CN106902852A - A kind of ZnFe2O4/ AgBr/Ag composite photo-catalysts and preparation method thereof - Google Patents
A kind of ZnFe2O4/ AgBr/Ag composite photo-catalysts and preparation method thereof Download PDFInfo
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- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 title claims abstract description 54
- 239000002131 composite material Substances 0.000 title claims abstract description 41
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 39
- 229910001308 Zinc ferrite Inorganic materials 0.000 title claims abstract description 33
- 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 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 24
- 238000007540 photo-reduction reaction Methods 0.000 claims abstract description 15
- 239000002105 nanoparticle Substances 0.000 claims abstract description 14
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 8
- 238000009938 salting Methods 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 7
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(I) nitrate Inorganic materials [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 239000000853 adhesive Substances 0.000 claims description 6
- 230000001070 adhesive effect Effects 0.000 claims description 6
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 5
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 5
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical class [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims description 5
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical class [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 5
- 230000001476 alcoholic effect Effects 0.000 claims description 5
- 150000001450 anions Chemical class 0.000 claims description 5
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 5
- 229910052794 bromium Inorganic materials 0.000 claims description 5
- 239000003093 cationic surfactant Substances 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 238000001556 precipitation Methods 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 4
- 229940006460 bromide ion Drugs 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 239000007791 liquid phase Substances 0.000 claims description 4
- 101710134784 Agnoprotein Proteins 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 229910052724 xenon Inorganic materials 0.000 claims description 3
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- 235000011187 glycerol Nutrition 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims 2
- 239000002184 metal Substances 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 claims 1
- 150000003839 salts Chemical class 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 15
- 238000007146 photocatalysis Methods 0.000 abstract description 14
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 239000004065 semiconductor Substances 0.000 description 19
- 230000001699 photocatalysis Effects 0.000 description 13
- 238000002474 experimental method Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 4
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 4
- 229940012189 methyl orange Drugs 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000011592 zinc chloride Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000002045 lasting effect Effects 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- STZCRXQWRGQSJD-UHFFFAOYSA-M sodium;4-[[4-(dimethylamino)phenyl]diazenyl]benzenesulfonate Chemical compound [Na+].C1=CC(N(C)C)=CC=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-UHFFFAOYSA-M 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 1
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- 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
- B01J27/06—Halogens; Compounds thereof
- B01J27/138—Halogens; Compounds thereof with alkaline earth metals, magnesium, beryllium, zinc, cadmium or mercury
-
- 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
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- 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)
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- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
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Abstract
The present invention provides a kind of ZnFe2O4/ AgBr/Ag composite photo-catalysts and preparation method thereof.The method that the catalyst is combined using hydro-thermal in preparation process with photo-reduction, the method flexible and convenient, low cost.By with ZnFe2O4Nano particle while composite photo-catalyst catalytic efficiency is improved, additionally it is possible to improve the photostability of photochemical catalyst, overcomes the ZnFe for being difficult to solve in the prior art always as the carrier of AgBr/Ag2O4Photocatalysis performance is poor and shortcoming of photochemical catalyst less stable containing AgBr.
Description
Technical field
The present invention relates to a kind of composite photo-catalyst and preparation method thereof.
Background technology
Environment is necessary condition for the survival of mankind, and with the development of society, concern of the people to environment is increasing.
Currently, the environmental problem such as atmosphere pollution, greenhouse effects, energy shortage, water resources shortage seriously threatens the existence of the mankind and holds
Supervention exhibition, the control and improvement of environmental problem are as mankind's important problem urgently to be resolved hurrily.Photocatalitic Technique of Semiconductor nearly 30
Widely paid close attention to over year.Japanese Scientists Fujishima and Honda have found within 1972, in light radiation lower semiconductor TiO2
Can be by water by photocatalysis Decomposition into H2(Nature, 1972,37：238~245), hereafter Photocatalitic Technique of Semiconductor is obtained
Extensive research.Semiconductor light-catalyst is generally either physically or chemically prepared from by various, be the advantage is that and is not required to
Extra energy is wanted, it is only necessary to absorb sunshine and can be achieved with photocatalysis, so that in decomposition water generation hydrogen and Decomposition Wastewater
Organic matter, efficiently solve environment and energy problem that the current mankind are faced.
It is TiO to study widest Nano semiconductor photochemical catalyst at present2(P25), but due to TiO2Band gap width be
3.2eV, can only absorb the light of the ultraviolet band for accounting for solar spectrum 5%, greatly reduce its photocatalysis efficiency.In order to inhale
More sunshines are received, photocatalysis efficiency is improved, narrow gap semiconductor receives extensive concern.But photocatalysis performance not only depends on
In the band gap width of semiconductor, also passed with the relative position of hydrogen-oxygen energy level, the carrier of semiconductor in semiconductor energy gap and solution
Defeated relevant, the single photocatalysis of property such as with separating power, the avtive spot quantity of light-catalyzed reaction, the stability of photochemical catalyst
Agent is difficult to meet these requirements, therefore composite photo-catalyst attract attention.Composite photo-catalyst passes through will be with not
Contact with each other to form hetero-junctions with the semiconductor of light absorpting ability, can both be effectively increased the absorbability to visible ray, again may be used
To drive carrier to move by the band curvature and built in field of interface, so as to strengthen the separation in light induced electron and hole
Efficiency simultaneously improves the stability of photochemical catalyst, and then obtains than the single more preferable photocatalysis performance (Ref. of two kinds of semiconductors：
Chem.Soc.Rev., 2013,42,2568-2580).Search out the semiconductor material with appropriate band structure and matched well
Material, and new heterojunction composite photocatalyst is synthesized by method physically or chemically, it is current problem demanding prompt solution.
The content of the invention
The problems such as to solve low single semiconductor light-catalyst efficiency in application process, poor activity, stability difference, need
Suitable semi-conducting material is searched out to design and realize new composite photo-catalyst.In design NEW TYPE OF COMPOSITE photochemical catalyst
During, it is ensured that selected semi-conducting material has different band gap widths to absorb the sunshine of different-waveband, carries
Utilization ratio to sunshine high；Ensureing that two kinds of fermi level positions of semiconductor are properly set up is conducive to carrier to pass
Defeated and separate built in field；Ensure that the valence band and conduction band positions of two kinds of semiconductors are suitable, to provide stronger oxidation also
Proper energy power；Additionally, also to ensure two kinds of quantity and biography of material carrier by the optimization of component ratio and combination etc.
Movement Capabilities match each other, so as to realize optimal photocatalysis effect.Therefore, we have carried out substantial amounts of theoretical and experimental work,
A series of semi-conducting materials for meeting primary condition are searched out, and further carries out screening and performance optimization, final choice
ZnFe2O4Synthesize composite construction photochemical catalyst with two kinds of semiconductors of AgBr/Ag.
The present invention provides a kind of ZnFe2O4/ AgBr/Ag composite photo-catalysts and preparation method thereof, are prepared using hydro-thermal method
ZnFe2O4Nano particle, and in ZnFe2O4Surface deposits AgBr (mass ratio is 3: 1), then generates Ag using photo-reduction method, most
End form is into ZnFe2O4/ AgBr/Ag composite photo-catalysts.The catalyst of this heterojunction structure promotes efficiently separating for carrier,
Make catalyst that there is catalytic efficiency higher, and possess good photocatalysis stability, and can be with Magnetic Isolation, with wide
Wealthy application prospect.
The present invention provide technical scheme be：A kind of ZnFe2O4/ AgBr/Ag composite photo-catalysts, it is characterised in that described
The preparation method of composite photo-catalyst is comprised the following steps
1) ZnFe is prepared using hydro-thermal method first2O4Nano particle；
1.1) soluble iron (III) salt, zinc (II) salt and adhesive are mixed with alcoholic solvent in the basic conditions equal
It is even to obtain mixed solution 1.1；
1.2) will be put into reactor in mixed solution 1.1, high-temperature heating, separated after cooling, washed, dried.
2) AgBr is deposited in step 1) ZnFe that obtains2O4Nano grain surface；Wherein ZnFe2O4With AgBr mass ratioes
It is 3: 0.1~15, preferably 3: 0.1~5；
2.1) step 1.2 is taken) ZnFe that obtains2O4Nano particle, anion are equal for the cationic surfactant and water of bromine
It is even to be mixed to get mixed liquor 2.1；
2.2) by Ag (I) salting liquid addition mixed liquor 2.1, continue stirring until bromide ion and be fully converted to AgBr and deposit
In ZnFe2O4Nano grain surface.
3) ZnFe is prepared using photoreduction met hod2O4/ AgBr/Ag composite photo-catalysts.To step 2.2) obtain product
AgBr carries out part photo-reduction, is separated afterwards, washed, dried.
A kind of described ZnFe2O4/ AgBr/Ag composite photo-catalysts, it is characterised in that described alcoholic solvent be ethylene glycol,
One or more in glycerine, polyvinyl alcohol, preferably ethylene glycol；Soluble iron (III) salt is selected from Fe (NO3)3With
FeCl3In one or more, preferably FeCl3；Soluble Zn (II) salt is selected from Zn (NO3)2And ZnCl2In one kind or several
Kind, preferably ZnCl2。
A kind of described ZnFe2O4/ AgBr/Ag composite photo-catalysts, it is characterised in that the alkalescence condition is slaine ring
Border, preferably sodium acetate.
A kind of described ZnFe2O4/ AgBr/Ag composite photo-catalysts, it is characterised in that described adhesive is polyvinyl pyrrole
Alkanone (PVP), the anion is cetyl trimethylammonium bromide (CTAB), Ag (I) for the cationic surfactant of bromine
Salting liquid is AgNO3Solution.
A kind of described ZnFe2O4/ AgBr/Ag composite photo-catalysts, it is characterized in that the photoreduction met hod uses ultraviolet light
Source, visible light source or full spectrum light source are irradiated, it is preferred to use ultraviolet source.The λ ＜ 420nm xenon sources for more preferably using
To step 2.2) reaction solution be irradiated.
A kind of described ZnFe2O4/ AgBr/Ag composite photo-catalysts, it is characterised in that Ag (I) salting liquid is 0.05
The AgNO of~1.50mol/L3Solution.
The invention provides a kind of ZnFe2O4/ AgBr/Ag composite photo-catalysts and preparation method thereof, using hydro-thermal method, liquid
It is prepared by the phase precipitation method and photoreduction met hod.Wherein, the first step prepares ZnFe using hydro-thermal method2O4Nano particle, technique is very simple
Just, mutually uniform, purity is high, monodispersed ZnFe can to prepare thing2O4Nano particle；Second step is existed using liquid-phase precipitation method
ZnFe2O4Nano grain surface deposits AgBr；3rd step carries out partial reduction using the method for photo-reduction to AgBr so that AgBr
Superficial growth goes out Argent grain, and method is simply controllable.By with ZnFe2O4Nano particle is being improved again as the carrier of AgBr/Ag
The catalytic efficiency of closing light catalyst is simultaneously, additionally it is possible to significantly improve the photostability of photochemical catalyst, overcomes in the prior art one
The straight ZnFe for being difficult to solve2O4Photocatalysis performance is poor, and photochemical catalyst photostability containing AgBr is poor, after being used for multiple times
The too fast shortcoming of catalytic efficiency reduction.The present invention effectively improves composite photocatalyst also by applying magnetic field in photocatalytic process
The photocatalysis performance of agent.
Specific embodiment
Below will the present invention is further illustrated by specific embodiment.
In the specific embodiment of the invention
1) ZnFe is prepared using hydro-thermal method first2O4Nano particle
1.1) will be used as the FeCl of soluble iron (III) salt3·6H2O (1.983mmol), as soluble Zn (II) salt
ZnCl2The CH of (0.992mmol), adhesive PVP (K=30,8.925mmol) and offer alkaline environment3COONa
(29.75mmol) is dissolved in ethylene glycol (35mL), 4h is persistently stirred under dark condition and obtains mixed solution 1.1；
1.2) mixed solution 1.1 is put into reactor, first heats 1h (180 DEG C), 8h (200 DEG C) is heated afterwards；Cooling
Centrifugation, deionized water and ethanol wash, vacuum drying 12h (40 DEG C) afterwards；Obtain dry ZnFe2O4Nano particle；
2) AgBr is deposited in by step 1.2 using liquid-phase precipitation method) ZnFe that obtains2O4Nano grain surface, obtains
ZnFe2O4/ AgBr composite photo-catalysts；
2.1) step 1.2 is taken) ZnFe that obtains2O4Nano particle 0.2g, cetyl trimethylammonium bromide (CTAB)
0.3g, is scattered in 100mL deionized waters, stirs 60min, is uniformly mixed to get mixed liquor 2.1
2.2) by AgNO3(2mL, 1mol/L) is slowly added in mixed liquor 2.1,60min is persistently stirred under dark condition, extremely
Bromide ion is fully converted to AgBr and is deposited on ZnFe2O4Nano grain surface.
3) photoreduction met hod is recycled to step 2) AgBr that obtains in product carries out part photo-reduction, using the xenon lamp of 300W
(λ ＜ 400nm) is to step 2.2) reaction solution be irradiated, light application time 10min.
Properties of product test experiments
1st, Photocatalytic Degradation of Methyl Orange efficiency experiment
Take the 20mg ZnFe of preparation2O4, AgBr/Ag and ZnFe2O4/ AgBr/Ag composite photo-catalysts, pour into 50mL respectively
During concentration is for the methyl orange solution of 7mg/L, lasting stirring, through adsorption equilibrium after an hour after, be placed under simulated solar irradiation
Row photocatalysis is tested, and per 10min, sampling detects methyl orange concentration C and calculates it with initial concentration C0The ratio between (C/C0).Experimental result
See the table below：
As can be seen that ZnFe from upper table data2O4The catalytic degradation effect of/AgBr/Ag composite photo-catalysts is significantly higher than
ZnFe2O4And AgBr/Ag, illustrate ZnFe2O4Compound with AgBr/Ag can significantly improve catalytic efficiency.
2nd, composite photo-catalyst Photostability experiments, step is as follows
Take 20mg ZnFe2O4/ AgBr/Ag samples (abbreviation composite photo-catalyst)
1) composite photo-catalyst is poured into the methyl orange solution that 50ml concentration is 7mg/L, lasting stirring, through after an hour
After adsorption equilibrium, being placed under simulated solar irradiation carries out photocatalysis experiment, and light-catalyzed reaction is 50min, and detection is sampled per 10min
Methyl orange concentration C simultaneously calculates it with initial concentration C0The ratio between (C/C0),
2) composite photo-catalyst is separated after reaction terminates, is washed and repeat step 1 after drying), 4 light are carried out altogether urges
Change reaction experiment.Experimental result see the table below：
As can be seen that composite photo-catalyst is in the experiment of continuous 4 photo-catalytic degradation of methyl-orange from upper table data, show
Good photostability is shown.
Claims (8)
1. a kind of ZnFe2O4/ AgBr/Ag composite photo-catalysts, it is characterised in that the preparation method of the composite photo-catalyst includes
Following steps：
1) ZnFe is prepared using hydro-thermal method2O4Nano particle；
2) AgBr is deposited in by step 1 using liquid-phase precipitation method) ZnFe that obtains2O4Nano grain surface, obtains ZnFe2O4/
AgBr composite photo-catalysts, wherein ZnFe2O4It is 3: 0.1~15, preferably 3: 0.1~5 with AgBr mass ratioes.
3) part photo-reduction is carried out to AgBr using photoreduction met hod.
2. a kind of ZnFe as claimed in claim 12O4/ AgBr/Ag composite photo-catalysts, it is characterised in that the ZnFe2O4With
AgBr mass ratioes are 3: 0.1~5.
3. a kind of ZnFe as claimed in claim 12O4/ AgBr/Ag composite photo-catalysts, it is characterized in that the step 1) include
1.1) soluble iron (III) salt, zinc (II) salt and adhesive are obtained with alcoholic solvent mixing and stirring in the basic conditions
To mixed solution 1.1；
1.2) will be put into reactor in mixed solution 1.1, high-temperature heating, separated after cooling, washed, dried；
The step 2) include
2.1) step 1.2 is taken) ZnFe that obtains2O4Nano particle, anion are uniformly mixed for the cationic surfactant and water of bromine
Conjunction obtains mixed liquor 2.1；
2.2) by Ag (I) salting liquid addition mixed liquor 2.1, continue stirring until bromide ion and be fully converted to AgBr and be deposited on
ZnFe2O4Nano grain surface.
The step 3) including to step 2.2) AgBr in product carries out part photo-reduction, separated afterwards, washed, done
It is dry.
4. a kind of ZnFe as claimed in claim 32O4/ AgBr/Ag composite photo-catalysts, it is characterised in that described alcoholic solvent
By one or more in ethylene glycol, glycerine, polyvinyl alcohol.
5. a kind of ZnFe as claimed in claim 32O4/ AgBr/Ag composite photo-catalysts, it is characterised in that the alkalescence condition
It is metal salt environment.
6. a kind of ZnFe as claimed in claim 32O4/ AgBr/Ag composite photo-catalysts, it is characterised in that described adhesive is
Polyvinylpyrrolidone (PVP), the anion is cetyl trimethylammonium bromide for the cationic surfactant of bromine
(CTAB), Ag (I) salting liquid is AgNO3Solution.
7. a kind of ZnFe as claimed in claim 32O4/ AgBr/Ag composite photo-catalysts, it is characterized in that the Ag (I) salting liquid
It is the AgNO of 0.05~1.50mol/L3Solution.
8. a kind of ZnFe as claimed in claim 12O4The preparation method of/AgBr/Ag composite photo-catalysts, it is characterised in that institute
The method of stating is comprised the following steps：
1) ZnFe is prepared using hydro-thermal method first2O4Nano particle
1.1) soluble iron (III) salt, zinc (II) salt and adhesive are obtained with alcoholic solvent mixing and stirring in the basic conditions
To mixed solution 1.1, the alkaline environment is the CH of 29.75mmol3COONa；
1.2) will be put into reactor in mixed solution 1.1, high-temperature heating, separated after cooling, washed, dried.
2) AgBr is deposited in by step 1 using liquid-phase precipitation method) ZnFe that obtains2O4Nano grain surface；
2.1) step 1.2 is taken) ZnFe that obtains2O4Nano particle, anion are uniformly mixed for the cationic surfactant and water of bromine
Conjunction obtains mixed liquor 2.1.
2.2) by Ag (I) salting liquid addition mixed liquor 2.1, continue stirring until bromide ion and be fully converted to AgBr and be deposited on
ZnFe2O4Nano grain surface, Ag (I) salting liquid is the AgNO of 1mol/L3Solution.
3) photoreduction met hod is recycled to step 2) AgBr in product carries out part photo-reduction；The photoreduction met hod is using λ ＜
420nm xenon sources are to step 2.2) reaction solution be irradiated, irradiation time 10min.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107497450A (en) * | 2017-09-25 | 2017-12-22 | 辽宁大学 | A kind of compound bismuth tantalate photochemical catalyst and its preparation method and application |
| CN107537522A (en) * | 2017-09-25 | 2018-01-05 | 中国科学院广州地球化学研究所 | Composite of silver-colored silver halide load iron nano-mineral and preparation method thereof |
| CN108273545A (en) * | 2018-02-05 | 2018-07-13 | 河南科技学院 | A kind of Jie's mesoporous-microporous composite molecular sieve loaded Ag-ZnFe2O4Composite photo-catalyst and preparation method thereof |
| CN108359985A (en) * | 2018-04-16 | 2018-08-03 | 沈阳建筑大学 | A method of hydro-thermal prepares gamma-alumina nano thin-film on FeCrAl alloys |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101333103A (en) * | 2008-07-30 | 2008-12-31 | 江苏工业学院 | Method for synthesizing ferrimagnetism hollow microballoons |
| CN102302933A (en) * | 2011-06-23 | 2012-01-04 | 常州大学 | Method for preparing magnetic oxide hollow microsphere/titanium dioxide composite photocatalyst |
| CN105233845A (en) * | 2015-10-09 | 2016-01-13 | 中国环境科学研究院 | ZnFe2O4/BiOBr magnetic photocatalyst and preparation method thereof |
| CN105879887A (en) * | 2016-05-31 | 2016-08-24 | 南开大学 | Cu2O@Cu/AgBr composite light catalyst and preparation method thereof |
| CN105879890A (en) * | 2016-04-18 | 2016-08-24 | 长沙学院 | Magnetic composite photocatalyst as well as preparation method and application thereof |
-
2017
- 2017-03-15 CN CN201710152621.5A patent/CN106902852A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101333103A (en) * | 2008-07-30 | 2008-12-31 | 江苏工业学院 | Method for synthesizing ferrimagnetism hollow microballoons |
| CN102302933A (en) * | 2011-06-23 | 2012-01-04 | 常州大学 | Method for preparing magnetic oxide hollow microsphere/titanium dioxide composite photocatalyst |
| CN105233845A (en) * | 2015-10-09 | 2016-01-13 | 中国环境科学研究院 | ZnFe2O4/BiOBr magnetic photocatalyst and preparation method thereof |
| CN105879890A (en) * | 2016-04-18 | 2016-08-24 | 长沙学院 | Magnetic composite photocatalyst as well as preparation method and application thereof |
| CN105879887A (en) * | 2016-05-31 | 2016-08-24 | 南开大学 | Cu2O@Cu/AgBr composite light catalyst and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| J.HE等: ""Construction of Z-scheme Cu2O/Cu/AgBr/Ag photocatalyst with enhanced photocatalytic activity and stability under visible light"", 《APPLIED CATALYSIS B：ENVIRONMENTAL》 * |
| SHOUHU XUAN等: ""Facile synthesis of size-controllable monodispersed ferrite nanospheres"", 《JOURNAL OF MATERIALS CHEMISTRY》 * |
| XIAOJUAN LI等: ""Preparation, characterization and photocatalytic activity of visiblelight-driven plasmonic Ag/AgBr/ZnFe2O4 nanocomposites"", 《MATERIALS RESEARCH BULLETIN》 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107497450A (en) * | 2017-09-25 | 2017-12-22 | 辽宁大学 | A kind of compound bismuth tantalate photochemical catalyst and its preparation method and application |
| CN107537522A (en) * | 2017-09-25 | 2018-01-05 | 中国科学院广州地球化学研究所 | Composite of silver-colored silver halide load iron nano-mineral and preparation method thereof |
| CN107537522B (en) * | 2017-09-25 | 2019-08-09 | 中国科学院广州地球化学研究所 | Silver-silver halide load iron nano-mineral composite material and preparation method |
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| CN108273545B (en) * | 2018-02-05 | 2020-09-11 | 河南科技学院 | Mesoporous-microporous composite molecular sieve loaded Ag-ZnFe2O4Composite photocatalyst and preparation method thereof |
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