CN112516991A - Preparation method of bismuth oxide photocatalyst with two-dimensional structure - Google Patents

Preparation method of bismuth oxide photocatalyst with two-dimensional structure Download PDF

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CN112516991A
CN112516991A CN202011546466.3A CN202011546466A CN112516991A CN 112516991 A CN112516991 A CN 112516991A CN 202011546466 A CN202011546466 A CN 202011546466A CN 112516991 A CN112516991 A CN 112516991A
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bismuth oxide
bismuth
dimensional structure
preparation
polyether
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CN112516991B (en
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周建伟
王储备
朵芳芳
贾春燕
周晨
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Xinxiang University
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/18Arsenic, antimony or bismuth
    • B01J35/39
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/30Treatment of water, waste water, or sewage by irradiation
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00Nature of the contaminant
    • C02F2101/30Organic compounds
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2305/00Use of specific compounds during water treatment
    • C02F2305/10Photocatalysts
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02WCLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00Technologies for wastewater treatment
    • Y02W10/30Wastewater or sewage treatment systems using renewable energies
    • Y02W10/37Wastewater or sewage treatment systems using renewable energies using solar energy

Abstract

The invention belongs to the field of novel catalysts, and discloses bismuth oxide (Bi) with a two-dimensional structure2O3) A preparation method of the photocatalyst. Which comprises the following steps: (1) preparing an ethanol/ethylene glycol solution of P123; (2) adding bismuth nitrate until the bismuth nitrate is completely dissolved, adding a certain amount of oxalic acid to adjust the pH value, and magnetically stirring; (3) and carrying out solvothermal reaction, washing, centrifuging and drying to obtain the bismuth oxide photocatalyst with the two-dimensional structure. The preparation method is simple and convenient, the cost is low, and the product has high purity, uniform appearance, good dispersibility and stable performance. The bismuth oxide nanosheet with the two-dimensional structure, which is prepared by the method, has the advantages of high solar energy utilization rate, high quantum efficiency and high photocatalytic activity, and can be applied to catalyzing degradation of organic pollutants in the field of environment.

Description

Preparation method of bismuth oxide photocatalyst with two-dimensional structure
Technical Field
The invention relates to the field of novel catalysts, in particular to a preparation method of a bismuth oxide photocatalyst with a two-dimensional structure.
Background
The adoption of semiconductor photocatalysis technology for treating environmental pollution is increasingly gaining attention. Theoretically, as long as the energy of the exciting light is larger than the energy value of the band gap of the semiconductorCan generate photogenerated electrons and holes, and the semiconductor can be possibly used as a photocatalytic material. However, due to the factors such as material cost, chemical stability and photo-corrosion resistance, the efficient and practical semiconductor photocatalytic material needs to be studied intensively. Common anatase phase TiO2Photocatalysts have been studied more and more extensively, but have a wider band gap (E g=3.2 eV) can only absorb ultraviolet light, the solar energy utilization rate is low, the light quantum efficiency is low, and the catalytic activity is low. Therefore, there is a need to develop a visible-light-driven photocatalyst having high performance. The bismuth-based compound has good photogenerated carrier separation capacity and visible light response performance, and compared with the traditional block nano material, the two-dimensional semiconductor nano sheet can effectively improve the electron transfer efficiency and the surface energy, ensure effective light absorption and absorption of target reactants, promote the occurrence of interface catalytic reaction, simultaneously facilitate the rapid transfer of photogenerated charges from the interior of the material to the surface, and ensure that bulk phase charges have higher separation efficiency. At present, relevant reports of a preparation method of a bismuth oxide photocatalyst based on a two-dimensional structure are rarely seen.
Disclosure of Invention
The invention aims to provide a controllable preparation method of a bismuth oxide nanosheet photocatalyst with a two-dimensional structure, in order to research and develop a novel high-performance visible light bismuth oxide photocatalyst.
In order to realize the purpose of the invention, the technical scheme is as follows:
the preparation method of the bismuth oxide photocatalyst with the two-dimensional structure comprises the following steps:
(1) weighing polyether, placing the polyether in an absolute ethyl alcohol-ethylene glycol mixed solvent, and magnetically stirring to obtain a uniform polyether alcoholic solution;
(2) adding carboxylic acid into the polyether alcoholic solution obtained in the step (1), and magnetically stirring to dissolve the carboxylic acid;
(3) adding a bismuth-containing compound into the solution obtained in the step (2), and carrying out ultrasonic treatment and stirring until the bismuth-containing compound is completely dissolved;
(4) and (4) transferring the solution obtained in the step (3) into a reaction kettle, carrying out solvothermal reaction, washing reaction products with deionized water and ethanol respectively, centrifuging and drying to obtain the bismuth oxide nanosheet photocatalyst.
In the step (1), the polyether is selected from PEO-PPO-PEO (p123) (Ma = 5800) nonionic surfactant, and the adding amount is 0.3-0.5 g.
The volume ratio of the absolute ethyl alcohol to the ethylene glycol in the step (1) is 2: 1-4: 1.
The carboxylic acid in the step (2) is selected from one of oxalic acid and glacial acetic acid.
And (3) adding carboxylic acid to adjust the pH = 4-5 of the solution in the step (2).
In the step (3), the bismuth-containing compound is Bi (NO)3)3·5H2O, the addition amount is 2 mmol, ultrasonic dispersion is carried out for 0.5 h, and stirring is carried out for 1 h.
The solvothermal reaction conditions in the step (4) are as follows: and transferring 80 ml of the solution into a 100 ml reaction kettle, wherein the reaction temperature is 160-180 ℃, and the constant temperature time is 8-12 hours.
The centrifugation conditions in the step (4) are as follows: the centrifugation speed is 4000 rpm, the centrifugation time is 5 min, and deionized water and absolute ethyl alcohol are respectively adopted for washing 3 times. The drying conditions were: the temperature is 60 ℃ and the time is 24 h.
The invention has the following principle or innovation points:
the invention provides a preparation method of a novel bismuth oxide photocatalyst with a two-dimensional structure. Bismuth nitrate is used as a precursor, ethylene glycol/ethanol mixed solution is used as a reaction medium, carboxylic acid is used for adjusting the pH value of the solution, preferably triblock compound is used as a morphology control agent of a bismuth oxide semiconductor, and a solvothermal method is adopted to prepare the efficient bismuth oxide photocatalyst with a two-dimensional sheet structure. According to the invention, the thickness of the two-dimensional bismuth oxide nanosheet is regulated and controlled by controlling the synthesis conditions (template agent, pH and solvent), and compared with other existing preparation methods of bismuth oxide, the method has more remarkable visible light catalytic activity and chemical stability, and is suitable for large-scale application in the field of photocatalysis; the photocatalyst has the advantages of easily available raw materials, low preparation cost and simple and convenient preparation method, and solves the technical problems of high synthesis cost, complicated steps and inconvenience for mass synthesis in the prior art.
The invention has the advantages that: the nano-sheet bismuth oxide photocatalyst is prepared by a template method, the preparation method is simple and convenient, the cost is low, the purity reaches more than 99.8 percent, the appearance is uniform, the dispersibility is good, and the performance is stable. The bismuth oxide with the two-dimensional structure prepared by the invention is flaky, has high solar energy utilization rate, high quantum efficiency and high photocatalytic activity, and can be applied to catalyzing the degradation of organic pollutants in the field of environment.
Drawings
FIG. 1 is a Scanning Electron Micrograph (SEM) (a) and a Transmission Electron Micrograph (TEM) (b) of a bismuth oxide material prepared according to the present invention.
Fig. 2 is an X-ray electron diffraction (XRD) pattern of the bismuth oxide material prepared in the present invention.
FIG. 3 is Bi2O3Atomic force microscopy of samples and nanoplate thickness profile, wherein, a, b- -Bi2O3(Solvothermal + p123), c, d- -Bi2O3(solvothermal).
FIG. 4 is a graph showing that the bismuth oxide material prepared by the invention is used as a photocatalyst to catalyze degradation of rhodamine B.
FIG. 5 is a graph showing the degradation curve of rhodamine B catalyzed by the bismuth oxide and carbon nitride composite material prepared by the invention.
Detailed Description
To better illustrate the invention, the examples are as follows:
example 1
Adding 0.5g P123 into 80 mL of mixed solution of ethylene glycol and absolute ethyl alcohol (the volume ratio of the ethylene glycol to the absolute ethyl alcohol is 2: 1) under the condition of stirring, stirring for dissolving, then adding 2 mmol of bismuth nitrate pentahydrate, stirring, adjusting the pH value of the solution to 4-5 by oxalic acid, and stirring for 1h to obtain a mixed solution. The mixed solution was transferred to an autoclave and kept at 160 ℃ for 8 hours for solvothermal reaction. After the reaction is finished, cooling to room temperature, centrifuging to obtain a precipitate, washing with distilled water, and drying at 60 ℃ for 24 hours to obtain the bismuth oxide nano material with the purity of 99.8%. From the electron microscope topography (fig. 1) of the material, it can be seen that the bismuth oxide is in the form of nano-platelets.
Example 2
Adding 0.3g of EO20PO70EO20 (Ma = 5800) into 80 mL of mixed solution of ethylene glycol and absolute ethyl alcohol (the volume ratio of the two is 4: 1) under stirring, stirring for dissolution, adding 2 mmol of bismuth nitrate pentahydrate, stirring and adjusting the pH of the solution to 4-5 with glacial acetic acid (stirring for 1 h) to obtain a mixed solution, transferring the mixed solution into an autoclave, keeping the mixed solution at 160 ℃ for 10 h for solvothermal reaction, cooling to room temperature after the reaction is finished, centrifuging to obtain a precipitate, washing with distilled water, drying at 60 ℃ for 24h to obtain 99.8% bismuth oxide nano-material, wherein the bismuth oxide nano-material is shown in a morphology graph of an electron microscope (figure 1) of the material and is in a nanosheet shape, the bismuth oxide nano-phase is shown in an X-ray electron diffraction image (figure 2) of the material, and the bismuth oxide nano-phase is shown in an Atomic Force Microscope (AFM) analysis result graph (figure 3) of the material, the thicknesses of the bismuth oxide nanosheets prepared by the two methods are different, and the bismuth oxide obtained by the method is thinner.
Application example 1
In the photocatalytic degradation experiment, the absorption spectrum of rhodamine B (RhB) in a solution is measured by using an ultraviolet-visible spectrophotometer. The change of the absorbance is used for measuring the change of the concentration of the rhodamine B in the solution. DrawingC/C 0With respect to timetCurve of (1), whereinC 0Is the initial concentration of RhB and,Cfor a period of time after light irradiationtMeasured RhB concentration values after.
The specific experimental steps are as follows: 0.025g of the bismuth oxide photocatalyst prepared according to the present invention was weighed. 50 mL of the solution was added at a concentration of 1X 10-5And (3) in mg/L RhB solution, stirring for 30 min in the dark, then reacting under visible light, sampling at 20 min intervals, centrifuging, and taking supernatant to detect by a spectrophotometer. As can be seen from fig. 4, the photocatalytic activity of the material is significantly greater than that of common commercial bismuth oxide. When the light reaction is carried out for 120 minutes, the bismuth oxide nano-sheets can catalyze and degrade over 70% of RhB, while the common commercial bismuth oxide can catalyze and degrade only about 15%. The research results show that the thickness of the bismuth oxide nanosheet has obvious positive correlation with the photocatalytic activity thereof, and the photocatalytic activity of the two-dimensional bismuth oxide nanomaterial prepared by the method is superior to that of bismuth oxide before modification. Bismuth oxide nano-sheet and nitridation prepared by the methodThe carbon nitride/bismuth oxide composite photocatalyst formed by carbon compounding has more excellent degradation performance, and the degradation rate of RhB reaches more than 95% in 40 minutes under the irradiation of visible light, as shown in figure 5.

Claims (4)

1. A preparation method of a bismuth oxide photocatalyst with a two-dimensional structure is characterized by comprising the following steps:
(1) weighing polyether, placing the polyether in an absolute ethyl alcohol-ethylene glycol mixed solvent, and magnetically stirring to obtain an alcoholic solution of the polyether;
(2) adding carboxylic acid into the polyether alcoholic solution obtained in the step (1), and magnetically stirring to dissolve the carboxylic acid;
(3) adding a bismuth-containing compound into the solution obtained in the step (2), and carrying out ultrasonic treatment and stirring until the bismuth-containing compound is completely dissolved;
(4) transferring the solution obtained in the step (3) into a reaction kettle, carrying out solvothermal reaction, washing reaction products with deionized water and ethanol respectively, centrifuging and drying to obtain a bismuth oxide photocatalyst;
the bismuth-containing compound is Bi (NO)3)3·5H2O;
The carboxylic acid is selected from one of oxalic acid and glacial acetic acid;
the polyether is selected from: polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer (PEO-PPO-PEO).
2. The preparation method of the bismuth oxide photocatalyst with the two-dimensional structure according to claim 1, wherein the volume ratio of the absolute ethyl alcohol to the ethylene glycol in the step (1) is 2: 1-4: 1.
3. The method for preparing a bismuth oxide photocatalyst having a two-dimensional structure according to claim 1, wherein a carboxylic acid is added in the step (2) to adjust the pH of the solution to be in a range of 4 to 5.
4. The method for preparing a bismuth oxide photocatalyst having a two-dimensional structure according to any one of claims 1 to 3, wherein the solvothermal reaction conditions in the step (4) are as follows: and transferring 80 ml of the solution into a 100 ml reaction kettle, wherein the reaction temperature is 160-180 ℃, and the constant temperature time is 8-12 hours.
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Cited By (1)

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Publication number Priority date Publication date Assignee Title
CN114944288A (en) * 2022-06-20 2022-08-26 江西科技师范大学 Flower-shaped bismuth trioxide, preparation method and application thereof, and prepared electrode
CN114944288B (en) * 2022-06-20 2023-04-25 江西科技师范大学 Flower-like bismuth trioxide, preparation method and application thereof, and prepared electrode

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