CN106513018B - A kind of core-shell structure ZnFe2O4The preparation method and its usage of@CdS composite photo-catalyst - Google Patents
A kind of core-shell structure ZnFe2O4The preparation method and its usage of@CdS composite photo-catalyst Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 35
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000011258 core-shell material Substances 0.000 title claims abstract description 12
- 229910001308 Zinc ferrite Inorganic materials 0.000 claims abstract description 66
- 239000002351 wastewater Substances 0.000 claims abstract description 6
- 230000000593 degrading effect Effects 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 67
- 229910001868 water Inorganic materials 0.000 claims description 50
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 44
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 39
- 238000003756 stirring Methods 0.000 claims description 38
- 238000006243 chemical reaction Methods 0.000 claims description 35
- NNGHIEIYUJKFQS-UHFFFAOYSA-L hydroxy(oxo)iron;zinc Chemical compound [Zn].O[Fe]=O.O[Fe]=O NNGHIEIYUJKFQS-UHFFFAOYSA-L 0.000 claims description 28
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 28
- 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
- 239000007788 liquid Substances 0.000 claims description 17
- 229910002554 Fe(NO3)3·9H2O Inorganic materials 0.000 claims description 13
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 12
- 239000000908 ammonium hydroxide Substances 0.000 claims description 12
- 239000004098 Tetracycline Substances 0.000 claims description 7
- 229960002180 tetracycline Drugs 0.000 claims description 7
- 229930101283 tetracycline Natural products 0.000 claims description 7
- 235000019364 tetracycline Nutrition 0.000 claims description 7
- 150000003522 tetracyclines Chemical class 0.000 claims description 7
- 239000013049 sediment Substances 0.000 claims description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 239000012265 solid product Substances 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Inorganic materials [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 2
- 230000003115 biocidal effect Effects 0.000 abstract description 6
- 239000003054 catalyst Substances 0.000 description 26
- 238000006731 degradation reaction Methods 0.000 description 20
- 230000015556 catabolic process Effects 0.000 description 19
- 235000019441 ethanol Nutrition 0.000 description 19
- 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
- 238000002156 mixing Methods 0.000 description 10
- 238000010907 mechanical stirring Methods 0.000 description 9
- 239000000376 reactant Substances 0.000 description 8
- 239000004094 surface-active agent Substances 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 5
- 229920002472 Starch Polymers 0.000 description 4
- 230000001699 photocatalysis Effects 0.000 description 4
- 235000019698 starch Nutrition 0.000 description 4
- 239000008107 starch Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000002242 deionisation method Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000007146 photocatalysis Methods 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 241001465754 Metazoa Species 0.000 description 2
- 238000002835 absorbance Methods 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
- 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
- 230000005389 magnetism Effects 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000002096 quantum dot Substances 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 238000000926 separation method Methods 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
- 238000005276 aerator Methods 0.000 description 1
- 238000013019 agitation 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
- 230000008033 biological extinction 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
- 230000004663 cell proliferation Effects 0.000 description 1
- 229960003405 ciprofloxacin Drugs 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000005516 engineering process Methods 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
- 230000005284 excitation Effects 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
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 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
- 230000001681 protective effect Effects 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
- 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
- 239000002699 waste material 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
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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
- 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)
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Abstract
The present invention provides a kind of core-shell structure ZnFe2O4The preparation method and its usage of@CdS composite photo-catalyst, includes the following steps: step 1, ZnFe2O4Preparation；Step 2, ZnFe2O4The preparation of@CdS composite photo-catalyst.The present invention is realized with CdS semiconductor-quantum-point and ZnFe2O4It is formed and heterogeneous becomes ZnFe2O4The purpose of@CdS composite photocatalyst for degrading antibiotic waste water.
Description
Technical field
The invention belongs to technical field of environmental material preparation, are related to a kind of core-shell structure ZnFe2O4@CdS composite photo-catalyst
Preparation method and its usage.
Background technique
Antibiotic (Antibiotics) is the chemical substance generated by certain micro-organisms or animals and plants, can inhibit microorganism
With the substance of other cell Proliferations, it is widely used in the drug treated various bacterium infections or inhibit pathogenic microorganism infection.Due to
The irrational utilization of antibiotic medicine produces biggish 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, eliminating the environmental pollution of antibiotic residue bring and the problems such as food chain product safety in environment has been that researcher is urgent
The significant problem for needing to solve.
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 has size small, and surface area is big etc.
Advantage.The key state on the surface QDs and electronic state are different from inside particle simultaneously, and surface atom coordination is not congruent to cause surface-active to increase
Add, is allowed to the primary condition for having as catalyst.CdS is a kind of forbidden bandwidth about 2.4eV semiconductor material, can directly be inhaled
The visible light that wavelength is lower than 550nm is received, is widely used in preparing many necks such as photoelectric tube, photo resistance and solar battery
Domain.Meanwhile it has fabulous photocatalysis performance, in visible light of the wavelength less than 500nm, can use CdS QDs generation
Redox reaction occurs for a large amount of electrons and holes, and Some Organic Pollutants can be oxidized to carbon dioxide, water inorganic salts etc..But
Quick compound due to electron hole pair, we introduce ZnFe2O4Electricity can be greatly reduced with the CdS structure for forming hetero-junctions
The recombination rate in sub- hole pair, while ZnFe2O4It can make catalyst recycling and reusing with magnetism.Therefore, ZnFe2O4@CdS is multiple
The waste water that light combination catalyst comes in processing environment is a kind of more satisfactory material.
Summary of the invention
The object of the present invention is to provide a kind of core-shell structure ZnFe2O4The preparation method of@CdS composite photo-catalyst, grinds simultaneously
Study carefully ZnFe2O4Degradation of the@CdS composite photo-catalyst 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-catalyst, includes the following steps:
Step 1, ZnFe2O4Preparation:
By Fe (NO3)3·9H2O and Zn (NO3)2·6H2O is added in ethylene glycol and stirs, and PVP is then added and stirs evenly,
Obtain mixed liquor A；Mixed liquor A is transferred to progress constant temperature thermal response in reaction kettle；After reaction, room temperature to be dropped to, spends
Ionized water, ethanol washing solid product, it is dry, obtain ZnFe2O4；
Step 2, ZnFe2O4The preparation of@CdS composite photo-catalyst:
By ZnFe2O4And CdCl2·H2O is added to the water mechanical stirring, and C is then added6H5Na3O7·H2O is mixed
Liquid B adjusts pH=9~11 with ammonium hydroxide 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, obtains mixed liquor D, and by mixed liquor D in 70 DEG C of stirred in water bath
Reaction；To after reaction, sediment be separated with solution with magnet, with deionized water, ethanol washing, vacuum drying is obtained
ZnFe2O4@CdS composite photo-catalyst.
In step 1, when preparing mixed liquor A, used Fe (NO3)3·9H2O、Zn(NO3)2·6H2O, ethylene glycol, PVP
Amount ratio be 4mmol:2mmol:60mL:15mmol；The temperature of the constant temperature thermal response is 150~210 DEG C, the reaction time
For 22~72h.
In step 2, pH=10.5~11.
In step 2, when preparing mixed liquid B, used ZnFe2O4、CdCl2·H2O, water, C6H5Na3O7·H2The dosage of O
Than for 0.207~0.622mmol:0.9354~2mmol:200mL:2mmol；When preparing mixed liquor C, the matter of used ammonium hydroxide
Measuring score is 25%~28%；The volume ratio of used thiourea solution and mixed liquid B is 3:20, and used thiocarbamide is water-soluble
The concentration of liquid is 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 stirred in 70 DEG C of water-baths
Mixing the reaction time is 2h.
Prepared ZnFe2O4In@CdS composite photo-catalyst, ZnFe2O4Mass fraction be 20~90%.
Prepared ZnFe2O4@CdS composite photo-catalyst is for the tetracycline in degrading waste water.
Photocatalytic activity evaluation: carrying out in DW-01 type photochemical reactor (being purchased from Educational Instrument Factory, Yangzhou University), can
100mL tetracycline simulated wastewater is added in reactor and measures its initial value, composite photocatalyst is then added by light-exposed light irradiation
Agent, magnetic agitation simultaneously open aerator and are passed through air and maintain the catalyst in suspension or afloat, be spaced in During Illumination
10min sampling analysis takes supernatant liquor to measure absorbance at spectrophotometer λ max=358nm, and passes through after centrifuge separation
Formula: DR=[(A0-Ai)/A0] × 100% calculates degradation rate, wherein A0The extinction of tetracycline when to reach adsorption equilibrium
Degree, AiFor the absorbance of the tetracycline of timing sampling measurement.
The utility model has the advantages that
The present invention is realized with CdS semiconductor-quantum-point and ZnFe2O4It is formed and heterogeneous becomes ZnFe2O4@CdS complex light is urged
The purpose of agent degradation antibiotic waste water.Semiconductor material is as photochemical catalyst, it is seen that light is as excitation, by dividing with pollutant
The interfacial interaction of son realizes special catalysis or conversion effet, and the oxygen of surrounding is made to be excited into freely bearing for great oxidizing force
Ion, to achieve the purpose that harmful organic substances in degradation environment, this method will not result in waste of resources and additional pollution
It is formed, and easy to operate, is a kind of environmentally protective efficient process technology.
Detailed description of the invention
Fig. 1 is ZnFe2O4@CdS composite photo-catalyst photocatalysis TEM spectrogram, wherein figure a, b, c are under different amplification
TEM spectrogram, figure d be figure c partial enlarged view；
Fig. 2 is ZnFe2O4The hysteresis loop figure of@CdS composite photo-catalyst；
Fig. 3 is ZnFe2O4The stability of@CdS composite photo-catalyst, which is degraded, to be schemed.
Specific embodiment
Below with reference to specific implementation example, the present invention will be further described.
Embodiment 1:
(1)ZnFe2O4Preparation:
Pure ZnFe is synthesized using hydro-thermal method2O4.By 4mmol Fe (NO3)3·9H2O and 2mmol Zn (NO3)2·6H2O is added
It is stirred into 60mL ethylene glycol, 15mmol PVP is then added and continues to stir 30min.When solution after mixing evenly, by solution from
It is poured into beaker in 100mL reaction kettle, reacts 72h under the conditions of 210 DEG C.After reaction, deionization is used after dropping to room temperature
Water, ethyl alcohol are washed for several times, are then dried 12h under the conditions of 60 DEG C, are obtained ZnFe2O4。
(2)ZnFe2O4The preparation of@CdS composite photo-catalyst:
By 0.414mmol ZnFe2O4With 2mmol CdCl2·H2O is added to mechanical stirring 30min in 200mL water, then
By 2mmol C6H5Na3O7·H2O, which is added in above-mentioned solution and moves into 70 DEG C of water-baths, to be continued to stir 20min, after being sufficiently stirred
With mass fraction be 25%~28% ammonium hydroxide adjust solution pH=10.5-11, after 0.3g thiocarbamide is dissolved in 30mL water by
It is added dropwise to above-mentioned solution, and solution is continued to stir 2h in 70 DEG C of water-baths.To after reaction, with magnet by sediment with
Solution separation, is washed for several times with deionized water, ethyl alcohol, is put into vacuum oven and dries, obtain ZnFe2O4@CdS composite photocatalyst
Agent.
(3) it takes 0.1g sample in (2) to carry out photocatalytic degradation test in photochemical reactor, measures the photochemical catalyst pair
The degradation rate of 100mL20mg/L tetracycline antibiotic reaches 95.31% in 90min.
Fig. 1 is ZnFe2O4@CdS composite photo-catalyst photocatalysis TEM spectrogram.What be will be apparent that in figure presents ZnFe2O4@
The core-shell structure of CdS.
Fig. 2 is ZnFe2O4The hysteresis loop figure of@CdS composite photo-catalyst, as can be seen from the figure photochemical catalyst has very
Good magnetism.
Fig. 3 is ZnFe2O4The stability of@CdS composite photo-catalyst, which is degraded, to be schemed, as can be seen from the figure CdS/Fe3O4/rGO
With good stability.
Embodiment 2:
By the step in embodiment 1, unlike (1) by 4mmol Fe (NO3)3·9H2O and 2mmol Zn (NO3)2·
6H2O is added in 60mL ethylene glycol and stirs, and 15mmol PVP is then added and continues to stir 30min as surfactant.When molten
Liquid after mixing evenly, by solution from being poured into 100mL reaction kettle in beaker, reacts 22h under the conditions of 150 DEG C.After reaction,
It is washed for several times after reactant drops to room temperature with deionized water, ethyl alcohol, then dries 12h under the conditions of 60 DEG C, obtain ZnFe2O4。
It takes 0.1g sample to carry out photocatalytic degradation test in photochemical reactor, measures the photochemical catalyst to 100mL
The degradation rate of 20mg/L tetracycline antibiotic reaches 56.05% in 90min.
Embodiment 3:
By the step in embodiment 1, unlike (1) by 4mmol Fe (NO3)3·9H2O and 2mmol Zn (NO3)2·
6H2O is added in 60mL ethylene glycol and stirs, and 15mmol CH is then added3COONa continues to stir 30min as surfactant.
When solution after mixing evenly, by solution from being poured into 100mL reaction kettle in beaker, react 22h under the conditions of 150 DEG C.Reaction knot
Shu Hou is washed for several times after reactant drops to room temperature with deionized water, ethyl alcohol, is then dried 12h under the conditions of 60 DEG C, is obtained
ZnFe2O4。
It takes 0.1g sample to carry out photocatalytic degradation test in photochemical reactor, measures the photochemical catalyst to 100mL
The degradation rate of 20mg/L tetracycline antibiotic reaches 55.83% in 90min.
Embodiment 4:
By the step in embodiment 1, unlike (1) by 4mmol Fe (NO3)3·9H2O and 2mmol Zn (NO3)2·
6H2O is added in 60mL ethylene glycol and stirs, and 15mmol CTAB is then added and continues to stir 30min as surfactant.When
Solution after mixing evenly, by solution from being poured into 100mL reaction kettle in beaker, reacts 22h under the conditions of 150 DEG C.Reaction terminates
Afterwards, it is washed for several times after reactant drops to room temperature with deionized water, ethyl alcohol, then dries 12h under the conditions of 60 DEG C, obtain
ZnFe2O4。
It takes 0.1g sample to carry out photocatalytic degradation test in photochemical reactor, measures the photochemical catalyst to 100mL
The degradation rate of 20mg/L tetracycline antibiotic reaches 50.06% in 90min.
Embodiment 5:
By the step in embodiment 1, unlike (1) by 4mmol Fe (NO3)3·9H2O and 2mmol Zn (NO3)2·
6H2O is added in 60mL ethylene glycol and stirs, and 15mmol PVP is then added and continues to stir 30min as surfactant.When molten
Liquid after mixing evenly, by solution from being poured into 100mL reaction kettle in beaker, reacts for 24 hours under the conditions of 150 DEG C.After reaction,
It is washed for several times after reactant drops to room temperature with deionized water, ethyl alcohol, then dries 12h under the conditions of 60 DEG C, obtain ZnFe2O4。
It takes 0.1g sample to carry out photocatalytic degradation test in photochemical reactor, measures the photochemical catalyst to 100mL
The degradation rate of 20mg/L tetracycline antibiotic reaches 52.86% in 90min.
Embodiment 6:
By the step in embodiment 1, unlike (1) by 4mmol Fe (NO3)3·9H2O and 2mmol Zn (NO3)2·
6H2O is added in 60mL ethylene glycol and stirs, and 15mmol PVP is then added and continues to stir 30min as surfactant.When molten
Liquid after mixing evenly, by solution from being poured into 100mL reaction kettle in beaker, reacts 26h under the conditions of 150 DEG C.After reaction,
It is washed for several times after reactant drops to room temperature with deionized water, ethyl alcohol, then dries 12h under the conditions of 60 DEG C, obtain ZnFe2O4。
It takes 0.1g sample to carry out photocatalytic degradation test in photochemical reactor, measures the photochemical catalyst to 100mL
The degradation rate of 20mg/L tetracycline antibiotic reaches 54.27% in 90min.
Embodiment 7:
By the step in embodiment 1, unlike (1) by 4mmol Fe (NO3)3·9H2O and 2mmol Zn (NO3)2·
6H2O is added in 60mL ethylene glycol and stirs, and 15mmol PVP is then added and continues to stir 30min as surfactant.When molten
Liquid after mixing evenly, by solution from being poured into 100mL reaction kettle in beaker, reacts 72h under the conditions of 150 DEG C.After reaction,
It is washed for several times after reactant drops to room temperature with deionized water, ethyl alcohol, then dries 12h under the conditions of 60 DEG C, obtain ZnFe2O4。
It takes 0.1g sample to carry out photocatalytic degradation test in photochemical reactor, measures the photochemical catalyst to 100mL
The degradation rate of 20mg/L tetracycline antibiotic reaches 57.09% in 90min.
Embodiment 8:
By the step in embodiment 1, unlike (1) by 4mmol Fe (NO3)3·9H2O and 2mmol Zn (NO3)2·
6H2O is added in 60mL ethylene glycol and stirs, and 15mmol PVP is then added and continues to stir 30min as surfactant.When molten
Liquid after mixing evenly, by solution from being poured into 100mL reaction kettle in beaker, reacts 72h under the conditions of 170 DEG C.After reaction,
It is washed for several times after reactant drops to room temperature with deionized water, ethyl alcohol, then dries 12h under the conditions of 60 DEG C, obtain ZnFe2O4。
It takes 0.1g sample to carry out photocatalytic degradation test in photochemical reactor, measures the photochemical catalyst to 100mL
The degradation rate of 20mg/L tetracycline antibiotic reaches 51.07% in 90min.
Embodiment 9:
By the step in embodiment 1, unlike (1) by 4mmol Fe (NO3)3·9H2O and 2mmol Zn (NO3)2·
6H2O is added in 60mL ethylene glycol and stirs, and 15mmol PVP is then added and continues to stir 30min as surfactant.When molten
Liquid after mixing evenly, by solution from being poured into 100mL reaction kettle in beaker, reacts 72h under the conditions of 190 DEG C.After reaction,
It is washed for several times after reactant drops to room temperature with deionized water, ethyl alcohol, then dries 12h under the conditions of 60 DEG C, obtain ZnFe2O4。
It takes 0.1g sample to carry out photocatalytic degradation test in photochemical reactor, measures the photochemical catalyst to 100mL
The degradation rate of the raw element of 20mg/L tetracycline reaches 53.46% in 90min.
Embodiment 10:
By the step in embodiment 1, unlike (2) by 0.207mmol ZnFe2O4With 1.821mmol CdCl2·H2O
It is added to mechanical stirring 30min in 200mL water, then by 2mmol C6H5Na3O7·H2O is added in above-mentioned solution and moves into 70 DEG C
Continue to stir 20min in water-bath, adjusts the pH=10.5 of solution after being sufficiently stirred with ammonium hydroxide, 0.3g thiocarbamide is dissolved in 30mL water
In after above-mentioned solution is added dropwise, and solution continued to stir 2h in 70 DEG C of water-baths.To after reaction, be sunk with magnet
Starch is separated with solution, is washed for several times with deionized water, ethyl alcohol, is put into vacuum oven and dries, obtains ZnFe2O4@CdS is compound
Photochemical catalyst.
It takes 0.1g sample to carry out photocatalytic degradation test in photochemical reactor, measures the photochemical catalyst to 100mL
The degradation rate of 20mg/L tetracycline antibiotic reaches 91.36% in 90min.
Embodiment 11:
By the step in embodiment 1, unlike (2) by 0.415mmol ZnFe2O4With 1.821mmol CdCl2·H2O
It is added to mechanical stirring 30min in 200mL water, then by 2mmol C6H5Na3O7·H2O is added in above-mentioned solution and moves into 70 DEG C
Continue to stir 20min in water-bath, adjusts the pH=10.5 of solution after being sufficiently stirred with ammonium hydroxide, 0.3g thiocarbamide is dissolved in 30mL water
In after above-mentioned solution is added dropwise, and solution continued to stir 2h in 70 DEG C of water-baths.To after reaction, be sunk with magnet
Starch is separated with solution, is washed for several times with deionized water, ethyl alcohol, is put into vacuum oven and dries, obtains ZnFe2O4@CdS is compound
Photochemical catalyst.
It takes 0.1g sample to carry out photocatalytic degradation test in photochemical reactor, measures the photochemical catalyst to 100mL
The degradation rate of 20mg/L tetracycline antibiotic reaches 95.31% in 90min.
Embodiment 12:
By the step in embodiment 1, unlike (2) by 0.622mmol ZnFe2O4With 1.821mmol CdCl2·H2O
It is added to mechanical stirring 30min in 200mL water, then by 2mmol C6H5Na3O7·H2O is added in above-mentioned solution and moves into 70 DEG C
Continue to stir 20min in water-bath, adjusts the pH=10.5 of solution after being sufficiently stirred with ammonium hydroxide, 0.3g thiocarbamide is dissolved in 30mL water
In after above-mentioned solution is added dropwise, and solution continued to stir 2h in 70 DEG C of water-baths.To after reaction, be sunk with magnet
Starch is separated with solution, is washed for several times with deionized water, ethyl alcohol, is put into vacuum oven and dries, obtains ZnFe2O4@CdS is compound
Photochemical catalyst.
It takes 0.1g sample to carry out photocatalytic degradation test in photochemical reactor, measures the photochemical catalyst to 100mL
The degradation rate of 20mg/L tetracycline antibiotic reaches 89.94% in 90min.
Embodiment 13:
By the step in embodiment 1, unlike (2) by 0.415mmol ZnFe2O4With 0.9354mmol CdCl2·
H2O is added to mechanical stirring 30min in 200mL water, then by 2mmol C6H5Na3O7·H2O is added in above-mentioned solution and moves into
Continue to stir 20min in 70 DEG C of water-baths, adjusts the pH=10.5 of solution after being sufficiently stirred with ammonium hydroxide, 0.3g thiocarbamide is dissolved in
Above-mentioned solution is added dropwise after in 30mL water, and solution is continued to stir 2h in 70 DEG C of water-baths.To after reaction, use magnetic
Iron separates sediment with solution, is washed for several times with deionized water, ethyl alcohol, is put into vacuum oven and dries, obtains ZnFe2O4@
CdS composite photo-catalyst.
It takes 0.1g sample to carry out photocatalytic degradation test in photochemical reactor, measures the photochemical catalyst to 100mL
The degradation rate of 20mg/L tetracycline antibiotic reaches 90.83% in 90min.
Embodiment 14:
By the step in embodiment 1, unlike (2) by 0.415mmol ZnFe2O4With 1.267mmol CdCl2·H2O
It is added to mechanical stirring 30min in 200mL water, then by 2mmol C6H5Na3O7·H2O is added in above-mentioned solution and moves into 70 DEG C
Continue to stir 20min in water-bath, adjusts the pH=10.5 of solution after being sufficiently stirred with ammonium hydroxide, 0.3g thiocarbamide is dissolved in 30mL water
In after above-mentioned solution is added dropwise, and solution continued to stir 2h in 70 DEG C of water-baths.To after reaction, be sunk with magnet
Starch is separated with solution, is washed for several times with deionized water, ethyl alcohol, is put into vacuum oven and dries, obtains ZnFe2O4@CdS is compound
Photochemical catalyst.
It takes 0.1g sample to carry out photocatalytic degradation test in photochemical reactor, measures the photochemical catalyst to 100mL
The degradation rate of 20mg/L tetracycline antibiotic reaches 92.20% in 90min.
Embodiment 15:
By the step in embodiment 1, unlike (2) by 0.415mmol ZnFe2O4With 1.821mmol CdCl2·H2O
It is added to mechanical stirring 30min in 200mL water, then by 2mmol C6H5Na3O7·H2O is added in above-mentioned solution and moves into 70 DEG C
Continue to stir 20min in water-bath, the pH=9 of solution is adjusted after being sufficiently stirred with ammonium hydroxide, after 30mL thiocarbamide is then added dropwise
Solution is continued to stir 2h in 70 DEG C of water-baths.To after reaction, sediment be separated with solution with magnet, uses deionization
Water, ethyl alcohol are washed for several times, are put into vacuum oven and are dried, and ZnFe is obtained2O4@CdS composite photo-catalyst.
It takes 0.1g sample to carry out photocatalytic degradation test in photochemical reactor, measures the photochemical catalyst to 100mL
The degradation rate of 20mg/L tetracycline antibiotic reaches 74.60% in 90min.
Embodiment 16:
By the step in embodiment 1, unlike (2) by 0.415mmol ZnFe2O4With 1.821mmol CdCl2·H2O
It is added to mechanical stirring 30min in 200mL water, then by 2mmol C6H5Na3O7·H2O is added in above-mentioned solution and moves into 70 DEG C
Continue to stir 20min in water-bath, the pH=11 of solution is adjusted after being sufficiently stirred with ammonium hydroxide, after 30mL thiocarbamide is then added dropwise
Solution is continued to stir 2h in 70 DEG C of water-baths.To after reaction, sediment be separated with solution with magnet, uses deionization
Water, ethyl alcohol are washed for several times, are put into vacuum oven and are dried, and ZnFe is obtained2O4@CdS composite photo-catalyst.
It takes 0.1g sample to carry out photocatalytic degradation test in photochemical reactor, measures the photochemical catalyst to 100mL
The degradation rate of 20mg/L tetracycline antibiotic reaches 94.60% in 90min.
Claims (5)
1. a kind of core-shell structure ZnFe2O4The preparation method of@CdS composite photo-catalyst, which is characterized in that include the following steps
Step 1, ZnFe2O4Preparation: by Fe (NO3)3·9H2O and Zn (NO3)2·6H2O is added in ethylene glycol and stirs, then
PVP is added to stir evenly, obtains mixed liquor A；Mixed liquor A is transferred to progress constant temperature thermal response in reaction kettle；After reaction,
Room temperature to be dropped to, it is dry with deionized water, ethanol washing solid product, obtain ZnFe2O4；
Step 2, ZnFe2O4The preparation of@CdS composite photo-catalyst: by ZnFe2O4And CdCl2·H2The O machinery that is added to the water stirs
It mixes, C is then added6H5Na3O7·H2O obtains mixed liquid B, is adjusted after mixed liquid B is sufficiently stirred in 70 DEG C of water-baths with ammonium hydroxide
PH=9~11 obtain mixed liquor C；Thiourea solution is added dropwise in mixed liquor C, obtains mixed liquor D, and mixed liquor D is existed
70 DEG C of stirred in water bath reactions；To which after reaction, sediment is separated with solution with magnet, with deionized water, ethanol washing,
Vacuum drying obtains ZnFe2O4@CdS composite photo-catalyst；
In the step 1, when preparing mixed liquor A, used Fe (NO3)3·9H2O、Zn(NO3)2·6H2O, ethylene glycol, PVP
Amount ratio be 4mmol:2mmol:60mL:15mmol；The temperature of the constant temperature thermal response is 150~210 DEG C, the reaction time
For 22~72h.
2. a kind of core-shell structure ZnFe according to claim 12O4The preparation method of@CdS composite photo-catalyst, feature
It is, in step 2, pH=10.5~11.
3. a kind of core-shell structure ZnFe according to claim 12O4The preparation method of@CdS composite photo-catalyst, feature
It is, in step 2, when preparing mixed liquid B, used ZnFe2O4、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 used ammonium hydroxide
Score is 25%~28%；The volume ratio of used thiourea solution and mixed liquid B is 3:20, used thiourea solution
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.
4. a kind of core-shell structure ZnFe according to claim 12O4Prepared by the preparation method of@CdS composite photo-catalyst
ZnFe2O4@CdS composite photo-catalyst, which is characterized in that the ZnFe2O4In@CdS composite photo-catalyst, ZnFe2O4Quality
Score is 20~90%.
5. the core-shell structure ZnFe of method preparation described in claim 12O4The purposes of@CdS composite photo-catalyst, feature exist
In prepared ZnFe2O4@CdS composite photo-catalyst is for the tetracycline in degrading waste water.
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| CN107149936B (en) * | 2017-04-10 | 2019-12-31 | 江苏大学 | CoFe2O4-AgI composite photocatalyst and preparation method thereof |
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| CN112844414A (en) * | 2021-01-29 | 2021-05-28 | 昆明理工大学 | Popcorn-shaped ZnFe2O4Preparation method of/CdS/GO heterojunction photocatalyst |
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