CN107175112A - A kind of micro motor photochemical catalyst and its preparation method and application - Google Patents
A kind of micro motor photochemical catalyst and its preparation method and application Download PDFInfo
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- CN107175112A CN107175112A CN201710321670.7A CN201710321670A CN107175112A CN 107175112 A CN107175112 A CN 107175112A CN 201710321670 A CN201710321670 A CN 201710321670A CN 107175112 A CN107175112 A CN 107175112A
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- micro motor
- photochemical catalyst
- znfe
- dyestuff
- waste water
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- 239000003054 catalyst Substances 0.000 title claims abstract description 75
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 229910001308 Zinc ferrite Inorganic materials 0.000 claims abstract description 45
- 239000000975 dye Substances 0.000 claims abstract description 28
- 239000002351 wastewater Substances 0.000 claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 230000015556 catabolic process Effects 0.000 claims abstract description 18
- 238000006731 degradation reaction Methods 0.000 claims abstract description 18
- GEYXPJBPASPPLI-UHFFFAOYSA-N manganese(III) oxide Inorganic materials O=[Mn]O[Mn]=O GEYXPJBPASPPLI-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000002105 nanoparticle Substances 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims abstract description 6
- 239000004005 microsphere Substances 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 24
- 229910002554 Fe(NO3)3·9H2O Inorganic materials 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 20
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 15
- 238000001354 calcination Methods 0.000 claims description 13
- 230000003197 catalytic effect Effects 0.000 claims description 12
- 229910003145 α-Fe2O3 Inorganic materials 0.000 claims description 11
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 10
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 10
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 238000004088 simulation Methods 0.000 claims description 8
- 238000013019 agitation Methods 0.000 claims description 5
- 238000007865 diluting Methods 0.000 claims description 5
- 238000004821 distillation Methods 0.000 claims description 5
- 239000012153 distilled water Substances 0.000 claims description 5
- 235000011187 glycerol Nutrition 0.000 claims description 5
- 229910052738 indium Inorganic materials 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 11
- 230000009286 beneficial effect Effects 0.000 abstract description 4
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 3
- 239000000446 fuel Substances 0.000 abstract description 3
- 238000011084 recovery Methods 0.000 abstract description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 abstract 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 16
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 10
- 229960000907 methylthioninium chloride Drugs 0.000 description 10
- 238000006555 catalytic reaction Methods 0.000 description 5
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 238000013507 mapping Methods 0.000 description 4
- 238000007146 photocatalysis Methods 0.000 description 4
- 230000001699 photocatalysis Effects 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- -1 iron ion Chemical class 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000002957 persistent organic pollutant Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000003911 water pollution Methods 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 241001062009 Indigofera Species 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000011953 bioanalysis Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000001045 blue dye Substances 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 230000000875 corresponding effect Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- NNGHIEIYUJKFQS-UHFFFAOYSA-L hydroxy(oxo)iron;zinc Chemical compound [Zn].O[Fe]=O.O[Fe]=O NNGHIEIYUJKFQS-UHFFFAOYSA-L 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 230000005415 magnetization Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000002663 nebulization Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000003642 reactive oxygen metabolite Substances 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000013077 target material Substances 0.000 description 1
- 229910000859 α-Fe Inorganic materials 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
-
- B01J35/39—
-
- B01J35/51—
-
- 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
- C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
-
- 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
- C02F1/722—Oxidation by peroxides
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
- H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
-
- 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
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/026—Fenton's reagent
-
- 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
The invention discloses a kind of micro motor photochemical catalyst, with solvent structure α Fe2O3‑ZnFe2O4Micro motor photochemical catalyst microballoon, wherein ZnFe2O4A diameter of 0.4 0.8 μm of tiny balloon, sheet α Fe2O3And Mn2O3Nanoparticle growth is in ZnFe2O4On microballoon.The invention also discloses its preparation method and application.The micro motor photochemical catalyst of the present invention has magnetic microsphere structure, beneficial to recovery and magnetic control, and can be catalyzed H2O2Produce bubble and carry out autokinetic movement, in H2O2There is preferable degradation efficiency to the organic pollution in waste water from dyestuff under the UV Fenton reactions of participation, the efficient process available for waste water from dyestuff.The H in the reaction system2O2Not only as the reagent but also conduct propulsion α Fe that UV Fenton react2O3‑ZnFe2O4The fuel of micro motor.
Description
Technical field
Drive motor photochemical catalyst in terms of the present invention relates to a kind of sewage disposal, and in particular to a kind of micro motor light is urged
Agent and its preparation method and application.
Background technology
Today's society water pollution is increasingly severe, and waste water from dyestuff therein is one of pollution of most serious in water pollution,
Typically there are the methods such as absorption method, catalysis method, chemistry, bioanalysis to the processing of waste water from dyestuff.Catalysis method therein can be realized to difficulty
The profound oxidation of degradation material obtains harmless inorganic matter and is used widely, and photocatalysis technology non-secondary pollution.
Fenton and its correlated response, are oxides（Usually H2O2）With the reaction of iron ion, formed and aoxidize organic or nothing
The reactive oxygen species of machine compound（·OH）.Fenton methods are simple to operate, green non-poisonous, and superior oxidation susceptibility can be realized to difficulty
The profound oxidation of degradation material.But it could effectively play its catalytic action in strong acid, and produce iron cement is brought two
Secondary pollution, processing cost are high, the ultraviolet-aided Fenton that Fenton methods are combined with light technology（UV-Fenton）It can solve so
The problem of, and improve H2O2Utilization rate.
ZnFe2O4Energy gap is narrow, can be as catalyst and catalyst carrier, and with magnetic, beneficial to recovery, still
Its photocatalysis degradation organic contaminant effect is poor, ZnFe2O4Can be with α-Fe2O3It is compound, with H2O2Generation UV-Fenton reaction lifes
Carry out degradable organic pollutant into hydroxyl radical free radical.Micro motor is to be converted into the energy of chemical energy or other forms on micro-meter scale
The artificial device of mechanical energy.Type of drive has chemistry, magnetic field, light, ultrasonic wave etc., and conventional is that catalyst reacts with hydrogen peroxide
Produce bubble and be used as driving.The present invention is by ZnFe2O4With α-Fe2O3、Mn2O3It is compound, Mn2O3With H2O2Reaction generation oxygen nebulization
Motor movement, ZnFe2O4With α-Fe2O3With H2O2Reaction generation hydroxyl radical free radical carrys out degradable organic pollutant, by light-Fenton skills
Art is combined with motor carrys out degradable organic pollutant.H2O2As the Fenton reagents reacted and be used as promote micro motor fuel.This
The importance of invention motor is the method for opening the autonomous microcosmic cleaning systems of manufacture, and it can be defeated in no external energy
Worked in the case of entering, and to be worked than its static faster mode of homologue.
The content of the invention
It is an object of the invention to provide a kind of micro motor photochemical catalyst.
Present invention also offers the preparation method and application of the micro motor photochemical catalyst.
The present invention is achieved through the following technical solutions：
A kind of micro motor photochemical catalyst, with solvent structure α-Fe2O3-ZnFe2O4Micro motor photochemical catalyst microballoon, wherein
ZnFe2O4A diameter of 0.4-0.8 μm of tiny balloon, sheet α-Fe2O3And Mn2O3Nanoparticle growth is in ZnFe2O4On microballoon.
Described, α-Fe2O3-ZnFe2O4The particle diameter of micro motor photochemical catalyst microballoon is 0.5-1 μm.
A kind of preparation method of micro motor photochemical catalyst, is as made from following steps：
1）By Zn (CH3COO)2·2H2O and Fe (NO3)3·9H2O adds to reactor after adding to mixed solution, magnetic agitation 10min
Middle reaction, is cooled to room temperature after terminating, distillation water washing 3 times, drying obtains ZnFe2O4The presoma of tiny balloon；
2）3-5mL50% manganese nitrate solution is taken, distilled water diluting obtains manganese nitrate weak solution to 15mL；By Fe (NO3)3·9H2O
Add in manganese nitrate weak solution and be well mixed, add 0.5g ZnFe2O4The presoma of tiny balloon, impregnates, and filters, drying,
Calcining, is cooled to room temperature, obtains micro motor photochemical catalyst.
The step 1）In, mixed solution is as made from 18mL glycerine and 60mL isopropanol；Zn
(CH3COO)2·2H2O addition is 1mmol；Fe(NO3)3·9H2O addition is 2mmol；Reaction temperature is 180 DEG C, instead
It is 12h between seasonable, drying temperature is 80 DEG C.
The step 2）In, Fe (NO3)3·9H2O consumption is 200mg；Dip time is 2h；Drying temperature is 80 DEG C；
Calcining heat is 500 DEG C, and calcination time is 1h.
The micro motor photochemical catalyst is used for catalytic degradation waste water from dyestuff；In H2O2Under participation, ultraviolet light condition is simulated
Catalytic degradation waste water from dyestuff.
Described, organic concentration is 5mg/L in waste water from dyestuff, and the consumption of micro motor photochemical catalyst is 1g/L, H2O2With dye
Expect the volume ratio 1 of solution:50, the simulation ultraviolet light time is 1-45min.
Described, H2O2Concentration be 30%.
Beneficial effects of the present invention：
The micro motor photochemical catalyst of the present invention has magnetic microsphere structure, beneficial to recovery and magnetic control, and can be catalyzed H2O2Produce
Bubble carries out autokinetic movement, in H2O2Have under the UV-Fenton reactions of participation to the organic pollution in waste water from dyestuff preferable
Degradation efficiency, the efficient process available for waste water from dyestuff.The H in the reaction system2O2Both the reagent reacted as UV-Fenton
Again as propulsion α-Fe2O3-ZnFe2O4The fuel of micro motor.The preparation method mild condition of the present invention, consume energy small, preparation process
It is easily operated.
Brief description of the drawings
Fig. 1 is degraded figure of the micro motor photochemical catalyst of embodiment 1-3 preparations under simulation ultraviolet light to methylene blue.
Fig. 2 is that the SEM figures, EDS spectrograms, TEM, HRTEM and mapping of micro motor photochemical catalyst prepared by embodiment 3 shine
Piece.
In figure,（a）、（b）With（c）Scheme for the SEM of micro motor photochemical catalyst；（d）Composed for the EDS of micro motor photochemical catalyst
Figure；（e）Scheme for the TEM of micro motor photochemical catalyst；（f）For the HRTEM photos of micro motor photochemical catalyst,（g）、（h）、（i）With（j）
It is corresponding micro motor photochemical catalyst mapping pictures.
Fig. 3 is the XRD curves of micro motor photochemical catalyst prepared by embodiment 3.
Fig. 4 is ZnFe prepared by embodiment 32O4The SEM figures of tiny balloon.
Fig. 5 is the hysteresis curve of the micro motor photochemical catalyst of the preparation of embodiment 3 at room temperature.
Fig. 6 is the micro motor photochemical catalyst of the preparation of embodiment 3 to the ultraviolet-visible light after the different catalysis times of methylene blue
Spectrogram.
Embodiment
With reference to embodiment, the present invention will be further described.
Embodiment 1
A kind of micro motor photochemical catalyst, with solvent structure α-Fe2O3-ZnFe2O4Micro motor photochemical catalyst microballoon, wherein
ZnFe2O4A diameter of 0.4-0.8 μm of tiny balloon, sheet α-Fe2O3And Mn2O3Nanoparticle growth is in ZnFe2O4On microballoon.
Described, α-Fe2O3-ZnFe2O4The particle diameter of micro motor photochemical catalyst microballoon is 0.5-1 μm.
A kind of preparation method of micro motor photochemical catalyst, is as made from following steps：
1）By Zn (CH3COO)2·2H2O and Fe (NO3)3·9H2O adds to reactor after adding to mixed solution, magnetic agitation 10min
Middle reaction, is cooled to room temperature after terminating, distillation water washing 3 times, drying obtains ZnFe2O4The presoma of tiny balloon；
The step 1）In, mixed solution is as made from 18mL glycerine and 60mL isopropanol；Zn(CH3COO)2·
2H2O addition is 1mmol；Fe(NO3)3·9H2O addition is 2mmol；Reaction temperature is 180 DEG C, and the reaction time is
12h, drying temperature is 80 DEG C.
2）3mL50% manganese nitrate solution is taken, distilled water diluting obtains manganese nitrate weak solution to 15mL；By Fe (NO3)3·
9H2O is added in manganese nitrate weak solution and is well mixed, and adds 0.5g ZnFe2O4The presoma of tiny balloon, impregnates, filtering,
Drying, calcining, is cooled to room temperature, obtains micro motor photochemical catalyst.
The step 2）In, Fe (NO3)3·9H2O consumption is 200mg；Dip time is 2h；Drying temperature is 80 DEG C；
Calcining heat is 500 DEG C, and calcination time is 1h.
The micro motor photochemical catalyst is used for catalytic degradation waste water from dyestuff；In H2O2Under participation, ultraviolet light condition is simulated
Catalytic degradation waste water from dyestuff.
Described, organic concentration is 5mg/L in waste water from dyestuff, and the consumption of micro motor photochemical catalyst is 1g/L, H2O2With dye
Expect the volume ratio 1 of solution:50, the simulation ultraviolet light time is 1-45min.
Described, H2O2Concentration be 30%.
Embodiment 2
A kind of micro motor photochemical catalyst, with solvent structure α-Fe2O3-ZnFe2O4Micro motor photochemical catalyst microballoon, wherein
ZnFe2O4A diameter of 0.4-0.8 μm of tiny balloon, sheet α-Fe2O3And Mn2O3Nanoparticle growth is in ZnFe2O4On microballoon.
Described, α-Fe2O3-ZnFe2O4The particle diameter of micro motor photochemical catalyst microballoon is 0.5-1 μm.
A kind of preparation method of micro motor photochemical catalyst, is as made from following steps：
1）By Zn (CH3COO)2·2H2O and Fe (NO3)3·9H2O adds to reactor after adding to mixed solution, magnetic agitation 10min
Middle reaction, is cooled to room temperature after terminating, distillation water washing 3 times, drying obtains ZnFe2O4The presoma of tiny balloon；
2）4mL50% manganese nitrate solution is taken, distilled water diluting obtains manganese nitrate weak solution to 15mL；By Fe (NO3)3·9H2O adds
It is well mixed into manganese nitrate weak solution, adds 0.5g ZnFe2O4The presoma of tiny balloon, is impregnated, and filters, and drying is forged
Burn, be cooled to room temperature, obtain micro motor photochemical catalyst.
The step 1）In, mixed solution is as made from 18mL glycerine and 60mL isopropanol；Zn
(CH3COO)2·2H2O addition is 1mmol；Fe(NO3)3·9H2O addition is 2mmol；Reaction temperature is 180 DEG C, instead
It is 12h between seasonable, drying temperature is 80 DEG C.
The step 2）In, Fe (NO3)3·9H2O consumption is 200mg；Dip time is 2h；Drying temperature is 80 DEG C；
Calcining heat is 500 DEG C, and calcination time is 1h.
The micro motor photochemical catalyst is used for catalytic degradation waste water from dyestuff；In H2O2Under participation, ultraviolet light condition is simulated
Catalytic degradation waste water from dyestuff.
Described, organic concentration is 5mg/L in waste water from dyestuff, and the consumption of micro motor photochemical catalyst is 1g/L, H2O2With dye
Expect the volume ratio 1 of solution:50, the simulation ultraviolet light time is 1-45min.
Described, H2O2Concentration be 30%.
Embodiment 3
A kind of micro motor photochemical catalyst, with solvent structure α-Fe2O3-ZnFe2O4Micro motor photochemical catalyst microballoon, wherein
ZnFe2O4A diameter of 0.4-0.8 μm of tiny balloon, sheet α-Fe2O3And Mn2O3Nanoparticle growth is in ZnFe2O4On microballoon.
Described, α-Fe2O3-ZnFe2O4The particle diameter of micro motor photochemical catalyst microballoon is 0.5-1 μm.
A kind of preparation method of micro motor photochemical catalyst, is as made from following steps：
1）By Zn (CH3COO)2·2H2O and Fe (NO3)3·9H2O adds to reactor after adding to mixed solution, magnetic agitation 10min
Middle reaction, is cooled to room temperature after terminating, distillation water washing 3 times, drying obtains ZnFe2O4The presoma of tiny balloon；
2）5mL50% manganese nitrate solution is taken, distilled water diluting obtains manganese nitrate weak solution to 15mL；By Fe (NO3)3·9H2O adds
It is well mixed into manganese nitrate weak solution, adds 0.5g ZnFe2O4The presoma of tiny balloon, is impregnated, and filters, and drying is forged
Burn, be cooled to room temperature, obtain micro motor photochemical catalyst.
The step 1）In, mixed solution is as made from 18mL glycerine and 60mL isopropanol；Zn
(CH3COO)2·2H2O addition is 1mmol；Fe(NO3)3·9H2O addition is 2mmol；Reaction temperature is 180 DEG C, instead
It is 12h between seasonable, drying temperature is 80 DEG C.
The step 2）In, Fe (NO3)3·9H2O consumption is 200mg；Dip time is 2h；Drying temperature is 80 DEG C；
Calcining heat is 500 DEG C, and calcination time is 1h.
The micro motor photochemical catalyst is used for catalytic degradation waste water from dyestuff；In H2O2Under participation, ultraviolet light condition is simulated
Catalytic degradation waste water from dyestuff.
Described, organic concentration is 5mg/L in waste water from dyestuff, and the consumption of micro motor photochemical catalyst is 1g/L, H2O2With dye
Expect the volume ratio 1 of solution:50, the simulation ultraviolet light time is 1-45min.
Described, H2O2Concentration be 30%.
Test case
Fig. 1 is degraded figure of the micro motor photochemical catalyst of embodiment 1-3 preparations under simulation ultraviolet light to methylene blue.With methylene
Organic pollution in base indigo plant solution dye wastewater, micro motor photochemical catalyst prepared by testing example 1-3 is ultraviolet in simulation
Degradation effect under light.Its method is：0.05g micro motor photochemical catalysts are taken to be put into 50mL5mg/L methylene blue solution, first
30min is placed under dark surrounds, to adsorption equilibrium.After adsorption saturation, 1mL30% H is added in methylene blue solution2O2,
UV-Fenton reactions are carried out under 500W Hg lamp irradiations, 4mL methylene blues are taken out after light irradiation 5,15,25,35,45min molten
Liquid centrifuges 5min as sample under 4000r/min, and it is molten to test methylene blue under different catalysis times with spectrophotometer
The absorbance of liquid is simultaneously converted into concentration, to characterize degradation effect.As seen from the figure, the micro motor prepared by 1-3 of the embodiment of the present invention
Photochemical catalyst is respectively 93.9%, 96.6% and 98.9% to methylene blue degradation rate in 45min, is shown prepared by embodiment 1-3
Micro motor photochemical catalyst efficient catalytic effect is respectively provided with to methylene blue dye, the efficient process available for waste water from dyestuff.
Fig. 2 is that the SEM figures, EDS spectrograms, TEM, HRTEM and mapping of micro motor photochemical catalyst prepared by embodiment 3 shine
Piece.In figure,（a）、（b）With（c）Scheme for the SEM of micro motor photochemical catalyst, it can be seen that the α-Fe prepared2O3-
ZnFe2O4Micro motor photochemical catalyst microballoon is uniformly dispersed, and is flower-shaped spherical, diameter is about 0.5-1 μm.（d）For micro motor photocatalysis
The EDS spectrograms of agent, by analysis, contain the elements, its mol ratio Zn such as Zn, Fe, Mn, O in sample：Fe：Mn：O=5.19：
37.63：7.94：49.24, this is consistent with expected stoichiometry.（e）Scheme for the TEM of micro motor photochemical catalyst, it can be seen that
ZnFe2O4And Mn2O3The position of the pore of nano particle correspondence thereon, α-Fe2O3Nanometer sheet is shown as in figure, this with
The result obtained in SEM photograph is consistent, indirectly demonstrates the successful synthesis of micro motor photochemical catalyst target material.（f）For
The HRTEM photos of micro motor photochemical catalyst, it can be seen that 0.487nm and 0.298nm are corresponded to and ZnFe respectively2O4(111) and
(220) crystal face, 0.270nm correspondence α-Fe2O3(104) crystal face, 0.277nm correspondence Mn2O3(104) crystal face.（g-j）It is phase
The micro motor photochemical catalyst mapping pictures answered, it was demonstrated that O, Zn, Fe and Mn coexist in α-Fe2O3-ZnFe2O4Micro motor photocatalysis
In agent microballoon.
Fig. 3 is the XRD curves of micro motor photochemical catalyst prepared by embodiment 3.It can be seen from XRD spectra sample by
ZnFe2O4、α-Fe2O3And Mn2O3Composition.
Fig. 4 is ZnFe prepared by embodiment 32O4The SEM figures of tiny balloon.As can be seen from the figure ZnFe2O4More to divide
Dissipate, the more uniform tiny balloon of size.Prepared ZnFe2O4Tiny balloon diameter is about 0.4-0.8um, and each is hollow
Microballoon is assembled by nano particle.
Fig. 5 is micro motor photochemical catalyst hysteresis curve at room temperature prepared by embodiment 3, scope from -10KOe to 10KOe,
Saturation magnetization is 1.37emug-1, remanent magnetism is 1.72 × 10-3emug-1, coercivity is 0.62Oe.As we can see from the figure
The hysteresis curve of micro motor photochemical catalyst microballoon is classical S type curves, shows as superparamagnetism.
Fig. 6 is the micro motor photochemical catalyst of the preparation of embodiment 3 to the ultraviolet-visible light after the different catalysis times of methylene blue
Spectrogram.As seen from the figure, there is maximum peak at 664nm, with the increase of light-Fenton times, each peak of methylene blue is obvious
Decline, be almost wholly absent after 45 minutes.
Claims (8)
1. a kind of micro motor photochemical catalyst, it is characterised in that with solvent structure α-Fe2O3-ZnFe2O4Micro motor photochemical catalyst
Microballoon, wherein ZnFe2O4A diameter of 0.4-0.8 μm of tiny balloon, sheet α-Fe2O3And Mn2O3Nanoparticle growth exists
ZnFe2O4On microballoon.
2. micro motor photochemical catalyst according to claim 1, it is characterised in that the α-Fe2O3-ZnFe2O4Micro motor light
The particle diameter of catalyst microspheres is 0.5-1 μm.
3. the preparation method of the micro motor photochemical catalyst described in a kind of claim 1, it is characterised in that be made by following steps
's：
1）By Zn (CH3COO)2·2H2O and Fe (NO3)3·9H2O adds to reactor after adding to mixed solution, magnetic agitation 10min
Middle reaction, is cooled to room temperature after terminating, distillation water washing 3 times, drying obtains ZnFe2O4The presoma of tiny balloon；
2）3-5mL50% manganese nitrate solution is taken, distilled water diluting obtains manganese nitrate weak solution to 15mL；By Fe (NO3)3·9H2O
Add in manganese nitrate weak solution and be well mixed, add 0.5g ZnFe2O4The presoma of tiny balloon, impregnates, and filters, drying,
Calcining, is cooled to room temperature, obtains micro motor photochemical catalyst.
4. preparation method according to claim 3, it is characterised in that the step 1）In, mixed solution is by 18mL
Made from glycerine and 60mL isopropanol；Zn(CH3COO)2·2H2O addition is 1mmol；Fe(NO3)3·9H2O's adds
Enter amount for 2mmol；Reaction temperature is 180 DEG C, and the reaction time is 12h, and drying temperature is 80 DEG C.
5. preparation method according to claim 3, it is characterised in that the step 2）In, Fe (NO3)3·9H2O consumption
For 200mg；Dip time is 2h；Drying temperature is 80 DEG C；Calcining heat is 500 DEG C, and calcination time is 1h.
6. the application of the micro motor photochemical catalyst described in a kind of claim 1, it is characterised in that the micro motor photochemical catalyst is used
In catalytic degradation waste water from dyestuff；In H2O2Under participation, ultraviolet light condition catalytic degradation waste water from dyestuff is simulated.
7. application according to claim 6, it is characterised in that organic concentration is 5mg/L, micro- horse in the waste water from dyestuff
Consumption up to photochemical catalyst is 1g/L, H2O2With the volume ratio 1 of dye solution:50, the simulation ultraviolet light time is 1-45min.
8. application according to claim 7, it is characterised in that the H2O2Concentration be 30%.
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