CN106513018A - Preparation method and application of ZnFe2O4@CdS composite photocatalyst with core-shell structure - Google Patents
Preparation method and application of ZnFe2O4@CdS composite photocatalyst with core-shell structure Download PDFInfo
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- 229910001308 Zinc ferrite Inorganic materials 0.000 title claims abstract description 60
- 239000002131 composite material Substances 0.000 title claims abstract description 36
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 36
- NNGHIEIYUJKFQS-UHFFFAOYSA-L hydroxy(oxo)iron;zinc Chemical compound [Zn].O[Fe]=O.O[Fe]=O NNGHIEIYUJKFQS-UHFFFAOYSA-L 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000011258 core-shell material Substances 0.000 title claims abstract description 14
- 239000002351 wastewater Substances 0.000 claims abstract description 6
- 230000000593 degrading effect Effects 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 61
- 229910001868 water Inorganic materials 0.000 claims description 44
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 42
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 39
- YKYOUMDCQGMQQO-UHFFFAOYSA-L cadmium dichloride Chemical compound Cl[Cd]Cl YKYOUMDCQGMQQO-UHFFFAOYSA-L 0.000 claims description 24
- 239000008367 deionised water Substances 0.000 claims description 17
- 229910021641 deionized water Inorganic materials 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 12
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 12
- 238000013019 agitation Methods 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 10
- 238000001291 vacuum drying Methods 0.000 claims description 10
- 239000004098 Tetracycline Substances 0.000 claims description 7
- 235000019364 tetracycline Nutrition 0.000 claims description 7
- 150000003522 tetracyclines Chemical class 0.000 claims description 7
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 6
- 239000013049 sediment Substances 0.000 claims description 5
- 229960002180 tetracycline Drugs 0.000 claims description 5
- 229930101283 tetracycline Natural products 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 238000002242 deionisation method Methods 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- 239000012265 solid product Substances 0.000 claims description 2
- 229910002554 Fe(NO3)3·9H2O Inorganic materials 0.000 claims 1
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Inorganic materials [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims 1
- 230000003115 biocidal effect Effects 0.000 abstract description 6
- 239000004065 semiconductor Substances 0.000 abstract description 4
- 239000002096 quantum dot Substances 0.000 abstract description 3
- 238000003756 stirring Methods 0.000 description 29
- 239000003054 catalyst Substances 0.000 description 27
- 230000015556 catabolic process Effects 0.000 description 17
- 238000006731 degradation reaction Methods 0.000 description 17
- 238000006552 photochemical reaction Methods 0.000 description 17
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 16
- 238000012360 testing method Methods 0.000 description 16
- 229940072172 tetracycline antibiotic Drugs 0.000 description 15
- 229910000608 Fe(NO3)3.9H2O Inorganic materials 0.000 description 10
- 239000004094 surface-active agent Substances 0.000 description 8
- 238000002156 mixing Methods 0.000 description 6
- 229920002472 Starch Polymers 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 235000019698 starch Nutrition 0.000 description 5
- 239000008107 starch Substances 0.000 description 5
- 230000001699 photocatalysis Effects 0.000 description 4
- 238000002835 absorbance Methods 0.000 description 3
- 238000007146 photocatalysis Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 241001465754 Metazoa Species 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 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 2
- 239000003814 drug Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 2
- 208000015181 infectious disease Diseases 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229940040944 tetracyclines Drugs 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 238000005276 aerator Methods 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 229940088710 antibiotic agent Drugs 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 229960003405 ciprofloxacin Drugs 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000005447 environmental material Substances 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 244000000010 microbial pathogen Species 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 210000003739 neck Anatomy 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 239000000725 suspension Substances 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/043—Sulfides with iron group metals or platinum group metals
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- 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
- C02F2101/34—Organic compounds containing oxygen
-
- 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
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- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Catalysts (AREA)
Abstract
The invention provides a preparation method and application of a ZnFe2O4@CdS composite photocatalyst with a core-shell structure. The preparation method comprises the following steps of (1) preparing ZnFe2O4; (2) preparing the ZnFe2O4@CdS composite photocatalyst. According to the preparation method and the application of the ZnFe2O4@CdS composite photocatalyst with the core-shell structure provided by the invention, the aim of degrading antibiotic wastewater through the ZnFe2O4@CdS composite photocatalyst as a heterojunction formed by CdS semiconductor quantum dots and the ZnFe2O4 is realized.
Description
Technical field
The invention belongs to technical field of environmental material preparation, is related to a kind of core shell structure ZnFe2O4@CdS composite photo-catalysts
Preparation method and its usage.
Background technology
Antibiotic (Antibiotics) is the chemical substance produced by certain micro-organisms or animals and plants, can suppress microorganism
With the material of other cell propagation, it is widely used in the various bacterium infections for the treatment of or suppresses the medicine of pathogenic microorganism infection.Due to
The irrational utilization of antibiotic medicine, generates larger harm to environment, and by taking Ciprofloxacin as an example, many research reports show
Antibiotic has been widely present in soil, surface water, underground water, deposit, municipal sewage and animal excrements oxidation pond.Cause
This, it has been that researcher is urgent to eliminate the problems such as environmental pollution for bringing of antibiotic residue and food chain product safety in environment
Need the significant problem for solving.
Quantum dot (Quantum dots, QDs) is also referred to as nanocrystalline, i.e., radius is less than or close to the half of exciton Bohr radius
The Nano semiconductor particle of conductor nanocrystal, usually II-VI, iii-v low energy gap, it is little with size, surface area is big etc.
Advantage.The key state on QDs surfaces and electronic state are different from inside particle simultaneously, and surface atom coordination is not congruent to cause surface-active to increase
Plus, it is allowed to the primary condition for possessing as catalyst.CdS is a kind of energy gap about 2.4eV semi-conducting materials, directly can be inhaled
Visible ray of the wavelength less than 550nm is received, is widely used in preparing many necks such as photoelectric tube, photo resistance and solar cell
Domain.Meanwhile, it has fabulous photocatalysis performance, in visible ray of the wavelength less than 500nm, it is possible to use CdS QDs are produced
There is redox reaction in a large amount of electronics and hole, Some Organic Pollutants can be oxidized to carbon dioxide, water inorganic salts etc..But
Quick due to electron hole pair is combined, and we introduce ZnFe2O4The structure that hetero-junctions is formed with CdS can greatly reduce electricity
The recombination rate in sub- hole pair, while ZnFe2O4Catalyst recycling can be made with magnetic.Therefore, ZnFe2O4@CdS are multiple
The waste water that closing light catalyst comes in processing environment is a kind of more satisfactory material.
The content of the invention
It is an object of the invention to provide a kind of core shell structure ZnFe2O4The preparation method of@CdS composite photo-catalysts, while grind
Study carefully ZnFe2O4Degraded of the@CdS composite photo-catalysts to tetracycline.
The present invention is achieved through the following technical solutions：
A kind of core shell structure ZnFe2O4The preparation method of@CdS composite photo-catalysts, comprises the steps：
Step 1, ZnFe2O4Preparation：
By Fe (NO3)3.9H2O and Zn (NO3)2.6H2O is stirred in being added to ethylene glycol, is subsequently added PVP and is stirred, obtains
To mixed liquor A；Mixed liquor A is transferred in reactor carries out constant temperature thermal response；Reaction terminate after, room temperature to be dropped to, spend from
Sub- water, ethanol washing solid product, are dried, obtain ZnFe2O4；
Step 2, ZnFe2O4The preparation of@CdS composite photo-catalysts：
By ZnFe2O4And CdCl2.H2O is added to the water mechanical agitation, is subsequently adding C6H5Na3O7.H2O, obtains mixed liquor
B, adjusts pH=9～11 with ammoniacal liquor after mixed liquid B is sufficiently stirred in 70 DEG C of water-baths, obtains mixed liquor C；
Thiourea solution is added dropwise in mixed liquor C, mixed liquor D is obtained, and by mixed liquor D in 70 DEG C of stirred in water bath
Reaction；After question response terminates, sediment is separated with solution with magnet, deionized water, ethanol washing, vacuum drying are obtained
ZnFe2O4@CdS composite photo-catalysts.
In step 1, when preparing mixed liquor A, the Fe (NO for being used3)3.9H2O、Zn(NO3)2.6H2O, ethylene glycol, PVP
Amount ratio is 4mmol：2mmol：60mL：15mmol；The temperature of described constant temperature thermal response is 150～210 DEG C, and the reaction time is
22～72h.
In step 1, pH=10.5～11.
In step 2, when preparing mixed liquid B, the ZnFe for being used2O4、CdCl2.H2O, water, C6H5Na3O7.H2The amount ratio of O
For 0.207～0.622mmol：0.9354～2mmol：200mL：2mmol；When preparing mixed liquor C, the quality of the ammoniacal liquor for being used
Fraction is 25%～28%；The thiourea solution for being used is 3 with the volume ratio of mixed liquid B：20, the thiourea solution for being used
Concentration be 0.01g/mL；Mixed liquid B is 20min in the time of 70 DEG C of stirred in water bath, and mixed liquor D is in 70 DEG C of stirred in water bath
Reaction time is 2h.
Prepared ZnFe2O4In@CdS composite photo-catalysts, ZnFe2O4Mass fraction be 20～90%.
Prepared ZnFe2O4The tetracycline that@CdS composite photo-catalysts are used in degrading waste water.
Photocatalytic activity evaluation：Carry out in DW-01 type photochemical reaction instrument (purchased from Educational Instrument Factory of Yangzhou University), can
See light light irradiation, 100mL tetracyclines simulated wastewater is added in reactor and its initial value is determined, composite photocatalyst is subsequently adding
Agent, magnetic agitation and open aerator be passed through air maintain the catalyst in suspension or afloat, in During Illumination be spaced
10min sample analysis, take supernatant liquor in spectrophotometer λ after centrifugationmaxMensuration absorbance at=358nm, and by public affairs
Formula：DR=[(A0-Ai)/A0] × 100% calculates degradation rate, wherein A0For reaching the absorbance of tetracycline during adsorption equilibrium,
AiThe absorbance of the tetracycline determined for timing sampling.
Beneficial effect：
Present invention achieves with CdS semiconductor-quantum-points and ZnFe2O4Formation is heterogeneous to become ZnFe2O4@CdS complex lights are urged
The purpose of agent degraded antibiotic waste water.Semi-conducting material is used as photochemical catalyst, it is seen that light as exciting, by with pollutant point
The interfacial interaction of son realizes special catalysis or conversion effet, makes the oxygen of surrounding be excited into freely bearing for great oxidizing force
Ion, so as to reach the purpose of harmful organic substances in degraded environment, the method does not result in the wasting of resources with additional pollution
Formed, and it is easy to operate, it is a kind of efficient process technology of environmental protection.
Description of the drawings
Fig. 1 is ZnFe2O4@CdS composite photo-catalyst photocatalysis TEM spectrograms, it is under different amplification wherein to scheme a, b, c
TEM spectrograms, scheme d be figure c partial enlarged drawing；
Fig. 2 is ZnFe2O4The hysteresis curve figure of@CdS composite photo-catalysts；
Fig. 3 is ZnFe2O4The stability degraded figure of@CdS composite photo-catalysts.
Specific embodiment
With reference to example is embodied as, the present invention will be further described.
Embodiment 1：
(1)ZnFe2O4Preparation：
Synthesize pure ZnFe using hydro-thermal method2O4.By 4mmol Fe (NO3)3.9H2O and 2mmol Zn (NO3)2.6H2O is added to
Stir in 60mL ethylene glycol, be subsequently added 15mmol PVP and continue stirring 30min.After solution stirs, by solution from burning
Pour in 100mL reactors in cup, 72h is reacted under the conditions of 210 DEG C.Reaction terminate after, after room temperature is dropped to deionized water,
Ethanol is washed for several times, is then dried 12h under the conditions of 60 DEG C, is obtained ZnFe2O4。
(2)ZnFe2O4The preparation of@CdS composite photo-catalysts：
By 0.414mmol ZnFe2O4With 2mmol CdCl2.H2O is added to mechanical agitation 30min in 200mL water, then
By 2mmol C6H5Na3O7.H2Continue stirring 20min during O adds above-mentioned solution and in moving into 70 DEG C of water-baths, use after being sufficiently stirred for
Mass fraction is the pH=10.5-11 that 25%～28% ammoniacal liquor adjusts solution, after 0.3g thiocarbamides are dissolved in 30mL water dropwise
Above-mentioned solution is added, and solution in 70 DEG C of water-baths is continued to stir 2h.After question response terminates, with magnet by sediment with it is molten
Liquid is separated, and deionized water, ethanol are washed for several times, dries, obtain ZnFe in being put into vacuum drying chamber2O4@CdS composite photo-catalysts.
(3) in taking (2), 0.1g samples carry out photocatalytic degradation test in photochemical reaction instrument, measure the photochemical catalyst pair
The degradation rate of 100mL20mg/L tetracycline antibiotics reaches 95.31% in 90min.
Fig. 1 is ZnFe2O4@CdS composite photo-catalyst photocatalysis TEM spectrograms.What is will be apparent that in figure presents ZnFe2O4@
The core shell structure of CdS.
Fig. 2 is ZnFe2O4The hysteresis curve figure of@CdS composite photo-catalysts, as can be seen from the figure photochemical catalyst is with very
Good magnetic.
Fig. 3 is ZnFe2O4The stability degraded of@CdS composite photo-catalysts is schemed, as can be seen from the figure CdS/Fe3O4/rGO
With good stability.
Embodiment 2：
By the step in embodiment 1, except for the difference that (1) is by 4mmol Fe (NO3)3.9H2O and 2mmol Zn (NO3)2.6H2O
Stir in being added to 60mL ethylene glycol, be subsequently added 15mmol PVP and continue stirring 30min as surfactant.When solution is stirred
After mixing uniformly, solution is poured in 100mL reactors from beaker, 22h is reacted under the conditions of 150 DEG C.After reaction terminates, treat anti-
After answering thing to drop to room temperature, deionized water, ethanol are washed for several times, are then dried 12h under the conditions of 60 DEG C, are obtained ZnFe2O4。
Taking 0.1g samples carries out photocatalytic degradation test in photochemical reaction instrument, measures the photochemical catalyst to 100mL
The degradation rate of 20mg/L tetracycline antibiotics reaches 56.05% in 90min.
Embodiment 3：
By the step in embodiment 1, except for the difference that (1) is by 4mmol Fe (NO3)3.9H2O and 2mmol Zn (NO3)2.6H2O
Stir in being added to 60mL ethylene glycol, be subsequently added 15mmol CH3COONa continues stirring 30min as surfactant.When
After solution stirs, solution is poured in 100mL reactors from beaker, 22h is reacted under the conditions of 150 DEG C.Reaction terminates
Afterwards, after question response thing drops to room temperature, deionized water, ethanol are washed for several times, are then dried 12h under the conditions of 60 DEG C, are obtained
ZnFe2O4。
Taking 0.1g samples carries out photocatalytic degradation test in photochemical reaction instrument, measures the photochemical catalyst to 100mL
The degradation rate of 20mg/L tetracycline antibiotics reaches 55.83% in 90min.
Embodiment 4：
By the step in embodiment 1, except for the difference that (1) is by 4mmol Fe (NO3)3.9H2O and 2mmol Zn (NO3)2.6H2O
Stir in being added to 60mL ethylene glycol, be subsequently added 15mmol CTAB and continue stirring 30min as surfactant.Work as solution
After stirring, solution is poured in 100mL reactors from beaker, 22h is reacted under the conditions of 150 DEG C.After reaction terminates, treat
After reactant drops to room temperature, deionized water, ethanol are washed for several times, are then dried 12h under the conditions of 60 DEG C, are obtained ZnFe2O4。
Taking 0.1g samples carries out photocatalytic degradation test in photochemical reaction instrument, measures the photochemical catalyst to 100mL
The degradation rate of 20mg/L tetracycline antibiotics reaches 50.06% in 90min.
Embodiment 5：
By the step in embodiment 1, except for the difference that (1) is by 4mmol Fe (NO3)3.9H2O and 2mmol Zn (NO3)2.6H2O
Stir in being added to 60mL ethylene glycol, be subsequently added 15mmol PVP and continue stirring 30min as surfactant.When solution is stirred
After mixing uniformly, solution is poured in 100mL reactors from beaker, 24h is reacted under the conditions of 150 DEG C.After reaction terminates, treat anti-
After answering thing to drop to room temperature, deionized water, ethanol are washed for several times, are then dried 12h under the conditions of 60 DEG C, are obtained ZnFe2O4。
Taking 0.1g samples carries out photocatalytic degradation test in photochemical reaction instrument, measures the photochemical catalyst to 100mL
The degradation rate of 20mg/L tetracycline antibiotics reaches 52.86% in 90min.
Embodiment 6：
By the step in embodiment 1, except for the difference that (1) is by 4mmol Fe (NO3)3.9H2O and 2mmol Zn (NO3)2.6H2O
Stir in being added to 60mL ethylene glycol, be subsequently added 15mmol PVP and continue stirring 30min as surfactant.When solution is stirred
After mixing uniformly, solution is poured in 100mL reactors from beaker, 26h is reacted under the conditions of 150 DEG C.After reaction terminates, treat anti-
After answering thing to drop to room temperature, deionized water, ethanol are washed for several times, are then dried 12h under the conditions of 60 DEG C, are obtained ZnFe2O4。
Taking 0.1g samples carries out photocatalytic degradation test in photochemical reaction instrument, measures the photochemical catalyst to 100mL
The degradation rate of 20mg/L tetracycline antibiotics reaches 54.27% in 90min.
Embodiment 7：
By the step in embodiment 1, except for the difference that (1) is by 4mmol Fe (NO3)3.9H2O and 2mmol Zn (NO3)2.6H2O
Stir in being added to 60mL ethylene glycol, be subsequently added 15mmol PVP and continue stirring 30min as surfactant.When solution is stirred
After mixing uniformly, solution is poured in 100mL reactors from beaker, 72h is reacted under the conditions of 150 DEG C.After reaction terminates, treat anti-
After answering thing to drop to room temperature, deionized water, ethanol are washed for several times, are then dried 12h under the conditions of 60 DEG C, are obtained ZnFe2O4。
Taking 0.1g samples carries out photocatalytic degradation test in photochemical reaction instrument, measures the photochemical catalyst to 100mL
The degradation rate of 20mg/L tetracycline antibiotics reaches 57.09% in 90min.
Embodiment 8：
By the step in embodiment 1, except for the difference that (1) is by 4mmol Fe (NO3)3.9H2O and 2mmol Zn (NO3)2.6H2O
Stir in being added to 60mL ethylene glycol, be subsequently added 15mmol PVP and continue stirring 30min as surfactant.When solution is stirred
After mixing uniformly, solution is poured in 100mL reactors from beaker, 72h is reacted under the conditions of 170 DEG C.After reaction terminates, treat anti-
After answering thing to drop to room temperature, deionized water, ethanol are washed for several times, are then dried 12h under the conditions of 60 DEG C, are obtained ZnFe2O4。
Taking 0.1g samples carries out photocatalytic degradation test in photochemical reaction instrument, measures the photochemical catalyst to 100mL
The degradation rate of 20mg/L tetracycline antibiotics reaches 51.07% in 90min.
Embodiment 9：
By the step in embodiment 1, except for the difference that (1) is by 4mmol Fe (NO3)3.9H2O and 2mmol Zn (NO3)2.6H2O
Stir in being added to 60mL ethylene glycol, be subsequently added 15mmol PVP and continue stirring 30min as surfactant.When solution is stirred
After mixing uniformly, solution is poured in 100mL reactors from beaker, 72h is reacted under the conditions of 190 DEG C.After reaction terminates, treat anti-
After answering thing to drop to room temperature, deionized water, ethanol are washed for several times, are then dried 12h under the conditions of 60 DEG C, are obtained ZnFe2O4。
Taking 0.1g samples carries out photocatalytic degradation test in photochemical reaction instrument, measures the photochemical catalyst to 100mL
The degradation rate of 20mg/L tetracyclines life element reaches 53.46% in 90min.
Embodiment 10：
By the step in embodiment 1, except for the difference that (2) are by 0.207mmol ZnFe2O4With 1.821mmol CdCl2.H2O
Mechanical agitation 30min in 200mL water is added to, then by 2mmol C6H5Na3O7.H2During O adds above-mentioned solution and move into 70 DEG C
Continue stirring 20min in water-bath, adjust the pH=10.5 of solution after being sufficiently stirred for ammoniacal liquor, 0.3g thiocarbamides are dissolved in into 30mL water
In after be added dropwise over above-mentioned solution, and solution is continued to stir 2h in 70 DEG C of water-baths.After question response terminates, will be heavy with magnet
Starch is separated with solution, and deionized water, ethanol are washed for several times, dries, obtain ZnFe in being put into vacuum drying chamber2O4@CdS are combined
Photochemical catalyst.
Taking 0.1g samples carries out photocatalytic degradation test in photochemical reaction instrument, measures the photochemical catalyst to 100mL
The degradation rate of 20mg/L tetracycline antibiotics reaches 91.36% in 90min.
Embodiment 11：
By the step in embodiment 1, except for the difference that (2) are by 0.415mmol ZnFe2O4With 1.821mmol CdCl2.H2O
Mechanical agitation 30min in 200mL water is added to, then by 2mmol C6H5Na3O7.H2During O adds above-mentioned solution and move into 70 DEG C
Continue stirring 20min in water-bath, adjust the pH=10.5 of solution after being sufficiently stirred for ammoniacal liquor, 0.3g thiocarbamides are dissolved in into 30mL water
In after be added dropwise over above-mentioned solution, and solution is continued to stir 2h in 70 DEG C of water-baths.After question response terminates, will be heavy with magnet
Starch is separated with solution, and deionized water, ethanol are washed for several times, dries, obtain ZnFe in being put into vacuum drying chamber2O4@CdS are combined
Photochemical catalyst.
Taking 0.1g samples carries out photocatalytic degradation test in photochemical reaction instrument, measures the photochemical catalyst to 100mL
The degradation rate of 20mg/L tetracycline antibiotics reaches 95.31% in 90min.
Embodiment 12：
By the step in embodiment 1, except for the difference that (2) are by 0.622mmol ZnFe2O4With 1.821mmol CdCl2.H2O
Mechanical agitation 30min in 200mL water is added to, then by 2mmol C6H5Na3O7.H2During O adds above-mentioned solution and move into 70 DEG C
Continue stirring 20min in water-bath, adjust the pH=10.5 of solution after being sufficiently stirred for ammoniacal liquor, 0.3g thiocarbamides are dissolved in into 30mL water
In after be added dropwise over above-mentioned solution, and solution is continued to stir 2h in 70 DEG C of water-baths.After question response terminates, will be heavy with magnet
Starch is separated with solution, and deionized water, ethanol are washed for several times, dries, obtain ZnFe in being put into vacuum drying chamber2O4@CdS are combined
Photochemical catalyst.
Taking 0.1g samples carries out photocatalytic degradation test in photochemical reaction instrument, measures the photochemical catalyst to 100mL
The degradation rate of 20mg/L tetracycline antibiotics reaches 89.94% in 90min.
Embodiment 13：
By the step in embodiment 1, except for the difference that (2) are by 0.415mmol ZnFe2O4With 0.9354mmol CdCl2.H2O
Mechanical agitation 30min in 200mL water is added to, then by 2mmol C6H5Na3O7.H2During O adds above-mentioned solution and move into 70 DEG C
Continue stirring 20min in water-bath, adjust the pH=10.5 of solution after being sufficiently stirred for ammoniacal liquor, 0.3g thiocarbamides are dissolved in into 30mL water
In after be added dropwise over above-mentioned solution, and solution is continued to stir 2h in 70 DEG C of water-baths.After question response terminates, will be heavy with magnet
Starch is separated with solution, and deionized water, ethanol are washed for several times, dries, obtain ZnFe in being put into vacuum drying chamber2O4@CdS are combined
Photochemical catalyst.
Taking 0.1g samples carries out photocatalytic degradation test in photochemical reaction instrument, measures the photochemical catalyst to 100mL
The degradation rate of 20mg/L tetracycline antibiotics reaches 90.83% in 90min.
Embodiment 14：
By the step in embodiment 1, except for the difference that (2) are by 0.415mmol ZnFe2O4With 1.267mmol CdCl2.H2O
Mechanical agitation 30min in 200mL water is added to, then by 2mmol C6H5Na3O7.H2During O adds above-mentioned solution and move into 70 DEG C
Continue stirring 20min in water-bath, adjust the pH=10.5 of solution after being sufficiently stirred for ammoniacal liquor, 0.3g thiocarbamides are dissolved in into 30mL water
In after be added dropwise over above-mentioned solution, and solution is continued to stir 2h in 70 DEG C of water-baths.After question response terminates, will be heavy with magnet
Starch is separated with solution, and deionized water, ethanol are washed for several times, dries, obtain ZnFe in being put into vacuum drying chamber2O4@CdS are combined
Photochemical catalyst.
Taking 0.1g samples carries out photocatalytic degradation test in photochemical reaction instrument, measures the photochemical catalyst to 100mL
The degradation rate of 20mg/L tetracycline antibiotics reaches 92.20% in 90min.
Embodiment 15：
By the step in embodiment 1, except for the difference that (2) are by 0.415mmol ZnFe2O4With 1.821mmol CdCl2.H2O
Mechanical agitation 30min in 200mL water is added to, then by 2mmol C6H5Na3O7.H2During O adds above-mentioned solution and move into 70 DEG C
Continue stirring 20min in water-bath, adjust the pH=9 of solution after being sufficiently stirred for ammoniacal liquor, after being then added dropwise over 30mL thiocarbamides
Solution in 70 DEG C of water-baths is continued to stir 2h.After question response terminates, sediment is separated with solution with magnet, use deionization
Water, ethanol are washed for several times, dry, obtain ZnFe in being put into vacuum drying chamber2O4@CdS composite photo-catalysts.
Taking 0.1g samples carries out photocatalytic degradation test in photochemical reaction instrument, measures the photochemical catalyst to 100mL
The degradation rate of 20mg/L tetracycline antibiotics reaches 74.60% in 90min.
Embodiment 16：
By the step in embodiment 1, except for the difference that (2) are by 0.415mmol ZnFe2O4With 1.821mmol CdCl2.H2O
Mechanical agitation 30min in 200mL water is added to, then by 2mmol C6H5Na3O7.H2During O adds above-mentioned solution and move into 70 DEG C
Continue stirring 20min in water-bath, adjust the pH=11 of solution after being sufficiently stirred for ammoniacal liquor, after being then added dropwise over 30mL thiocarbamides
Solution in 70 DEG C of water-baths is continued to stir 2h.After question response terminates, sediment is separated with solution with magnet, use deionization
Water, ethanol are washed for several times, dry, obtain ZnFe in being put into vacuum drying chamber2O4@CdS composite photo-catalysts.
Taking 0.1g samples carries out photocatalytic degradation test in photochemical reaction instrument, measures the photochemical catalyst to 100mL
The degradation rate of 20mg/L tetracycline antibiotics reaches 94.60% in 90min.
Claims (6)
1. a kind of core shell structure ZnFe2O4The preparation method of@CdS composite photo-catalysts, it is characterised in that comprise the steps：
Step 1, ZnFe2O4Preparation：
By Fe (NO3)3·9H2O and Zn (NO3)2·6H2O is stirred in being added to ethylene glycol, is subsequently added PVP and is stirred, obtains
Mixed liquor A；Mixed liquor A is transferred in reactor carries out constant temperature thermal response；After reaction terminates, room temperature to be dropped to uses deionization
Water, ethanol washing solid product, are dried, obtain ZnFe2O4；
Step 2, ZnFe2O4The preparation of@CdS composite photo-catalysts：
By ZnFe2O4And CdCl2·H2O is added to the water mechanical agitation, is subsequently adding C6H5Na3O7·H2O, obtains mixed liquid B,
PH=9～11 are adjusted with ammoniacal liquor after mixed liquid B is sufficiently stirred in 70 DEG C of water-baths, mixed liquor C is obtained；
Thiourea solution is added dropwise in mixed liquor C, mixed liquor D is obtained, and mixed liquor D is anti-in 70 DEG C of stirred in water bath
Should；After question response terminates, sediment is separated with solution with magnet, deionized water, ethanol washing, vacuum drying are obtained
ZnFe2O4@CdS composite photo-catalysts.
2. a kind of core shell structure ZnFe according to claim 12O4The preparation method of@CdS composite photo-catalysts, its feature
It is, in step 1, when preparing mixed liquor A, the Fe (NO for being used3)3·9H2O、Zn(NO3)2·6H2O, ethylene glycol, the use of PVP
Amount is than being 4mmol：2mmol：60mL：15mmol；The temperature of described constant temperature thermal response is 150～210 DEG C, and the reaction time is 22
～72h.
3. a kind of core shell structure ZnFe according to claim 1 and 22O4The preparation method of@CdS composite photo-catalysts, which is special
Levy and be, in step 1, pH=10.5～11.
4. a kind of core shell structure ZnFe according to claim 12O4The preparation method of@CdS composite photo-catalysts, its feature
It is, in step 2, when preparing mixed liquid B, the ZnFe for being used2O4、CdCl2·H2O, water, C6H5Na3O7·H2The amount ratio of O
For 0.207～0.622mmol：0.9354～2mmol：200mL：2mmol；When preparing mixed liquor C, the quality of the ammoniacal liquor for being used
Fraction is 25%～28%；The thiourea solution for being used is 3 with the volume ratio of mixed liquid B：20, the thiourea solution for being used
Concentration be 0.01g/mL；Mixed liquid B is 20min in the time of 70 DEG C of stirred in water bath, and mixed liquor D is in 70 DEG C of stirred in water bath
Reaction time is 2h.
5. a kind of core shell structure ZnFe according to claim 12O4Prepared by the preparation method of@CdS composite photo-catalysts
ZnFe2O4@CdS composite photo-catalysts, it is characterised in that the ZnFe2O4In@CdS composite photo-catalysts, ZnFe2O4Quality
Fraction is 20～90%.
6. the core shell structure ZnFe that prepared by the method described in claim 12O4The purposes of@CdS composite photo-catalysts, its feature exist
In prepared ZnFe2O4The tetracycline that@CdS composite photo-catalysts are used in degrading waste water.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106964366A (en) * | 2017-03-24 | 2017-07-21 | 南京理工大学 | A kind of CdS/ZnFe2O4Composite photo-catalyst and preparation method thereof |
| CN107029786A (en) * | 2017-05-23 | 2017-08-11 | 江苏大学 | A kind of magnetic composite photocatalyst Ppy@CdS/ZnFe2O4And its production and use |
| CN107149936A (en) * | 2017-04-10 | 2017-09-12 | 江苏大学 | A kind of CoFe2O4AgI composite photo-catalysts and preparation method thereof |
| CN110592596A (en) * | 2019-08-02 | 2019-12-20 | 西北师范大学 | Ternary semiconductor composite film 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 |
| CN113976150A (en) * | 2021-10-15 | 2022-01-28 | 江苏大学 | CdS/Bi responding to visible light4TaO8Preparation method of Cl photocatalyst |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1559911A (en) * | 2004-02-20 | 2005-01-05 | 浙江大学 | Process for preparing hollow ball of single dispersion cadmium sulfide |
| CN102205224A (en) * | 2011-04-20 | 2011-10-05 | 浙江理工大学 | Method for preparing CdS/TiO2 nanocomposite |
-
2016
- 2016-09-30 CN CN201610873372.4A patent/CN106513018B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1559911A (en) * | 2004-02-20 | 2005-01-05 | 浙江大学 | Process for preparing hollow ball of single dispersion cadmium sulfide |
| CN102205224A (en) * | 2011-04-20 | 2011-10-05 | 浙江理工大学 | Method for preparing CdS/TiO2 nanocomposite |
Non-Patent Citations (2)
| Title |
|---|
| PAN XIONG,ET.AL.: "Cadmium Sulfide−Ferrite Nanocomposite as a Magnetically Recyclable Photocatalyst with Enhanced Visible-Light-Driven Photocatalytic Activity and Photostability", 《INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH》 * |
| PIL SUN YOO,ET.AL.: "Magnetic core-shell ZnFe2O4/ZnS nanocomposites for photocatalytic application under visible light", 《JOURNAL OF COLLOID AND INTERFACE SCIENCE》 * |
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| CN106964366A (en) * | 2017-03-24 | 2017-07-21 | 南京理工大学 | A kind of CdS/ZnFe2O4Composite photo-catalyst and preparation method thereof |
| CN107149936A (en) * | 2017-04-10 | 2017-09-12 | 江苏大学 | A kind of CoFe2O4AgI composite photo-catalysts and preparation method thereof |
| CN107149936B (en) * | 2017-04-10 | 2019-12-31 | 江苏大学 | CoFe2O4-AgI composite photocatalyst and preparation method thereof |
| CN107029786A (en) * | 2017-05-23 | 2017-08-11 | 江苏大学 | A kind of magnetic composite photocatalyst Ppy@CdS/ZnFe2O4And its production and use |
| CN110592596A (en) * | 2019-08-02 | 2019-12-20 | 西北师范大学 | Ternary semiconductor composite film 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 |
| CN113976150A (en) * | 2021-10-15 | 2022-01-28 | 江苏大学 | CdS/Bi responding to visible light4TaO8Preparation method of Cl photocatalyst |
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