CN109331836A - It is a kind of to prepare β-Bi2O3/MnxZn1-xFe2O4The new method of composite magnetic catalysis material - Google Patents
It is a kind of to prepare β-Bi2O3/MnxZn1-xFe2O4The new method of composite magnetic catalysis material Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 47
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(III) oxide Inorganic materials O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 43
- 238000000034 method Methods 0.000 title claims abstract description 41
- 239000002131 composite material Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 claims abstract description 33
- 239000011159 matrix material Substances 0.000 claims abstract description 6
- 238000001354 calcination Methods 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 26
- 239000000725 suspension Substances 0.000 claims description 13
- 238000010907 mechanical stirring Methods 0.000 claims description 12
- 239000002243 precursor Substances 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000012065 filter cake Substances 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 8
- 230000003197 catalytic effect Effects 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- 230000000694 effects Effects 0.000 claims description 7
- 238000000227 grinding Methods 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 5
- 238000013019 agitation Methods 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 3
- 239000012153 distilled water Substances 0.000 claims description 2
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 2
- 229910000357 manganese(II) sulfate Inorganic materials 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- 238000005086 pumping Methods 0.000 claims 1
- 238000002604 ultrasonography Methods 0.000 claims 1
- 238000006731 degradation reaction Methods 0.000 abstract description 11
- 230000015556 catabolic process Effects 0.000 abstract description 10
- 230000001699 photocatalysis Effects 0.000 abstract description 10
- 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 abstract description 8
- 229940043267 rhodamine b Drugs 0.000 abstract description 8
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 6
- 238000007146 photocatalysis Methods 0.000 abstract description 6
- 238000011084 recovery Methods 0.000 abstract description 6
- 238000005265 energy consumption Methods 0.000 abstract description 4
- 238000005286 illumination Methods 0.000 abstract description 3
- 229910052724 xenon Inorganic materials 0.000 abstract description 3
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 abstract description 3
- 230000005389 magnetism Effects 0.000 abstract description 2
- 238000005297 material degradation process Methods 0.000 abstract description 2
- 239000000356 contaminant Substances 0.000 abstract 1
- 230000006641 stabilisation Effects 0.000 abstract 1
- 238000011105 stabilization Methods 0.000 abstract 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 59
- 239000011572 manganese Substances 0.000 description 52
- 239000011701 zinc Substances 0.000 description 51
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 13
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 10
- 238000004064 recycling Methods 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 6
- 238000005352 clarification Methods 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 239000011941 photocatalyst Substances 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000000862 absorption spectrum Methods 0.000 description 3
- 229910052797 bismuth Inorganic materials 0.000 description 3
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- 229910001289 Manganese-zinc ferrite Inorganic materials 0.000 description 2
- JIYIUPFAJUGHNL-UHFFFAOYSA-N [O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[Mn++].[Mn++].[Mn++].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Zn++].[Zn++] Chemical compound [O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[Mn++].[Mn++].[Mn++].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Zn++].[Zn++] JIYIUPFAJUGHNL-UHFFFAOYSA-N 0.000 description 2
- 229910000416 bismuth oxide Inorganic materials 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000005415 magnetization Effects 0.000 description 2
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 2
- 229940012189 methyl orange Drugs 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 229910052596 spinel Inorganic materials 0.000 description 2
- 239000011029 spinel Substances 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910017135 Fe—O Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 229910007541 Zn O Inorganic materials 0.000 description 1
- 229960000583 acetic acid Drugs 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 229940056319 ferrosoferric oxide Drugs 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000000593 microemulsion method Methods 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910000161 silver phosphate Inorganic materials 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
Classifications
-
- 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
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
-
- 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
-
- B01J35/33—
-
- B01J35/39—
-
- B01J35/613—
-
- 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
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
-
- 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
-
- 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
- C02F2101/38—Organic compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
Abstract
It is a kind of to prepare β-Bi2O3/MnxZn1‑xFe2O4The new method of composite magnetic catalysis material belongs to inorganic catalysis material field.The present invention is first prepared for soft magnetism matrix material Mn with hydro-thermal methodxZn1‑xFe2O4, then β-Bi prepared by hydro-thermal-co-precipitation-calcination process2O3/MnxZn1‑xFe2O4Composite magnetic catalysis material.The method of the present invention preparation process is simple, few using equipment sheet, and less energy consumption is at low cost.β-the Bi of preparation2O3/MnxZn1‑xFe2O4Magnetic property stabilization, large specific surface area, photocatalytic activity are high, under the xenon lamp irradiation of simulated solar irradiation, the rhodamine B solution for being 10mg/L with the composite magnetic catalysis material degradation 50mL concentration of 0.1g preparation, illumination 3h reaches 98.2% to the degradation rate of rhodamine B, it is 92.0% to the degradation rate of rhodamine B after reusing 3 times, average recovery rate 89.7%.The product that the present invention prepares can be widely used in the field of photocatalysis degradation organic contaminant.
Description
Technical field
β-Bi is prepared the present invention relates to a kind of2O3/MnxZn1-xFe2O4The new method of composite magnetic catalysis material, belongs to nothing
Machine catalysis material technical field.
Background technique
Photocatalitic Technique of Semiconductor due to degradation in terms of have boundless application prospect, by
Gradually become one of the heat subject of research.The development of Photocatalitic Technique of Semiconductor is concentrated mainly on both direction, first is that tradition
The research of catalysis material titanium dioxide, but its greater band gap, can only absorb ultraviolet light, not have to the visible light for accounting for solar energy 43%
There is response；Second is that carrying out other novel photocatalysis material (such as Ag3PO4And its compound, sulfide, bismuth based compound and cobalt race
Close object etc.) development and its application.Wherein the bismuth oxide in bismuth based compound because the features such as band gap is narrow, absorbing wavelength is larger by
Concern, becomes one of the hot spot of novel photocatalysis developing material.In the development of novel photocatalysis material, β-Bi2O3(beta oxidation
Bismuth) be typical tetragonal semiconductor light-catalyst, it is visible greater than 400nm to can absorb wavelength band gap 2.58eV
Light.β-Bi2O3Preparation method mainly have chemical precipitation method, sol-gel method, micro emulsion method, hydrothermal synthesis method and solid phase room temperature method
Deng.Photochemical catalyst is in suspension in light-catalyzed reaction system more, pulpous state is presented after light reaction, it is difficult to separation and recycling and reusing
It is the principal element for restricting catalysis material application process.Composite magnetic catalysis material realizes that recycling is sharp again by externally-applied magnetic field
With overcoming the defect that suspension catalysis material is not easily recycled.
MnxZn1-xFe2O4(manganese-zinc ferrite) and traditional metal soft magnetic material such as Fe3O4(ferroso-ferric oxide) is compared, no
Only have the characteristics that high saturation and magnetic intensity, high magnetic permeability, and stable etc. with high production efficiency, at low cost and properties of product
Advantage.Therefore, with MnxZn1-xFe2O4The magnetism for preparing composite photo-catalyst for magnetic matrix is strong, convenient for separating and recycling.
The research of composite magnetic catalysis material at this stage, which is concentrated mainly on, improves its catalytic activity, and studies and how to prepare
The report for the composite magnetic catalysis material that high catalytic activity is stable and the rate of recovery is high is less.Such as a kind of patent of invention " MnZn iron
Oxysome-bismuth oxide magnetic photocatalyst preparation method " (publication number: CN104437536A) (documents 1), disclosed method
It is: prepares Mn first with roasting methodxZn1-xFe2O4, impregnation-calcination method is recycled to prepare MnxZn1-xFe2O4/β-Bi2O3Compound magnetic
Property catalysis material.The major defect of this method is: (1) roasting method prepares manganese-zinc ferrite (MnxZn1-xFe2O4) temperature be
1200 DEG C, energy consumption is high, and the sample particle size prepared is larger, and specific surface area is smaller, is unfavorable for MnxZn1-xFe2O4With β-Bi2O3
Abundant combination, not can guarantee the stability of compound；(2) the compound β-Bi of roasting method preparation2O3/MnxZn1-xFe2O4Compare table
Area is smaller, is unfavorable for coming into full contact with and reacting for catalyst itself and organic pollutant in Photocatalytic Degradation Process；(3) it roasts
The Mn of method preparationxZn1-xFe2O4Coercivity is smaller, and magnetic holding capacity is limited, is unfavorable for MnxZn1-xFe2O4/β-Bi2O3Recycling
It utilizes.For another example " Research on Chemical Intermediates " the 8th phase of volume 40 in October, 2014 " Synthesis
and properties of magnetically separable Fe3O4/TiO2/Bi2O3Photocatalysts " (Magneto separate
Photochemical catalyst Fe3O4/TiO2/Bi2O3Preparation and performance) in (documents 2) text, Fe is prepared with solvent-thermal method3O4, then
Sol-gal process preparation Fe is respectively adopted3O4/TiO2And Fe3O4/TiO2/Bi2O3.The shortcoming of this method is: (1) this is compound
The efficiency of magnetic photocatalytic material is lower, the Fe under simulated solar irradiation3O4/TiO2/Bi2O3Composite magnetic catalysis material 150min
Degradation rate to methyl orange is 69%, the Fe of recycling3O4/TiO2/Bi2O3Degradation rate to methyl orange is 57.5%, and is not investigated
To the stress efficacy of dyestuff more difficult to degrade such as rhodamine B；(2) the composite magnetic catalysis material rate of recovery is not high, and only 80%；
(3) solvent-thermal method of use, sol-gel method prepare composite catalyst, and step of preparation process is complicated, and preparation process is time-consuming；(4)
Ethyl alcohol, glacial acetic acid dosage are big in preparation process, and production cost is higher, and a large amount of volatilizations are discharged in subsequent drying and heat treatment process
Property organic matter, pollutes atmospheric environment, and corrosion experiment equipment.
The Mn of hydro-thermal method preparationxZn1-xFe2O4It is the composite photocatalyst of matrix preparation by it with better magnetic stability
Material is more conducive to magnetic recycling, and without secondary pollution to environment；Hydro-thermal method has more compared to the product that roasting method is prepared
Small particle size and bigger specific surface area can preferably guarantee the firm connection between catalysis matrix and magnetic matrix, make
In conjunction with having better stability.Therefore, Mn is prepared using hydro-thermal methodxZn1-xFe2O4, then with β-Bi2O3Compound improvement β-Bi2O3
Catalytic effect, the rate of recovery and magnetic stability be very necessary.
Summary of the invention
The purpose of the present invention is the Bi for roasting method preparation2O3、MnxZn1-xFe2O4There are energy consumption height and compound object lights
The problems such as catalytic activity is unstable, magnetic holding capacity is limited proposes to prepare Mn using hydro-thermal methodxZn1-xFe2O4And hydro-thermal-is altogether
Precipitating-roasting method prepares β-Bi2O3/MnxZn1-xFe2O4The new method of composite magnetic catalysis material had both solved β-Bi2O3Hardly possible is returned
The problem of receipts, while the activity and stability of composite magnetic catalysis material are also improved, the process of preparing is simple, production
At low cost, the period is short, and catalytic activity is high, and convenient for separating and recycling from liquid phase suspension system by externally-applied magnetic field, after recycling
Catalysis material catalytic activity still with higher, both realization resource reutilizations of simple and efficient, in turn avoiding catalysis material can
It can bring secondary pollution.
β-Bi of the present invention2O3/MnxZn1-xFe2O4Composite magnetic catalysis material the preparation method is as follows:
(1)MnxZn1-xFe2O4Preparation
According to molar ratio ZnO:MnO:Fe2O3=13.3:32.8:53.9 weighs suitable zinc sulfate, ferric sulfate, sulphur respectively
Sour manganese, is added 25mL deionized water, and ultrasonic vibration makes it dissolve to obtain mixed solution；Under magnetic agitation effect, to mixed solution
Middle that certain density NaOH solution is added dropwise, the pH for adjusting solution is 13, continues to stir 15min；Solution after stirring is transferred to
In the reaction kettle of 100mL, it is made to react 5h at 200 DEG C；After the reaction was completed, cooling, suction filtration, filter cake use distilled water and second respectively
Alcohol washs 8 times, and dry 12h, grinding obtain Mn at 80 DEG CxZn1-xFe2O4。
(2)β-Bi2O3/MnxZn1-xFe2O4The preparation of composite magnetic
Weigh the Bi (NO of 4mmol3)3·5H2O is added to the dilute HNO of 10mL3In, ultrasonic and mechanical stirring half an hour to solution
Above-mentioned clear solution, is added drop-wise to the Na of 40mL, 0.6mol/L by clarification with certain speed2CO3In solution, mechanical stirring 0.5h,
Obtain suspension A；It weighs and generates β-Bi with theoretical2O3Mass ratio is the Mn of 5~15:100xZn1-xFe2O4It is added to suspension A
In, mechanical stirring 2h is filtered, and filter cake is dried with baking oven, and grinding obtains precursor B；Precursor B is placed in Muffle furnace, 380
10min is roasted at DEG C, is taken out from Muffle furnace at once, obtains composite magnetic catalysis material β-Bi after cooling2O3/MnxZn1- xFe2O4。
The present invention by adopting the above technical scheme, mainly has the following effects:
(1) β-Bi of the method for the present invention preparation2O3/MnxZn1-xFe2O4Composite magnetic catalysis material light with higher is urged
Change activity, under the xenon lamp irradiation of simulated solar irradiation (340~800nm), β-Bi prepared by 0.1g2O3/MnxZn1-xFe2O4It is multiple
Closing magnetic photocatalytic material to be scattered in 50mL concentration is in 10mg/L rhodamine B solution, and illumination 3h, degradation rate reaches
98.2%.
(2) β-Bi of the method for the present invention preparation2O3/MnxZn1-xFe2O4Composite magnetic catalysis material is adding magnetic fields outside
Under, the rate of recovery after 3 reuses still reaches 92.0% to the degradation rate of rhodamine B in 89.7% or more, 3 reuse
Above (better than Bi prepared by documents one2O3/MnxZn1-xFe2O4)。
(3) present invention is reached using hydro-thermal-co-precipitation-calcination process preparation, composite magnetic catalysis material specific surface area
17.9m2/ g, stability is strong, and preparation manipulation is simple, and required equipment is few, and low energy consumption.
Detailed description of the invention
Fig. 1 is β-Bi2O3、MnxZn1-xFe2O4With β-Bi2O3/MnxZn1-xFe2O4X ray diffracting spectrum.
Fig. 2 is β-Bi2O3、MnxZn1-xFe2O4With β-Bi2O3/MnxZn1-xFe2O4Infrared spectrogram.
Fig. 3 is the hysteresis loop figure of magnetic sample.
Specific embodiment
With reference to embodiment, the present invention is further illustrated.
Embodiment 1
It is a kind of to prepare β-Bi2O3/MnxZn1-xFe2O4The new method of composite magnetic catalysis material, the specific steps are as follows:
(1)MnxZn1-xFe2O4Preparation
According to molar ratio ZnO:MnO:Fe2O3=13.3:32.8:53.9 weighs 1.28g ZnSO respectively4、7.72g Fe2
(SO4)3、1.84g MnSO4, 50mL deionized water is added, ultrasonic vibration makes it dissolve to obtain mixed solution；Magnetic agitation effect
Under, to the NaOH solution of mixed solution and dripping 5mol/L, the pH for adjusting solution is 13, continues to stir 15min；After stirring
Solution is transferred in the reaction kettle of 100mL, and 5h is reacted at 200 DEG C, and after the reaction was completed, cooling, suction filtration, filter cake is respectively with distillation
Water and ethanol washing 8 times, dry 12h, grinding obtain Mn at 80 DEG CxZn1-xFe2O4。
(2)β-Bi2O3/MnxZn1-xFe2O4The preparation of composite magnetic catalysis material
Weigh the Bi (NO of 4mmol3)3·5H2O is added to the dilute HNO of 10mL3In, ultrasonic and mechanical stirring half an hour to solution
Clarification；Above-mentioned clear solution is added drop-wise to the Na of 40mL, 0.6mol/L with certain speed2CO3In solution, mechanical stirring 0.5h,
Suspension A is obtained, weighs and generates β-Bi with theoretical2O3Mass ratio is the Mn of 5:100xZn1-xFe2O4It is added in suspension A, machine
Tool stirs 2h, filtering, and filter cake is dried with baking oven, and grinding obtains precursor B；Precursor B is placed in Muffle furnace, at 380 DEG C
10min is roasted, is taken out from Muffle furnace at once, obtains composite magnetic catalysis material β-Bi after cooling2O3/MnxZn1-xFe2O4。
Embodiment 2
It is a kind of to prepare β-Bi2O3/MnxZn1-xFe2O4The new method of composite magnetic catalysis material, the specific steps are as follows:
(1) with (1) in embodiment 1.
(2)β-Bi2O3/MnxZn1-xFe2O4The preparation of composite magnetic catalysis material
Weigh the Bi (NO of 4mmol3)3·5H2O is added to the dilute HNO of 10mL3In, ultrasonic and mechanical stirring half an hour to solution
Above-mentioned clear solution, is added drop-wise to the Na of 40mL, 0.6mol/L by clarification with certain speed2CO3In solution, mechanical stirring 0.5h,
Suspension A is obtained, weighs and generates β-Bi with theoretical2O3Mass ratio is the Mn of 10:100xZn1-xFe2O4It is added in suspension A, machine
Tool stirs 2h, filtering, and filter cake is dried with baking oven, and grinding obtains precursor B；Precursor B is placed in Muffle furnace, at 380 DEG C
10min is roasted, is taken out from Muffle furnace at once, obtains composite magnetic catalysis material β-Bi after cooling2O3/MnxZn1-xFe2O4。
Embodiment 3
It is a kind of to prepare β-Bi2O3/MnxZn1-xFe2O4The new method of composite magnetic catalysis material, the specific steps are as follows:
(1) with (1) in embodiment 1.
(2)β-Bi2O3/MnxZn1-xFe2O4The preparation of composite magnetic catalysis material
Weigh the Bi (NO of 4mmol3)3·5H2O is added to the dilute HNO of 10mL3In, ultrasonic and mechanical stirring half an hour to solution
Above-mentioned clear solution, is added drop-wise to the Na of 40mL, 0.6mol/L by clarification with certain speed2CO3In solution, mechanical stirring 0.5h,
Suspension A is obtained, weighs and generates β-Bi with theoretical2O3Mass ratio is the Mn of 15:100xZn1-xFe2O4It is added in suspension A, machine
Tool stirs 2h, filtering, and filter cake is dried with baking oven, and grinding obtains precursor B；Precursor B is placed in Muffle furnace, at 380 DEG C
10min is roasted, is taken out from Muffle furnace at once, obtains composite magnetic catalysis material β-Bi after waiting it to cool down2O3/MnxZn1- xFe2O4。
Experimental result
Composite magnetic catalysis material β-Bi prepared by embodiment 22O3/MnxZn1-xFe2O4Catalytic degradation activity is best.For
Facilitate comparison, is prepared for β-Bi2O3Sample.β-Bi2O3Preparation method is to be added without Mn in 2 step of implementing regulations (2)xZn1- xFe2O4。
β-Bi2O3XRD diagram such as Fig. 1 (b) shown in, each diffraction maximum both corresponds to pure β-Bi2O3Characteristic peak (JCPDS#27-
0050) the feature reflection peak, having includes { 210 }, { 201 }, { 220 }, { 222 }, { 200 } and { 400 } etc., this demonstrate that sample
Product are the β-Bi of pure square crystal structure2O3。β-Bi2O3Infrared absorption spectrum such as Fig. 2 (b) shown in, in 1383cm-1、
846.3cm-1、585.6cm-1The peak at place is for β-Bi2O3Typical Bi-O key absorption peak.
MnxZn1-xFe2O4XRD diagram such as Fig. 1 (a), its characteristic diffraction peak and spinel structure MnxZn1-xFe2O4
(JCPDS pdf document 7No.4-2400) crystal face corresponds, and shows the Mn of preparationxZn1-xFe2O4For spinel structure.
MnxZn1-xFe2O4Infrared absorption spectrum such as Fig. 2 (a) in, in 585.6cm-1And 472cm-1Two peaks that place occurs are respectively
The vibration peak of Zn-O, Fe-O key.MnxZn1-xFe2O4Magnetic parameter test such as Fig. 3 (a), saturation magnetization is
75.13emu/g, coercivity 34.98Oe.
Shown in XRD diffraction such as Fig. 1 (c) of composite magnetic catalysis material, MnxZn1-xFe2O4Introducing and for change β-
Bi2O3Crystal form, do not observe Mn in figurexZn1-xFe2O4Characteristic diffraction peak, this may be due in unit mass sample
MnxZn1-xFe2O4Content it is lower, and MnxZn1-xFe2O4Peak by β-Bi2O3Caused by strong diffraction maximum is covered.β-Bi2O3/
MnxZn1-xFe2O4Infrared absorption spectrum such as Fig. 2 (c), with 585.6cm-1And 472cm-1The Mn at placexZn1-xFe2O4Feature
Absorption peak, the whole process that further explanation load prepares catalyst do not change MnxZn1-xFe2O4This body structure, show
MnxZn1-xFe2O4Be it is existing, good supplement has been done to XRD result；In 1383cm-1、846.3cm-1、585.6cm-1Place
Bi-O key absorption peak illustrates the β-Bi that sample contains complete crystal form2O3。β-Bi2O3/MnxZn1-xFe2O4Magnetic parameter such as Fig. 3
(b), saturation magnetization and coercivity are respectively 9.22emu/g and 49.90Oe.
Photocatalysis experiment display, under the xenon lamp irradiation of simulated solar irradiation, with the composite magnetic photocatalysis material of 0.1g preparation
The rhodamine B solution that material degradation 50mL concentration is 10mg/L, illumination 3h reach 98.2% to the degradation rate of rhodamine B, and recycling makes
It is 92.0% with 3 degradation rates；Test shows that the average recovery rate recycled three times is 89.7%, illustrates using present invention system
Standby β-Bi2O3/MnxZn1-xFe2O4Composite magnetic catalysis material photocatalytic activity with higher and stability.
Claims (2)
1. a kind of prepare β-Bi2O3/MnxZn1-xFe2O4The new method of composite magnetic catalysis material, method include following step
It is rapid:
(1)MnxZn1-xFe2O4Preparation: according to molar ratio ZnO:MnO:Fe2O3=13.3:32.8:53.9, weighs 1.28g respectively
ZnSO4、7.72g Fe2(SO4)3、1.84g MnSO4, be added 50mL deionized water, ultrasonic vibration make it dissolve to obtain mix it is molten
Liquid；Under magnetic agitation effect, to the NaOH solution of mixed solution and dripping 5mol/L, the pH for adjusting solution is 13, continues to stir
15min；Solution after stirring is transferred in the reaction kettle of 100mL, 5h is reacted at 200 DEG C, after the reaction was completed, cooling, pumping
Filter, filter cake use distilled water and ethanol washing 8 times respectively, and dry 12h, grinding obtain Mn at 80 DEG CxZn1-xFe2O4；
(2)β-Bi2O3/MnxZn1-xFe2O4The preparation of composite magnetic: the Bi (NO of 4mmol is weighed3)3·5H2O is added to
The dilute HNO of 10mL3In, ultrasound simultaneously clarify by mechanical stirring half an hour to solution, and above-mentioned clear solution is added drop-wise to certain speed
The Na of 40mL, 0.6mol/L2CO3In solution, mechanical stirring 0.5h obtains suspension A；It weighs and generates β-Bi with theoretical2O3Quality
Than the Mn for 5~15:100xZn1-xFe2O4It is added in suspension A, mechanical stirring 2h, filters, filter cake is dried with baking oven, is ground
Obtain precursor B；Precursor B is placed in Muffle furnace, 10min is roasted at 380 DEG C, is taken out from Muffle furnace at once, it is cooling
After obtain composite magnetic catalysis material β-Bi2O3/MnxZn1-xFe2O4。
2. β-Bi according to claim 12O3/MnxZn1-xFe2O4The preparation method of composite magnetic catalysis material, it is special
Sign is hydro-thermal-co-precipitation-calcination process preparation, realizes catalytic active component β-Bi2O3With magnetic matrix MnxZn1-xFe2O4Between
Firm connection.
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