CN107029786A - A kind of magnetic composite photocatalyst Ppy@CdS/ZnFe2O4And its production and use - Google Patents
A kind of magnetic composite photocatalyst Ppy@CdS/ZnFe2O4And its production and use Download PDFInfo
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 30
- 239000002131 composite material Substances 0.000 title claims abstract description 29
- 238000004519 manufacturing process Methods 0.000 title abstract description 3
- 229910001308 Zinc ferrite Inorganic materials 0.000 claims abstract description 100
- 238000002360 preparation method Methods 0.000 claims abstract description 22
- 230000001699 photocatalysis Effects 0.000 claims abstract description 13
- 239000004098 Tetracycline Substances 0.000 claims description 37
- 235000019364 tetracycline Nutrition 0.000 claims description 36
- 229960002180 tetracycline Drugs 0.000 claims description 35
- 229930101283 tetracycline Natural products 0.000 claims description 35
- 150000003522 tetracyclines Chemical class 0.000 claims description 34
- NNGHIEIYUJKFQS-UHFFFAOYSA-L hydroxy(oxo)iron;zinc Chemical compound [Zn].O[Fe]=O.O[Fe]=O NNGHIEIYUJKFQS-UHFFFAOYSA-L 0.000 claims description 29
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 23
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- 238000003756 stirring Methods 0.000 claims description 15
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- 239000012265 solid product Substances 0.000 claims description 12
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 11
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 11
- 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 10
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- 239000011261 inert gas Substances 0.000 claims description 9
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- 238000005406 washing Methods 0.000 claims description 7
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- MYSWGUAQZAJSOK-UHFFFAOYSA-N ciprofloxacin Chemical compound C12=CC(N3CCNCC3)=C(F)C=C2C(=O)C(C(=O)O)=CN1C1CC1 MYSWGUAQZAJSOK-UHFFFAOYSA-N 0.000 description 4
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- 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
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- PXFBZOLANLWPMH-UHFFFAOYSA-N 16-Epiaffinine Natural products C1C(C2=CC=CC=C2N2)=C2C(=O)CC2C(=CC)CN(C)C1C2CO PXFBZOLANLWPMH-UHFFFAOYSA-N 0.000 description 1
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- 244000052616 bacterial pathogen Species 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
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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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
-
- B01J35/39—
-
- 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
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Abstract
The invention provides a kind of magnetic composite photocatalyst Ppy@CdS/ZnFe2O4And its production and use, preparation process is as follows：Step 1, ZnFe2O4Preparation；Step 2, CdS/ZnFe2O4Preparation；Step 3, Ppy@CdS/ZnFe2O4Preparation.The present invention passes through the Ppy@CdS/ZnFe constructed by molecular imprinting technology2O4Composite photo-catalyst, due to the selectivity of imprinted layer, and CdS and ZnFe2O4The energy gap of matching, can form Z-type hetero-junctions so that the composite photocatalyst material for preparing of the present invention has certain selectivity and photocatalytic activity.
Description
Technical field
The invention belongs to technical field of environmental material preparation, and in particular to a kind of functional magnetic composite photo-catalyst
Ppy@CdS/ZnFe2O4The Preparation method and use of composite photo-catalyst.
Background technology
Tetracycline is that a class is usually used in the suppression of various germs and the antibiotic killed on adjacent bed, due to Tetracyclines antibiosis
The a large amount of of element make its generally existing in the environment, so that the drug resistance of bacterium is result in, on the other hand, the residual of tetracycline
Considerable influence can be produced to environment, it may be present in soil, surface water, underground water etc., human body is produced compared with major injury, therefore,
The effective tetracycline that removes is particularly important.In recent years, many experts and scholars are solved the above problems using many methods, but this
A little methods are less efficient, and secondary pollution is easily caused again, and people have found a kind of new technology-photocatalysis technology by studying, and it is one
The green technology of rationality is planted, can be the inorganic matters such as carbon dioxide, the water of environmental sound by organic matter degradation.
CdS is a kind of typical cadmium based semiconductor nano-photocatalyst material, because its unique crystal structure is shown well
Photocatalytic activity, become study hotspot (H.McDaniel, M.Shim, Size the and growth of lot of domestic and foreign scholar
rate dependent structural diversification of Fe3O4/CdS anisotropic nanocrystal
heterostructures,Nano, 2009(3):434-440).CdS is as a kind of N-type semiconductor nano material, and its forbidden band is wide
Spend for 2.4eV or so, there is good assimilation effect, and the absorption spectrum and the spectrum of sunshine of CdS semiconductors to visible ray
It is much like, solar radiation photocatalytic degradation organic pollution can be directly utilized, is a kind of photochemical catalyst with applications well prospect
(L.Ge,J.Liu,Efficient visible light-induced photocatalytic degradation of
methyl orange by quantum dots sensitized CdS-Bi2WO6,Appl.Catal.B-Environ.,2011
(105):289-297).Ge in 2011 etc. [is prepared for CdS quantum dot sensitization BiWO6Photochemical catalyst, and study its to methyl orange and
The photocatalytic degradation effect of phenol.2013, Li etc. (G.S.Li, L. Wu, F.Li, P.P.Xu, D.Q.Zhang, H.X.Li,
Photoelectrocatalytic degradation of organic pollutants via a CdS quantum
dots enhanced TiO2nanotube array electrode under visible light irradiation,
Nanoscale,2013(5):2118-2125).CdS sensitizations are prepared for by the method for cathode ion exchange and deposition (CEDIE)
TiO2Nanotube, the catalyst shows the catalytic activity that single catalyst can not compare.Therefore, when it partly leads again with other
During conjunction, more preferable catalytic activity and stably may be shown.ZnFe2O4As a kind of magnetic semiconductor material by scientific research work
Extensive concern (J.T.Feng, L.C.Li.In-depth study on the adsorption and of author
photocatalytic performance of novel reduced graphene oxide-ZnFe2O4-polyaniline
Composites.Journal of Alloys and Compounds, 681 (2016) 157-166), when itself and CdS complexs
During into hetero-junctions, it can effectively suppress the compound of electron-hole pair, substantial amounts of photo-generated carrier is joined rapidly in the short period of time
With redox reaction and then strengthening photocatalytic activity, and good magnetic makes photochemical catalyst more reasonably recycle, and embodies
Go out sustainable, low energy consumption, the green chemical concept of low stain.
But common CdS/ZnFe2O4Photochemical catalyst have can not in plurality of target pollutant degradation selectivity it is single wait mesh
The shortcoming of thing is marked, meanwhile, degradation time length also turns into an obstacle of photocatalyst for degrading pollutant.And the present invention utilizes molecule
Engram technology, using the covalently or non-covalently effect between template molecule and monomer, tool is prepared by cross-linked polymeric and elution
There is the technology of specific structure, the affine adsorptivity to template molecule and identifiability polymer, realize that selective removal is a certain
Or certain several pollutant.Therefore, we modify molecularly imprinted polymer in CdS/ZnFe2O4Photocatalyst surface, from realizing
To the purpose of degradation selectivity in high density pollution thing.
The content of the invention
Herein using hydro-thermal method as preparation means and microwave radiation technology polymerization technique, prepare a kind of functional magnetic complex light and urge
Agent Ppy@CdS/ZnFe2O4Composite photo-catalyst, can be good at the tetracycline in degradation selectivity environmental wastewater, with conjunction
Into simple and degradation rate it is high the characteristics of.
The technical scheme is that：
A kind of magnetic composite photocatalyst Ppy@CdS/ZnFe2O4, the magnetic composite photocatalyst Ppy@CdS/
ZnFe2O4It is by ZnFe2O4, CdS particles and Ppy imprinted layers be composited, the CdS particulate loads are in ZnFe2O4Surface,
The Ppy imprinted layers are coated on the ZnFe2O4With CdS particle surfaces.
A kind of magnetic composite photocatalyst Ppy@CdS/ZnFe2O4Preparation method, step is as follows：
Step 1, ZnFe2O4Preparation：FeCl3·6H2O is added in ethylene glycol, stirring to FeCl3·6H2O is all molten
Solution, adds ammonium acetate, adds ZnCl2Continue to stir, become to solution and clarify, obtained mixed solution A is then shifted paramount
Press reactor and be put into baking oven and carry out solvent thermal reaction for a period of time；After baking oven naturally cools to room temperature, reactor is taken
Go out and the solid sample in washing reaction kettle, it is then that sample drying is standby, it is designated as ZnFe2O4；
Step 2, CdS/ZnFe2O4Preparation：By ZnFe2O4Disperse in deionized water, the cadmium sulfate and sulphur urine added
And ammoniacal liquor, stir to being uniformly dispersed, then by obtained dispersion liquid B under the conditions of water bath with thermostatic control and inert gas shielding it is anti-
Should, question response terminates and naturally cooled to after room temperature, washs solid product, and drying for standby is designated as CdS/ZnFe2O4；
Step 3, magnetic composite photocatalyst Ppy@CdS/ZnFe2O4Preparation：By pyrroles (pyrrole) and CdS/
ZnFe2O4It is added in chloroform, adds TRIM (acrylate, crosslinking agent), mixed liquor C is carried out ultrasonically treated scattered
Added after uniform after tetracycline (TC) and azodiisobutyronitrile (AIBN, initiator), continue to have children outside the state plan stirring, be subsequently placed in micro-
In ripple reactor, microwave reaction is carried out；After reaction terminates, solid product is washed, then the solid product after washing is transferred to stone
In English light-catalyzed reaction bottle, add after deionized water, be put into mercury lamp reactor, directly into the reaction bulb containing solid product
Turn on light, open stirring, lead to inert gas, illumination is collected and wash solid sample, then dries solid sample standby afterwards for a period of time
With obtaining magnetic composite photocatalyst Ppy@CdS/ZnFe2O4。
In step 1, the FeCl3·6H2O, ethylene glycol, anhydrous sodium acetate, ZnCl2Amount ratio be 2~4mmol: 40
~100mL:20~40mmol:1~2mmol；The temperature of the solvent thermal reaction is 210 DEG C, and the time is 24~72h.
In step 2, the ZnFe2O4, deionized water, cadmium sulfate, thiocarbamide, ammoniacal liquor amount ratio be 0.1~0.4g:50~
150mL:0.05~0.15g:0.03~0.09g:5~15mL；The inert gas is nitrogen；The temperature of water bath with thermostatic control is 60
DEG C, the reaction time is 3 hours.
In step 3, the pyrroles, CdS/ZnFe2O4, chloroform, TRIM, AIBN, the amount ratio of tetracycline for 0.2~
0.6 mL:0.1~0.3g:10~20mL:0.05~0.15mL:0.002~0.08mL:0.002~0.08g；The microwave is anti-
The condition answered is 40 DEG C, 600W power, and 800 rotating speeds react 1h；The inert gas is nitrogen.
Obtained magnetic composite photocatalyst Ppy@CdS/ZnFe2O4For existing in selective photocatalysis degrading waste water
Tetracycline pollutant.
The present invention technique effect be：
(1) present invention describes a kind of functional magnetic composite photo-catalyst Ppy@CdS/ZnFe2O4And preparation method thereof and
Using Ppy is a kind of novel organic semi-conductor and electric conductivity, can simultaneously serve as a kind of function monomer.ZnFe2O4Nanoparticle
Son has excellent magnetic and visible light-responded ability, but its own electron hole pair is easily combined.In addition, CdS is used as one kind
With preferably visible light-responded inorganic semiconductor, its most bandwidth has and ZnFe in 2.0-2.3eV2O4The taboo matched
Band structure, but make it less desirable in the application of photocatalysis field due to its own easy photoetch.Therefore, according to valence band
Theoretical and document report CdS can be with ZnFe2O4Form the Z-type heterojunction composite photocatalyst with high light catalytic activity.Together
When, in CdS/ZnFe2O4It is outside carry out molecular imprinting modification, the catalysis material of this special structure effect is reduced electronics-sky
Cave extends the photo-generated carrier life-span, can effectively suppress CdS photoetch phenomenon to compound, and then improves photocatalytic degradation effect
Really.
(2) ZnFe is being prepared2O4During, the present invention is main to be made magnetic ZnFe using one step hydro thermal method2O4Photocatalysis material
Material, contributes to the recycling of photochemical catalyst, substantially reduces cost.
(3) CdS introducing makes whole composite formation hetero-junctions, improves the absorption of electron-hole separative efficiency and light
Utilization rate, catalytic activity is further improved.
(4) present invention passes through the Ppy@CdS/ZnFe constructed by molecular imprinting technology2O4Composite photo-catalyst, due to trace
The selectivity of layer, and CdS and ZnFe2O4The energy gap of matching, can form Z-type hetero-junctions so that prepared by the present invention compound
Catalysis material has certain selectivity and photocatalytic activity.
Brief description of the drawings
Fig. 1 is the TEM and EDS of sample prepared by embodiment 1；Wherein, a is ZnFe2O4TEM figure, b is CdS/
ZnFe2O4TEM figure, c be trace Ppy@CdS/ZnFe2O4TEM figure, d be trace Ppy@CdS/ZnFe2O4EDS figure；
Fig. 2 is the absorption figure of sample prepared by embodiment 1；Wherein, a is the adsorption curve of different materials, and b is different materials
Absorption percentage composition；
Fig. 3 is the degradation effect figure of different samples prepared by embodiment 1；A is the degraded tetracycline design sketch of different materials.
Trace Ppy@CdS/ZnFe prepared by b2O4Close CdS/ZnFe2O4Degraded comparison diagram；
Fig. 4 a are the absorbance change curve of sample degradation tetracycline prepared by embodiment 1, and Fig. 4 b-4d are prepared sample
The m/z change curves of product；
Fig. 5 a are that embodiment 1 adds different capturing agents to trace Ppy@CdS/ZnFe2O4The influence figure of photocatalytic activity；5b
For the free radical capture figure of prepared sample；
Fig. 6 recycles curve map for sample degradation tetracycline prepared by embodiment 1.
Embodiment
Method used in the present invention is as follows：
Step 1, ZnFe2O4Preparation：FeCl3·6H2O is added in ethylene glycol, stirring to FeCl3·6H2O is all molten
Solution, adds anhydrous sodium acetate, adds ZnCl2Continue to stir, become to solution and clarify, then shift obtained mixed solution A
To autoclave and be put into baking oven carry out solvent thermal reaction for a period of time；After baking oven naturally cools to room temperature, it will react
Kettle takes out and the solid sample in washing reaction kettle, then that sample drying is standby, is designated as ZnFe2O4；
Step 2, CdS/ZnFe2O4Preparation：By ZnFe2O4Disperse in deionized water, the cadmium sulfate and sulphur added
Urine, stirs to being uniformly dispersed, then obtained dispersion liquid B is reacted under the conditions of water bath with thermostatic control and inert gas shielding, is treated
Reaction terminates and naturally cooled to after room temperature, washs solid product, and drying for standby is designated as CdS/ZnFe2O4；
Step 3, Ppy@CdS/ZnFe2O4Preparation：By pyrroles (pyrrole) and CdS/ZnFe2O4It is added to chloroform
In, TRIM (acrylate, crosslinking agent) is added, tetracycline is added after mixed liquor C is carried out into ultrasonically treated be uniformly dispersed
(TC) and after azodiisobutyronitrile AIBN (initiator), continue to have children outside the state plan stirring, be subsequently placed in microwave reactor, carry out microwave
Reaction；After reaction terminates, solid product is washed, then the solid product after washing is transferred in quartzy light-catalyzed reaction bottle, to
Added in reaction bulb containing solid product after deionized water, be put into mercury lamp reactor, directly turn on light, open stirring, lead to N2, light
According to being collected after a period of time and washing solid sample, then by solid sample drying for standby, it is designated as： Ppy@CdS/ZnFe2O4。
Embodiment 1：
In step 1, by FeCl3·6H2O and ZnCl2Consumption be 2mmol and 1mmol, the consumption of anhydrous sodium acetate is
20mmol, the consumption of ethylene glycol is that hydrothermal temperature is 210 DEG C in 40mL, stainless steel autoclave, and the time is 24h.
In step 2, the ZnFe2O4, cadmium sulfate, thiocarbamide, deionized water, the consumption of ammoniacal liquor be followed successively by 0.1g, 10mL,
0.05g、0.03g、50mL、5mL。
In step 3, the CdS/ZnFe2O4, chloroform, pyrroles, TRIM, AIBN, the consumption of tetracycline be followed successively by
0.1g、10mL、0.2mL、0.05mL、0.002mL、0.002g；The microwave reaction bottle is put into microwave reactor, is imposed a condition
For 40 DEG C, 600W power, 800 rotating speeds react 1h, finally obtained trace Ppy@CdS/ZnFe2O4Photochemical catalyst.
Embodiment 2：
In step 1, by FeCl3·6H2O and ZnCl2Consumption be 4mmol and 2mmol, the consumption of anhydrous sodium acetate is
40mmol, the consumption of ethylene glycol is that hydrothermal temperature is 210 DEG C in 100mL, stainless steel autoclave, and the time is 72h.
In step 2, the ZnFe2O4, cadmium sulfate, thiocarbamide, deionized water, the consumption of ammoniacal liquor be followed successively by 0.4g, 30mL,
0.15g、0.09g、150mL、15mL。
In step 3, the CdS/ZnFe2O4, chloroform, pyrroles, TRIM, AIBN, the consumption of tetracycline be followed successively by
0.3g、20mL、0.6mL、0.15mL、0.08mL、0.08g；Microwave reaction bottle is put into microwave reactor, impose a condition for
40 DEG C, 600W power, 800 rotating speeds react 1h, finally obtained trace Ppy@CdS/ZnFe2O4Photochemical catalyst.
Embodiment 3：
In step 1, by FeCl3·6H2O and ZnCl2Consumption be 3mmol, 1.5mmol, the consumption of anhydrous sodium acetate is
30mmol, the consumption of ethylene glycol is that hydrothermal temperature is 210 DEG C in 75mL, stainless steel autoclave, and the time is 36h.
In step 2, the ZnFe2O4, cadmium sulfate, thiocarbamide, deionized water, the consumption of ammoniacal liquor be followed successively by 0.3g, 20mL,
0.1g、0.06g、100mL、10mL。
In step 3, the CdS/ZnFe2O4, chloroform, pyrroles, TRIM, AIBN, the consumption of tetracycline be followed successively by
0.2g、15mL、0.4mL、0.1mL、0.05mL、0.05g；Microwave reaction bottle is put into microwave reactor, impose a condition for
40 DEG C, 600W power, 800 rotating speeds react 1h, finally obtained trace Ppy@CdS/ZnFe2O4Photochemical catalyst.
Photocatalytic activity evaluation：Photocatalytic degradation reaction is carried out in DW-01 type photochemical reaction instrument, and light source is 300W xenons
Lamp, by 100mL 20mg L-1Tetracycline wastewater (100mL 20mg L-1Ciprofloxacin waste water) it is added to light-catalyzed reaction bottle
It is placed under light source and determines the initial absorbance of tetracycline, then in magnetic agitation and opens aerator and be passed through air
Photochemical catalyst is added, suspension or afloat is maintained the catalyst in.Interval 15min light application time starts after dark adsorption equilibrium
Sampling, supernatant liquor is taken after separating solid catalyst by magnet, then with spectrophotometer measurement tetracycline and ring and husky star
Absorbance, and pass through formula：η=[(C0-Ci)/C0] × 100% calculates degradation rate, investigates the degraded selectivity of the material.
Fig. 1 a are ZnFe2O4、CdS/ZnFe2O4, trace Ppy@CdS/ZnFe2O4The TEM figures and trace of photochemical catalyst
Ppy@CdS/ZnFe2O4EDS figure.It can be seen that pure ZnFe2O4Surface is relatively smooth, ZnFe2O4It is average straight
Footpath about 100nm and size is than more uniform.It is worth noting that, there is some little particles to be supported on ZnFe2O4On surface, and these are small
Particle is then the CdS nano-particles introduced.Thickened in addition, can be seen that prepared imprinted material is relative in figure c, and can
Its surface is covered in be seen that there is layer of substance, this is probably caused by imprinted layer.In addition, shown from EDS energy spectrum analysis, can
To find out that the elements such as Fe, O, S, Cd and N are clearly detected, therefore, from TEM and EDS analysis, provable trace Ppy@
CdS/ZnFe2O4Successfully prepared.
As Fig. 2 a be respectively it is shown be ZnFe2O4, non-trace Ppy@CdS/ZnFe2O4With trace Ppy@CdS/ZnFe2O4Three
Plant the adsorption curve of material, it can be seen that non-imprinted material Ppy@CdS/ZnFe2O4Adsorptivity is worst, ZnFe2O4Adsorptivity time
It, trace Ppy@CdS/ZnFe2O4Adsorptivity is most strong, and this illustrates that non-imprinted material lacks imprinted cavity when not eluting, no
Target molecule can be recognized.After elution, there is abundant traces hole, strengthening absorption naturally.Fig. 2 b have corresponded to several respectively
Plant the absorption percentage composition of different materials
Fig. 3 a are ZnFe2O4、CdS/ZnFe2O4With trace Ppy@CdS/ZnFe2O4Degradation curve figure, it can be seen that
ZnFe2O4With it is certain can be by photocatalytic activity, and CdS/ZnFe2O4Activity be higher than ZnFe2O4Activity, and the marking
Ppy@CdS/ZnFe2O4, and trace Ppy@CdS/ZnFe2O4Best catalytic activity is then shown to tetracycline, this also illustrates
Trace hole serves the effect of identification target molecule, and can preferably degrade target molecule.In addition, we also provide a comparison
CdS/ZnFe2O4With trace Ppy@CdS/ZnFe2O4Degraded Ciprofloxacin and tetracycline, CdS/ is can be seen that from Fig. 3 b
ZnFe2O4Trace Ppy@CdS/ZnFe are higher than to the degradation effect of Ciprofloxacin2O4, and the Ppy@CdS/ZnFe of trace2O4Pair
The degradation effect of tetracycline is then higher than the degradation effect to Ciprofloxacin, while also above CdS/ZnFe2O4To the drop of tetracycline
Effect is solved, this also absolutely proves that the material that we prepare has good selectivity.
Fig. 4 a are trace Ppy@CdS/ZnFe2O4The absorbance change curve map of degraded tetracycline, it can be seen that with illumination
The extension of time, characteristic peak of the tetracycline at 357 gradually dies down, and this explanation tetracycline molecule is gradually transformed into small molecule.
In addition from Mass Spectrometer Method Fig. 4 b-d it can also be seen that for degraded when tetracycline m/z values be 445, over time, go out again
Show a lot of other small molecule peaks, and the proton peak of tetracycline is gradually reduced, this absolutely proves that tetracycline molecule is converted to
Boy, or even last mineralising are CO2And H2O.
Fig. 5 is different types of capturing agent to trace Ppy@CdS/ZnFe2O4The influence of photocatalytic activity；It is well known that working as
Photochemical catalyst can be produced some active materials (h during radiation of visible light+, OH, O2 -).Generally, benzoquinones (BQ) is used for capturing
Superoxide radical (O2 -).Isopropanol (IPA) can be captured effectively with hydroxyl radical free radical (OH), and and triethanolamine (TEAO)
To hole (h+) capture play an important role.It is can be seen that from the kinetic curve of capture experiment when addition IPA capturing agents
When, the degradation rate of tetracycline is not substantially reduced.On the contrary, when adding reactive specy capturing agent capture TEAO, tetracycline
Degradation rate only has 40% or so, it means that h+Degraded to tetracycline plays a crucial role.In addition, when use BQ as super oxygen oneself
By base capturing agent when, degradation rate drops to 10%.Therefore, during tetracycline light degradation different activities material to degradation effect
Influence order be：·O2 ->h+>·OH。
Fig. 6 is trace Ppy@CdS/ZnFe2O45 circulation experiment figures of photochemical catalyst, it can be seen that catalyst
By 5 times reuse after its catalytic activity almost do not decline.So, on the one hand the photocatalysis is illustrated by circulation experiment
Material has good stability, on the other hand illustrates that this composite photo-catalyst has necessarily in terms of the pollution controls such as industrial wastewater
Potential using value.
Claims (6)
1. a kind of magnetic composite photocatalyst Ppy@CdS/ZnFe2O4, it is characterised in that the magnetic composite photocatalyst Ppy@
CdS/ZnFe2O4It is by ZnFe2O4, CdS particles and Ppy imprinted layers be composited, the CdS particulate loads are in ZnFe2O4
Surface, the Ppy imprinted layers are coated on the ZnFe2O4With CdS particle surfaces.
2. a kind of magnetic composite photocatalyst Ppy@CdS/ZnFe2O4Preparation method, it is characterised in that step is as follows：
Step 1, ZnFe2O4Preparation：FeCl3·6H2O is added in ethylene glycol, stirring to FeCl3·6H2O all dissolves, plus
Enter anhydrous sodium acetate, add ZnCl2Continue to stir, become to solution and clarify, obtained mixed solution A is then transferred to high pressure
Reactor and be put into baking oven carry out solvent thermal reaction for a period of time；After baking oven naturally cools to room temperature, reactor is taken out
And the solid sample in washing reaction kettle, it is then that sample drying is standby, it is designated as ZnFe2O4；
Step 2, CdS/ZnFe2O4Preparation：By ZnFe2O4Disperse in deionized water, the cadmium sulfate and sulphur urine and ammonia added
Water, stirs to being uniformly dispersed, then obtained dispersion liquid B is reacted under the conditions of water bath with thermostatic control and inert gas shielding, is treated
Reaction terminates and naturally cooled to after room temperature, washs solid product, and drying for standby is designated as CdS/ZnFe2O4；
Step 3, magnetic composite photocatalyst Ppy@CdS/ZnFe2O4Preparation：By pyrroles and CdS/ZnFe2O4It is added to three chloromethanes
In alkane, acrylate is added, tetracycline and azodiisobutyronitrile are added after mixed liquor C is carried out into ultrasonically treated be uniformly dispersed
Afterwards, continue to have children outside the state plan stirring, be subsequently placed in microwave reactor, carry out microwave reaction；After reaction terminates, solid product is washed,
The solid product after washing is transferred in quartzy light-catalyzed reaction bottle again, added into the reaction bulb containing solid product go from
After sub- water, it is put into mercury lamp reactor, directly turns on light, open stirring, lead to inert gas, illumination is collected and washs solid afterwards for a period of time
Body sample, then by solid sample drying for standby, obtains magnetic composite photocatalyst Ppy@CdS/ZnFe2O4。
3. a kind of magnetic composite photocatalyst Ppy@CdS/ZnFe according to claim 22O4Preparation method, its feature
It is, in step 1, the FeCl3·6H2O, ethylene glycol, ammonium acetate, ZnCl2Amount ratio be 2~4mmol:mL:40~
100ml:20~40mmol:1~2mmol；The temperature of the solvent thermal reaction is 210 DEG C, and the time is 24~72h.
4. a kind of magnetic composite photocatalyst Ppy@CdS/ZnFe according to claim 22O4Preparation method, its feature
It is, in step 2, the ZnFe2O4, deionized water, cadmium sulfate, thiocarbamide, ammoniacal liquor amount ratio be 0.1~0.4g:50~
150mL:0.05~0.15g:0.03~0.09g:5~15mL；The inert gas is nitrogen；The temperature of water bath with thermostatic control is 60
DEG C, the reaction time is 3 hours.
5. a kind of magnetic composite photocatalyst Ppy@CdS/ZnFe according to claim 22O4Preparation method, its feature
It is, in step 3, the pyrroles, CdS/ZnFe2O4, chloroform, acrylate, azodiisobutyronitrile, the consumption of tetracycline
Than for 0.2~0.6mL:0.1~0.3g:10~20mL:0.05~0.15mL:0.002~0.08mL:0.002~0.08g；Institute
The condition for stating microwave reaction is 40 DEG C, 600W power, 800 rotating speeds, reacts 1h, and the inert gas is nitrogen.
6. the magnetic composite photocatalyst Ppy@CdS/ZnFe described in claim 12O4For in selective photocatalysis degrading waste water
There is the purposes of tetracycline pollutant.
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| CN108273510A (en) * | 2018-01-18 | 2018-07-13 | 三明学院 | A kind of visible light-responded composite photo-catalyst of Z-type and preparation method thereof |
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| CN105032493A (en) * | 2015-06-02 | 2015-11-11 | 江苏大学 | Surface molecular imprinting composite photocatalytic material as well as preparation method and application thereof |
| CN106513018A (en) * | 2016-09-30 | 2017-03-22 | 江苏大学 | Preparation method and application of ZnFe2O4@CdS composite photocatalyst with core-shell structure |
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| CN105032493A (en) * | 2015-06-02 | 2015-11-11 | 江苏大学 | Surface molecular imprinting composite photocatalytic material as well as preparation method and application thereof |
| CN106513018A (en) * | 2016-09-30 | 2017-03-22 | 江苏大学 | Preparation method and application of ZnFe2O4@CdS composite photocatalyst with core-shell structure |
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| CN109174194A (en) * | 2018-08-14 | 2019-01-11 | 江苏大学 | A kind of preparation method and applications of the magnetic photocatalytic nano-reactor of degradation selectivity tetracycline |
| CN110592596A (en) * | 2019-08-02 | 2019-12-20 | 西北师范大学 | Ternary semiconductor composite film and preparation method and application thereof |
| CN111495432A (en) * | 2020-06-05 | 2020-08-07 | 深圳职业技术学院 | Polypyrrole/cadmium sulfide imprinted composite photocatalyst and preparation method and application thereof |
| CN111495432B (en) * | 2020-06-05 | 2023-05-16 | 深圳职业技术学院 | Polypyrrole/cadmium sulfide imprinting composite photocatalyst and preparation method and application thereof |
| CN112844414A (en) * | 2021-01-29 | 2021-05-28 | 昆明理工大学 | Popcorn-shaped ZnFe2O4Preparation method of/CdS/GO heterojunction photocatalyst |
| CN113231099A (en) * | 2021-05-21 | 2021-08-10 | 吉林大学 | Preparation and application of Z-type polypyrrole-bismuth tungstate photocatalyst |
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