CN106311109A - Embedded hollow magnetic imprinted photocatalytic nanoreactor and preparation method thereof - Google Patents
Embedded hollow magnetic imprinted photocatalytic nanoreactor and preparation method thereof Download PDFInfo
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- CN106311109A CN106311109A CN201610753333.0A CN201610753333A CN106311109A CN 106311109 A CN106311109 A CN 106311109A CN 201610753333 A CN201610753333 A CN 201610753333A CN 106311109 A CN106311109 A CN 106311109A
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- 230000001699 photocatalysis Effects 0.000 title claims abstract description 103
- 238000002360 preparation method Methods 0.000 title claims abstract description 36
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 claims abstract description 31
- 229910001308 Zinc ferrite Inorganic materials 0.000 claims abstract description 27
- NNGHIEIYUJKFQS-UHFFFAOYSA-L hydroxy(oxo)iron;zinc Chemical compound [Zn].O[Fe]=O.O[Fe]=O NNGHIEIYUJKFQS-UHFFFAOYSA-L 0.000 claims abstract description 10
- 239000004098 Tetracycline Substances 0.000 claims description 29
- 229960002180 tetracycline Drugs 0.000 claims description 29
- 229930101283 tetracycline Natural products 0.000 claims description 29
- 235000019364 tetracycline Nutrition 0.000 claims description 29
- 150000003522 tetracyclines Chemical class 0.000 claims description 28
- 238000006243 chemical reaction Methods 0.000 claims description 24
- 238000006555 catalytic reaction Methods 0.000 claims description 19
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 18
- 238000013019 agitation Methods 0.000 claims description 18
- 230000015556 catabolic process Effects 0.000 claims description 18
- 238000006731 degradation reaction Methods 0.000 claims description 18
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 14
- 238000007146 photocatalysis Methods 0.000 claims description 12
- 239000000047 product Substances 0.000 claims description 12
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 12
- 239000012265 solid product Substances 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 8
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 7
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 7
- 239000012279 sodium borohydride Substances 0.000 claims description 7
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 claims description 6
- 238000007664 blowing Methods 0.000 claims description 6
- 238000013033 photocatalytic degradation reaction Methods 0.000 claims description 6
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 6
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 5
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims description 5
- 239000005695 Ammonium acetate Substances 0.000 claims description 5
- 229940043376 ammonium acetate Drugs 0.000 claims description 5
- 235000019257 ammonium acetate Nutrition 0.000 claims description 5
- 239000012153 distilled water Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 4
- JMGZBMRVDHKMKB-UHFFFAOYSA-L disodium;2-sulfobutanedioate Chemical compound [Na+].[Na+].OS(=O)(=O)C(C([O-])=O)CC([O-])=O JMGZBMRVDHKMKB-UHFFFAOYSA-L 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000000693 micelle Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 229910052709 silver Inorganic materials 0.000 claims description 4
- 239000004332 silver Substances 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- 239000011592 zinc chloride Substances 0.000 claims description 4
- 238000005352 clarification Methods 0.000 claims description 3
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 3
- WQQPDTLGLVLNOH-UHFFFAOYSA-M sodium;4-hydroxy-4-oxo-3-sulfobutanoate Chemical class [Na+].OC(=O)CC(C([O-])=O)S(O)(=O)=O WQQPDTLGLVLNOH-UHFFFAOYSA-M 0.000 claims description 3
- 229910001220 stainless steel Inorganic materials 0.000 claims description 3
- 239000010935 stainless steel Substances 0.000 claims description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- 230000001678 irradiating effect Effects 0.000 claims description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims 1
- 239000007789 gas Substances 0.000 claims 1
- -1 tetracycline compound Chemical class 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 7
- 238000000034 method Methods 0.000 abstract description 5
- 239000000178 monomer Substances 0.000 abstract description 3
- 239000013543 active substance Substances 0.000 abstract description 2
- 238000001179 sorption measurement Methods 0.000 description 12
- 230000000694 effects Effects 0.000 description 10
- 238000005516 engineering process Methods 0.000 description 9
- 238000010521 absorption reaction Methods 0.000 description 7
- 238000006552 photochemical reaction Methods 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 4
- 230000004087 circulation Effects 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- PZJWYUDBXNNVLZ-UHFFFAOYSA-N 1-cyclopropyl-7-(4-ethylpiperazin-1-yl)-6-fluoro-4-oxoquinoline-3-carboxylic acid;hydrochloride Chemical compound Cl.C1CN(CC)CCN1C(C(=C1)F)=CC2=C1C(=O)C(C(O)=O)=CN2C1CC1 PZJWYUDBXNNVLZ-UHFFFAOYSA-N 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 230000005415 magnetization Effects 0.000 description 3
- 238000002336 sorption--desorption measurement Methods 0.000 description 3
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000009977 dual effect Effects 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000011835 investigation Methods 0.000 description 2
- 238000004088 simulation Methods 0.000 description 2
- WHLUQAYNVOGZST-UHFFFAOYSA-N tifenamil Chemical group C=1C=CC=CC=1C(C(=O)SCCN(CC)CC)C1=CC=CC=C1 WHLUQAYNVOGZST-UHFFFAOYSA-N 0.000 description 2
- GKWLILHTTGWKLQ-UHFFFAOYSA-N 2,3-dihydrothieno[3,4-b][1,4]dioxine Chemical compound O1CCOC2=CSC=C21 GKWLILHTTGWKLQ-UHFFFAOYSA-N 0.000 description 1
- SPFYMRJSYKOXGV-UHFFFAOYSA-N Baytril Chemical compound C1CN(CC)CCN1C(C(=C1)F)=CC2=C1C(=O)C(C(O)=O)=CN2C1CC1 SPFYMRJSYKOXGV-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 229960000740 enrofloxacin Drugs 0.000 description 1
- 239000005447 environmental material Substances 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 238000001782 photodegradation Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
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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
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
- B01J19/12—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electromagnetic waves
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D3/00—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances
- A62D3/10—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by subjecting to electric or wave energy or particle or ionizing radiation
- A62D3/17—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by subjecting to electric or wave energy or particle or ionizing radiation to electromagnetic radiation, e.g. emitted by a laser
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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
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
- B01J19/12—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electromagnetic waves
- B01J19/122—Incoherent waves
- B01J19/123—Ultraviolet light
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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
- C02F1/30—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
- C02F1/30—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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
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- Chemical Kinetics & Catalysis (AREA)
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- General Health & Medical Sciences (AREA)
- Electromagnetism (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Engineering & Computer Science (AREA)
- Water Supply & Treatment (AREA)
- Life Sciences & Earth Sciences (AREA)
- Optics & Photonics (AREA)
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Abstract
The invention provides an embedded hollow magnetic imprinted photocatalytic nanoreactor and a preparation method thereof. The method comprises steps as follows: step 1, preparation of ZnFe2O4; step 2, preparation of PEDOT (poly(3,4-ethylenedioxythiophene)); step 3, preparation of Ag-PEDOT; step 4, preparation of the embedded hollow magnetic imprinted photocatalytic nanoreactor. PEDOT is adopted as a photocatalytic active substance and embedded in an organic imprinted layer as a functional monomer, so that a target object entering an imprinted hole through selective recognition can directly contact with the PEDOT and is degraded, the problem of low photocatalytic activity of a common imprinted photocatalytic material is solved, and the photocatalytic activity and selectivity are both improved.
Description
Technical field
The invention belongs to technical field of environmental material preparation, be specifically related to a kind of embedded hollow magnetic trace photocatalysis and receive
Rice reactor and preparation method thereof.
Background technology
Normal light catalytic nanometer reactor can not be comformed selective removal specific objective thing in multi-pollutant, and surface imprinted
Technology can give normal light catalytic nanometer reactor selective removal ability, but inorganic partly leads owing to surface imprinted layer can cover
The photocatalytic activity site of body, causes its degradation rate to be substantially reduced, and therefore, the present invention uses organic engram technology, organic trace
Photocatalysis system is as carrier material by the material without photocatalytic activity, and surface directly covers organic imprinted layer, will have simultaneously
Machine photocatalytic substance is incorporated in organic imprinted layer, and is exposed to inside trace hole, so that being entered by selectivity identification
The object in trace hole can directly contact organic photocatalytic substance and be degraded.
The photocatalytic activity of current most of organic photocatalytic substance is the most not ideal enough, urges at numerous organic light
Changing in active substance, the expression activitiy of poly-3,4-rthylene dioxythiophene (PEDOT) is high, has that molecular structure is simple, band gap is narrow, changes
Learn the advantage such as stable in properties, photoelectric properties uniqueness, be one of current popular research material.In order to promote its photocatalysis further
Activity, is continuing with Ag and carrys out load P EDOT, and the load of Ag can displaced the light induced electron that PEDOT produces effectively；In Tong Shi
Empty spherical ZnFe2O4The magnetic material excellent as a kind of physical and chemical performance, the intensity of magnetization is high, can improve normal light catalysis material
Separation and recovery ability.
Therefore, first inventor is prepared for hollow sphere ZnFe with solvent-thermal method2O4And with it as carrier；Simultaneously with 3,4-
Ethene dioxythiophene is monomer, is prepared for poly-3,4-rthylene dioxythiophene (PEDOT), and loaded Ag is prepared for Ag-further
PEDOT；Finally utilize organic engram technology and Microwave Emulsifier-Free Polymerization method, prepare embedded hollow magnetic trace photocatalytic nanometer anti-
Answer device.This photocatalytic nanometer reactor not only has good Magneto separate characteristic, also has high light catalysis activity and selectivity and knows
The ability of not/selective photocatalysis degraded tetracycline.
Summary of the invention
The present invention, with solvent-thermal method, organic engram technology and Microwave Emulsifier-Free Polymerization method etc. as preparation means, prepares a kind of embedding
Formula hollow magnetic trace photocatalytic nanometer reactor.Have an advantage in that to construct that both there is good Magneto separate characteristic, have again relatively
Highlight catalytic active, also has the most selective photocatalytic nanometer reactor；The introducing of organic engram technology imparts light and urges
Change the Selective recognition ability of nano-reactor；Using PEDOT in system is photocatalytic substance, and is considered as function list
Body is embedded in organic imprinted layer, so that being entered the object in trace hole by selectivity identification can directly contact PEDOT, from
And making it degrade, this is avoided the problem that common trace catalysis material photocatalytic activity is low, it is achieved that photocatalytic activity and selection
The dual lifting of property, simplifies preparation process simultaneously；The load of Ag, effectively displaced the light induced electron that PEDOT produces, enters one
Step improves photocatalytic activity；Additionally, carrier hollow sphere ZnFe2O4Introducing to impart photocatalytic nanometer reactor excellent
Magneto separate characteristic.
The technical solution used in the present invention is:
A kind of embedded hollow magnetic trace photocatalytic nanometer reactor, described embedded hollow magnetic trace photocatalysis
Nano-reactor is by ZnFe2O4, Ag, PEDOT and the alternative organic imprinted layer identifying tetracycline be composited；Described have
Machine imprinted layer is coated on ZnFe2O4Outer surface；Described Ag-PEDOT is to be supported on PEDOT by Ag；Described Ag-PEDOT is embedding
Enter in the middle of organic imprinted layer；This embedded hollow magnetic trace photocatalytic nanometer reactor of 0.02g is used for 100mL 20mg/
The simulated solar irradiation photocatalytic degradation of the tetracycline of L, in 120min, degradation rate has reached 71.77%.
The preparation method of a kind of embedded hollow magnetic trace photocatalytic nanometer reactor, is carried out as steps described below:
Step 1, ZnFe2O4Preparation:
By FeCl3·6H2O and ZnCl2Join in ethylene glycol, after forming the solution of clarification, add ammonium acetate, and
Stir under room temperature condition, afterwards this mixture is put into and stainless steel autoclave carries out constant temp. heating reaction, after reaction terminates, will be anti-
Answer still to be cooled to room temperature, collect solid product with Magnet and wash, more i.e. obtain ZnFe after solid product vacuum drying2O4；
Step 2, the preparation of poly-3,4-ethene dioxythiophene (PEDOT):
Double (2-second hexyl) sodium sulfo-succinates are dissolved in normal hexane, obtain mixed liquor A, add in mixed liquor A
Liquor ferri trichloridi, stirring, to forming reversed micelle solution, adds 3,4-rthylene dioxythiophene, ultrasonic, obtains mixed liquid B,
Mechanical agitation again, has reacted rear washed product and has been vacuum dried, and i.e. obtains poly-3,4-rthylene dioxythiophene (PEDOT)；
Step 3, the preparation of Ag-PEDOT:
Poly-3,4-rthylene dioxythiophene is joined in silver nitrate solution, ultrasonic mechanical agitation, obtain mixed liquor C, then by
It is added dropwise to sodium borohydride solution, obtains mixed liquor D, mechanical agitation, afterwards washed product being vacuum dried, obtain the poly-of silver load
3,4-rthylene dioxythiophene, is designated as Ag-PEDOT；
Step 4, the preparation of embedded hollow magnetic trace photocatalytic nanometer reactor:
By Ag-PEDOT and ZnFe2O4It is dispersed in the microwave reaction bottle containing dimethyl sulfoxide, obtains mixed liquor E, stirring,
It is added thereto to tetracycline again, obtains mixed liquor F, then mixed liquor F is kept in Dark Place under nitrogen atmosphere, the most wherein
Add trimethylol-propane trimethacrylate and azodiisobutyronitrile, obtain mixed liquor G, microwave reaction bottle is put into microwave
Reactor reacts, after reaction terminates, takes out reaction bulb washed product, after vacuum drying, then by above-mentioned dried solid
Product is immersed in the distilled water in light-catalyzed reaction bottle, puts in photochemical reactor by this light-catalyzed reaction bottle, stirring, logical
Air, after irradiating with simulated solar irradiation, washed product is also vacuum dried, and i.e. obtains embedded hollow magnetic trace photocatalytic nanometer
Reactor.
In step 1, the FeCl used3·6H2O、ZnCl2, the amount ratio of ethylene glycol and ammonium acetate be 4mmol:2mmol:
70mL:30mmol；The time of described stirring is 0.5h；The temperature of described constant temp. heating reaction is 210 DEG C, and the response time is 72h.
In step 2, during preparation mixed liquor A, double (2-second hexyl) sodium sulfo-succinate, the amount ratios of normal hexane used
For 3.8g:15mL；When preparing reversed micelle solution, the liquor ferri trichloridi used is 0.47 with the volume ratio of mixed liquor A:
15, the concentration of liquor ferri trichloridi is 10.2mol L-1；During preparation mixed liquid B, the 3,4-rthylene dioxythiophene used is with double
The mass ratio of (2-second hexyl) sodium sulfo-succinate is 0.45:3.8；The described ultrasonic time is 10min；Described churned mechanically
Time is 12h.
In step 3, when preparing mixed liquor C, the poly-3,4-rthylene dioxythiophene, the amount ratio of silver nitrate solution that are used are
1.45g、320mL；When preparing mixed liquor D, the sodium borohydride solution used is 16:19 with the volume ratio of mixed liquor C；Described nitre
The concentration of acid silver solution and sodium borohydride solution is 0.025mol L-1；The ultrasonic machinery mixing time of described mixed liquor C is
1h；The mechanical agitation time of described mixed liquor D is 1.5h.
In step 4, when preparing mixed liquor E, Ag-PEDOT, the ZnFe used2O4, the amount ratio of dimethyl sulfoxide be 0.001
～0.1g:0.1g:20mL；When preparing mixed liquor F, the tetracycline used is 0.05mmol with the amount ratio of dimethyl sulfoxide:
20mL；When preparing mixed liquor G, trimethylol-propane trimethacrylate, azodiisobutyronitrile and the dimethyl sulfoxide used
Amount ratio be 0.5mL:0.01g:20mL；Mixing time to mixed liquor E is 0.5h；The described time kept in Dark Place is 12h；
The described response time in microwave reactor is 0.1～2h, and reaction temperature is 60 DEG C, and power is 700W, magnetic agitation rotating speed
For 600rpm/min；Described after adding distilled water and being placed in photo catalysis reactor, the rotating speed of magnetic agitation is 600rpm/
Min, the flow velocity of blowing air is 2mL/min, and the time that simulated solar irradiation irradiates is 2h.
Additionally, this embedded hollow magnetic trace photocatalytic nanometer reactor also has good Selective recognition/light and urges
Change degradation capability.
Beneficial effects of the present invention:
(1) introducing of organic engram technology imparts the Selective recognition ability of photocatalytic nanometer reactor；
(2) using PEDOT in system is photocatalytic substance, and is considered as function monomer and is embedded into organic imprinted layer
In, so that being entered the object in trace hole by selectivity identification can directly contact PEDOT, so that its degraded, this is avoided
The problem that common trace catalysis material photocatalytic activity is low, it is achieved that photocatalytic activity and selective dual lifting, simultaneously
Simplify preparation process；
(3) load of Ag, effectively displaced the light induced electron that PEDOT produces, improves photocatalytic activity further；
(4) carrier hollow sphere ZnFe2O4Introducing impart the Magneto separate characteristic that photocatalytic nanometer reactor is excellent.
Accompanying drawing explanation
Fig. 1 is the XRD spectra of different sample, a be Ag-PEDOT, b be ZnFe2O4, c be embedded hollow magnetic trace light
Catalytic nanometer reactor；
Fig. 2 is the FT-IR spectrogram of different sample, and a is ZnFe2O4, b be that embedded hollow magnetic trace photocatalytic nanometer is anti-
Answer device；
Fig. 3 is TEM and the SEM spectrogram of different sample, a and c is ZnFe2O4, b and d be that embedded hollow magnetic trace light is urged
Change nano-reactor；
Fig. 4 is the N of embedded hollow magnetic trace photocatalytic nanometer reactor2Adsorption-desorption curve；
Fig. 5 is the outer diffuse-reflectance spectrogram of solid violet of different sample, and a is ZnFe2O4, b be that embedded hollow magnetic trace light is urged
Change nano-reactor；
Fig. 6 is the magnetization curve of different sample, and a is ZnFe2O4, b be embedded hollow magnetic trace photocatalytic nanometer reaction
Device；
Fig. 7 is the adsorption capacity investigation figure of different photocatalyst, and a is ZnFe2O4, b be Ag-PEDOT, c be embedded hollow
Magnetic blotting photocatalytic nanometer reactor；
Fig. 8 is that the photocatalysis of embedded hollow magnetic trace photocatalytic nanometer reactor is lived by different Ag-PEDOT addition
The impact of property；
Fig. 9 is the different Microwave Emulsifier-Free Polymerization time photocatalytic activities to embedded hollow magnetic trace photocatalytic nanometer reactor
Impact；
Figure 10 is that the photocatalytic activity contrast of different pollutant is investigated by different sample, and a is ZnFe2O4, b be Ag-PEDOT,
C be embedded hollow magnetic trace photocatalytic nanometer reactor, d be non-trace photocatalytic nanometer reactor；
Figure 11 is that under different cycle-index, the degradation rate of embedded hollow magnetic trace photocatalytic nanometer reactor is investigated.
Detailed description of the invention
Below in conjunction with being embodied as example, the present invention will be further described.
Adsorption activity is evaluated: is joined by 0.02g sample in the tetracycline of 100mL 20mg/L, is placed in dark place,
Design temperature is 30 DEG C, opens magnetic agitation (rotating speed is 600rpm/min), takes a sample every 10min, get 60min,
Measure out the concentration of tetracycline in liquid, and pass through formula: Q=(C0-C) V/m calculates its adsorption capacity Q, wherein C0At the beginning of tetracycline
Beginning concentration, the concentration of tetracycline when C is to reach adsorption equilibrium, V is the volume of solution, and m is the quality of the sample added.
Photocatalytic activity evaluation: carry out in GHX-3 type photochemical reaction instrument, by 0.02g sample and 100mL 20mg/L
Tetracycline join in light-catalyzed reaction bottle, then this light-catalyzed reaction bottle is put in light-catalyzed reaction instrument, sets temperature
Degree is 30 DEG C, after dark absorption a period of time, opens magnetic agitation (rotating speed is 600rpm/min), and (flow is 2mL/ to blowing air
Min), irradiate with simulated solar irradiation, take a sample every 20min, until 120min, measure out the concentration of tetracycline in liquid,
And pass through formula: Dr=(C0-C)×100/C0Calculate its degradation rate Dr, wherein C0For reaching concentration after adsorption equilibrium, when C is t
Carving the concentration of the tetracycline measured, t is the response time.
Selective evaluation: carry out in GHX-3 type photochemical reaction instrument, by 0.02g sample and the salt of 100mL 20mg/L
Acid enrofloxacin solution joins in light-catalyzed reaction bottle, then puts in light-catalyzed reaction instrument by this light-catalyzed reaction bottle, sets
Temperature is 30 DEG C, after dark absorption a period of time, opens magnetic agitation (rotating speed is 600rpm/min), and (flow is 2mL/ to blowing air
Min), irradiate with simulated solar irradiation, take a sample every 20min, until 120min, measure out Enrofloxacin HCL in liquid
Concentration, and pass through formula: Dr=(C0-C)×100/C0Calculate its degradation rate Dr, wherein C0For reaching concentration after adsorption equilibrium, C
For the concentration of the Enrofloxacin HCL solution that t measures, t is the response time.
Estimation of stability: carry out in GHX-3 type photochemical reaction instrument, urges embedded for 0.02g hollow magnetic trace light
The tetracycline changing nano-reactor and 100mL 20mg/L joins in light-catalyzed reaction bottle, then by this light-catalyzed reaction bottle
Putting in light-catalyzed reaction instrument, design temperature is 30 DEG C, and after dark absorption a period of time, (rotating speed is 600rpm/ to open magnetic agitation
Min), blowing air (flow is 2mL/min), irradiates 120min with simulated solar irradiation, measures out the concentration of tetracycline in liquid, and calculate
Go out its degradation rate Dr, the more embedded hollow magnetic trace photocatalytic nanometer reactor sample after separating carries out second time and circulates
Degradation experiment also calculates its degradation rate Dr, until terminating after the 5th circulation degradation experiment.
Embodiment 1:
(1)ZnFe2O4Preparation: by 4mmolFeCl3·6H2O and 2mmolZnCl2Join in 70mL ethylene glycol, formed
After the solution of clarification, add 30mmol ammonium acetate, and be stirred vigorously 0.5h at ambient temperature, afterwards this mixture is put into
Stainless steel autoclave seals, at 210 DEG C, keeps 72h, after question response still is cooled to room temperature, collect solid product also with Magnet
Washing, more i.e. obtain ZnFe after solid product is vacuum dried 12h at 40 DEG C2O4。
(2) preparation of poly-3,4-ethene dioxythiophene (PEDOT): double for 3.8g (2-second hexyl) sodium sulfo-succinates are dissolved
In 15mL normal hexane, it is added thereto to 0.47mL 10.2mol L the most again-1Liquor ferri trichloridi, stirring is to being formed reversely
Micellar solution, then the 3,4-rthylene dioxythiophene of 0.45g is joined in above-mentioned solution, after ultrasonic 10min, then mechanical agitation
12h, afterwards washed product and at 40 DEG C be vacuum dried 12h, i.e. obtain poly-3,4-rthylene dioxythiophene (PEDOT).
(3) preparation of Ag-PEDOT: 1.45g PEDOT is joined 320mL 0.025mol L-1Silver nitrate solution in
And ultrasonic mechanical agitation 1h, afterwards by 380mL 0.025mol L-1Sodium borohydride solution be added dropwise in above-mentioned beaker, then
Mechanical agitation 1.5h, afterwards washed product and at 40 DEG C be vacuum dried 12h, be designated as silver load poly-3,4-rthylene dioxythiophene
(Ag-PEDOT)。
(4) preparation of embedded hollow magnetic trace photocatalytic nanometer reactor: by 0.01gAg-PEDOT and
0.1gZnFe2O4It is dissolved in the special microwave reaction bulb containing 20mL dimethyl sulfoxide, stirs 0.5h, after reaction terminates, then to it
Middle addition 0.05mmol tetracycline, then keep in Dark Place under nitrogen atmosphere 12h by this solution, is added thereto to the most again
0.5mL trimethylol-propane trimethacrylate and 0.01g azodiisobutyronitrile, put into microwave reactor by microwave reaction bottle
In, design temperature is 60 DEG C, and power is 700W, and magnetic agitation rotating speed is 600rpm/min, reacts 1h, after reaction terminates, takes out
Reaction bulb washed product, be vacuum dried after 12h at 40 DEG C, more above-mentioned dried solid product is immersed into containing
In the light-catalyzed reaction bottle of 200mL distilled water, this light-catalyzed reaction bottle is put in photochemical reactor, open stirring and (set and turn
Speed is 600rpm/min), blowing air (sets flow velocity as 2mL/min), irradiates after 2h with simulated solar irradiation, washed product 40
After being vacuum dried 12h at DEG C, i.e. obtain embedded hollow magnetic trace photocatalytic nanometer reactor.
(5) take sample in 0.02g (4) in photochemical reaction instrument, carry out dark adsorption test, record this embedded hollow magnetic
Property trace photocatalytic nanometer reactor tetracycline adsorption capacity can be reached 1.47mg/g when the dark absorption of 30min, show
This embedded hollow magnetic trace photocatalytic nanometer reactor has preferable adsorption activity.
(6) take sample in 0.02g (4) in photochemical reaction instrument, carry out photocatalytic degradation test, record this embedded in
The photodegradation rate of tetracycline can be reached in the simulated solar irradiation of 120min irradiates by empty magnetic blotting photocatalytic nanometer reactor
To 71.77%, show that this embedded hollow magnetic trace photocatalytic nanometer reactor has preferable photocatalytic activity.
(7) take sample in 0.02g (4) and in photochemical reaction instrument, carry out photocatalytic degradation test, in the simulation of 120min
In sunlight, record this embedded hollow magnetic trace photocatalytic nanometer reactor and the photocatalysis of Enrofloxacin HCL is dropped
Solution rate.
(8) take sample in 0.02g (4) and in photochemical reaction instrument, carry out photocatalytic degradation test, in the simulation of 120min
Under sunlight, circulation experiment 5 times, record every time this embedded hollow magnetic trace photocatalytic nanometer reactor to tetracycline
Degradation rate.
Embodiment 2:
Carrying out by the embodiment 1 same step of preparation technology, except for the difference that in step (4), the addition of Ag-PEDOT is respectively
0.001g, 0.005g, 0.01g, 0.05g, 0.1g, prepare different embedded hollow magnetic trace photocatalytic nanometer reactions
Device, the addition of the different Ag-PEDOT of the investigation shadow to embedded hollow magnetic trace photocatalytic nanometer reactor photocatalytic activity
Ring, investigate the activity of light degradation tetracycline by (6) step in embodiment 1.Photocatalysis effect is as shown in Figure 8, it can be seen that
The embedded hollow magnetic trace photocatalytic nanometer reactor light degradation Fourth Ring prepared when the addition of Ag-PEDOT is 0.01g
The effect of element is best.
Embodiment 3:
Carrying out by the embodiment 1 same step of preparation technology, except for the difference that in step (4), the Microwave Emulsifier-Free Polymerization time is respectively
0.1h, 0.5h, 1h, 1.5h, 2h, prepare different embedded hollow magnetic trace photocatalytic nanometer reactors, investigates difference
The impact on embedded hollow magnetic trace photocatalytic nanometer reactor photocatalytic activity of the Microwave Emulsifier-Free Polymerization time, by embodiment 1
(6) step investigates the activity of light degradation tetracycline.Photocatalysis effect is as shown in Figure 9, it can be seen that when the Microwave Emulsifier-Free Polymerization time
The effect of the embedded hollow magnetic trace photocatalytic nanometer reactor light degradation tetracycline prepared during for 1h is best.
As can be seen from Figure 1: figure a and ZnFe2O4Standard spectrogram (PDF#65-3111) consistent, figure b Yu Ag mark
Quasi-spectrogram (PDF#65-2871) is consistent, Ag and ZnFe is described2O4The most successfully synthesize.Additionally, figure c does not contains only
ZnFe2O4Whole characteristic peaks, but also containing the strongest characteristic peak of Ag, this shows this embedded hollow magnetic trace photocatalysis
Containing ZnFe in the composition of nano-reactor2O4And Ag, but owing to the addition of Ag-PEDOT is fewer, the therefore spy of Ag in figure c
Levy peak smaller.
Fig. 2 is the FT-IR spectrogram of different sample, it can be seen that and ZnFe2O4Spectrogram ratio, embedded hollow magnetic
The spectrogram of property trace photocatalytic nanometer reactor is at 1716cm-1、1641cm-1、1331cm-1、1197cm-1、1076cm-1With
973cm-1Etc. occur in that extra absworption peak, wherein 1716cm-1Place is the characteristic absorption peak of-C=O, 1641cm-1Place is three
In TRIM in C=C or thiphene ring C=C absworption peak, 1331cm-1Place is in thiphene ring
The absworption peak of C-C and C=C, 1197cm-1And 1076cm-1Place is the characteristic absorption peak of C-O-C, 1189cm-1Place is the absorption of C-S
Peak.The appearance of above-mentioned absworption peak demonstrates organic imprinted layer by PEDOT, trimethylol-propane trimethacrylate and removal four
The trace hole composition stayed after ring element, and organic imprinted layer to do exist in embedded hollow magnetic trace photocatalytic nanometer anti-
Answer in device, illustrate that this embedded hollow magnetic trace photocatalytic nanometer reactor is successfully synthesized.
Fig. 3 is TEM and the SEM spectrogram of different sample, it can be seen that ZnFe from figure a and figure c2O4For in spherical and part
Hollow structure, diameter is about at about 470nm；Compared with figure a and figure c, figure b can be clearly observed an outer surface cladding
Layer, this shows that organic imprinted layer is the most successfully coated on ZnFe2O4Surface, additionally, from figure b and figure d it can be seen that
After being coated with organic imprinted layer, embedded hollow magnetic trace photocatalytic nanometer reactor remains as spherical and part hollow knot
Structure, diameter is about at about 480nm.
Fig. 4 is the N of embedded hollow magnetic trace photocatalytic nanometer reactor2Adsorption-desorption curve, can from figure
Go out, the N of embedded hollow magnetic trace photocatalytic nanometer reactor2Adsorption-desorption curve is iv type curve, belongs to mesoporous material
Material.Understand through calculating: the specific surface area of this embedded hollow magnetic trace photocatalytic nanometer reactor is 181.53m2/g。
From figure 5 it can be seen that ZnFe2O4There is preferable ultraviolet-ray visible absorbing, after being coated with organic imprinted layer, embedding
Enter formula hollow magnetic trace photocatalytic nanometer reactor and still there is good ultraviolet-ray visible absorbing ability；
Fig. 6 is the magnetization curve of different sample, it can be seen that ZnFe2O4Urge with embedded hollow magnetic trace light
Change nano-reactor and all have good magnetic saturation intensity, respectively 82.65emu/g and 69.36emu/g.
From Fig. 7, the adsorption curve of different samples is it can be seen that adsorbing 30min when, almost adsorption equilibrium,
Compared to ZnFe2O4And Ag-PEDOT, the adsorption capacity of embedded hollow magnetic trace photocatalytic nanometer reactor is higher, reaches
1.47mg/g,.This be due to embedded hollow magnetic trace photocatalytic nanometer reactor has can Selective recognition tetracycline
Trace hole cause.
From fig. 10 it can be seen that the degradation rate of tetracycline is existed by embedded hollow magnetic trace photocatalytic nanometer reactor
The simulated solar irradiation of 120min irradiates lower degradation rate can reach 71.77%, substantially other sample；And for the fall of tetracycline
For solution, other sample is but apparently higher than embedded hollow magnetic trace photocatalytic nanometer reactor；The above results shows that this is embedding
Enter formula hollow magnetic trace photocatalytic nanometer reactor and tetracycline is had extraordinary Selective recognition/photocatalytic degradation energy
Power.
From circulation experiment in Figure 11, this embedded hollow magnetic trace photocatalytic nanometer reactor is real 5 circulations
After testing, still there is preferable Photocatalytic activity, illustrate that this embedded hollow magnetic trace photocatalytic nanometer reactor has
Preferably stability.
Claims (6)
1. an embedded hollow magnetic trace photocatalytic nanometer reactor, it is characterised in that described embedded hollow magnetic
Trace photocatalytic nanometer reactor is by ZnFe2O4, Ag, PEDOT and the alternative organic imprinted layer identifying tetracycline compound and
Become；Described organic imprinted layer is coated on ZnFe2O4Outer surface；Described Ag-PEDOT is to be supported on PEDOT by Ag；Described
Ag-PEDOT is embedded in the middle of organic imprinted layer；This embedded hollow magnetic trace photocatalytic nanometer reactor of 0.02g is used for
The simulated solar irradiation photocatalytic degradation of the tetracycline of 100mL 20mg/L, in 120min, degradation rate has reached 71.77%.
2. the preparation method of a kind of embedded hollow magnetic trace photocatalytic nanometer reactor described in claim 1, its feature
It is, carries out as steps described below:
Step 1, ZnFe2O4Preparation:
By FeCl3·6H2O and ZnCl2Join in ethylene glycol, after forming the solution of clarification, add ammonium acetate, and in room temperature
Under the conditions of stir, afterwards this mixture is put into and stainless steel autoclave carries out constant temp. heating reaction, reaction terminate after, by reactor
It is cooled to room temperature, collects solid product with Magnet and wash, more i.e. obtain ZnFe after solid product vacuum drying2O4；
Step 2, the preparation of poly-3,4-ethene dioxythiophene:
Double (2-second hexyl) sodium sulfo-succinates are dissolved in normal hexane, obtain mixed liquor A, in mixed liquor A, add trichlorine
Changing ferrous solution, stirring, to forming reversed micelle solution, adds 3,4-rthylene dioxythiophene, ultrasonic, obtains mixed liquid B, then machine
Tool stirs, and has reacted rear washed product and has been vacuum dried, i.e. having obtained poly-3,4-rthylene dioxythiophene；
Step 3, the preparation of Ag-PEDOT:
Poly-3,4-rthylene dioxythiophene is joined in silver nitrate solution, ultrasonic mechanical agitation, obtain mixed liquor C, more dropwise add
Enter sodium borohydride solution, obtain mixed liquor D, mechanical agitation, afterwards washed product being vacuum dried, obtain poly-the 3,4-of silver load
Ethene dioxythiophene, is designated as Ag-PEDOT；
Step 4, the preparation of embedded hollow magnetic trace photocatalytic nanometer reactor:
By Ag-PEDOT and ZnFe2O4It is dispersed in the microwave reaction bottle containing dimethyl sulfoxide, obtains mixed liquor E, stirring, then to
Wherein add tetracycline, obtain mixed liquor F, then mixed liquor F is kept in Dark Place under nitrogen atmosphere, be added thereto to the most again
Trimethylol-propane trimethacrylate and azodiisobutyronitrile, obtain mixed liquor G, and microwave reaction bottle is put into microwave reaction
Device reacts, after reaction terminates, takes out reaction bulb washed product, after vacuum drying, then by above-mentioned dried solid product
It is immersed in the distilled water in light-catalyzed reaction bottle, this light-catalyzed reaction bottle is put in photochemical reactor, stirring, logical sky
Gas, after irradiating with simulated solar irradiation, washed product is also vacuum dried, and i.e. obtains embedded hollow magnetic trace photocatalytic nanometer anti-
Answer device.
The preparation method of a kind of embedded hollow magnetic trace photocatalytic nanometer reactor the most according to claim 2, its
It is characterised by, in step 1, the FeCl used3·6H2O、ZnCl2, the amount ratio of ethylene glycol and ammonium acetate be 4mmol:
2mmol:70mL:30mmol；The time of described stirring is 0.5h；The temperature of described constant temp. heating reaction is 210 DEG C, and the response time is
72h。
The preparation method of a kind of embedded hollow magnetic trace photocatalytic nanometer reactor the most according to claim 2, its
It is characterised by, in step 2, during preparation mixed liquor A, double (2-second hexyl) sodium sulfo-succinate, the consumptions of normal hexane used
Ratio is 3.8g:15mL；When preparing reversed micelle solution, the liquor ferri trichloridi used is 0.47 with the volume ratio of mixed liquor A:
15, the concentration of liquor ferri trichloridi is 10.2mol L-1；During preparation mixed liquid B, the 3,4-rthylene dioxythiophene used is with double
The mass ratio of (2-second hexyl) sodium sulfo-succinate is 0.45:3.8；The described ultrasonic time is 10min；Described churned mechanically
Time is 12h.
The preparation method of a kind of embedded hollow magnetic trace photocatalytic nanometer reactor the most according to claim 2, its
It is characterised by, in step 3, when preparing mixed liquor C, the poly-3,4-rthylene dioxythiophene that used, the amount ratio of silver nitrate solution
For 1.45g, 320mL；When preparing mixed liquor D, the sodium borohydride solution used is 16:19 with the volume ratio of mixed liquor C；Described
The concentration of silver nitrate solution and sodium borohydride solution is 0.025mol L-1；The ultrasonic machinery mixing time of described mixed liquor C is
1h；The mechanical agitation time of described mixed liquor D is 1.5h.
The preparation method of a kind of embedded hollow magnetic trace photocatalytic nanometer reactor the most according to claim 2, its
It is characterised by, in step 4, when preparing mixed liquor E, Ag-PEDOT, the ZnFe used2O4, the amount ratio of dimethyl sulfoxide be
0.001～0.1g:0.1g:20mL；When preparing mixed liquor F, the tetracycline used with the amount ratio of dimethyl sulfoxide is
0.05mmol:20mL；When preparing mixed liquor G, the trimethylol-propane trimethacrylate that used, azodiisobutyronitrile with
The amount ratio of dimethyl sulfoxide is 0.5mL:0.01g:20mL；Mixing time to mixed liquor E is 0.5h；Described keep in Dark Place time
Between be 12h；The described response time in microwave reactor is 0.1～2h, and reaction temperature is 60 DEG C, and power is 700W, magnetic force
Speed of agitator is 600rpm/min；Described after adding distilled water and being placed in photo catalysis reactor, the rotating speed of magnetic agitation is
600rpm/min, the flow velocity of blowing air is 2mL/min, and the time that simulated solar irradiation irradiates is 2h.
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