CN111013570B - C/Bi/Bi 2 MoO 6 Polarized material, preparation method thereof and application thereof in photocatalytic degradation of dye - Google Patents
C/Bi/Bi 2 MoO 6 Polarized material, preparation method thereof and application thereof in photocatalytic degradation of dye Download PDFInfo
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- 238000013033 photocatalytic degradation reaction Methods 0.000 title claims abstract description 10
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- 230000010287 polarization Effects 0.000 claims abstract description 29
- 229940107698 malachite green Drugs 0.000 claims abstract description 17
- FDZZZRQASAIRJF-UHFFFAOYSA-M malachite green Chemical compound [Cl-].C1=CC(N(C)C)=CC=C1C(C=1C=CC=CC=1)=C1C=CC(=[N+](C)C)C=C1 FDZZZRQASAIRJF-UHFFFAOYSA-M 0.000 claims abstract description 17
- 239000002243 precursor Substances 0.000 claims abstract description 15
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
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- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 8
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- RWVGQQGBQSJDQV-UHFFFAOYSA-M sodium;3-[[4-[(e)-[4-(4-ethoxyanilino)phenyl]-[4-[ethyl-[(3-sulfonatophenyl)methyl]azaniumylidene]-2-methylcyclohexa-2,5-dien-1-ylidene]methyl]-n-ethyl-3-methylanilino]methyl]benzenesulfonate Chemical compound [Na+].C1=CC(OCC)=CC=C1NC1=CC=C(C(=C2C(=CC(C=C2)=[N+](CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C)C=2C(=CC(=CC=2)N(CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C)C=C1 RWVGQQGBQSJDQV-UHFFFAOYSA-M 0.000 description 1
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- 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
- B01J23/16—Catalysts 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
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/31—Chromium, molybdenum or tungsten combined with bismuth
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- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- 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
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- 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
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- 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
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- 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
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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Abstract
The invention discloses C/Bi 2 MoO 6 Polarized material, preparation method thereof and application thereof in photocatalytic degradation of dye, and C/Bi 2 MoO 6 The polarization material is prepared by firstly preparing EDTA-Bi precursor and then preparing C/Bi through the EDTA-Bi precursor 2 MoO 6 Composite material, and finally preparing to obtain C/Bi 2 MoO 6 Polarizing the material; C/Bi of the present invention 2 MoO 6 The polarization material has the advantages of low price, simple preparation method, good stability and the like, shows better effect in photocatalytic degradation of colored dye malachite green and colorless dye bisphenol A, is not only suitable for removing organic pollutants and purifying water, but also suitable for industrial cyclic utilization.
Description
Technical Field
The invention relates to the technical field of photocatalytic materials, in particular to C/Bi 2 MoO 6 A polarized material, a preparation method thereof and application thereof in photocatalytic degradation of dyes.
Background
With the rapid development of industry, the environmental pollution problem becomes more serious. Therefore, environmental protection has become one of the most important jobs in future development. TiO has been demonstrated since Honda and Fujishima in the 1970 s 2 Photocatalytic applications consisting of semiconductor materials have been considered as one of the reliable solutions to environmental problems since they can be applied to photocatalysis under ultraviolet light. PhotocatalysisThe agent readily absorbs artificial light or natural solar energy, which is distributed throughout the world. Nowadays, semiconductor-based photocatalytic technology is receiving much attention due to its great potential in environmental protection and sustainable energy, for example, elimination of organic pollutants and decomposition of water to produce energy substances such as hydrogen. TiO 2 2 Is a well-known semiconductor material, and has good photocatalytic activity on the oxidative degradation of organic pollutants. However, tiO 2 The band gap of (2) is large (about 3.5 eV), the visible light utilization efficiency is also poor, and the application of the visible light utilization efficiency in the field of photocatalysis is hindered.
Bismuth-based photocatalysts have attracted the interest of researchers because of their wide variety, unique electronic structure, excellent visible light absorption capability and higher organic compound degradation capability. And Bi having a band gap of about 2.70eV 2 MoO 6 The photocatalyst has good advantages (such as suitability for visible light excitation, controllable morphology and the like) and is considered to be one of promising photocatalysts. Bi 2 MoO 6 Is one member of the family of oxides related to Aurivillius in lamellar form, consisting of MoO 4 2- And [ Bi ] 2 O 2 ] 2+ The structural composition of (a) as a Bi-based ternary metal oxide photocatalyst generally shows strong photocatalytic performance under visible light irradiation. However, photocatalytic activity is limited due to the rapid recombination of photogenerated charges. Thus, modifying Bi 2 MoO 6 To improve the photocatalytic activity of semiconductors is a serious challenge.
Researchers have tried various strategies including noble metal deposition, elemental doping, and semiconductor composites, among others. Among them, the Surface Plasmon Resonance (SPR) effect of noble metals is considered as a key method for improving photocatalytic efficiency, and noble metals such as Au, ag and Pt have been widely reported to be applied to improve photocatalytic activity of semiconductors. However, the use of noble metal-based semiconductor materials to address environmental pollution problems has resulted in significant expense and the materials are not readily recyclable. Recently, researchers found that metal Bi has an ultraviolet-mediated SPR effect, is a good direct plasma exciton photocatalyst and can replace precious metals to be applied toAnd (3) modifying the material of the semiconductor. And element doping (C, N, S and other elements) can stabilize the surface property of the catalyst and can also enhance the photocatalytic activity. Meanwhile, the ferroelectric polarization modified semiconductor is proved to be a feasible strategy for effectively separating photon-generated carriers through internal polarization, and the photocatalytic performance can be further improved. Therefore, the invention develops a C/Bi 2 MoO 6 The polarization material, the preparation method thereof and the application thereof in catalytic dyes have very important significance.
Disclosure of Invention
The invention aims to provide a C/Bi material, which aims to solve the problems that the cost is too high due to the environmental pollution caused by the prior precious metal-based semiconductor material treatment, the material is not easy to recycle and the like 2 MoO 6 The polarized material, the preparation method thereof and the application thereof in catalytic dyes, the C/Bi of the invention 2 MoO 6 The polarization material has the advantages of low price, simple preparation method, good photocatalysis effect on the colored dye malachite green and the colorless dye bisphenol A, and the like, and has good application prospect.
In order to realize the purpose, the invention is realized by the following technical scheme:
C/Bi of the present invention 2 MoO 6 A method of preparing a poled material comprising the steps of:
(1) Preparation of EDTA-Bi precursor
Diluting concentrated nitric acid in water, wherein the volume ratio of the concentrated nitric acid to the water is 1:25 to 30, and then adding Bi (NO) into the nitric acid solution 3 ) 3 ·5H 2 O and EDTA, said Bi (NO) 3 ) 3 ·5H 2 The mass ratio of O to EDTA is 1 3 ·H 2 Adjusting the pH of the solution to be 6.5 by O, stirring for 2h, centrifuging, collecting solid sediment, and drying at 95-105 ℃ for 18-22h to obtain an EDTA-Bi precursor;
(2)C/Bi/Bi 2 MoO 6 preparation of composite materials
Weighing Bi (NO) 3 ) 3 ·5H 2 Dissolving O in ethylene glycol to obtainTo the nail fluid, in which Bi (NO) is present 3 ) 3 ·5H 2 The mass volume ratio of O to glycol is 300-350; weighing Na 2 MoO 4 ·2H 2 Dissolving O in ethylene glycol to obtain an ethylene solution, wherein Na in the ethylene solution 2 MoO 4 ·2H 2 The mass volume ratio of O to glycol is 80-90; the volume of the solution A is equal to that of the solution B, and the solution A and the solution B are Bi (NO) 3 ) 3 ·5H 2 O and Na 2 MoO 4 ·2H 2 The mass ratio of O is 2-3;
adding the EDTA-Bi precursor prepared in the step (1) into the nail liquid, wherein the EDTA-Bi precursor and Bi (NO) in the nail liquid 3 ) 3 ·5H 2 C, mixing the solution A and the solution B in a mass ratio of 1; adding ethanol into the propane solution, wherein the volume of the ethanol is 2 times of that of the propane solution, fully stirring, transferring into a high-pressure kettle, reacting at 150-170 ℃ for 9-11h, naturally cooling to room temperature, alternately washing the obtained solid with deionized water and absolute ethanol for 3 times, drying at 55-65 ℃, and calcining in a muffle furnace at 380-420 ℃ for 3h to obtain powdery C/Bi 2 MoO 6 A composite material;
(3)C/Bi/Bi 2 MoO 6 preparation of poled materials
Accurately weighing polymethyl methacrylate (PMMA) and dissolving the PMMA in ethyl acetate, wherein the mass volume ratio of the PMMA to the ethyl acetate is 1-2 2 MoO 6 Powder of said C/Bi 2 MoO 6 Stirring for 20-40min with polymethyl methacrylate at a mass ratio of 15-17 2 MoO 6 And polarizing the material.
C/B provided by the inventioni/Bi 2 MoO 6 The polarized material is prepared by the method.
The invention also provides C/Bi 2 MoO 6 Use of a polarising material in a catalytic dye.
Preferably, the dyes of the present invention are malachite green and bisphenol a.
Bismuth nitrate pentahydrate (Bi (NO) used in the present invention 3 ) 3 ·5H 2 O), sodium molybdate dihydrate (Na) 2 MoO 4 ·2H 2 O), disodium ethylenediaminetetraacetate (C) 10 H 14 N 2 Na 2 O 8 ·2H 2 O), anhydrous ethanol (C) 2 H 5 OH), ethylene glycol (C) 2 H 6 O 2 ) And rhodamine B (C) 28 H 37 ClN 2 O 3 ) All reagents were analytically pure.
Based on the advantages of metal Bi and non-metal C modified semiconductor materials, the invention synthesizes EDTA-Bi precursor by a simple method, and prepares C/Bi by a solvothermal method 2 MoO 6 The prepared composite photocatalyst is dissolved in soluble organic (polymethyl methacrylate is dissolved in ethyl acetate) -inorganic (C/Bi) 2 MoO 6 ) Preparing C/Bi with the aid of composite films 2 MoO 6 And polarizing the material. Under the condition of simulating visible light, the crystal is compared with original Bi 2 MoO 6 And C/Bi 2 MoO 6 Comparison of composite materials, C/Bi 2 MoO 6 The performance of the polarization material for photodegradation of malachite green and bisphenol A is obviously improved. The method for introducing C and Bi by using the cheap and easily prepared precursor EDTA-Bi well avoids the pollution of a reducing agent to the environment and saves the experiment cost. In addition, the auxiliary method of the soluble organic-inorganic composite film is an effective way for manufacturing polarized materials on a large scale, and can promote the ferroelectric polarization photocatalyst to develop towards a better direction.
The invention has the advantages that:
(1) C/Bi of the present invention 2 MoO 6 The polarized material has good photocatalytic degradation performance and stronger performanceThe photocatalyst has high stability, can effectively degrade the colored dyes of Malachite Green (MG) and the leuco dye of bisphenol A (BPA), is relatively suitable for removing organic pollutants and purifying water, and is suitable for industrial cyclic utilization.
(2) C/Bi of the present invention 2 MoO 6 The preparation method of the polarization material is simple, the synthetic raw materials are nontoxic and easy to collect, the cost is low, and the pollution of reducing agents to the environment in the preparation process is avoided.
(3) The invention prepares C/Bi with the assistance of a soluble organic-inorganic composite film 2 MoO 6 Polarized material, such a method being suitable for mass production of polarized semiconductor material.
(4) C/Bi prepared by the invention 2 MoO 6 Composite material and C/Bi 2 MoO 6 The micro-morphology of the polarized material is uniform, and the layered structure is favorable for improving the utilization rate of light and is suitable for the photocatalysis direction.
Drawings
FIG. 1 shows pure Bi 2 MoO 6 And C/Bi 2 MoO 6 XRD contrast of the composite material;
FIG. 2 shows pure Bi 2 MoO 6 And C/Bi 2 MoO 6 XRD pattern of magnification of the composite material;
FIG. 3 is C/Bi 2 MoO 6 Composite material and C/Bi 2 MoO 6 XRD contrast pattern of the poled material;
FIG. 4 shows pure Bi 2 MoO 6 SEM picture of (g);
FIG. 5 shows pure Bi 2 MoO 6 SEM image of (d);
FIG. 6 is C/Bi 2 MoO 6 SEM images of the composite;
FIG. 7 is C/Bi 2 MoO 6 SEM images of the composite at magnification;
FIG. 8 is C/Bi 2 MoO 6 SEM images of polarized material;
FIG. 9 is C/Bi 2 MoO 6 SEM images of the polarization material at magnification;
FIG. 10 shows Bi 2 MoO 6 、C/Bi/Bi 2 MoO 6 Composite material and C/Bi 2 MoO 6 An infrared spectrum of the polarized material;
FIG. 11 is C/Bi 2 MoO 6 Composite material and C/Bi 2 MoO 6 XPS survey of the poled material;
FIG. 12 is C/Bi 2 MoO 6 Composite material and C/Bi 2 MoO 6 High resolution XPS spectra of C1s of poled materials;
FIG. 13 is C/Bi 2 MoO 6 Composite material and C/Bi 2 MoO 6 High resolution XPS spectra of Bi 4f of the poled material;
FIG. 14 is C/Bi 2 MoO 6 Composite material and C/Bi 2 MoO 6 High resolution XPS spectra of O1s of poled materials;
FIG. 15 is C/Bi 2 MoO 6 Composite material and C/Bi 2 MoO 6 High resolution XPS spectra of Mo 3d of the poled material;
FIG. 16 shows pure Bi 2 MoO 6 、C/Bi/Bi 2 MoO 6 Composite material and C/Bi 2 MoO 6 Ultraviolet-visible diffuse reflectance spectra of the polarized material;
FIG. 17 shows Bi 2 MoO 6 、C/Bi/Bi 2 MoO 6 Composite material and C/Bi 2 MoO 6 A forbidden band width distribution diagram of the polarized material;
FIG. 18 is Bi 2 MoO 6 、C/Bi/Bi 2 MoO 6 Composite material and C/Bi 2 MoO 6 A graph of the catalytic degradation of malachite green by three catalysts of the polarization material under visible light;
FIG. 19 is C/Bi 2 MoO 6 A photocatalysis stability test chart for degrading malachite green by using a polarization material;
FIG. 20 is C/Bi 2 MoO 6 Infrared spectrograms before and after a polarized material cycle experiment;
FIG. 21 shows Bi 2 MoO 6 An ultraviolet absorption spectrum of degraded BPA;
FIG. 22 is C/Bi 2 MoO 6 An ultraviolet absorption spectrum chart of the composite material for degrading BPA;
FIG. 23 is C/Bi 2 MoO 6 An ultraviolet absorption spectrum chart of the polarized material for degrading BPA;
FIG. 24 shows Bi 2 MoO 6 、C/Bi/Bi 2 MoO 6 Composite material and C/Bi 2 MoO 6 A plot of BPA degradation for poled materials;
FIG. 25 shows Bi 2 MoO 6 、C/Bi/Bi 2 MoO 6 Composite material and C/Bi 2 MoO 6 A photoluminescence spectrum of the polarized material;
FIG. 26 is Bi 2 MoO 6 、C/Bi/Bi 2 MoO 6 Composite material and C/Bi 2 MoO 6 Electrical impedance spectroscopy of polarized materials.
Detailed Description
Example 1
C/Bi of the present example 2 MoO 6 A method of preparing a poled material comprising the steps of:
(1) Preparation of EDTA-Bi precursor
1.0mL of concentrated nitric acid was dissolved in 29.0mL of water, and 4.8500g of Bi (NO) was added to the nitric acid solution 3 ) 3 ·5H 2 O and 2.92g EDTA, ultrasonically dissolving for 20min, and then using NH with the mass fraction of 14 percent 3 ·H 2 Adjusting the pH of the solution by O =6.5, stirring for 2h, centrifuging, collecting a solid deposit, and drying at 100 ℃ for 20h to obtain the EDTA-Bi precursor.
(2)C/Bi/Bi 2 MoO 6 Preparation of composite materials
Weighing 1.6866g Bi (NO) 3 ) 3 ·5H 2 Dissolving O in 5.0mL of glycol to obtain solution A; then 0.4210g of Na is weighed 2 MoO 4 ·2H 2 Dissolving O in 5.0mL of glycol to obtain solution B;
adding 0.0530g of EDTA-Bi precursor prepared in the step (1) into the solution A, fully stirring, then dripping the solution B into the solution A, and stirring to fully react to obtain solution C; then 20.0mL of ethanol is added into the third solution,stirring thoroughly, transferring into high pressure kettle, reacting at 160 deg.C for 10 hr, naturally cooling to room temperature, washing the obtained solid with deionized water and anhydrous ethanol for 3 times, drying at 60 deg.C, calcining in 400 deg.C muffle furnace for 3 hr to obtain powdered C/Bi 2 MoO 6 A composite material;
(3)C/Bi/Bi 2 MoO 6 preparation of poled materials
Accurately weighing 0.0250g of polymethyl methacrylate (PMMA) and dissolving in 20.0mL of ethyl acetate, and adding 0.40g of C/Bi prepared in step (2) thereto 2 MoO 6 Stirring the powder for 30min, coating the mixed solution on ITO conductive glass, drying the conductive glass at 60 ℃, covering a layer of ITO conductive glass, fixing the ITO conductive glass, applying 30V direct current voltage to two ends of the conductive glass, electrifying for 1h, soaking and dispersing the powder on the ITO conductive glass by using an acetone solution, centrifuging the solution, collecting the solid, and drying at 60 ℃ to obtain C/Bi 2 MoO 6 And polarizing the material.
C/Bi of the present example 2 MoO 6 The polarized material is prepared by the method.
Example 2
To verify the C/Bi of example 1 of the present invention 2 MoO 6 Whether the preparation of the polarization material is successful or not, the applicant separately compares Bi 2 MoO 6 、C/Bi/Bi 2 MoO 6 Composite material and C/Bi 2 MoO 6 The polarized material was subjected to XRD analysis, SEM analysis, FT-IR analysis, and XPS analysis, and the specific experimental results were as follows.
Bi used in the present example 2 MoO 6 The preparation method comprises the following steps: 1.6866g of Bi (NO) are weighed 3 ) 3 ·5H 2 Dissolving O in 5.0mL of ethylene glycol to obtain Bi (NO) 3 ) 3 A solution; then 0.4210g of Na is weighed 2 MoO 4 ·2H 2 O was dissolved in 5.0mL of ethylene glycol to give Na 2 MoO 4 A solution; stirring while adding Na 2 MoO 4 Adding Bi (NO) dropwise into the solution 3 ) 3 Adding 20.0 ethanol into the solution,stirring thoroughly, transferring the obtained suspension to 45.0mL stainless steel autoclave, reacting at 160 deg.C for 10h, naturally cooling to room temperature, washing the obtained solid with deionized water and anhydrous ethanol for 3 times, oven drying at 60 deg.C, calcining in 400 deg.C muffle furnace for 3h to obtain Bi 2 MoO 6 。
(1) XRD analysis
This example separately compares the synthesized pure Bi by the analysis method of X-ray powder diffraction 2 MoO 6 、C/Bi/Bi 2 MoO 6 Composite material and C/Bi 2 MoO 6 The crystalline structure of the poled material was characterized as shown in figures 1-3.
As can be seen from FIG. 1, for pure Bi 2 MoO 6 In other words, the main diffraction peaks can be indexed to the (1 3 1), (0 0 2), (2 0 2), (3 1) crystal planes of the PDF card (JCPDS: 21-0102) at 2 θ =28.20 °, 32.64 °, 46.73 °, 55.43 °, respectively, which indicates that Bi is Bi 2 MoO 6 The successful preparation shows that the prepared material has higher crystallinity if the special diffraction peak is sharp. As can be seen from FIG. 2, FIG. 2 shows C/Bi 2 MoO 6 XRD pattern of composite sample at 2 θ =54 to 60 °. C/Bi 2 MoO 6 Characteristic peak of composite material and pure Bi 2 MoO 6 In contrast, the peaks only shifted or disappeared at 55.65, 56.37 and 58.65 °, and the rest did not shift significantly. The characteristic peaks of Bi at 55.49 and 58.37 degrees, corresponding to the (0 4) and (1 4 0) crystal planes in PDF card (JCPDS: 51-0765), respectively, show that the introduction of C and Bi does not affect Bi 2 MoO 6 Original crystal structure. As can be seen from FIG. 3, C/Bi 2 MoO 6 Polarizing material and Bi 2 MoO 6 And C/Bi 2 MoO 6 The composite material is not obviously shifted, and the reduction of the intensity of the diffraction peak is possibly related to ferroelectric polarization experiments. The comprehensive XRD experiment result can preliminarily consider that C/Bi 2 MoO 6 The composite material and the polarization material have good preparation conditions.
(2) SEM analysis
This example separately deals with pure Bi 2 MoO 6 、C/Bi/Bi 2 MoO 6 Composite material and C/Bi 2 MoO 6 The crystalline structure of the poled material was SEM analyzed as shown in figures 4-9.
FIGS. 4 and 5 are each pure Bi 2 MoO 6 The overall appearance and surface appearance of (A), it can be clearly seen that Bi 2 MoO 6 Is a microsphere structure self-assembled by nano-sheets, and the size is 2-3 μm.
FIG. 6 and FIG. 7 are C/Bi, respectively 2 MoO 6 From the overall view and surface morphology of the composite material, it can be seen that substances of different sizes are formed on the surface of the microspheres, and the size of the microspheres becomes 1-2 μm, which may be related to the introduced C and Bi.
FIG. 8 and FIG. 9 are C/Bi, respectively 2 MoO 6 The overall picture and the surface appearance of the polarized material can observe that the sample after polarization modification can keep the appearance of relatively complete microspheres, and granular substances exist on the surface, which shows that the appearance of the catalyst is not changed basically in the ferroelectric polarization experiment.
(3) FT-IR analysis
This example separately for pure Bi 2 MoO 6 、C/Bi/Bi 2 MoO 6 Composite material and C/Bi 2 MoO 6 The crystal structure of the poled material was subjected to FT-IR analysis as shown in FIG. 10.
As can be seen from the infrared spectrum of FIG. 10, for pure Bi 2 MoO 6 At 450cm -1 The absorption peaks at (A) are due to deformation and stretching vibration of Bi-O bond, at 558 and 732cm -1 Respectively has an absorption peak of MoO 6 6- Bending vibration and asymmetric stretching modes of octahedron at 797 and 843cm -1 The absorption peak at (A) is then due to the Mo-O bond stretching mode and is at 1635cm -1 The absorption peak at (b) then corresponds to C = C. For C/Bi 2 MoO 6 Composite material and C/Bi 2 MoO 6 Polarized material capable of well corresponding to Bi 2 MoO 6 All samples are illustrated by Bi-O, mo-O and MoO 6 6- And (4) forming.
(4) XPS analysis
The true bookExamples also for C/Bi 2 MoO 6 Composite material and C/Bi 2 MoO 6 XPS analysis of the poled material was performed and the results are shown in FIGS. 11-15.
FIG. 11 shows C/Bi 2 MoO 6 Composite material and C/Bi 2 MoO 6 The full spectrum of the polarized material shows that the two materials are composed of four elements of Bi, O, C and Mo.
FIG. 12 shows C/Bi 2 MoO 6 Composite material and C/Bi 2 MoO 6 High resolution XPS spectra of C1s of poled materials, it can be seen that 284.7eV corresponds to sp in the instrument calibrated carbon 2 C atom, 285.9eV corresponds to C-C bonds in carbon-containing pollutants, 288.8eV corresponds to atmospheric CO 2 C = O bond in (1).
FIG. 13 shows C/Bi 2 MoO 6 Composite material and C/Bi 2 MoO 6 The high resolution XPS spectrum of Bi 4f for the poled material, as can be seen in the figure, corresponds to Bi 4f at 164.1eV and 158.6eV respectively 5/2 And Bi 4f 7/2 [ Bi ] of 2 O 2 ] 2+ The metal Bi is attributed to the regions 162.2eV and 156.8 eV.
FIG. 14 shows C/Bi 2 MoO 6 Composite material and C/Bi 2 MoO 6 High resolution XPS spectrum of O1s for poled materials, it can be seen that 529.8eV corresponds to [ Bi ] 2 O 2 ] 2+ In (2), 530.8eV corresponds to hydroxyl group, 532.2eV corresponds to chemically adsorbed water, and polarization is shifted at a binding energy corresponding to the hydroxyl group and the chemically adsorbed water, probably because the catalyst is washed with an organic reagent such as ethyl acetate and acetone.
FIG. 15 shows C/Bi 2 MoO 6 Composite material and C/Bi 2 MoO 6 The high resolution XPS spectra of Mo 3d for poled materials, as can be seen, 235.2eV and 232.1eV correspond to MoO 4 2- 235.9eV and 232.7eV correspond to Mo in the Mo-O bond 6+ . Comprehensive analysis of the above, C/Bi 2 MoO 6 The composite material is basically successfully prepared, and the chemical properties of the catalyst are not influenced after the ferroelectric polarization experiment is carried out。
(5) DRS analysis
This example separately for pure Bi 2 MoO 6 、C/Bi/Bi 2 MoO 6 Composite material and C/Bi 2 MoO 6 The ultraviolet-visible diffuse reflectance spectra of the polarized material are shown in FIGS. 16-17.
FIG. 16 shows pure Bi 2 MoO 6 、C/Bi/Bi 2 MoO 6 Composite material and C/Bi 2 MoO 6 Ultraviolet-visible diffuse reflectance spectrum of the polarized material, bi can be seen from the figure 2 MoO 6 、C/Bi/Bi 2 MoO 6 Composite material and C/Bi 2 MoO 6 The light absorption range of the poled materials is similar. FIG. 17 is Bi obtained by transformation according to the Kubelka-Munk function 2 MoO 6 、C/Bi/Bi 2 MoO 6 Composite material and C/Bi 2 MoO 6 The distribution of the forbidden band width of the polarized material is shown in the figure, bi 2 MoO 6 The band gap of (A) was estimated to be 2.77eV 2 MoO 6 The band gap of the composite material is 2.74eV 2 MoO 6 The bandgap of the poled material was 2.68eV. It can be concluded from this that ferroelectric polarization can reduce the band gap value of the catalyst, which is probably also the C/Bi of the present invention 2 MoO 6 One of the reasons why the photocatalytic performance of the polarized material is improved.
Example 3
C/Bi of the present example 2 MoO 6 The application of the polarization material in catalyzing and degrading the colored dye malachite green is that three 50mL malachite green solutions with the concentration of 10mg/L are taken and numbered as #1, #2 and #3 respectively, and 0.02g Bi is added into the #1, #2 and #3 solutions respectively 2 MoO 6 、0.02g C/Bi/Bi 2 MoO 6 Composite material and 0.02g of C/Bi 2 MoO 6 The polarization materials each act as catalysts, and the solution maintains the original pH. The adsorption-desorption balance is achieved by dark light treatment for 30min, and then the light is irradiated for 60min, and the test is carried out once every 10 min. FIG. 18 is a graph showing the photocatalytic degradation of malachite green by three different catalysts, from which it can be seen that pure Bi 2 MoO 6 The degradation rate is only within 60min53.1% of C/Bi after the introduction of C and Bi 2 MoO 6 The degradation rate of the composite material can be improved to 71.3 percent, and the polarized C/Bi 2 MoO 6 The degradation rate of the polarized material can reach 93.9 percent. Illustrating that Bi is modified after C and Bi modification and ferroelectric polarization modification 2 MoO 6 The photocatalytic degradation performance of the catalyst is obviously improved.
This example also applies to C/Bi since the stability of the catalyst affects its photocatalytic performance 2 MoO 6 The poled materials were tested for stability. This example is for C/Bi 2 MoO 6 Polarization materials cycle experiments for degrading malachite green were performed using a 300W xenon lamp (CEL-HXF 300) and filtering the ultraviolet light (. Lamda.<420 nm) to simulate a visible light source. 20mg of C/Bi 2 MoO 6 The polarized material catalyst and 50mL of malachite green solution with the concentration of 10mg/L are added into the photoreactor at the same time, and after dark light treatment for 30min, adsorption-desorption equilibrium is established. The illumination time was 10min, about 3mL of the supernatant was removed, centrifuged at 10000rmp for 2min, and the absorbance of the malachite green solution was measured at 617nm using a 722s spectrophotometer. This is the first photocatalytic degradation and is also the first cycle experiment. After the first circulation experiment is finished, standing the solution for 30min to enable the catalyst to be deposited on the bottom layer of the malachite green solution, centrifugally separating the catalyst from the malachite green solution, drying the catalyst at 60 ℃, and weighing the mass of the rest catalyst. If the catalyst is less than 20mg, the catalyst is added to 20mg, then the second cycle experiment is started, the absorbance of the supernatant at 617nm is tested, and so on to the fifth cycle experiment, and the experimental results are shown in fig. 19. As can be seen from FIG. 19, C/Bi 2 MoO 6 The degradation rate of the polarized material in the first experiment is 94.8%, and the degradation rate after the fifth experiment can still reach 89.3%. In addition, this embodiment also combines C/Bi 2 MoO 6 Infrared spectroscopy before and after the polarization material test was conducted, referring to FIG. 20, it can be seen from FIG. 20 that C/Bi 2 MoO 6 The infrared spectrum before and after the cycle experiment of the polarized material has no obvious change, and the infrared spectrum after the cycle experiment is 1700cm -1 On the left and rightThe characteristic peak of water disappears, possibly associated with multiple washing and drying of the sample. As can be seen from FIGS. 19 to 20, C/Bi 2 MoO 6 The polarized material has high photocatalytic stability.
Example 4
C/Bi of the present example 2 MoO 6 The polarization material is applied to catalytic degradation of leuco dye bisphenol A (BPA), three 50mL BPA solutions with the concentration of 10mg/L are taken and numbered as #1, #2 and #3 respectively, and 0.02g Bi is added into the #1, #2 and #3 solutions respectively 2 MoO 6 、0.02g C/Bi/Bi 2 MoO 6 Composite material and 0.02g of C/Bi 2 MoO 6 The polarization materials each act as catalysts, and the solution maintains the original pH. The adsorption-desorption equilibrium is achieved by performing dark light treatment for 30min, and then the light irradiation is performed for 120min, and the test is performed once every 30 min. Bi in FIGS. 21, 22 and 23 2 MoO 6 、C/Bi/Bi 2 MoO 6 Composite material and C/Bi 2 MoO 6 The ultraviolet absorption spectrum of the polarized material for degrading BPA can show that all samples have absorption peaks at 276nm, and C/Bi is obtained along with the prolonging of illumination time 2 MoO 6 The absorption peak of the poled material was significantly weaker, indicating that the BPA molecules were gradually degraded. FIG. 24 shows Bi 2 MoO 6 、C/Bi/Bi 2 MoO 6 Composite material and C/Bi 2 MoO 6 The graph of the degradation of BPA by the polarized material can be seen, and C/Bi can be seen 2 MoO 6 The degradation rate of the polarized material is the highest and reaches 66.3 percent at 120 min.
Example 5
As the recombination rate of the photo-generated charges is one of the means for analyzing the good and bad performance of the photocatalyst, the higher the recombination rate is, the lower the performance is, and the lower the recombination rate is, the higher the performance is.
This example also deals with Bi 2 MoO 6 、C/Bi/Bi 2 MoO 6 Composite material and C/Bi 2 MoO 6 The polarized materials were analyzed for the recombination rate of photo-generated charges, and for the analysis of the recombination condition of photo-generated carriers, the three materials were tested for photoluminescence spectra and electrical impedance, see fig. 25-26, respectively. As shown in FIG. 25, bi shows that Bi shows a maximum excitation wavelength of 280nm 2 MoO 6 Has a fluorescence emission peak at 301nm, the recombination of photo-generated charges is more serious, and after C and Bi are introduced, C/Bi 2 MoO 6 The recombination rate of photon-generated carriers of the composite material is inhibited, and the polarization modification further promotes the separation of the photon-generated carriers, so that the C/Bi 2 MoO 6 The photocatalytic performance of the polarized material is enhanced. C/Bi in FIG. 26 2 MoO 6 The circular arc radius of the Nyquist curve of the polarized material is less than Bi 2 MoO 6 And C/Bi 2 MoO 6 The smaller circular arc radius of the composite material shows that the charge transfer resistance of a sample is lower, which is more beneficial to the improvement of the photocatalytic performance.
Claims (1)
1.C/Bi/Bi 2 MoO 6 The application of the polarization material in the photocatalytic degradation of malachite green is characterized in that the C/Bi 2 MoO 6 The preparation method of the polarized material comprises the following steps:
(1) Preparation of EDTA-Bi precursor
Diluting concentrated nitric acid in water, wherein the volume ratio of the concentrated nitric acid to the water is 1:25-30, adding Bi (NO) into the nitric acid solution 3 ) 3 ·5H 2 O and EDTA, said Bi (NO) 3 ) 3 ·5H 2 The mass ratio of O to EDTA is 1 3 ·H 2 Adjusting the pH of the solution to be 6.5 by O, stirring for 2h, centrifuging, collecting a solid deposit, and drying at 95-105 ℃ for 18-22h to obtain an EDTA-Bi precursor;
（2）C/Bi/Bi 2 MoO 6 preparation of composite materials
Weighing Bi (NO) 3 ) 3 ·5H 2 Dissolving O in ethylene glycol to obtain solution A, wherein Bi (NO) in the solution A 3 ) 3 ·5H 2 The mass volume ratio of O to glycol is 300-350; weighing Na 2 MoO 4 ·2H 2 Dissolving O in ethylene glycol to obtain an ethylene solution, wherein Na in the ethylene solution 2 MoO 4 ·2H 2 The mass volume ratio of O to glycol is 80-90; the volume of the solution A is equal to that of the solution B, and Bi(NO 3 ) 3 ·5H 2 O and Na 2 MoO 4 ·2H 2 The mass ratio of O is 2-3;
adding the EDTA-Bi precursor prepared in the step (1) into the nail liquid, wherein the EDTA-Bi precursor and Bi (NO) in the nail liquid 3 ) 3 ·5H 2 The mass ratio of O is 1; adding ethanol into the solution C, stirring thoroughly, transferring into high-pressure kettle, reacting at 150-170 deg.C for 9-11h, naturally cooling to room temperature, washing the obtained solid with deionized water and anhydrous ethanol for 3 times, drying at 55-65 deg.C, calcining in a muffle furnace at 380-420 deg.C for 3h to obtain powdered C/Bi 2 MoO 6 A composite material;
（3）C/Bi/Bi 2 MoO 6 preparation of poled materials
Accurately weighing polymethyl methacrylate, dissolving the polymethyl methacrylate in ethyl acetate, wherein the mass volume ratio of the polymethyl methacrylate to the ethyl acetate is 1-2 2 MoO 6 Powder of said C/Bi 2 MoO 6 Stirring for 20-40min at the mass ratio of 15-17 to polymethyl methacrylate (PMMA) to coat the mixed solution on ITO conductive glass, drying the conductive glass at 50-60 ℃, covering a layer of ITO conductive glass, fixing the ITO conductive glass, applying 30V direct current voltage to two ends of the conductive glass, electrifying for 1h, soaking and dispersing powder on the ITO conductive glass by using acetone solution, centrifuging the solution, collecting the solid, and drying at 60 ℃ to obtain C/Bi 2 MoO 6 And polarizing the material.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106984299A (en) * | 2017-05-27 | 2017-07-28 | 北方民族大学 | Hydrothermal Synthesiss three-dimensional Bi4MoO9/TiO2The method of nanostructure heterojunction |
| CN107684914A (en) * | 2017-08-14 | 2018-02-13 | 浙江工业大学 | A kind of magnetic Bi2MoO6/CuFe2O4Composite photocatalyst material and preparation method thereof |
| CN109718800A (en) * | 2019-01-16 | 2019-05-07 | 湖北师范大学 | Co3O4/Bi2MoO6Composite photo-catalyst and preparation method and application of the catalyst in degradating organic dye |
-
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106984299A (en) * | 2017-05-27 | 2017-07-28 | 北方民族大学 | Hydrothermal Synthesiss three-dimensional Bi4MoO9/TiO2The method of nanostructure heterojunction |
| CN107684914A (en) * | 2017-08-14 | 2018-02-13 | 浙江工业大学 | A kind of magnetic Bi2MoO6/CuFe2O4Composite photocatalyst material and preparation method thereof |
| CN109718800A (en) * | 2019-01-16 | 2019-05-07 | 湖北师范大学 | Co3O4/Bi2MoO6Composite photo-catalyst and preparation method and application of the catalyst in degradating organic dye |
Non-Patent Citations (3)
| Title |
|---|
| Guoquan Huang et al.."Enhanced visible-light-driven photocatalytic activity of BiFeO3 via electric-field control of spontaneous polarization".《Journal of Alloys and Compounds》.2019,第783卷第943-951页. * |
| Mengjun Liang et al.."One-step introduction of metallic Bi and non-metallic C in Bi2WO6 with enhanced photocatalytic activity".《Journal of Materials Science: Materials in Electronics》.2018,第1310-1321页. * |
| 张志等."C/Bi2MoO6复合材料的合成及其可见光光催化性能研究".《湖北大学学报（自然科学版）》.2019,第41卷(第6期),第636-643页. * |
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