CN107042119A - A kind of CdS/Fe3O4/C3N4Composite photo-catalyst and preparation method and purposes - Google Patents
A kind of CdS/Fe3O4/C3N4Composite photo-catalyst and preparation method and purposes Download PDFInfo
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- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 title claims abstract description 140
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 239000002131 composite material Substances 0.000 claims abstract description 35
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 23
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 239000004098 Tetracycline Substances 0.000 claims description 16
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 15
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 15
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 235000019364 tetracycline Nutrition 0.000 claims description 12
- 150000003522 tetracyclines Chemical class 0.000 claims description 12
- 229960002180 tetracycline Drugs 0.000 claims description 11
- 229930101283 tetracycline Natural products 0.000 claims description 11
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 229920001223 polyethylene glycol Polymers 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 8
- QCUOBSQYDGUHHT-UHFFFAOYSA-L cadmium sulfate Chemical compound [Cd+2].[O-]S([O-])(=O)=O QCUOBSQYDGUHHT-UHFFFAOYSA-L 0.000 claims description 7
- 229910000331 cadmium sulfate Inorganic materials 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 7
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 229910016874 Fe(NO3) Inorganic materials 0.000 claims description 4
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- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
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- 238000005070 sampling Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
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- 229910052724 xenon Inorganic materials 0.000 description 3
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 206010059866 Drug resistance Diseases 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
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- 244000144972 livestock Species 0.000 description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 2
- 238000006552 photochemical reaction Methods 0.000 description 2
- 230000005622 photoelectricity Effects 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 244000144977 poultry Species 0.000 description 2
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- 238000002604 ultrasonography Methods 0.000 description 2
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- 238000005727 Friedel-Crafts reaction Methods 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- KIPLYOUQVMMOHB-MXWBXKMOSA-L [Ca++].CN(C)[C@H]1[C@@H]2[C@@H](O)[C@H]3C(=C([O-])[C@]2(O)C(=O)C(C(N)=O)=C1O)C(=O)c1c(O)cccc1[C@@]3(C)O.CN(C)[C@H]1[C@@H]2[C@@H](O)[C@H]3C(=C([O-])[C@]2(O)C(=O)C(C(N)=O)=C1O)C(=O)c1c(O)cccc1[C@@]3(C)O Chemical compound [Ca++].CN(C)[C@H]1[C@@H]2[C@@H](O)[C@H]3C(=C([O-])[C@]2(O)C(=O)C(C(N)=O)=C1O)C(=O)c1c(O)cccc1[C@@]3(C)O.CN(C)[C@H]1[C@@H]2[C@@H](O)[C@H]3C(=C([O-])[C@]2(O)C(=O)C(C(N)=O)=C1O)C(=O)c1c(O)cccc1[C@@]3(C)O KIPLYOUQVMMOHB-MXWBXKMOSA-L 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000005276 aerator Methods 0.000 description 1
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- 238000004458 analytical method Methods 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
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- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011218 binary composite Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- CYDMQBQPVICBEU-UHFFFAOYSA-N chlorotetracycline Natural products C1=CC(Cl)=C2C(O)(C)C3CC4C(N(C)C)C(O)=C(C(N)=O)C(=O)C4(O)C(O)=C3C(=O)C2=C1O CYDMQBQPVICBEU-UHFFFAOYSA-N 0.000 description 1
- 229960004475 chlortetracycline Drugs 0.000 description 1
- CYDMQBQPVICBEU-XRNKAMNCSA-N chlortetracycline Chemical compound C1=CC(Cl)=C2[C@](O)(C)[C@H]3C[C@H]4[C@H](N(C)C)C(O)=C(C(N)=O)C(=O)[C@@]4(O)C(O)=C3C(=O)C2=C1O CYDMQBQPVICBEU-XRNKAMNCSA-N 0.000 description 1
- 235000019365 chlortetracycline Nutrition 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000005447 environmental material Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007952 growth promoter Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000004941 influx Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 210000003734 kidney Anatomy 0.000 description 1
- 210000004185 liver Anatomy 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
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- 244000000010 microbial pathogen Species 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
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- 239000002105 nanoparticle Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 150000002830 nitrogen compounds Chemical class 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 210000000056 organ Anatomy 0.000 description 1
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- 230000001717 pathogenic effect Effects 0.000 description 1
- 230000002688 persistence Effects 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 238000002256 photodeposition Methods 0.000 description 1
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- 239000000843 powder Substances 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
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- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229940063650 terramycin Drugs 0.000 description 1
- 229940072172 tetracycline antibiotic Drugs 0.000 description 1
- 229940040944 tetracyclines Drugs 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000005945 translocation Effects 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 229920002554 vinyl polymer Polymers 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
- B01J27/24—Nitrogen compounds
-
- 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
- C02F2101/38—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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- 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 invention provides a kind of CdS/Fe3O4/C3N4Composite photo-catalyst and preparation method and purposes, are prepared as follows：Step 1, g C3N4Preparation；Step 2, Fe3O4/g‑C3N4The preparation of magnetic composite；Step 3, CdS/Fe3O4/g‑C3N4The preparation of composite photo-catalyst.CdS/Fe prepared by method of the present invention3O4/g‑C3N4The separation and recovery of composite photo-catalyst is more convenient, efficient；The CdS/Fe3O4/g‑C3N4Composite photo-catalyst has preferable photocatalytic activity and stability.
Description
Technical field
The invention belongs to technical field of environmental material preparation, and in particular to a kind of polynary CdS/Fe based on carbonitride3O4/
C3N4The Preparation method and use of the preparation method composite photo-catalyst of composite photo-catalyst.
Background technology
In numerous antibiotic, tetracycline antibiotics be the antibiotic that is worldwide most widely used it
One, main species includes tetracycline, terramycin, aureomycin etc., because antibiotic can play antibacterial, sterilization to varying degrees
Various diseases are treated with bacteriostasis and being used for and delivered as the growth promoter of livestock and poultry and arrived livestock and poultry and culture fishery.
Research shows, no matter people is used or after veterinary antibiotic enters in animal or human body, and about 70% can not be absorbed, but by with
The form of parent compound, which is directly excreted, to be entered in environment, and potential threat is constituted to health and the ecosystem.
It is mainly shown as：First：Cause the enhancing of the drug resistance of pathogenic microbes.The enhancing of drug resistance causes most antibiotics pair
Pathogenic microorganisms loses sensitiveness, loses the effect for the treatment of disease.Second：Suppress or kill original micro- in aquatic environment
Biology, destroys ecosystem balance.3rd：Damage every organ of body.Entered into the antibiotic after water body by food chain
Enter after human body, burden can be not only brought to liver, the kidney of human body but also toxicity can be produced to some normal cells of human body
Even trigger canceration.Therefore, the removal for Tetracyclines pollutant has increasingly been closed by increasing researcher
Note, so, realize to effective removal of this persistence organic pollutant of tetracycline, reduce risk that it exists in the environment still
It is urgent problem to be solved for a long time.At present, the processing method for the organic pollution has a lot, such as, absorption method, life
Thing edman degradation Edman, micro-electrolysis method, the method such as photocatalysis.Wherein, research in terms of removal organic polluter is gone using photocatalysis technology
Through obtaining certain progress.It is a kind of preferable green technology, can give birth to organic matter degradation for the small molecule of environmental sound,
Even carbon dioxide, water etc..
g-C3N4(carbonitride) is the new organic photochemical catalyst of a class, g-C3N4It is a kind of spy for comprising only C and N atoms
Different organic photocatalytic semiconductor, belongs to low energy gap (2.7eV) excited by visible light material.Its discovery can trace back to 1834
Liebig etc. (Liebig J.About some nitrogen compounds [J] .Ann Pharm.1834,10,10.) is closed
Into a variety of g-C3N4Presoma.But g-C3N4The application of photocatalysis field be then Goettmann etc. (Goettmann F,
Fischer A,Antonietti M,et al.Metal-free catalysis of sustainable Friedel-
Crafts reactions:direct activation of benzene by carbon nitrides to avoid the
use of metal chlorides and halogenated compounds[J].Chemical communications,
2006,43,4530-4532.) publish an article on magazine after., (Wang the X C, KazuhikoM, Arne such as Wang in 2009
T,et al.A metal-free polymeric photocatalyst for hydrogen production from
water under visible light[J].Nature Material,2009,8:76-80.) report g-C3N4Visible
Decomposable asymmetric choice net aquatic products H under light2And photocatalysis goes after the performance of removal organic polluter to cause the further investigation of numerous scholars, including
A series of technological means is taken to g-C3N4Photochemical catalyst carries out modification and improved its photocatalytic activity.(Zhu Z,Lu
Z.Y,Wang D.D, Tang X,et al.Construction of high-dispersed Ag/Fe3O4/g-
C3N4photocatalyst byselective photo-deposition and improved photocatalytic
activity[J].Applied Catalysis B:Environmential, 2016,182:115-122.).Water is used herein
Ternary CdS/Fe of the hot method synthesis with visible light catalysis activity3O4/C3N4Magnetic composite photocatalyst, the composite photo-catalyst
Not only there is preferable magnetic also greatly strengthen contact of the composite photo-catalyst to antibiotic contamination simultaneously, improve and urge
Absorption of the agent to pollutant, so as to improve photocatalytic activity.In addition, we select Fe3O4It is used as magnetic material.It is main to consider
Its good Magneto separate characteristic reduction financial cost, greatly improves cost recovery and secondary utilization rate.
The content of the invention
The present invention prepares a kind of CdS/Fe using hydro-thermal method as preparation means3O4/C3N4The preparation side of composite photo-catalyst
Tetracycline in method, the environmental wastewater that can be good at degrading, with synthesis is simple and the characteristics of high degradation rate.
The technical scheme is that：
A kind of CdS/Fe3O4/C3N4Composite photo-catalyst, the CdS/Fe3O4/C3N4Composite photo-catalyst is by CdS
Grain, Fe3O4、C3N4It is composited；The C3N4For irregular sheet；The Fe3O4To be spherical, C is carried on3N4On, shape
Into Fe3O4/C3N4；The CdS particulate loads are in the Fe3O4/C3N4Surface.
A kind of CdS/Fe3O4/C3N4The preparation method of composite photo-catalyst, step is as follows：
Step 1, g-C3N4Preparation：Melamine is added in crucible, then will be transferred them in high temperature Muffle furnace
Carry out heat polymerization；After muffle furnace is cooled to room temperature, crucible is taken out and the solid sample in crucible is ground to form
Sample, is then put into baking oven and dries, obtain yellow g-C by powder3N4, it is standby；
Step 2, Fe3O4/g-C3N4The preparation of magnetic composite：Thin g-C will be ground3N4It is scattered in ethylene glycol,
Keep ultrasonic magnetic agitation to be reacted in water-bath, then add Fe(NO3)39H2O, sodium acetate, polyethylene glycol thereto again
2000th, polyvinylpyrrolidone (PVP), continues ultrasonic agitation, until the sample added is dispersed or dissolves；Then incite somebody to action
To dispersion liquid be fitted into polytetrafluoroethylene (PTFE) water heating kettle, carry out solvent thermal reaction, reaction terminates and be cooled to after room temperature to collect solid
Body product, is washed, and drying obtains Fe3O4/g-C3N4Magnetic composite；
Step 3, CdS/Fe3O4/g-C3N4The preparation of composite photo-catalyst：The Fe that step 2 is obtained3O4/g-C3N4Magnetic is answered
Deionized water is added in condensation material to be stirred, cadmium sulfate, sulphur urine, polyvinylpyrrolidone is added, continues to stir, and will be burnt
Cup is transferred to constant temperature waters pot interior sealing, continues constant temperature and stirs and be maintained at reaction, question response knot under conditions of logical inert gas
Room temperature is naturally cooled to after beam, beaker is taken out and the solid sample in beaker is collected, washs, then dries solid sample standby
With being designated as CdS/Fe3O4/g-C3N4The preparation of composite photo-catalyst.
In step 1, it is characterised in that the calcining manners are that first stage constant temperature at 500 DEG C keeps 2h, described second
Stage calcining manners are that constant temperature keeps 2h at 550 DEG C, and the first stage calcining, second stage calcining heating rate are
2.0 DEG C~10 DEG C/min.
In step 2, the g-C3N4, ethylene glycol, Fe(NO3)39H2O, sodium acetate, polyethylene glycol 2000, polyvinyl pyrrole
The amount ratio of alkanone is 0.5~2.0g:10~30mL:0.05~0.1g:0.05~0.8g:0.2~0.4g:0.005~
0.008g；The temperature of solvent thermal reaction is 160~220 DEG C, and the reaction time is 10~15h.
In step 3, the Fe3O4/g-C3N4, deionized water, cadmium sulfate, thiocarbamide, the amount ratio of polyvinylpyrrolidone be
0.1~0.3g:50~150mL:0.7~2.1g:0.05~0.2g:0.01~0.09g；The temperature of the reaction is 60~80
DEG C, the reaction time is 3~8h；The inert gas is nitrogen.
Described CdS/Fe3O4/g-C3N4Composite photo-catalyst is used for photocatalytic degradation tetracycline.
Beneficial effect：
CdS/Fe prepared by method of the present invention3O4/g-C3N4The separation and recovery of composite photo-catalyst is more convenient,
Efficiently；The CdS/Fe3O4/g-C3N4Composite photo-catalyst has preferable photocatalytic activity and stability.
Brief description of the drawings
Fig. 1 is the XRD of sample prepared by embodiment 1；Respectively g-C3N4,Fe3O4, CdS, CdS/Fe3O4/g-C3N4's
XRD curves；
Fig. 2 is the TEM spectrograms of sample, and wherein a is g-C3N4TEM figure, b is Fe3O4/g-C3N4TEM figure, c is CdS/
Fe3O4/g-C3N4TEM figure, d for part amplification CdS/Fe3O4/g-C3N4The High-Resolution Map of figure and CdS；
Fig. 3 schemes for the UV-Vis of different samples；
Fig. 4 is the VSM figures and circulation degraded design sketch of different synthetic samples, and wherein a figures are Fe3O4/g-C3N4And CdS/
Fe3O4/g-C3N4VSM figure；B figures are CdS/Fe3O4/g-C3N4Circulation degraded design sketch
Fig. 5 is the photoelectricity flow graph and impedance diagram that different samples are different synthetic samples, and wherein A figures are g-C3N4, Fe3O4/g-
C3N4And CdS/Fe3O4/g-C3N4Photoelectricity flow graph；B figures are g-C3N4, Fe3O4/g-C3N4And CdS/Fe3O4/g-C3N4Impedance
Figure.
Fig. 6 is the PL figures and FL figures that different samples are different synthetic samples, and wherein A figures are g-C3N4, CdS/g-C3N4With
CdS/Fe3O4/g-C3N4PL figure；B figures are g-C3N4, CdS/g-C3N4And CdS/Fe3O4/g-C3N4FL figure.
Embodiment
With reference to specific embodiment, the invention will be further described：
Photocatalytic activity evaluation：Carried out in D1 type photochemical reactions instrument (being purchased from Educational Instrument Factory of Yangzhou University), will
100mL 20mg/L tetracycline simulated wastewater is added in reaction bulb, adds magneton and 0.05g photochemical catalysts, opens visible ray
Power supply and aerator carry out Dynamic Adsorption, start external thermostatic water-circulator bath and control temperature of reaction system to be 30 DEG C.Reach and inhale
Illumination reaction is carried out after attached balance, every sampling in 15 minutes once, is centrifuged, is surveyed the concentration of tetracycline in supernatant, pass through
C/C0To judge the degradation effect of tetracycline.Wherein, C0For the concentration of tetracycline after adsorption equilibrium, Fourth Ring when C is reaction time T
The concentration of element
Embodiment 1：
Step 1, g-C3N4Preparation：The melamine for taking 3g to buy is placed in crucible, is placed in Muffle furnace, in air
Calcined in atmosphere, with 2 DEG C of min-1Heating rate be warming up to 500 DEG C, and constant temperature keeps 2h, with same heating rate after
It is continuous to be warming up to 550 DEG C, and constant temperature keeps 2h, naturally cools to room temperature and finely ground, that is, obtains g-C3N4Photochemical catalyst
Step 2, preparation Fe3O4/g-C3N4：By g-C3N4It is dispersed in ethylene glycol and ultrasound, g-C is made3N4Suspension；
By Fe (NO3)3·9H2O, PVP, PEG and CH3COONa·3H2O is dissolved in above-mentioned g-C respectively3N4Suspension in；Will be above-mentioned
Mixed liquor continues ultrasound to abundant dissolving, reaction mixture is transferred into constant temperature heating in 50mL ptfe autoclaves afterwards anti-
Should a period of time；Finally, by obtained sediment Fe3O4/g-C3N4Kept dry；Reaction uses deionized water and anhydrous after terminating
Ethanol is repeatedly washed, vacuum drying, that is, obtains binary composite photocatalyst material Fe3O4/g-C3N4.Used g-C3N4, second
Glycol, Fe (NO3)3·9H2O, PVP, PEG and CH3COONa·3H2O consumption be followed successively by 0.5g, 10mL, 0.05g,
0.005g、0.2g、0.05g；Constant temperature heating reaction temperature is 180 DEG C, and the reaction time is 15h.
Step 3, preparation CdS/Fe3O4/g-C3N4Photocatalytic nanometer reactor：By Fe3O4/g-C3N4, cadmium sulfate, thiocarbamide,
PVP, the consumption of deionized water are followed successively by 0.1g, 0.7g, 0.05g, 0.01g, 50mL；The temperature of solvent thermal reaction is 60 DEG C, instead
Answer 8h.Question response dries solid sample after terminating.
In step 2, step 3, the drying temperature of sample is 60 DEG C.
Step 4, the CdS/Fe taken in 0.05g steps 33O4/g-C3N4It is added to 100mL and contains 20mg L-1Tetracycline
Reactor in, at 30 DEG C lucifuge stirring reaches adsorption equilibrium；Open xenon lamp and be aerated, sample at regular intervals once, often
Secondary take takes clarified solution after 5mL, centrifugation, and it is the absorbance at 357nm to be determined with ultraviolet spectrometry photometry in wavelength.
Embodiment 2：
In step 1, the calcining manners are that first stage constant temperature at 500 DEG C keeps 2h, the second stage calcining side
Formula is that constant temperature keeps 2h at 550 DEG C, and the heating rate is 10 DEG C/min.
In step 2, the g-C3N4, ethylene glycol, Fe (NO3)3·9H2O, PVP, PEG and CH3COONa·3H2O consumption
It is followed successively by 2.0g, 30mL, 0.1g, 0.008g, 0.4g, 0.8g；The temperature of solvent thermal reaction is 220 DEG C, and the reaction time is 10h.
In step 3, the Fe3O4/g-C3N4, cadmium sulfate, thiocarbamide, PVP, the consumption of deionized water be followed successively by 0.3g,
2.1g, 0.05~0.2g, 0.09g, 150mL；The temperature of solvent thermal reaction is 80 DEG C, reacts 3h.
Step 4, the CdS/Fe taken in 0.05g steps 33O4/g-C3N4It is added to 100mL and contains 20mg L-1Tetracycline
Reactor in, at 30 DEG C lucifuge stirring reaches adsorption equilibrium；Open xenon lamp and be aerated, sample at regular intervals once, often
Secondary take takes clarified solution after 7mL, centrifugation, and it is the absorbance at 357nm to be determined with ultraviolet spectrometry photometry in wavelength.
Embodiment 3：
In step 1, the calcining manners are that first stage constant temperature at 500 DEG C keeps 2h, the second stage calcining side
Formula is that constant temperature keeps 2h at 550 DEG C, and the first stage calcining, second stage calcining heating rate are 6 DEG C/min.
In step 2, the g-C3N4, ethylene glycol, Fe (NO3)3·9H2O, PVP, PEG and CH3COONa·3H2O consumption
It is followed successively by 1g, 20mL, 0.08g, 0.006g, 0.3g, 0.4g；The temperature of solvent thermal reaction is 200 DEG C, and the reaction time is 12h.
In step 3, the Fe3O4/g-C3N4, cadmium sulfate, thiocarbamide, PVP, the consumption of deionized water be followed successively by 0.2g,
1.5g、 1g、0.05g、80mL；The temperature of solvent thermal reaction is 70 DEG C, reacts 5h.
Step 4, the CdS/Fe taken in 0.05g steps 33O4/g-C3N4It is added to 100mL and contains 20mg L-1Tetracycline
Reactor in, at 30 DEG C lucifuge stirring reaches adsorption equilibrium；Open xenon lamp and be aerated, every 20min samplings once, take every time
Clarified solution is taken after 3~6mL, centrifugation, and it is the absorbance at 357nm to be determined with ultraviolet spectrometry photometry in wavelength.
Photocatalytic activity evaluation：Carried out in DW-01 type photochemical reaction instrument, it is seen that light light irradiation, by 100mL 20mg
L-1Tetracycline simulated wastewater adds in reactor and determines its initial value, then adds photochemical catalyst, magnetic agitation simultaneously opens exposure
Device of air is passed through air and maintains the catalyst in suspension or afloat, samples after dark adsorption equilibrium, is spaced in During Illumination
Supernatant liquor is taken after 20min sampling analyses, centrifugation in spectrophotometer λmaxAbsorbance is determined at=357nm, and passes through public affairs
Formula：DC=[(C0-Ci)/C0] × 100% calculates degradation rate, wherein C0To reach the absorbance of tetracycline during adsorption equilibrium, CiFor
What timing sampling was determined is the absorbance of tetracycline.
The sample that Fig. 1 demonstrates prepared by the application is g-C really3N4And CdS/Fe3O4/g-C3N4Composite photo-catalyst.
Fig. 2 is the TEM of different samples, from a it can be seen from the figure thats, pure g-C3N4Random sheet-like morphology is presented in photochemical catalyst,
From b figures it can be seen that spherical Fe3O4It is carried on g-C3N4Material surface, c figures are it can be seen that CdS particulate loads are in Fe3O4/g-
C3N4, scheme from d it can be seen that being supported on Fe3O4/g-C3N4The particle on surface is CdS nano-particles
As can be seen that g-C in Fig. 33N4Photochemical catalyst has stronger absorption in visible region, CdS/g- after being combined
C3N4Composite photo-catalyst has influx and translocation, CdS/Fe in visible region3O4/g-C3N4Composite photo-catalyst also shows stronger
Absorbing properties.
Fig. 4 is the VSM figures and circulation degraded figure of sample, and figure a is Fe3O4/g-C3N4And CdS/Fe3O4/g-C3N4Complex light is urged
Agent shows preferable magnetic, and illustration can be seen that figure CdS/Fe3O4/g-C3N4It is easy to be attracted by external magnet.From figure
CdS/Fe can be drawn in b3O4/g-C3N4Composite photo-catalyst still has good catalytic effect after 5 circulation experiments.
Fig. 5 is the photoelectricity flow graph and impedance diagram that different samples are different synthetic samples, wherein g-C3N4Photoelectric current it is minimum,
Fe3O4/g-C3N4Take second place, CdS/Fe3O4/g-C3N4Photocurrent response it is most strong, show CdS/Fe3O4/g-C3N4With higher
Electron hole transmission performance；B figures are g-C3N4, CdS/g-C3N4And CdS/Fe3O4/g-C3N4Impedance diagram, wherein g-C3N4Half
Circle is maximum, shows that impedance is maximum, CdS/Fe3O4/g-C3N4Semi arch is minimum, shows that impedance is minimum, further illustrates CdS/
Fe3O4/g-C3N4With preferable conductive performance, with preferable photocatalytic activity.
Fig. 6 is the PL figures and FL figures that different samples are different synthetic samples, and wherein a figures are g-C3N4, CdS/g-C3N4With
CdS/Fe3O4/g-C3N4PL figure, wherein g-C3N4Peak value is higher, illustrates that its electron-hole recombination rate is higher, and CdS/Fe3O4/
g-C3N4Peak value is relatively low, illustrates that its electron-hole recombination rate is relatively low, can make full use of photo-generate electron-hole；B figures are g-C3N4,
CdS/g-C3N4And CdS/Fe3O4/g-C3N4FL figures, as can be seen from the figure CdS/Fe3O4/g-C3N4With shorter electronics
The hole-recombination time, illustrate that the electron hole produced is preferably utilized.
Claims (5)
1. a kind of CdS/Fe3O4/C3N4Composite photo-catalyst, it is characterised in that the CdS/Fe3O4/C3N4Composite photo-catalyst is
By CdS particles, Fe3O4、C3N4It is composited；The C3N4For irregular sheet；The Fe3O4To be spherical, C is carried on3N4It
On, form Fe3O4/C3N4；The CdS particulate loads are in the Fe3O4/C3N4Surface.
2. a kind of CdS/Fe3O4/C3N4The preparation method of composite photo-catalyst, it is characterised in that step is as follows：
Step 1, g-C3N4Preparation；
Step 2, Fe3O4/g-C3N4The preparation of magnetic composite：Thin g-C will be ground3N4It is scattered in ethylene glycol, in water-bath
It is middle to keep ultrasonic magnetic agitation to be reacted, then again thereto addition Fe(NO3)39H2O, sodium acetate, polyethylene glycol 2000,
Polyvinylpyrrolidone, continues ultrasonic agitation, until the sample added is dispersed or dissolves；Then by obtained dispersion liquid
It is fitted into polytetrafluoroethylene (PTFE) water heating kettle, carries out solvent thermal reaction, reaction terminates and is cooled to after room temperature to collect solid product, washes
Wash, dry, obtain Fe3O4/g-C3N4Magnetic composite；
Step 3, CdS/Fe3O4/g-C3N4The preparation of composite photo-catalyst：The Fe that step 2 is obtained3O4/g-C3N4Magnetic coupling material
Deionized water is added in material to be stirred, cadmium sulfate, sulphur urine, polyvinylpyrrolidone is added, and continues to stir, and beaker is turned
Constant temperature waters pot interior sealing is moved to, continues constant temperature and stirs and be maintained at reaction under conditions of logical inert gas, after question response terminates
Room temperature is naturally cooled to, beaker is taken out and the solid sample in beaker is collected, is washed, then by solid sample drying for standby,
Obtain CdS/Fe3O4/g-C3N4Composite photo-catalyst.
3. a kind of CdS/Fe according to claim 23O4/C3N4The preparation method of composite photo-catalyst, it is characterised in that step
In rapid 2, the g-C3N4, ethylene glycol, Fe(NO3)39H2O, sodium acetate, polyethylene glycol 2000, the consumption of polyvinylpyrrolidone
Than for 0.5~2.0g:10~30mL:0.05~0.1g:0.05~0.8g:0.2~0.4g:0.005~0.008g；Solvent heat is anti-
The temperature answered is 160~220 DEG C, and the reaction time is 10~15h.
4. a kind of CdS/Fe according to claim 23O4/C3N4The preparation method of composite photo-catalyst, it is characterised in that step
In rapid 3, the Fe3O4/g-C3N4, deionized water, cadmium sulfate, thiocarbamide, polyvinylpyrrolidone amount ratio be 0.1~0.3g:
50~150ml:0.7~2.1g:0.05~0.2g:0.01~0.09g；The temperature of the reaction is 60~80 DEG C, reaction time
For 3~8h；The inert gas is nitrogen.
5. the CdS/Fe described in claim 13O4/g-C3N4Composite photo-catalyst is used for the purposes of photocatalytic degradation tetracycline.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107570196A (en) * | 2017-09-20 | 2018-01-12 | 广东工业大学 | The graphite phase carbon nitride of a kind of modification/CdS composite photo-catalysts, its preparation method and hydrogen production process |
| CN109126868A (en) * | 2018-08-01 | 2019-01-04 | 河南师范大学 | A kind of g-C for terramycin wastewater of degrading3N4The preparation method of-PANI composite photocatalyst material |
| CN109317181A (en) * | 2018-11-02 | 2019-02-12 | 平顶山学院 | A kind of ferroferric oxide/carbon/carbon nitride material and its manufacturing method and purposes |
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| CN113976150A (en) * | 2021-10-15 | 2022-01-28 | 江苏大学 | CdS/Bi responding to visible light4TaO8Preparation method of Cl photocatalyst |
| CN114029080A (en) * | 2021-12-17 | 2022-02-11 | 江苏科技大学 | Ternary heterojunction visible-light-driven photocatalyst and preparation method thereof |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102489284A (en) * | 2011-11-22 | 2012-06-13 | 浙江大学 | Graphene composite titanium dioxide photocatalyst capable of magnetic separation and recovery, and preparation method thereof |
| CN103551150A (en) * | 2013-07-12 | 2014-02-05 | 江苏大学 | Preparation method for magnetic composite photocatalyst based on carbonaceous material |
| CN105148968A (en) * | 2015-08-06 | 2015-12-16 | 江苏大学 | Composite photocatalytic material, preparation method and application thereof |
-
2017
- 2017-05-23 CN CN201710367916.4A patent/CN107042119A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102489284A (en) * | 2011-11-22 | 2012-06-13 | 浙江大学 | Graphene composite titanium dioxide photocatalyst capable of magnetic separation and recovery, and preparation method thereof |
| CN103551150A (en) * | 2013-07-12 | 2014-02-05 | 江苏大学 | Preparation method for magnetic composite photocatalyst based on carbonaceous material |
| CN105148968A (en) * | 2015-08-06 | 2015-12-16 | 江苏大学 | Composite photocatalytic material, preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| ZHI ZHU ET AL.: ""Construction of high-dispersed Ag/Fe3O4/g-C3N4 photocatalyst by selective photo-deposition and improved photocatalytic activity"", 《APPLIED CATALYSIS B:ENVIRONMENTAL》 * |
| 朱志: ""基于有机污染物去除的Fe3O4/g-C3N4复合光催化剂的制备及其吸附/光催化行为和机理研究"", 《中国学位论文全文数据库》 * |
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| CN107570196B (en) * | 2017-09-20 | 2020-04-28 | 广东工业大学 | Modified graphite-phase carbon nitride/CdS composite photocatalyst, preparation method thereof and hydrogen production method |
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| CN111136280A (en) * | 2020-02-29 | 2020-05-12 | 中原工学院 | Flower-shaped Fe/Fe3C/Fe3O4Composite wave-absorbing material and preparation method thereof |
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Application publication date: 20170815 |