CN111111683A - Composite photocatalyst and preparation method thereof - Google Patents
Composite photocatalyst and preparation method thereof Download PDFInfo
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- CN111111683A CN111111683A CN201911412970.1A CN201911412970A CN111111683A CN 111111683 A CN111111683 A CN 111111683A CN 201911412970 A CN201911412970 A CN 201911412970A CN 111111683 A CN111111683 A CN 111111683A
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- 239000002131 composite material Substances 0.000 title claims abstract description 39
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 105
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 105
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 claims abstract description 73
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 50
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 50
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229910000859 α-Fe Inorganic materials 0.000 claims abstract description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000008367 deionised water Substances 0.000 claims abstract description 20
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
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- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 claims description 15
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- 239000004098 Tetracycline Substances 0.000 claims description 2
- 239000003242 anti bacterial agent Substances 0.000 claims description 2
- 229940088710 antibiotic agent Drugs 0.000 claims description 2
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- IQFVPQOLBLOTPF-HKXUKFGYSA-L congo red Chemical compound [Na+].[Na+].C1=CC=CC2=C(N)C(/N=N/C3=CC=C(C=C3)C3=CC=C(C=C3)/N=N/C3=C(C4=CC=CC=C4C(=C3)S([O-])(=O)=O)N)=CC(S([O-])(=O)=O)=C21 IQFVPQOLBLOTPF-HKXUKFGYSA-L 0.000 claims description 2
- 229960000740 enrofloxacin Drugs 0.000 claims description 2
- 239000010842 industrial wastewater Substances 0.000 claims description 2
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 claims description 2
- 229940043267 rhodamine b Drugs 0.000 claims description 2
- 229960002180 tetracycline Drugs 0.000 claims description 2
- 229930101283 tetracycline Natural products 0.000 claims description 2
- 235000019364 tetracycline Nutrition 0.000 claims description 2
- 150000003522 tetracyclines Chemical class 0.000 claims description 2
- 238000012546 transfer Methods 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 22
- 230000001699 photocatalysis Effects 0.000 description 15
- 239000000463 material Substances 0.000 description 13
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 13
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- 239000011259 mixed solution Substances 0.000 description 7
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- 230000003197 catalytic effect Effects 0.000 description 3
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- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 2
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- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 2
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- 229940045105 silver iodide Drugs 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 238000001132 ultrasonic dispersion Methods 0.000 description 2
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- HHSDZLLPIXMEIU-UHFFFAOYSA-N 1-bromoheptadecane Chemical compound CCCCCCCCCCCCCCCCCBr HHSDZLLPIXMEIU-UHFFFAOYSA-N 0.000 description 1
- 229910020350 Na2WO4 Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- FBXVOTBTGXARNA-UHFFFAOYSA-N bismuth;trinitrate;pentahydrate Chemical compound O.O.O.O.O.[Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FBXVOTBTGXARNA-UHFFFAOYSA-N 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 1
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- 239000002440 industrial waste Substances 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 238000001782 photodegradation Methods 0.000 description 1
- -1 polytetrafluoroethylene Polymers 0.000 description 1
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- 238000011160 research Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
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- 238000004729 solvothermal method Methods 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/888—Tungsten
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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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B01J35/39—
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
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- 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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- 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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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract
The invention discloses a preparation method of a bismuth tungstate/reduced graphene oxide/bismuth ferrite composite photocatalyst, which comprises the following steps: (1) preparing bismuth tungstate; (2) preparing a reduced graphene oxide dispersion liquid; (3) dissolving bismuth tungstate in deionized water, adding ferric nitrate, adjusting the pH value to 10-11, adding the reduced graphene oxide dispersion liquid, stirring, and transferring to a high-pressure reaction kettle for reaction to obtain the composite photocatalyst. The composite photocatalyst is prepared by a hydrothermal method, and the preparation method is simple, low in organic solvent consumption, low in preparation cost and environment-friendly.
Description
Technical Field
The invention belongs to the technical field of nano composite materials and photocatalysis, and particularly relates to a bismuth tungstate/reduced graphene oxide/bismuth ferrite composite photocatalyst and a preparation method thereof.
Background
With the rapid development of economy, the water environment pollution problem seriously threatens the ecological civilization construction, dye wastewater in the textile industry is one of the dye wastewater which is very difficult to remove, and the traditional methods for treating the wastewater comprise an adsorption method, a flocculation method, a biological treatment method and the like, so that the elbow is restricted from further use due to low efficiency and high cost. The elimination and degradation of pollutants by using a photocatalytic technology is one of the most active researches in the field of current wastewater treatment, and more photocatalytic materials are applied to environmental protection and organic matter degradation.
The recyclability and environmental friendliness of photocatalysis, particularly visible light photocatalysis, make it an ideal water treatment and pollutant removal method. The bismuth tungstate is firstly reported to have the catalytic activity of visible light in 1999, the forbidden band width of the bismuth tungstate is 2.72eV, and the visible light absorption range is 420-470nm, so that the bismuth tungstate is widely researched in the field of visible light catalysts in recent years. Graphene is an allotrope of a carbon material, and can be used as a carrier to better disperse and load a nano material, and the prepared graphene-based composite material has good photocatalytic performance. The bismuth tungstate photocatalyst can be only excited by ultraviolet light or partial visible light, and the photo-generated electron hole pairs are easy to recombine, while the reduced graphene oxide has excellent electron transfer performance and can rapidly transfer photo-generated electrons on the bismuth tungstate.
Patent document CN201811434456.3 discloses an all-solid-state silver iodide/carbon nitride/bismuth tungstate double-Z-type ternary heterojunction photocatalyst, which comprises a carbon nitride/bismuth tungstate heterojunction material formed by compounding bismuth tungstate and carbon nitride, and silver iodide nanoparticles are modified on the surface of the carbon nitride/bismuth tungstate heterojunction material. The preparation method of the photocatalyst comprises the following steps: (1) mixing and stirring bismuth nitrate pentahydrate, carbon nitride and a nitric acid solution to obtain a carbon nitride/bismuth nitrate mixed solution; (2) mixing the carbon nitride/bismuth nitrate mixed solution with a sodium tungstate solution, and stirring to obtain a carbon nitride/bismuth nitrate/sodium tungstate mixed solution; (3) carrying out hydrothermal reaction on the mixed solution of carbon nitride/bismuth nitrate/sodium tungstate, centrifuging, washing and drying to obtain a carbon nitride/bismuth tungstate heterojunction material; (4) mixing the carbon nitride/bismuth tungstate heterojunction material with ultrapure water, and performing ultrasonic dispersion to obtain a carbon nitride/bismuth tungstate heterojunction material mixed solution; (5) and mixing the mixed solution of the carbon nitride/bismuth tungstate heterojunction material with silver nitrate, stirring, adding a potassium iodide solution, carrying out precipitation reaction under a dark condition, centrifuging, washing and drying to obtain the photocatalyst. The preparation process of the bismuth tungstate photocatalyst is complex, so that the preparation cost of the photocatalyst is high, and in addition, the complex preparation process causes more industrial wastes, which is not beneficial to effective utilization of resources and environmental protection.
Patent document cn201910406088.x discloses a preparation method of a flower-shaped spherical bismuth tungstate-graphene-cuprous oxide composite material, which comprises the following steps: (1) adding Bi (NO)3)3·5H2Dissolving O in ethylene glycol, adding Na2WO4·2H2Stirring O and CTAB (cetyltrimethylammonium bromide) for 1-3h at 35-45 ℃ in a water bath, transferring the suspension into a stainless steel reaction kettle lined with polytetrafluoroethylene after forming a uniform suspension, and carrying out solvent heat treatment to obtain bismuth tungstate powder; (2) ultrasonically dispersing bismuth tungstate powder into ethylene glycol solution containing graphene oxide GO, and adding Cu (NO)3)2·3H2O, magnetically stirring for 1-3h, transferring the obtained suspension into a reaction kettle, carrying out solvothermal reaction, naturally cooling to room temperature after the reaction is finished, centrifugally washing, and freeze-drying to obtain Bi2WO6/RGO/Cu2And (3) an O ternary composite material. Although the preparation process of the bismuth tungstate composite material is optimized, the ethylene glycol solution and the hexadecyl methyl bromide are continuously used in the preparation processAmmonium and other organic solvents, high cost and environmental friendliness.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a bismuth tungstate/reduced graphene oxide/bismuth ferrite composite visible light catalytic material prepared by taking bismuth ferrite, bismuth tungstate and graphene oxide as raw materials and using a hydrothermal method. The technical personnel of the invention find that the composite catalyst formed by compounding the bismuth ferrite and the bismuth tungstate has better photocatalysis performance than the composite of the cuprous oxide and the bismuth tungstate. The reason is that the energy level of the bismuth ferrite and the energy level of the bismuth tungstate have small difference, the bismuth ferrite and the bismuth tungstate can be well compounded, and the photocatalysis capability of the bismuth tungstate can be obviously enhanced by compounding the bismuth ferrite.
The invention aims to provide a bismuth tungstate/reduced graphene oxide/bismuth ferrite composite visible-light-driven photocatalyst and a preparation method thereof, and the invention also aims to provide application of the bismuth tungstate/reduced graphene oxide/bismuth ferrite composite visible-light-driven photocatalyst.
In a first aspect, the invention provides a preparation method of a bismuth tungstate/reduced graphene oxide/bismuth ferrite composite photocatalyst, which comprises the following steps:
(1) preparing bismuth tungstate: dissolving sodium tungstate and bismuth nitrate in deionized water to obtain a clear solution, transferring the clear solution to a high-pressure reaction kettle, and reacting at the temperature of 150 ℃ and 220 ℃ for 20-24 hours to obtain bismuth tungstate;
(2) dissolving graphene oxide in deionized water, adding ascorbic acid, and performing ultrasonic treatment for 10-20min to obtain a reduced graphene oxide dispersion liquid;
(3) dissolving bismuth tungstate in deionized water, adding ferric nitrate, adjusting the pH value to 10-11, adding the reduced graphene oxide dispersion liquid obtained in the step (2), stirring, transferring to a high-pressure reaction kettle, and reacting at the temperature of 180 ℃ and 220 ℃ for 6-8h to obtain the composite photocatalyst.
Preferably, the molar mass ratio of sodium tungstate to bismuth nitrate in the step (1) is 1: 1-5; preferably, the molar mass ratio of sodium tungstate to bismuth nitrate is 1: 2-3; in a preferred embodiment of the invention, the molar mass ratio of sodium tungstate to bismuth nitrate is 1: 2.
In the most preferred embodiment of the invention, in the step (1), sodium tungstate is dissolved in deionized water to obtain a sodium tungstate solution with the concentration of 0.05-0.1mol/L, bismuth nitrate is dissolved in deionized water to obtain a bismuth nitrate solution with the concentration of 0.1-0.25mol/L, the two solutions are slowly mixed, and the mixture is transferred to a high-pressure reaction kettle after being magnetically stirred for 30-45min and then reacts for 24 hours at 160 ℃ to obtain bismuth tungstate.
And (2) after the hydrothermal reaction is finished, cooling to room temperature, respectively carrying out centrifugal washing on precipitates generated by ethanol and deionized water, and drying for 10-12h at 50-60 ℃.
The concentration of the reduced graphene oxide dispersion liquid obtained in the step (2) is preferably 1.0-1.5 mg/mL.
Preferably, the adding amount of the ascorbic acid in the step (2) is 1/10-1/15 of the mass of the graphene oxide.
In the step (3), the mass ratio of the bismuth tungstate to the ferric nitrate is 60-10:1, such as 60:1, 40:1, 30:1, 20:1, 15:1, 12:1 and 10: 1; preferably, the mass ratio of the bismuth tungstate to the ferric nitrate is 20-15: 1.
In the most preferred embodiment of the present invention, the mass ratio of bismuth tungstate to ferric nitrate is 20: 1.
Preferably, the volume of the reduced graphene oxide dispersion liquid added in the step (3) accounts for 15-25% of the total volume of the reaction system.
The step (3) further comprises the steps of centrifugally washing the generated precipitate for 3-5 times by using ethanol and deionized water respectively, and drying at the temperature of 100-120 ℃ for 10-12 h.
The ethanol concentration of the invention is 60-95% (v/v, specifically 60%, 70%, 80%, 90% or 95%), and ethanol with a concentration of 70% is preferred.
In a second aspect, the invention provides a bismuth tungstate/reduced graphene oxide/bismuth ferrite composite photocatalyst, which is prepared by the method disclosed above.
In a third aspect, the invention provides an application of a bismuth tungstate/reduced graphene oxide/bismuth ferrite composite photocatalyst in degradation of organic dyes and/or antibiotics.
Preferably, the organic dye and/or antibiotic is derived from industrial waste water.
More preferably, the concentration of the organic dye in the wastewater is selected from 20-40mg/L, and the concentration of the antibiotic is 5-15 mg/L.
The organic dye is selected from: one or more than two of methylene blue, rhodamine B dye and Congo red; preferably, the organic dye is selected from methylene blue.
The antibiotic is selected from: one or more of norfloxacin, tetracycline, ciprofloxacin and enrofloxacin; preferably, the antibiotic is selected from norfloxacin.
Photocatalytic degradation experiments prove that the bismuth tungstate/reduced graphene oxide/bismuth ferrite composite photocatalyst prepared by the method has stronger catalytic degradation capability on organic dyes.
The invention has the beneficial effects that: the bismuth tungstate is compounded with the bismuth ferrite, the graphene oxide is added for modification, the graphene oxide is reduced into reduced graphene oxide, the reduced graphene oxide has strong conductivity and electron transmission capacity, a better electron and hole transmission environment is provided for the bismuth tungstate photocatalyst, the defect that the bismuth tungstate photocatalyst is unstable under the illumination condition is overcome, and the photocatalytic performance is improved. Solves the problems that the existing photocatalyst has low utilization rate of visible light, slow degradation speed and low degradation efficiency of organic dye and antibiotic, and the like. In addition, the composite photocatalyst is prepared by a hydrothermal method, the preparation method is simple, expensive equipment is not needed, and the preparation cost is low.
Drawings
FIG. 1 scanning electron microscope image of bismuth tungstate/reduced graphene oxide/bismuth ferrite composite photocatalyst
FIG. 2 is a transmission electron microscope image of a bismuth tungstate/reduced graphene oxide/bismuth ferrite composite photocatalyst
FIG. 3 is an X-ray diffraction diagram of a bismuth tungstate/reduced graphene oxide/bismuth ferrite composite photocatalyst
FIG. 4 is a graph showing the degradation curve of the composite photocatalyst of bismuth tungstate/reduced graphene oxide/bismuth ferrite on methylene blue and norfloxacin
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only some embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
S1: weighing 0.33g of sodium tungstate (1mmol) and dissolving in 20mL of deionized water, stirring to obtain a clear solution, weighing 0.97g of bismuth nitrate (2mmol) and dissolving in 20mL of deionized water, and stirring to obtain a clear solution;
s2: slowly mixing the two solutions, magnetically stirring for 30min, transferring to a high-pressure reaction kettle, and reacting at 160 ℃ for 24 h; after the hydrothermal reaction is finished, after the temperature is reduced to room temperature, respectively carrying out centrifugal washing on precipitates generated after the reaction by using ethanol and deionized water, and drying at 60 ℃ for 12 hours to obtain bismuth tungstate;
s3: dissolving 0.01g of graphene oxide in 10mL of deionized water, adding 1mg of ascorbic acid, and carrying out ultrasonic treatment for 10 min;
s4: dissolving 0.3g of bismuth tungstate in 40mL of deionized water, stirring, adding 0.005g of ferric nitrate, and adjusting the pH value of the solution to 10 by using 10M NaOH;
s5: mixing and stirring the two solutions obtained in the steps S3 and S4 for 1h, transferring the stirred mixed solution into a high-pressure reaction kettle, and reacting for 6h at 180 ℃; and respectively carrying out centrifugal washing on the precipitates generated after the reaction by using ethanol and deionized water, and drying at 100 ℃ for 10 hours to obtain the bismuth tungstate/reduced graphene oxide/bismuth ferrite composite photocatalyst.
Fig. 1 is a scanning electron microscope image of the bismuth tungstate/reduced graphene oxide/bismuth ferrite composite photocatalytic material prepared in example 1, from which it can be clearly seen that a large number of bismuth tungstate nanoparticles are attached to the reduced graphene oxide, and a two-dimensional layered structure of the reduced graphene oxide can also be seen.
Fig. 2 is a transmission electron microscope image of the bismuth tungstate/reduced graphene oxide/bismuth ferrite composite photocatalytic material prepared in example 1, and it is clearly seen that bismuth tungstate and bismuth ferrite are attached to reduced graphene oxide.
Fig. 3 is an X-ray diffraction experimental graph of the bismuth tungstate/reduced graphene oxide/bismuth ferrite composite photocatalytic material prepared in example 1, and all diffraction peaks in the diffraction graph correspond to responding bismuth tungstate and bismuth ferrite well.
Example 2
The preparation method and the preparation raw materials are the same as those in example 1 except that the amount of the ferric nitrate added in step S4 is 0.01g, and the mass ratio of the bismuth tungstate to the ferric nitrate is 30: 1.
Example 3
The preparation method and the preparation raw materials are the same as those in example 1 except that the amount of the ferric nitrate added in step S4 is 0.015g, and the mass ratio of the bismuth tungstate to the ferric nitrate is 20: 1.
Example 4
The preparation method and the preparation raw materials are the same as those in example 1, except that the amount of the ferric nitrate added in step S4 is 0.02g, and the mass ratio of the bismuth tungstate to the ferric nitrate is 15: 1.
Example 5
The preparation method and the preparation raw materials are the same as those in example 1, except that the amount of the ferric nitrate added in the step S4 is 0.025g, and the mass ratio of the bismuth tungstate to the ferric nitrate is 12: 1.
Effect example 1
Purpose of the experiment: the bismuth tungstate/reduced graphene oxide/bismuth ferrite composite photocatalyst prepared in the embodiment 3 is used for photocatalytic degradation experiments of organic dyes methylene blue and antibiotic norfloxacin, and the photocatalytic degradation capability of the composite photocatalyst prepared in the invention is detected.
The experimental method comprises the following steps: respectively preparing 50mL of methylene blue with the concentration of 20mg/L and 50mL of norfloxacin solution with the concentration of 5mg/L, adding 40mg of photocatalytic composite material, performing ultrasonic dispersion for 5min, and stirring for 30min in a dark environment to achieve adsorption-desorption balance. The reaction was then carried out under a 200W incandescent lamp, the light source being 15cm from the reactor, 3mL of suspension being taken every 5min and the catalyst being separated from the solution by means of a filter. And then, measuring the absorbance at different photocatalytic times by using an ultraviolet spectrophotometer to obtain the photocatalytic degradation curves of the bismuth tungstate/reduced graphene oxide/bismuth ferrite composite photocatalyst to methylene blue and norfloxacin under the irradiation of visible light at various time periods.
The experimental results are as follows: fig. 4 is a graph showing the photocatalytic degradation of methylene blue and norfloxacin by the bismuth tungstate/reduced graphene oxide/bismuth ferrite composite photocatalyst prepared in example 3 under visible light conditions, and as can be seen from fig. 4, the degradation rate of the composite photocatalytic material to methylene blue is 98% after visible light irradiation for 30min, and the degradation rate to norfloxacin is 78% after irradiation for 30min, which indicates that the composite photocatalyst has stronger photodegradation capability to organic dyes.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. A preparation method of a bismuth tungstate/reduced graphene oxide/bismuth ferrite composite photocatalyst comprises the following steps:
(1) preparing bismuth tungstate: dissolving sodium tungstate and bismuth nitrate in deionized water to obtain a clear solution, transferring the clear solution to a high-pressure reaction kettle, and reacting at the temperature of 150 ℃ and 220 ℃ for 20-24 hours to obtain bismuth tungstate;
(2) dissolving graphene oxide in deionized water, adding ascorbic acid, and performing ultrasonic treatment for 10-20min to obtain a reduced graphene oxide dispersion liquid;
(3) dissolving bismuth tungstate in deionized water, adding ferric nitrate, adjusting the pH value to 10-11, adding the reduced graphene oxide dispersion liquid obtained in the step (2), stirring, transferring to a high-pressure reaction kettle, and reacting at the temperature of 180 ℃ and 220 ℃ for 6-8h to obtain the composite photocatalyst.
2. The preparation method according to claim 1, wherein the molar mass ratio of sodium tungstate to bismuth nitrate in the step (1) is 1:1-5, and the mass ratio of bismuth tungstate to ferric nitrate in the step (3) is 60-100: 1.
3. The preparation method according to claim 2, wherein the step (1) is to dissolve sodium tungstate in deionized water to obtain a sodium tungstate solution with a concentration of 0.05-0.1mol/L, dissolve bismuth nitrate in deionized water to obtain a bismuth nitrate solution with a concentration of 0.1-0.25mol/L, slowly mix the two solutions, magnetically stir for 30-45min, transfer the mixture to a high-pressure reaction kettle, and react at 160 ℃ for 24 hours to obtain bismuth tungstate.
4. The preparation method according to claim 3, wherein the step (1) further comprises cooling to room temperature after the hydrothermal reaction is finished, respectively centrifugally washing the precipitate with ethanol and deionized water, and drying at 50-60 ℃ for 10-12 h.
5. The preparation method according to claim 1, wherein the concentration of the reduced graphene oxide dispersion obtained in step (2) is preferably 1.0-1.5mg/mL, and the addition amount of the ascorbic acid is 1/10-1/15 of the mass of the graphene oxide.
6. The preparation method according to claim 1, wherein the mass ratio of bismuth tungstate to ferric nitrate in the step (3) is 60-10:1, such as 60:1, 40:1, 30:1, 20:1, 15:1, 12:1, 10: 1; in addition, the volume of the reduced graphene oxide dispersion liquid accounts for 15-25% of the total volume of the reaction system.
7. A bismuth tungstate/reduced graphene oxide/bismuth ferrite composite photocatalyst, which is prepared by the method of any one of claims 1 to 6.
8. An application of the bismuth tungstate/reduced graphene oxide/bismuth ferrite composite photocatalyst as claimed in claim 7 in degradation of organic dyes and/or antibiotics.
9. Use according to claim 8, wherein the organic dye and/or antibiotic is derived from industrial waste water, preferably wherein the concentration of the organic dye in the waste water is selected from the range of 20-40mg/L and the concentration of the antibiotic is 5-15 mg/L.
10. Use according to claim 8, wherein the organic dye is selected from: one or more than two of methylene blue, rhodamine B dye and Congo red; the antibiotic is selected from: one or more of norfloxacin, tetracycline, ciprofloxacin and enrofloxacin.
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