically stirring the precursor solution for 2 hours, filtering, washing a filter cake with distilled water, then placing the filter cake in a drying oven at 60 ℃ for drying for 12 hours, and grinding to obtain composite precursor powder; putting the precursor powder into a muffle furnace, roasting at 380 ℃ for 10min, then quickly taking out the precursor powder from the muffle furnace, and naturally cooling to obtain Mn with different mass ratiosxZn1-xFe2O4/β-Bi2O3/BiVO4。
Results of the experiment
Magnetic composite photocatalyst Mn prepared in example 2xZn1-xFe2O4/β-Bi2O3/BiVO4The catalytic degradation activity is optimal. For easy comparison, beta-Bi was prepared2O3Sample and BiVO4。β-Bi2O3The preparation method is that BiVO is not added in the step (3) of the example 24/MnxZn1-xFe2O4；BiVO4The preparation method is that no Mn is added in the step (2) of the example 1xZn1-xFe2O4。
β-Bi2O3The XRD pattern of (A) is shown in FIG. 1(b), and each diffraction peak corresponds to pure β -Bi2O3The characteristic peak (JCPDS #27-0050) with characteristic reflection peaks including (210), (201), (220), (222), (200) and (400) etc. proves that the sample is the pure square crystal structure of beta-Bi2O3。β-Bi2O3The infrared absorption spectrum of (2) is as shown in FIG. 2(c), and it is 1383cm-1、846.3cm-1、585.6cm-1Has a peak of beta-Bi2O3Typical Bi-O bond absorption peak。
BiVO4The XRD pattern of (A) is shown in FIG. 1(c), and BiVO is prepared4According to the JCPDS PDF document No.14-0688, strong diffraction peaks exist in the crystal faces (110), (011), (121), (040), (200), (002), (211), (150), (240), (042), (220), (161), (321) and (123), and the prepared sample is m-BiVO4。BiVO4The infrared absorption spectrum of (c) is as shown in FIG. 2(b), at 615cm-1Is attributed to VO4At 430cm-1The peak of (A) is VO4Caused by inconsistent contraction movement of V1[9]The presence of BiVO in the sample is also proved4The complete crystal form of (a).
Magnetic composite photocatalyst MnxZn1-xFe2O4/β-Bi2O3/BiVO4XRD diffraction of (B) is shown in FIG. 1(a), MnxZn1- xFe2O4For modifying beta-Bi2O3In which Mn is not observedxZn1-xFe2O4Characteristic diffraction peaks, which may be due to Mn in the sample per unit massxZn1-xFe2O4Is low in content of (2), and MnxZn1-xFe2O4Peak of (2) is represented by beta-Bi2O3The strong diffraction peak is covered. MnxZn1-xFe2O4/β-Bi2O3/BiVO4Has an infrared absorption spectrum of 585.6cm as shown in FIG. 2(a)-1And 472cm-1Mn of (C)xZn1-xFe2O4Characteristic absorption peak, further shows that the whole process of preparing the catalyst by loading does not change MnxZn1-xFe2O4The self structure of (B) shows MnxZn1-xFe2O4Is present, which complements the XRD result well; at 1383cm-1、846.3cm-1、585.6cm-1The absorption peak of Bi-O bond shows that the sample contains the beta-Bi with complete crystal form2O3(ii) a At 635cm-1、480cm-1Peak pair ofThe inconsistent contraction oscillation peak of V2 p of V-O indicates that the sample contains BiVO4。MnxZn1-xFe2O4The magnetic parameters of (A) were measured as shown in FIG. 3(a), and the saturation magnetization was 75.13 emu/g. MnxZn1-xFe2O4/β-Bi2O3/BiVO4The magnetic parameters of (a) were measured as in FIG. 3(b), and the saturation magnetization was 2.67 emu/g.
The photocatalysis experiment shows that 0.1g of magnetic composite photocatalyst Mn is used for preparing under the irradiation of a xenon lamp simulating sunlightxZn1-xFe2O4/β-Bi2O3/BiVO450mL of 10mg/L rhodamine B solution is degraded, the degradation rate of the rhodamine B after 3 hours of illumination reaches 92.8%, and the degradation rate after 3 times of recycling still reaches 84.9%; the test showed that the average recovery of the three recoveries was 89.7%, indicating that Mn was prepared using the present inventionxZn1-xFe2O4/β-Bi2O3/BiVO4The magnetic composite photocatalyst has higher photocatalytic activity and stability.

Claims (2)

1. Magnetic bismuth oxide/bismuth vanadate composite photocatalyst MnxZn1-xFe2O4/β-Bi2O3/BiVO4The preparation method comprises the following steps:
(1)MnxZn1-xFe2O4the preparation of (1): ZnO according to a molar ratio: MnO: fe2O313.3: 32.8: 53.9, respectively weighing a proper amount of zinc sulfate, ferric sulfate and manganese sulfate, adding 25mL of deionized water, and dissolving by ultrasonic oscillation to obtain a mixed solution; under the action of magnetic stirring, dropwise adding a NaOH solution with a certain concentration into the mixed solution, adjusting the pH of the solution to 13, and continuously stirring for 15 min; transferring the stirred solution into a 100mL reaction kettle, and reacting for 5h at 200 ℃; after the reaction is finished, cooling and suction filtering are carried out, filter cakes are respectively washed for 5 times by distilled water and ethanol, the filter cakes are dried for 12 hours at the temperature of 80 ℃, and Mn is obtained by grindingxZn1-xFe2O4；
(2)MnxZn1-xFe2O4/BiVO4The preparation of (1): weighing a certain amount of bismuth nitrate pentahydrate, and adding HNO with the concentration of 2mol/L3In the solution, ultrasonic oscillation is carried out to dissolve the solution to obtain a solution A; according to Bi (NO)3)3·5H2Weighing tartaric acid according to different proportions, and dissolving the tartaric acid in hot water at the temperature of 80 ℃ to obtain a solution B; in a molar ratio of Bi (NO)3)3·5H2O:NH4VO3Weighing ammonium metavanadate at the ratio of 1:1, and dissolving the ammonium metavanadate in hot water at the temperature of 80 ℃ to obtain a solution C; dripping the solution B into the solution C to obtain a mixed solution D; then adding the solution A into the mixed solution D, cooling the solution, and adjusting the pH of the solution to 7.5 by using ammonia water to obtain BiVO4A precursor of (a); according to Mn1-xZnxFe2O4:BiVO4The mass ratio is 10:100 weighing the Mn obtained above1-xZnxFe2O4Adding into BiVO4Performing water bath reaction on the precursor at 80 ℃ for 30min, filtering, drying, grinding, placing in a muffle furnace at 450 ℃ for reaction for 3h, taking out, and cooling to room temperature to obtain MnxZn1-xFe2O4/BiVO4；
(3)MnxZn1-xFe2O4/β-Bi2O3/BiVO4The preparation of (1): weighing a proper amount of bismuth nitrate, adding the bismuth nitrate into 10mL of 2mol/L HNO3Dissolving with ultrasound to obtain clear solution, and adding into 40mL of 0.6mol/L Na2CO3In the solution, mechanically stirring for 2h to obtain beta-Bi2O3Precursor solution; in the form of beta-Bi2O3:MnxZn1-xFe2O4/BiVO4Weighing Mn according to the mass ratio of 5-15: 100xZn1-xFe2O4/BiVO4To beta-Bi2O3Mechanically stirring the precursor solution for 2 hours, filtering, washing a filter cake with distilled water, then placing the filter cake in a drying oven at 60 ℃ for drying for 12 hours, and grinding to obtain composite precursor powder; putting the precursor powder into a muffle furnace, roasting at 380 ℃ for 10min, then quickly taking out the precursor powder from the muffle furnace, and naturally cooling the precursor powderThereby obtaining Mn with different mass ratiosxZn1- xFe2O4/β-Bi2O3/BiVO4。
2. The magnetic bismuth oxide/bismuth vanadate composite photocatalyst Mn according to claim 1xZn1-xFe2O4/β-Bi2O3/BiVO4The preparation method is characterized in that the preparation method is prepared by a hydrothermal-coprecipitation-roasting method, and the catalytic active component beta-Bi is realized2O3、BiVO4The magnetic material is firmly combined with the magnetic material and the matrix.
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