CN111744504A - Method for preparing magnetic chlorine-bismuth tetroxide composite photocatalyst - Google Patents

Method for preparing magnetic chlorine-bismuth tetroxide composite photocatalyst Download PDF

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CN111744504A
CN111744504A CN202010625577.7A CN202010625577A CN111744504A CN 111744504 A CN111744504 A CN 111744504A CN 202010625577 A CN202010625577 A CN 202010625577A CN 111744504 A CN111744504 A CN 111744504A
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composite photocatalyst
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王海龙
徐龙君
冯岐
刘成伦
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Chongqing University
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    • 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
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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    • B01J37/10—Heat treatment in the presence of water, e.g. steam
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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    • C—CHEMISTRY; METALLURGY
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    • C—CHEMISTRY; METALLURGY
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    • C02F2305/00—Use of specific compounds during water treatment
    • C02F2305/10—Photocatalysts

Abstract

Magnetic materialA method for preparing a bismuth oxychloride composite photocatalyst belongs to the technical field of inorganic catalytic materials. The invention firstly prepares the Mn-Zn ferrite Mn of the soft magnetic material by a hydrothermal methodxZn1‑xFe2O4Then preparing the magnetic chlorine-bismuth oxide composite photocatalyst (Bi) by a hydrothermal-roasting method3O4Cl/MnxZn1‑ xFe2O4). The method has the advantages of simple preparation process, less used equipment and low energy consumption. Prepared Bi3O4Cl/MnxZn1‑xFe2O4The magnetic property is stable, the photocatalytic activity is high, under the irradiation of a simulated sunlight xenon lamp, 100mL of rhodamine B solution with the concentration of 10mg/L is degraded by 0.1g of magnetic composite photocatalyst, the degradation rate of rhodamine B in 100min reaches 99.5%, the magnetic recovery rate of the photocatalyst under an external magnetic field is 91.3%, and the degradation rate of rhodamine B after repeated use for 3 times is 92.2%. The product prepared by the invention can be widely used in the field of photocatalytic degradation of organic pollutants.

Description

Method for preparing magnetic chlorine-bismuth tetroxide composite photocatalyst
Technical Field
The invention relates to a method for preparing magnetic chlorine bismuth oxide (Bi)3O4Cl/MnxZn1-xFe2O4) A method for compounding a photocatalyst belongs to the technical field of inorganic catalysts.
Background
Bismuth oxychloride (Bi)3O4Cl) is an oxygen-rich bismuth-based oxyhalide nano-photocatalyst. Due to its excellent electrical properties, suitable band placement and high efficiency photocatalytic activity, it has received much attention in the degradation of organic contaminants. Bi3O4The structure of Cl is represented by [ Cl]Ionic layer and sandwich between two [ Cl]Between layers [ Bi3O4]The unique structure facilitates the establishment of an internal electrostatic field, thereby promoting the separation and transfer of photogenerated electrons and holes. Bi3O4The common preparation methods of Cl mainly include a hydrothermal method, a coprecipitation method, a baking method, and the like. Bi3O4Cl is dispersed in liquid when pollutants are degraded in a photocatalysis mode, and the practical application of the photocatalyst is limited due to the difficulty in separation and recovery. The composite magnetic photocatalyst realizes the recycling of the catalyst through an external magnetic field, and overcomes the defects of high energy consumption, long time consumption and complex process of the conventional recycling modes such as centrifugation or filtration and the like.
Manganese zinc ferrite (Mn)xZn1-xFe2O4) Belongs to a soft magnetic ferrite material, and refers to mMnFe with a spinel structure2O4·nZnFe2O4With a small amount of Fe3O4Single phase solid solutions of composition, with conventional metalsSoft magnetic material (Fe)3O4) In contrast, MnxZn1-xFe2O4Has the advantages of high saturation magnetization, high magnetic conductivity, low loss, strong product stability and the like. Thus, the Mn content isxZn1-xFe2O4The composite photocatalyst prepared for the magnetic matrix has stable magnetism, and is convenient for the recovery and the recycling of the catalyst. Common MnxZn1-xFe2O4The preparation method comprises a chemical coprecipitation method, a sol-gel method, a calcination method and the like.
At present, to Bi3O4The research on Cl mainly focuses on improving the photocatalytic activity of the Bi, and the research on how to prepare the magnetic Bi3O4The Cl composite photocatalyst is reported less. Such as "Preparation, characterization of Bi" in Journal of Water Process Engineering "volume 18 of 20173O4Cl/g-C3N4composite and iterative activity in dye degradation "(reference 1), pure Bi was prepared by a baking method3O4Cl and g-C3N4Then preparing Bi by a roasting method3O4Cl/g-C3N4A composite photocatalyst is provided. The method has the following disadvantages: (1) bi3O4Cl is prepared from BiOCl and Bi2O3Roasting at 650 deg.C for 6h to obtain g-C3N4Is prepared by roasting melamine at 520 ℃ for 4h, and Bi3O4Cl/g-C3N4Is prepared from Bi3O4Cl and g-C3N4The material is prepared by roasting at the high temperature of 400 ℃ for 2h, and the preparation process is complex, the energy consumption is high, and the cost is high; (2) prepared Bi3O4Cl and Bi3O4Cl/g-C3N4The catalytic activity is not high, and the degradation rate of rhodamine B in 100min is lower than 90 percent; (3) the photocatalyst is difficult to recycle, the operation cost is high, and secondary pollution is easily caused.
In another example of the invention patent, "a method for preparing a manganese-zinc-ferrite-bismuth oxide magnetic photocatalyst" (publication No. CN104437536A) (reference 2), a manganese-zinc-ferrite is prepared by a baking method, and then a manganese-zinc-ferrite/bismuth oxide composite magnetic photocatalyst is prepared by a dip-baking method. The method has the following disadvantages: (1) the manganese-zinc ferrite is prepared by roasting at 1200 ℃ for 3h, and the energy consumption is high; (2) the manganese-zinc ferrite sample prepared by the roasting method has large particle size and small specific surface area, is not beneficial to the full combination of the manganese-zinc ferrite and bismuth oxide, and cannot ensure the combination stability; (3) the composite magnetic photocatalyst is prepared by adopting a roasting method, so that the specific surface area of the composite magnetic photocatalyst is small, and the full contact and reaction between the catalyst and organic pollutants in the photocatalytic degradation process are not facilitated.
Disclosure of Invention
The purpose of the invention is to provide Bi3O4The problem that Cl is difficult to recycle is provided with a magnetic Bi3O4Cl/MnxZn1- xFe2O4The preparation method of the composite photocatalyst is simple and low in cost. Prepared magnetic Bi3O4Cl/MnxZn1-xFe2O4The composite photocatalyst has higher photocatalytic efficiency under the irradiation of simulated sunlight, is convenient to separate and recover from a liquid phase system through an external magnetic field, and the recovered catalyst still has higher photocatalytic activity. The method not only realizes resource recycling simply and efficiently, but also avoids secondary pollution possibly brought by the catalyst.
Bi of the invention3O4Cl/MnxZn1-xFe2O4The preparation method comprises the following steps:
(1)MnxZn1-xFe2O4preparation of
Preparation of Mn by hydrothermal methodxZn1-xFe2O41.386g of manganese sulfate, 0.9652g of zinc sulfate and 5.3884g of ferric sulfate are respectively weighed, and are dissolved by ultrasonic oscillation after 50mL of distilled water is added; dropwise adding NaOH solution with a certain concentration into the solution under the action of magnetic stirring, adjusting the pH of the solution to 13, and continuing stirring for 15 min; after the stirring was completed, the solution was transferred to a 100mL reaction vessel at 200 deg.CReacting for 5 hours; cooling and filtering after the reaction is finished, washing the reaction product for 5 times by using distilled water and ethanol respectively, drying the reaction product for 12 hours at the temperature of 80 ℃, and grinding the reaction product to obtain MnxZn1-xFe2O4。
(2) Magnetic Bi3O4Cl/MnxZn1-xFe2O4Preparation of composite photocatalyst
0.97g of Bi (NO) is weighed3)3·5H2Adding O into a beaker filled with 20mL of glycol, and carrying out ultrasonic treatment for 10min to obtain a suspension; weighing 0.039g of NaCl and dissolving in 50mL of distilled water to obtain a NaCl solution; weighing 10-20% of Mn by mass fractionxZn1-xFe2O4Adding the suspension into the suspension, mechanically stirring for 10min, and dropwise adding NaCl solution into the mixed suspension; continuously mechanically stirring for 10min, transferring to a 100mL reaction kettle, and reacting for 12h at 160 ℃; cooling to room temperature, performing suction filtration to obtain a filter cake as an intermediate product, washing with distilled water and absolute ethyl alcohol for multiple times, and drying at 75 ℃ for 12 hours; grinding the dried sample, putting the ground sample into a 100mL ceramic crucible, roasting the ceramic crucible in a muffle furnace at the temperature of 500 ℃ for 2 hours, naturally cooling the baked sample to room temperature, and grinding the baked sample to obtain magnetic Bi3O4Cl/MnxZn1-xFe2O4A composite photocatalyst is provided.
By adopting the technical scheme, the invention mainly has the following effects:
(1) magnetic Bi prepared by the method of the invention3O4Cl/MnxZn1-xFe2O4The composite photocatalyst has higher photocatalytic activity, and 0.1g of magnetic Bi is irradiated by a simulated sunlight xenon lamp3O4Cl/MnxZn1-xFe2O4The composite photocatalyst is dispersed in 100mL of 10mg/L rhodamine B solution, and the degradation rate of rhodamine B after 100min of illumination reaches 99.5 percent (better than Bi prepared by the comparison document 1)3O4Cl/g-C3N4A composite photocatalyst).
(2) Magnetic Bi prepared by the method of the invention3O4Cl/MnxZn1-xFe2O4The recovery rate of the composite photocatalyst under the action of an applied magnetic field is up to 91.3%, and the degradation rate after 3 times of repeated use is still up to 92.2%.
(3) Magnetic Bi prepared by the method of the invention3O4Cl/MnxZn1-xFe2O4The specific surface area of the composite photocatalyst is 7.27m2The preparation method has the advantages of simple preparation operation, less required equipment and low energy consumption.
Drawings
FIG. 1 shows Bi3O4Cl、MnxZn1-xFe2O4And Bi3O4Cl/MnxZn1-xFe2O4X-ray diffraction pattern of (a).
FIG. 2 shows Bi3O4Cl/MnxZn1-xFe2O4Scanning electron microscopy of (a).
FIG. 3 shows MnxZn1-xFe2O4And Bi3O4Cl/MnxZn1-xFe2O4Magnetic hysteresis loop diagram of (1).
Detailed Description
The present invention will be further described with reference to the following specific embodiments.
Example 1
Preparation of Bi3O4Cl/MnxZn1-xFe2O4The preparation method of the magnetic composite catalyst comprises the following specific steps:
(1)MnxZn1-xFe2O4preparation of
Preparation of Mn by hydrothermal methodxZn1-xFe2O41.386g of manganese sulfate, 0.9652g of zinc sulfate and 5.3884g of ferric sulfate are respectively weighed, and are dissolved by ultrasonic oscillation after 50mL of distilled water is added; dropwise adding NaOH solution with a certain concentration into the solution under the action of magnetic stirring, adjusting the pH of the solution to 13, and continuing stirring for 15 min; after stirring, transferring the solution into a 100mL reaction kettle, and reacting for 5h at 200 ℃; cooling and filtering after the reaction is finished, and respectively using distilled waterWashing with ethanol for 5 times, drying at 80 deg.C for 12 hr, and grinding to obtain MnxZn1-xFe2O4。
(2)Bi3O4Cl/MnxZn1-xFe2O4Preparation of magnetic composite photocatalyst
0.97g of Bi (NO) is weighed3)3·5H2Adding O into a beaker filled with 20mL of glycol, and carrying out ultrasonic treatment for 10min to obtain a suspension; weighing 0.039g of NaCl and dissolving in 50mL of distilled water to obtain a NaCl solution; weighing Mn with the mass fraction of 10%xZn1-xFe2O4Adding the suspension into the suspension, mechanically stirring for 10min, and dropwise adding a NaCl solution into the mixed suspension; continuously mechanically stirring for 10min, transferring to a 100mL reaction kettle, and reacting for 12h at 160 ℃; cooling to room temperature, performing suction filtration to obtain a filter cake as an intermediate product, washing with distilled water and absolute ethyl alcohol for multiple times, and drying at 75 ℃ for 12 hours; grinding the dried sample, putting the ground sample into a 100mL ceramic crucible, placing the ceramic crucible into a muffle furnace at the temperature of 500 ℃ for continuous roasting for 2 hours, naturally cooling the roasted sample to room temperature, and grinding the roasted sample to obtain magnetic Bi3O4Cl/MnxZn1-xFe2O4A composite photocatalyst is provided.
Example 2
Preparation of Bi3O4Cl/MnxZn1-xFe2O4The preparation method of the composite magnetic catalyst comprises the following specific steps:
(1)MnxZn1-xFe2O4preparation of
The same as in (1) in example 1.
(2)Bi3O4Cl/MnxZn1-xFe2O4Preparation of magnetic composite photocatalyst
0.97g of Bi (NO) is weighed3)3·5H2Adding O into a beaker filled with 20mL of glycol, and carrying out ultrasonic treatment for 10min to obtain a suspension; weighing 0.039g of NaCl and dissolving in 50mL of distilled water to obtain a NaCl solution; weighing 15% of Mn by mass fractionxZn1-xFe2O4Adding the suspension into the suspension, mechanically stirring for 10min, and dropwise adding a NaCl solution into the mixed suspension; continuously mechanically stirring for 10min, transferring to a 100mL reaction kettle, and reacting for 12h at 160 ℃; cooling to room temperature, performing suction filtration to obtain a filter cake as an intermediate product, washing with distilled water and absolute ethyl alcohol for multiple times, and drying at 75 ℃ for 12 hours; grinding the dried sample, putting the ground sample into a 100mL ceramic crucible, placing the ceramic crucible into a muffle furnace at the temperature of 500 ℃ for continuous roasting for 2 hours, naturally cooling the roasted sample to room temperature, and grinding the roasted sample to obtain magnetic Bi3O4Cl/MnxZn1-xFe2O4A composite photocatalyst is provided.
Example 3
Preparation of Bi3O4Cl/MnxZn1-xFe2O4The preparation method of the composite magnetic catalyst comprises the following specific steps:
(1)MnxZn1-xFe2O4preparation of
The same as in (1) in example 1.
(2)Bi3O4Cl/MnxZn1-xFe2O4Preparation of magnetic composite photocatalyst
0.97g of Bi (NO) is weighed3)3·5H2Adding O into a beaker filled with 20mL of glycol, and carrying out ultrasonic treatment for 10min to obtain a suspension; weighing 0.039g of NaCl and dissolving in 50mL of distilled water to obtain a NaCl solution; weighing 20 percent of Mn by mass fractionxZn1-xFe2O4Adding the suspension into the suspension, mechanically stirring for 10min, and dropwise adding a NaCl solution into the mixed suspension; continuously mechanically stirring for 10min, transferring to a 100mL reaction kettle, and reacting for 12h at 160 ℃; cooling to room temperature, performing suction filtration to obtain a filter cake as an intermediate product, washing with distilled water and absolute ethyl alcohol for multiple times, and drying at 75 ℃ for 12 hours; grinding the dried sample, putting the ground sample into a 100mL ceramic crucible, placing the ceramic crucible into a muffle furnace at the temperature of 500 ℃ for continuous roasting for 2 hours, naturally cooling the roasted sample to room temperature, and grinding the roasted sample to obtain magnetic Bi3O4Cl/MnxZn1-xFe2O4A composite photocatalyst is provided.
Results of the experiment
Magnetic Bi prepared in example 13O4Cl/MnxZn1-xFe2O4The composite photocatalyst has the best catalytic degradation activity on rhodamine B. For convenience of comparison, Bi was prepared3O4And (4) Cl samples. Bi3O4Cl preparation method in example 1 step (2) without adding MnxZn1-xFe2O4。
Bi3O4The X-ray diffraction pattern of Cl is shown in FIG. 1, in which all diffraction peaks can be indexed to monoclinic (monoclinic) Bi3O4Cl (JCPDS No.:36-0760), X-ray diffraction peaks appearing at α ═ γ ═ 90 °, β ═ 0 °, 2 θ of 24.31 °, 29.13 °, 29.68 °, 31.65 °, 38.77 °, 43.36 ° and 45.25 ° in the drawing correspond to the (211), (41-1), (411), (020), (800), (620) and (022) crystal planes, respectively.
MnxZn1-xFe2O4The X-ray diffraction pattern of (A) is shown in FIG. 1, all diffraction peaks can be indexed to cubic MnxZn1-xFe2O4(JCPDS No.: 74-2399); diffraction peaks appearing at 29.81 °, 35.18 °, 42.80 °, 56.55 ° and 62.04 ° of 2 θ in the figure correspond to the (220), (311), (400), (511) and (440) crystal planes, respectively.
Magnetic Bi3O4Cl/MnxZn1-xFe2O4The X-ray diffraction spectrum of the composite photocatalyst is shown in figure 1, and the main diffraction peaks and Bi of the composite photocatalyst3O4Cl was substantially the same, but the diffraction peak at 29.13 ℃ was significantly enhanced, indicating MnxZn1-xFe2O4Of composite pair Bi3O4The preferred growth direction and crystal structure of the Cl crystal have a certain influence. Mn occurs at 29.91 °, 42.94 ° and 62.01 °xZn1-xFe2O4Diffraction peak, indicating that Bi3O4Cl and MnxZn1-xFe2O4And (4) successfully compounding.
Magnetic Bi3O4Cl/MnxZn1-xFe2O4The scanning electron microscope image of the composite photocatalyst is shown in FIG. 2, and it can be seen that Bi3O4Cl is composed of irregularly shaped nanosheets, MnxZn1-xFe2O4Is in the form of particles, and Bi3O4Cl and MnxZn1-xFe2O4Closely combined together, indicating that the magnetic Bi is successfully prepared3O4Cl/MnxZn1-xFe2O4A composite photocatalyst is provided.
MnxZn1-xFe2O4And magnetic Bi3O4Cl/MnxZn1-xFe2O4The magnetic parameter of the composite photocatalyst is tested as shown in figure 3, MnxZn1-xFe2O4The saturation magnetization of (1) is 70emu/g, the residual magnetization (Mr) is 6.8emu/g, the higher magnetic induction and lower hysteresis loss are in favor of MnxZn1-xFe2O4Is used as a magnetic matrix for synthesizing the magnetic composite photocatalyst. Magnetic Bi3O4Cl/MnxZn1-xFe2O4The saturation magnetization of the composite photocatalyst is 6.4emu/g, and the composite photocatalyst can still be effectively magnetically recycled.
A photocatalysis experiment shows that under the irradiation of a simulated sunlight xenon lamp, 0.1g of magnetic composite photocatalyst is used for degrading 100mL of 10mg/L rhodamine B solution, the degradation rate of rhodamine B in 100min of illumination reaches 99.5%, the magnetic recovery rate of the photocatalyst under an external magnetic field is 91.3%, the degradation rate after repeated use for 3 times is 92.2%, and the Bi prepared by the method is proved to be capable of degrading the rhodamine B solution with the concentration of 10mg/L3O4Cl/MnxZn1-xFe2O4The magnetic composite photocatalyst has higher photocatalytic activity and stable magnetic recovery performance.

Claims (2)

1. A method for preparing a magnetic chlorine bismuth oxide composite photocatalyst is characterized by comprising the following steps:
(1)MnxZn1-xFe2O4preparation of
Preparation of Mn by hydrothermal methodxZn1-xFe2O41.386g of manganese sulfate, 0.9652g of zinc sulfate and 5.3884g of ferric sulfate are respectively weighed, and are dissolved by ultrasonic oscillation after 50mL of distilled water is added; dropwise adding NaOH solution with a certain concentration into the solution under the action of magnetic stirring, adjusting the pH of the solution to 13, and continuing stirring for 15 min; after stirring, transferring the solution into a 100mL reaction kettle, and reacting for 5h at 200 ℃; cooling and filtering after the reaction is finished, washing the reaction product for 5 times by using distilled water and ethanol respectively, drying the reaction product for 12 hours at the temperature of 80 ℃, and grinding the reaction product to obtain MnxZn1-xFe2O4。
(2) Magnetic Bi3O4Cl/MnxZn1-xFe2O4Preparation of composite photocatalyst
0.97g of Bi (NO) is weighed3)3·5H2Adding O into a beaker filled with 20mL of glycol, and carrying out ultrasonic treatment for 10min to obtain a suspension; weighing 0.039g of NaCl and dissolving in 50mL of distilled water to obtain a NaCl solution; weighing 10-20% of Mn by mass fractionxZn1-xFe2O4Adding the suspension into the suspension, mechanically stirring for 10min, and dropwise adding a NaCl solution into the mixed suspension; continuously mechanically stirring for 10min, transferring to a 100mL reaction kettle, and reacting for 12h at 160 ℃; cooling to room temperature, performing suction filtration to obtain a filter cake as an intermediate product, washing with distilled water and absolute ethyl alcohol for multiple times, and drying at 75 ℃ for 12 hours; grinding the dried sample, putting the ground sample into a 100mL ceramic crucible, placing the ceramic crucible into a muffle furnace at the temperature of 500 ℃ for continuous roasting for 2 hours, naturally cooling the roasted sample to room temperature, and grinding the roasted sample to obtain magnetic Bi3O4Cl/MnxZn1-xFe2O4A composite photocatalyst is provided.
2. The preparation method of the magnetic composite bismuth chlorotetraoxide photocatalyst as claimed in claim 1, wherein the preparation method is a hydrothermal-roasting method, so that effective compounding of the active component of chlorotetrabismuth oxide and the magnetic matrix of manganese zinc ferrite is realized.
CN202010625577.7A 2020-07-02 2020-07-02 Method for preparing magnetic chlorine-bismuth tetroxide composite photocatalyst Pending CN111744504A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113058624A (en) * 2021-03-09 2021-07-02 南阳师范学院 Bi3O4Cl/g-C3N4Preparation method and application of 2D/2D van der Waals heterojunction

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