CN104624179A - Quantum-dot modified nano ZnO transparent photocatalyst emulsion and preparation method thereof - Google Patents
Quantum-dot modified nano ZnO transparent photocatalyst emulsion and preparation method thereof Download PDFInfo
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- CN104624179A CN104624179A CN201510071973.9A CN201510071973A CN104624179A CN 104624179 A CN104624179 A CN 104624179A CN 201510071973 A CN201510071973 A CN 201510071973A CN 104624179 A CN104624179 A CN 104624179A
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- 239000002096 quantum dot Substances 0.000 title claims abstract description 96
- 239000000839 emulsion Substances 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000011941 photocatalyst Substances 0.000 title abstract description 37
- 238000004945 emulsification Methods 0.000 title 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 68
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 60
- 239000002244 precipitate Substances 0.000 claims abstract description 27
- 238000003756 stirring Methods 0.000 claims abstract description 21
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 18
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 16
- 239000000243 solution Substances 0.000 claims description 70
- 230000001699 photocatalysis Effects 0.000 claims description 58
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 42
- 239000004246 zinc acetate Substances 0.000 claims description 42
- 238000010009 beating Methods 0.000 claims description 19
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 16
- 150000001875 compounds Chemical class 0.000 claims description 16
- 238000010992 reflux Methods 0.000 claims description 15
- 238000003828 vacuum filtration Methods 0.000 claims description 15
- 230000004048 modification Effects 0.000 claims description 11
- 238000012986 modification Methods 0.000 claims description 11
- 239000011259 mixed solution Substances 0.000 claims description 8
- 150000002500 ions Chemical class 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 5
- 125000002091 cationic group Chemical group 0.000 claims description 4
- 239000000975 dye Substances 0.000 abstract description 11
- -1 formaldehyde, benzenes Chemical class 0.000 abstract description 6
- 244000005700 microbiome Species 0.000 abstract description 3
- 238000000746 purification Methods 0.000 abstract description 3
- 239000004065 semiconductor Substances 0.000 abstract description 3
- 239000005416 organic matter Substances 0.000 abstract description 2
- 238000013033 photocatalytic degradation reaction Methods 0.000 abstract description 2
- 230000000593 degrading effect Effects 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 abstract 1
- 239000002957 persistent organic pollutant Substances 0.000 abstract 1
- 239000000575 pesticide Substances 0.000 abstract 1
- 238000004537 pulping Methods 0.000 abstract 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc oxide Inorganic materials [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 148
- 239000011787 zinc oxide Substances 0.000 description 108
- 239000012065 filter cake Substances 0.000 description 30
- 230000015556 catabolic process Effects 0.000 description 24
- 238000006731 degradation reaction Methods 0.000 description 24
- 239000011734 sodium Substances 0.000 description 19
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 18
- 229910052708 sodium Inorganic materials 0.000 description 18
- 238000000034 method Methods 0.000 description 16
- 239000011701 zinc Substances 0.000 description 15
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 14
- LQJVOKWHGUAUHK-UHFFFAOYSA-L disodium 5-amino-4-hydroxy-3-phenyldiazenylnaphthalene-2,7-disulfonate Chemical compound [Na+].[Na+].OC1=C2C(N)=CC(S([O-])(=O)=O)=CC2=CC(S([O-])(=O)=O)=C1N=NC1=CC=CC=C1 LQJVOKWHGUAUHK-UHFFFAOYSA-L 0.000 description 13
- 239000012153 distilled water Substances 0.000 description 13
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- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 12
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- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 10
- XSOKHXFFCGXDJZ-UHFFFAOYSA-N telluride(2-) Chemical compound [Te-2] XSOKHXFFCGXDJZ-UHFFFAOYSA-N 0.000 description 9
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- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 description 8
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 8
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 7
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 7
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 7
- JGIATAMCQXIDNZ-UHFFFAOYSA-N calcium sulfide Chemical compound [Ca]=S JGIATAMCQXIDNZ-UHFFFAOYSA-N 0.000 description 7
- 235000019253 formic acid Nutrition 0.000 description 7
- 235000010356 sorbitol Nutrition 0.000 description 7
- 229960002920 sorbitol Drugs 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
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- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 description 5
- XIEPJMXMMWZAAV-UHFFFAOYSA-N cadmium nitrate Inorganic materials [Cd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XIEPJMXMMWZAAV-UHFFFAOYSA-N 0.000 description 5
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- 238000001556 precipitation Methods 0.000 description 5
- ZEGFMFQPWDMMEP-UHFFFAOYSA-N strontium;sulfide Chemical compound [S-2].[Sr+2] ZEGFMFQPWDMMEP-UHFFFAOYSA-N 0.000 description 5
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 4
- NWGKJDSIEKMTRX-AAZCQSIUSA-N Sorbitan monooleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O NWGKJDSIEKMTRX-AAZCQSIUSA-N 0.000 description 4
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 4
- LWZFANDGMFTDAV-BURFUSLBSA-N [(2r)-2-[(2r,3r,4s)-3,4-dihydroxyoxolan-2-yl]-2-hydroxyethyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O LWZFANDGMFTDAV-BURFUSLBSA-N 0.000 description 4
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 4
- CJDPJFRMHVXWPT-UHFFFAOYSA-N barium sulfide Chemical compound [S-2].[Ba+2] CJDPJFRMHVXWPT-UHFFFAOYSA-N 0.000 description 4
- RJWLRCHYHHXJLX-UHFFFAOYSA-N barium(2+);selenium(2-) Chemical compound [Se-2].[Ba+2] RJWLRCHYHHXJLX-UHFFFAOYSA-N 0.000 description 4
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- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 2
- 241000588724 Escherichia coli Species 0.000 description 2
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- IYFATESGLOUGBX-YVNJGZBMSA-N Sorbitan monopalmitate Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O IYFATESGLOUGBX-YVNJGZBMSA-N 0.000 description 2
- HVUMOYIDDBPOLL-XWVZOOPGSA-N Sorbitan monostearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O HVUMOYIDDBPOLL-XWVZOOPGSA-N 0.000 description 2
- 229910004411 SrTe Inorganic materials 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
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- Catalysts (AREA)
Abstract
The invention discloses a quantum-dot modified nano ZnO transparent photocatalyst emulsion. The quantum-dot modified nano ZnO transparent photocatalyst emulsion is prepared from 0.05wt%-50wt% of quantum-dot modified nano ZnO, 0.1wt%-6wt% of carboxylic acid, 1wt%-10wt% of an emulsifier, 0.1wt%-10wt% of hydrogen peroxide and the balance of water, wherein quantum dots are group II-VI semiconductor quantum dots. The prepared transparent photocatalyst emulsion can be used for fully degrading organic pollutants such as pesticides, formaldehyde, benzenes, microorganisms and dyes in a visible light region and even under the weak light of a fluorescent lamp, so that the photocatalytic degradation speed and efficiency of organic matter can be improved, and the purification of environment can be realized. The invention further discloses a preparation method of the quantum-dot modified nano ZnO transparent photocatalyst emulsion, and the preparation method comprises the following steps: (a) adding carboxylic acid into quantum-dot modified nano ZnO, adding water, pulping, adding hydrogen peroxide, stirring for 20-70 hours, adding the emulsifier, heating, stirring and enabling the solution to flow backward to obtain the quantum-dot modified nano ZnO transparent photocatalyst emulsion. The quantum-dot modified nano ZnO transparent photocatalyst emulsion prepared by adopting the preparation method is good in stability and can not precipitate after being preserved at room temperature for 1 year.
Description
Technical field
The present invention relates to nano zine oxide photocatalyst, nano-ZnO transparent photo-catalytic emulsion of a kind of quantum dot modification specifically and preparation method thereof.
Background technology
In recent years, along with society and economic fast development, the waste water,waste gas and industrial residue that various industry, agricultural and daily life produce makes environment increasingly worsen, simultaneously, a large amount of synthesis toxic materials in household, work, life affect the physical and mental health of people day by day, in various toxic pollutant Study on degradation field, photocatalysis technology shows its incomparable advantage just gradually.Catalysis material finally can be decomposed into inorganic molecules macromolecule pollutant under light illumination, and treatment effeciency is high, and operating condition is easy to control, and non-secondary pollution.
From rattan island clear professor's Late Cambrian TiO of Nihon University
2since having photo-catalysis function, photocatalysis technology starts to be widely used in the depollution of environment fields such as degraded, antifouling, sterilization, deodorizing.Nano-ZnO is the TiO that continues
2another kind is afterwards widely used in the material of photocatalysis field, itself and TiO
2band-gap energy similar, all effectively can absorb ultraviolet light, have been reported and show that, in the toxic pollutant of degradation biological difficult degradation, nano-ZnO photocatalysis performance and quantum yield are better than TiO
2.
But the Related product of nano-ZnO photocatalyst at present not yet can by large-scale development and application, its reason is that ZnO only can absorb the sunshine lower than below 368nm as a kind of wide-band gap material (3.37eV), 4% is only had to the utilization rate of sunshine, and electron-hole commute compound, photo-generated carrier interfacial migration rate is low, and these unfavorable factors greatly have impact on the development of ZnO photocatalyst.In order to develop can by excited by visible light, the ZnO photocatalyst with high catalytic activity, people have carried out many good tries, adopt various method to modify ZnO, attempt to improve its photocatalysis performance.The people such as Lu pass through noble metal loading, one step hydro thermal method is used to prepare three-dimensional Ag/ZnO hollow microsphere, the Ag that experiment shows ZnO surface deposition not only can promote being separated of light induced electron and hole as electronic library, but also improve the amount of surface hydroxyl, show higher photocatalytic activity, but noble metal loading method raw material costly, is unfavorable for large-scale production.The ZnO photocatalyst of the people such as Guan Wei province Fe, Co, Ni adulterant Fe-Co, Fe-Ni codope that adopted hydro-thermal method to prepare, experiment shows that the doping of metal cations Fe improves photocatalytic activity, but the doping of metal Co and Ni but inhibits its photocatalysis performance.The people such as Lahiri deposited one deck ZnS film on ZnO, make the overall forbidden band of material be reduced to 2.8eV, make the Absorption edge red shift of material, improve its photocatalysis performance, but the polar orientation of strict control of material is wanted in its preparation used, and complicated process of preparation, is difficult to realize industrialization.
Although these above methods improve the photocatalytic activity of ZnO photocatalyst to a certain extent, but the photocatalytic activity of gained ZnO photocatalyst still can not meet the demand of industrialization, and also substantially all because there is some inevitable defects or problem and cannot commercial application in these methods.
Summary of the invention
The object of this invention is to provide that a kind of photocatalytic activity is high, nano-ZnO transparent photo-catalytic emulsion that the quantum dot of good stability is modified, to solve, ZnO photocatalyst product photocatalytic activity prepared by existing method is bad, the problem of poor stability.Another object of the present invention is to provide the preparation method of nano-ZnO transparent photo-catalytic emulsion that a kind of quantum dot is modified, to solve existing method or the prices of raw and semifnished materials are expensive or be difficult to the problem of industrialization because of complicated process of preparation.
First object of the present invention realizes by following technical scheme:
The nano-ZnO transparent photo-catalytic emulsion that quantum dot is modified, it contains following component:
Quantum dot modify nano-ZnO 0.05-50wt%, carboxylic acid 0.1-6wt%, emulsifying agent 1-10wt%, hydrogen peroxide 0.1-10wt% and water surplus;
Wherein, in the nano-ZnO that described quantum dot is modified, quantum dot and nano-ZnO mol ratio are 0.1-20%, and described quantum dot is II-VI race's semiconductor-quantum-point; Described hydrogen peroxide is the hydrogen peroxide of mass concentration 25-35%.
Preferably, the nano-ZnO transparent photo-catalytic emulsion that quantum dot of the present invention is modified, the hydrogen peroxide 1-4wt% of nano-ZnO 0.05-0.5wt%, carboxylic acid 1-4wt% containing quantum dot modification, emulsifying agent 1-4wt%, mass concentration 30% and water surplus; More preferred, described carboxylic acid, described emulsifying agent are equal with described hydrogen peroxide content.
Preferably, in the nano-ZnO that described quantum dot is modified, quantum dot and nano-ZnO mol ratio are 0.1-10%.
Described II-VI race's semiconductor-quantum-point be in cadmium sulfide, cadmium selenide, cadmium telluride, vulcanized lead, lead selenide, lead telluride, magnesium sulfide, magnesium selenide, telluride magnesium, calcium sulfide, calcium selenide, telluride calcium, barium sulphide, barium selenide, telluride barium, zinc sulphide, zinc selenide, zinc telluridse, strontium sulfide, selenizing strontium or telluride strontium any one or arbitrarily two or more.
Described carboxylic acid is C
1-4aliphatic carboxylic acid, preferably, described C
1-4aliphatic carboxylic acid is any one in formic acid, acetic acid, butyric acid, malic acid or tartaric acid.
Described emulsifying agent is any one in D-glucitol, Arlacel-20, Arlacel-40, Arlacel-60, Arlacel-80, Tween-20, tween-21, Tween-40, Tween-60, tween-61, Tween-80, Tween-81, Tween-85, OP-9, OP-10 or OP-15; Preferably, emulsifying agent used is D-glucitol.
Second object of the present invention realizes by following technical scheme:
A preparation method for the nano-ZnO transparent photo-catalytic emulsion that quantum dot is modified, it comprises the following steps:
A) in the nano-ZnO of 0.5-500g quantum dot modification, add 1-60g carboxylic acid, then add suitable quantity of water making beating, after making beating, add the hydrogen peroxide 1-100g of mass concentration 25-35% again, then stir 20-70 hour, obtain transparent complex solution;
The nano-ZnO that described quantum dot is modified is the nano-ZnO that II-VI race's semiconductor-quantum-point is modified, the preparation method of the nano-ZnO that described II-VI race's semiconductor-quantum-point is modified is: be slowly added to the water by zinc acetate and fully dissolve, then the ratio of Cu Suan Xin ︰ quantum dot Yang Li Yuan ︰ quantum dot negative ion source=5-1000 ︰ 1 ︰ 1 in molar ratio, in zinc acetate solution, add quantum dot cationic source and quantum dot negative ion source while stirring successively, obtain mixed solution; In gained mixed solution, slowly drip the ammoniacal liquor of mass concentration 30-50%, adjust pH, to 8-9, makes to produce complex precipitate in described mixed solution, then vacuum filtration, washing, obtains the nano-ZnO that II-VI race's semiconductor-quantum-point is modified;
B) in the transparent complex solution of gained, add emulsifying agent 10-100g, then heat stirring and refluxing 0.5-20h under 70-100 DEG C of condition and decompose complex compound, obtain the nano-ZnO transparent photo-catalytic emulsion that quantum dot is modified;
Wherein, the amount added water when pulling an oar in step a) reaches 1000g for benchmark with step b) gained photo-catalytic emulsion quality.
Stir described in step a) and carry out under 2-7 DEG C of condition for 20-70 hour.
Preferably, the preparation method of the nano-ZnO transparent photo-catalytic emulsion that quantum dot of the present invention is modified, the consumption of the nano-ZnO that described quantum dot is modified is 0.5-5g, the consumption of described carboxylic acid is 10-40g, the consumption of described hydrogen peroxide is 10-40g, the consumption of described emulsifying agent is 10-40g, and described hydrogen peroxide is the hydrogen peroxide of mass concentration 30%; More preferred, described carboxylic acid, described hydrogen peroxide are equal with described emulsifier.
Preferably, in step a), zinc acetate, quantum dot cationic source, quantum dot negative ion source consumption mol ratio are 100-1000 ︰ 1 ︰ 1.
Described quantum dot cationic source be in cadmium nitrate, plumbi nitras, magnesium sulfate, calcium nitrate, barium nitrate, zinc nitrate or strontium chloride any one or arbitrarily two or more; Described quantum dot negative ion source be in vulcanized sodium, sodium selenide or telluride sodium any one or arbitrarily two or more.
Described carboxylic acid is C
1-4aliphatic carboxylic acid, preferably, described C
1-4aliphatic carboxylic acid is any one in formic acid, acetic acid, butyric acid, malic acid or tartaric acid.
Described emulsifying agent is any one in D-glucitol, Arlacel-20, Arlacel-40, Arlacel-60, Arlacel-80, polysorbas20, tween-21, Tween-40, Tween-60, tween-61, Tween-80, Tween-81, Tween-85, OP-9, OP-10 or OP-15; Preferably, emulsifying agent used is D-glucitol.
OP-9, OP-10 or OP-15 used in the present invention belong to OP class emulsifying agent, and it is the trade name of APES class emulsifying agent.
II-VI race's semiconductor-quantum-point, due to its characteristic such as quantum size effect, skin effect, presents excellent performance in optical, electrical, magnetic, heat etc.Quantum dot by changing its grain size simply, can regulate the wavelength of radiating light, obtaining the utilizing emitted light that excitation is higher.Its spectral line of emission is narrow, PLE live width, wavelength of fluorescence make it have broad application prospects in fields such as cell imaging, DNA sequencing, immune detection, TEMP, white light LEDs with the performance of many physicochemical property aspects such as change of size continuously adjustabe, stable performance.The people such as Cong Min report and use pamam dendrimer molecule to be Template preparation CdS quantum dot, make its avtive spot not easily passivation on quantum dot surface, and be degraded object with methyl orange, improve photocatalysis efficiency, but this mode being used alone quantum dot photocatalyst strictly must control the size of quantum dot, complex manufacturing technology, is unfavorable for realizing the marketization.The present invention utilizes II-VI race's semiconductor-quantum-point of low energy gap to modify nano ZnO particles, controllable photochemical catalyst absorbs the light of different wavelength range, realize expanding spectral response interval when not destroying nano-ZnO structure, two or more semiconductor-quantum-point modifies the cooperative effect that can realize between semiconductor, effectively reduce the recombination rate of photo-generate electron-hole, be conducive to being separated of light induced electron and hole, produce more activating oxide, the spectral response of expansion nano-ZnO, expand the active face of nano-ZnO, and enhance the photostability of catalyst.II-VI race's semiconductor-quantum-point makes its conduction band and valence-band level more discrete because of its quantum size effect, and meanwhile, it has highly excited conduction band, and electronics and hole-recombination probability reduce, and are widely used in photocatalysis field.The advantages such as its catalytic activity is easily reduced, can repeatedly reuse, high stability.
Emulsion prepared by the present invention, under visible region, even under more weak fluorescent lamp, what realize at organic pollutions such as agricultural chemicals, formaldehyde, benzene class, microorganism, dyestuffs is degradable, improve speed and the efficiency of photocatalysis to degrade organic matter, thus realize the purification to environment.
Emulsion prepared by the present invention, range of application is fairly widespread.As at automotive interior: the various parts of automotive interior such as the surface such as articles for use, ornament in carpet, steering wheel cover for automobile, sunshading board, roof flannelette, vehicle door interior trim and other car can be widely used in and form one deck nano protective film, resolving harmful gas, eliminate peculiar smell, mildew-resistant.Exterior decoration: pottery, construction equipment, illuminating lamp etc.Household is indoor: upholstery, purification of air etc.Working environment: office, workshop, factory building, meeting room can be widely applied to.Public place: hotel, hospital, public place of entertainment, megastore, school, public lavatory, station etc.Sewage disposal: process sanitary sewage, benzene class sewage, dye wastewater, microorganism sewage water etc. can be widely used in.Strong mechanical property of the present invention, non-secondary pollution, can realize the depollution of environment of 100%, and the catalysis material that this quantum dot is modified has efficient practical value.
The present invention adopts low temperature complexing-control precipitation reaction to prepare the nano-ZnO of II-VI race semiconductor-quantum-point modification, prepared semiconductor-quantum-point is that radius is less than or close to the quantum dot of Exciton Bohr Radius, the transition state of semi-conducting material between molecule and crystal, there is the multiple novel effects such as unique skin effect, quantum confined effect and macro quanta tunnel effect, there is the optical property being different from bulk material.The nano-ZnO adopting the quantum dot prepared by method of the present invention to modify has the advantages that its material prepared has small particle diameter, wide light absorption range.
In addition, adopt the photo-catalytic emulsion good stability prepared by method of the present invention, ambient temperatare is put does not have deposited phenomenon to occur in 1 year.
figure of description
Fig. 1 is the Particle Size of Nanometer ZnO distribution map that the quantum dot prepared by the embodiment of the present invention 3 is modified.
Fig. 2 is that the present invention and other photocatalyst samples are to degradation of organic dyes rate result.
In Fig. 2: sample 1 is transparent photo-catalytic emulsion prepared by embodiment 1, the ZnO photocatalyst that sample 2 is produced for Jing Rui Co., Ltd, sample 3 is that Kai Rui bio tech ltd, Shanghai produces ZnO photocatalyst, sample 4 is the ZnO photocatalyst that Shanghai Xiu Zi chemical products Co., Ltd produces, and sample 5 is commercially available nano-ZnO white powder.
Detailed description of the invention
In following examples 1-14, ammoniacal liquor used is in mass concentration, and its concentration range is 30-50wt%; Hydrogen peroxide used is in mass concentration, and its concentration is 30%.
Embodiment 1
(1) at room temperature, get in 100mL water to beaker stand-by with graduated cylinder, get the zinc acetate (Zn (CH of 0.01moL
3cOO)
2) be slowly added to the water, be stirred to and dissolve completely, obtain transparent zinc acetate solution;
(2) in zinc acetate solution, add the cadmium nitrate (Cd (NO of zinc acetate mole 0.3% successively
3)
2) and 0.3% vulcanized sodium (Na
2s), be stirred to whole dissolving, then slowly add the ammoniacal liquor of concentration 30%, adjust ph is 8-9, produces complex precipitate;
(3) then vacuum filtration with distilled water washing gained complex precipitate, namely obtain with ZnO mol ratio be 0.3% the nano-ZnO filter cake modified of cadmium sulfide (CdS) quantum dot;
(4) in gained filter cake, add 12.5g formic acid, then add water to gross weight 967.5g making beating, after making beating, in gained slurries, add 20g hydrogen peroxide, then at 3 DEG C, stirred 40 hours with magnetic rotation agitator, obtain transparent complex solution;
(5) in above-mentioned transparent complex solution, add the D-glucitol of 12.5g, at 100 DEG C, then heat stirring and refluxing 20h decompose complex compound, obtain the nano-ZnO transparent photo-catalytic emulsion that CdS quantum dot is modified.
Embodiment 2
(1) at room temperature, get in 100mL water to beaker stand-by with graduated cylinder, get the Zn (CH of 0.02moL
3cOO)
2slowly be added to the water, be stirred to and dissolve completely, obtain transparent zinc acetate solution;
(2) in zinc acetate solution, add the calcium nitrate (Ca (NO of zinc acetate mole 0.1% successively
3)
2) and 0.1% vulcanized sodium, be stirred to whole dissolving, then slowly add the ammoniacal liquor of concentration 30%, adjust ph is 8 ~ 9, produce complex precipitate;
(3) then vacuum filtration with distilled water washing gained complex precipitate, namely obtain with ZnO mol ratio be 0.1% the nano-ZnO filter cake modified of calcium sulfide (CaS) quantum dot;
(4) in gained filter cake, add 20g formic acid, then add water to gross weight 965g making beating, after making beating, in gained slurries, add 15g hydrogen peroxide, then at 3 DEG C, stirred 10 hours with magnetic rotation agitator, obtain transparent complex solution;
(5) in above-mentioned transparent complex solution, add the D-glucitol of 20g, at 100 DEG C, then heat stirring and refluxing 20h decompose complex compound, obtain the nano-ZnO transparent photo-catalytic emulsion that CaS quantum dot is modified.
Embodiment 3
(1) at room temperature, get in 200mL water to beaker stand-by with graduated cylinder, get the Zn (CH of 0.03moL
3cOO)
2slowly be added to the water, be stirred to and dissolve completely, obtain transparent zinc acetate solution;
(2) add successively in the solution of obtained zinc acetate the barium nitrate of zinc acetate mole 1%, the vulcanized sodium of 0.5% and 0.5% sodium selenide, be stirred to whole dissolving, then slowly add the ammoniacal liquor of concentration 30%, adjust ph is 8 ~ 9, produce complex precipitate;
(3) then vacuum filtration with distilled water washing gained complex precipitate, namely obtains being with ZnO mol ratio barium sulphide (BaS) quantum dot and the nano-ZnO filter cake modified of barium selenide (BaSe) quantum dot of 0.5%;
(4) in gained filter cake, add 20g formic acid, then add water to gross weight 960g making beating, in gained slurries, add 20g hydrogen peroxide, then at 3 DEG C, stirred 30 hours with magnetic rotation agitator, obtain transparent complex solution;
(5) in above-mentioned transparent complex solution, add 20g D-glucitol, at 80 DEG C, then heat stirring and refluxing 20h decompose complex compound, obtain the nano-ZnO transparent photo-catalytic emulsion of BaS quantum dot and the modification of BaSe quantum dot.
The particle diameter of the nano-ZnO that quantum dot is modified in photo-catalytic emulsion prepared by detection, as shown in Figure 1, as seen from Figure 1, the nano particle prepared by the inventive method has the little advantage of particle diameter to result, and centralized particle diameter is between 3.8-14.5nm.
Embodiment 4
(1) at room temperature, get in 200mL water to beaker stand-by with graduated cylinder, get the Zn (CH of 0.03moL
3cOO)
2slowly be added to the water, be stirred to and dissolve completely, obtain transparent zinc acetate solution;
(2) by add successively in above-mentioned obtained zinc acetate solution the calcium nitrate of zinc acetate mole 1%, the strontium chloride of 0.5% and 1.5% vulcanized sodium, be stirred to whole dissolving, then in gained mixed solution, add the ammoniacal liquor of concentration 30%, adjust ph is 8 ~ 9, produces complex precipitate;
(3) vacuum filtration by above-mentioned precipitation distilled water washes clean, obtaining is the nano-ZnO filter cake that calcium sulfide (CaS) quantum dot of 1% and strontium sulfide (SrS) quantum dot of 0.5% are modified with ZnO mol ratio;
(4) in gained filter cake, adding 10g acetic acid, then add water to gross weight 970g making beating, in gained slurries, add 30g hydrogen peroxide, then being stirred 40 hours with magnetic rotation agitator at 4 DEG C, obtaining transparent complex solution;
(5) in above-mentioned transparent complex solution, add 10g Tween-40, at 70 DEG C, then heat stirring and refluxing 15h decompose complex compound, obtain the nano-ZnO transparent photo-catalytic emulsion that CaS and SrS quantum dot is modified.
Embodiment 5
(1) at room temperature, get in 200mL water to beaker stand-by with graduated cylinder, get the Zn (CH of 0.01moL
3cOO)
2slowly be added to the water, be stirred to and dissolve completely, obtain transparent zinc acetate solution;
(2) by add in above-mentioned obtained zinc acetate solution the cadmium nitrate of zinc acetate mole 1%, the strontium chloride of 1% and 2% sodium selenide, be stirred to whole dissolving, in gained mixed solution, add the ammoniacal liquor of concentration 30% again, adjust ph is 8 ~ 9, produces complex precipitate;
(3) vacuum filtration by above-mentioned precipitation distilled water washes clean, obtaining is the nano-ZnO filter cake that cadmium selenide (CdSe) quantum dot of 1% and selenizing strontium (SrSe) quantum dot of 1% are modified with ZnO mol ratio;
(4) in gained filter cake, add 10g acetic acid, then add water to gross weight 972g making beating, in gained slurries, add 18g hydrogen peroxide, then at 7 DEG C, stirred 30 hours with magnetic rotation agitator, obtain transparent complex solution;
(5) in above-mentioned transparent complex solution, add 10g Arlacel-20, at 100 DEG C, then heat stirring and refluxing 15h decompose complex compound, obtain the nano-ZnO transparent photo-catalytic emulsion that CdSe and SrSe quantum dot is modified;
The amount added water during making beating in step (4) with the quality of gained photo-catalytic emulsion at 1000g for benchmark.
Embodiment 6
(1) at room temperature, get in 100mL water to beaker stand-by with graduated cylinder, get the Zn (CH of 0.01moL
3cOO)
2slowly be added to the water, be stirred to and dissolve completely, obtain transparent zinc acetate solution;
(2) by slowly add successively while stirring in above-mentioned obtained zinc acetate solution the % strontium chloride of zinc acetate mole 1, the vulcanized sodium of 1%, the zinc nitrate of 1% and 1% telluride sodium, then in gained solution, add the ammoniacal liquor of concentration 40%, adjust ph is 8 ~ 9, produces complex precipitate;
(3) vacuum filtration, by gained complex precipitate filter cake distilled water washes clean, namely obtain with ZnO mol ratio be 1% strontium sulfide (SrS) quantum dot and the nano-ZnO filter cake modified of 1% zinc telluridse (ZnTe) quantum dot;
(4) in gained filter cake, add 12.5g formic acid, then add water to gross weight 957.5g making beating, in gained slurries, add 30g hydrogen peroxide, then at 4 DEG C, stirred 40 hours with magnetic rotation agitator, obtain transparent complex solution;
(5) in obtained transparent complex solution, add 12.5g Arlacel-80, at 100 DEG C, then heat stirring and refluxing 15h decompose complex compound, obtain the nano-ZnO transparent photo-catalytic emulsion that SrS and ZnTe quantum dot is modified.
Embodiment 7
(1) at room temperature, get in 200mL water to beaker stand-by with graduated cylinder, get the Zn (CH of 0.03moL
3cOO)
2slowly be added to the water, be stirred to and dissolve completely, obtain transparent zinc acetate solution;
(2) by successively add while stirring in above-mentioned obtained zinc acetate solution the % strontium chloride of zinc acetate mole 1, the vulcanized sodium of 1%, the zinc nitrate of 1% and 1% telluride sodium, be stirred to whole dissolving, the ammoniacal liquor of concentration 40% is added again in this solution, adjust ph is 8 ~ 9, produces complex precipitate;
(3) vacuum filtration, by gained complex precipitate filter cake distilled water washes clean, namely obtains being the ZnO filter cake that 1%SrS quantum dot and 1%ZnTe quantum dot are modified with ZnO mol ratio;
(4) in gained filter cake, add 12.5g formic acid, then add water to gross weight 957.5g making beating, in gained slurries, add 30g hydrogen peroxide, then at 4 DEG C, stirred 40 hours with magnetic rotation agitator, obtain transparent complex solution;
(5) get the complex solution that gained is transparent, add 12.5gD-sorbierite, at 100 DEG C, then add hot reflux 12h decompose complex compound, obtain the nano-ZnO transparent photo-catalytic emulsion that SrS and ZnTe quantum dot is modified.
Embodiment 8
(1) at room temperature, get in 200mL water to beaker stand-by with graduated cylinder, get the Zn (CH of 0.01moL
3cOO)
2slowly be added to the water, be stirred to and dissolve completely, obtain transparent zinc acetate solution;
(2) by adding the plumbi nitras of zinc acetate mole 1% and the vulcanized sodium of 1% in above-mentioned obtained zinc acetate solution, be stirred to whole dissolving, then add the ammoniacal liquor of concentration 40% in this solution, adjust ph is 8 ~ 9, produces complex precipitate;
(3) vacuum filtration by gained complex precipitate filter cake distilled water washes clean, namely obtain with ZnO mol ratio be 1% the nano-ZnO filter cake modified of vulcanized lead (PbS) quantum dot;
(4) in gained filter cake, add 32.5g butyric acid, then add water to gross weight 937.5g making beating, in gained slurries, add 30g hydrogen peroxide, then at 5 DEG C, stirred 70 hours with magnetic rotation agitator, obtain transparent complex solution;
(5) get above-mentioned transparent complex solution, add 32.5g emulsifier op-10, at 100 DEG C, then add hot reflux 10h decompose complex compound, obtain the nano-ZnO transparent photo-catalytic emulsion that PbS quantum is modified.
Embodiment 9
(1) at room temperature, get in 100mL water to beaker stand-by with graduated cylinder, get the Zn (CH of 0.02moL
3cOO)
2slowly be added to the water, be stirred to and dissolve completely, obtain transparent zinc acetate solution;
(2) by add in above-mentioned obtained zinc acetate solution the plumbi nitras of zinc acetate mole 0.5%, the zinc nitrate of 0.5% and 1% vulcanized sodium, be stirred to whole dissolving, in this solution, add the ammoniacal liquor of concentration 40% again, adjust ph is 8 ~ 9, produces complex precipitate;
(3) vacuum filtration by gained complex precipitate distilled water washes clean, namely obtain being the nano-ZnO filter cake that 0.5%PbS quantum dot and 0.5%ZnS quantum dot are modified with ZnO mol ratio;
(4) in gained filter cake, add 25g butyric acid, then add water to gross weight 955g making beating, in gained slurries, add 30g hydrogen peroxide, then at 5 DEG C, stirred 30 hours with magnetic rotation agitator, obtain transparent complex solution;
(5) get above-mentioned transparent complex solution, add 25g Arlacel-20, at 100 DEG C, then add hot reflux 5h decompose complex compound, obtain the nano-ZnO transparent photo-catalytic emulsion of PbS and ZnS quantum dot modification.
Embodiment 10
(1) at room temperature, get in 100mL water to beaker stand-by, by 30mL(2.0moL/L with graduated cylinder) Zn (CH
3cOO)
2the aqueous solution is slowly added to the water, and obtains transparent zinc acetate solution;
(2) by successively add while stirring in above-mentioned obtained zinc acetate solution the cadmium nitrate of zinc acetate mole 3%, the sodium selenide of 3%, the zinc nitrate of 3% and 3% vulcanized sodium, finally be stirred to whole dissolving, the ammoniacal liquor of concentration 50% is added again in this solution, adjust ph is 8 ~ 9, produces complex precipitate;
(3) vacuum filtration by gained complex precipitate distilled water washes clean, obtain being the nano-ZnO filter cake that 3%CdSe quantum dot and 3%ZnS quantum dot are modified with zinc oxide mol ratio;
(4) add 12.5g malic acid in gained filter cake, then add water to gross weight 457.5 and pull an oar, in gained slurries, add 30g hydrogen peroxide, then at 6 DEG C, stirred 40 hours with magnetic rotation agitator, obtain transparent complex solution;
(5) get above-mentioned transparent complex solution, add 12.5g emulsifier op-10, at 100 DEG C, add hot reflux 15h decompose complex compound, obtain the nano-ZnO transparent photo-catalytic emulsion of CdSe and ZnS quantum dot modification.
Embodiment 11
(1) at room temperature, get in 200mL water to beaker stand-by with graduated cylinder, get the Zn (CH of 0.03moL
3cOO)
2slowly be added to the water, be stirred to and dissolve completely, obtain transparent SAS;
(2) by add in above-mentioned obtained SAS the plumbi nitras of sodium acetate mole 1%, the magnesium sulfate of 1% and 2% vulcanized sodium, be stirred to whole dissolving, then add the ammoniacal liquor of concentration 50% in this solution, adjust ph is 8 ~ 9, produce complex precipitate;
(3) vacuum filtration by the complex precipitate of gained distilled water washes clean, namely obtains being respectively with ZnO mol ratio the nano-ZnO filter cake that 1%PbS and 1%MgS quantum dot is modified;
(4) in gained filter cake, add 10g malic acid, then add water to gross weight 457.5g making beating, in gained slurries, add 30g hydrogen peroxide, then at 4 DEG C, stirred 40 hours with magnetic rotation agitator, obtain transparent complex solution;
(5) get the complex solution that gained is transparent, add 12.5g polyoxyethylene nonylphenol ether-15, at 100 DEG C, then add hot reflux 15h decompose complex compound, obtain the nano-ZnO transparent photo-catalytic emulsion that PbS and MgS quantum dot is modified.
Embodiment 12
(1) at room temperature, get in 100mL water to beaker stand-by with graduated cylinder, get the Zn (CH of 0.03moL
3cOO)
2slowly be added to the water, be stirred to and dissolve completely, obtain transparent zinc acetate solution;
(2) by successively add while stirring in above-mentioned obtained zinc acetate solution zinc acetate mole 1% cadmium nitrate, 1% sodium selenide, 0.5% magnesium sulfate, the vulcanized sodium of 0.5%, the barium nitrate of 1% and 1% telluride sodium, finally be stirred to whole dissolving, the ammoniacal liquor of concentration 50% is added again in this solution, adjust ph is 8 ~ 9, produces complex precipitate;
(3) vacuum filtration by the complex precipitate filter cake distilled water washes clean of gained, the nano-ZnO filter cake that CdSe, 0.5%MgS and 1%BaTe quantum dot namely obtaining being respectively 1% with ZnO mol ratio is modified;
(4) add 10g tartaric acid in gained filter cake, then add water to gross weight 475g making beating, in gained slurries, add 15g hydrogen peroxide, then at 6 DEG C, stirred 20 hours with magnetic rotation agitator, obtain transparent complex solution;
(5) get above-mentioned transparency complex solution, add 10g Tween-85, at 100 DEG C, add hot reflux 12h decompose complex compound, obtain the nano-ZnO transparent photo-catalytic emulsion that CdSe, MgS and BaTe quantum dot is modified.
Embodiment 13
(1) at room temperature, get in 100mL water to beaker stand-by with graduated cylinder, get the Zn (CH of 0.01moL
3cOO)
2slowly be added to the water, be stirred to and dissolve completely, obtain transparent zinc acetate solution;
(2) by successively add while stirring in above-mentioned obtained zinc acetate solution zinc acetate mole 3% barium nitrate, 3% sodium selenide, 0.5% calcium nitrate, 2% strontium chloride, 2.5% telluride sodium, the plumbi nitras of 1% and the vulcanized sodium of 1%, be stirred to whole dissolving, the ammoniacal liquor of concentration 50% is added again in this solution, adjust ph is 8 ~ 9, produces complex precipitate;
(3) vacuum filtration by gained complex precipitate distilled water washes clean, the nano-ZnO filter cake that PbS, 0.5%CaTe, 2%SrTe and 3%BaSe quantum dot namely obtaining being respectively 1% with ZnO mol ratio is modified;
(4) in gained filter cake, add 12.5g tartaric acid, then add water to 482.5g making beating, in gained slurries, add 5g hydrogen peroxide, at 5 DEG C, stirred 40 hours with magnetic rotation agitator, obtain transparent complex solution;
(5) get above-mentioned transparent complex solution, add 12.5g Arlacel-80, at 100 DEG C, add hot reflux 12h decompose complex compound, obtain the nano-ZnO transparent photo-catalytic emulsion that PbS, CaTe, SrTe and BaSe quantum dot is modified.
Experimental example 1: the emulsion intercalation method test prepared by embodiment 1-13
Place 1-2 by under the emulsion room temperature state prepared by embodiment 1-13, observe whether occur deposited phenomenon, statistics is in table 1.
Table 1: precipitation status statistics
In table 1, "None" represents that thing precipitation occurs, " on a small quantity " represents that in emulsion, sedimentary quality accounts for dry substance mixture < 50% in emulsion, and " in a large number " represents that in emulsion, sedimentary quality accounts for dry substance mixture >=50% in emulsion.
Experimental example 2: the emulsion prepared by embodiment 1-13 is tested degradation of organic dyes under fluorescent light
It is parallel that to get 28 parts of concentration be that the Acid Red B solution of 20 mg/L is placed in beaker, every part of 15mL, in contained ZnO=0.1 mol, at the freshly prepd transparent photo-catalytic emulsion sample of lucifuge place difference Example 1-13, the sample of placement after 1 year and the photo-catalytic emulsion prepared by embodiment 3 place 1.5 years respectively respectively, sample after 2 years, join in above-mentioned beaker respectively, then 400 mL are added water to, the pH value of reaction system is regulated to be 3 with watery hydrochloric acid again, in the dark magnetic agitation 40-50min, make fully to contact between photo-catalytic emulsion and organic dyestuff to keep sorption and desorption balance, then sample with test tube, then the test tube of sampling is put under fluorescent light (400 nm ~ 750 nm) and carry out light-catalyzed reaction, sampling and testing at set intervals, its A ~ λ curve carries out the scanning of 200 ~ 1200nm wave band by UV-4100 ultraviolet-visible spectrophotometer, record absorbance and the concentration thereof at this dye solution maximum extinction wavelength (507nm) place, calculate its degradation rate maximum and arrive the time of maximum.
Degradation rate statistics shows, transparent photo-catalytic emulsion of the present invention reaches maximum to the degradation rate of Acid Red B after about 90 ~ 100 min, and average degradation rate is up to about 97 ~ 98%.In addition, table 2 gives the concrete degradation rate data of photocatalyst of the present invention when 50min, as can be seen from the data in table 2, the degradation rate of sample to Acid Red B that the co-modified sample of multi layered quantum dots is modified compared with single quantum dot is faster, and after all samples placement 1-2, decline not obvious to the degradation effect of Acid Red B.
Table 2: Acid Red B degradation rate
Experimental example 3: the nano-ZnO of different doping is to the degradation experiment of different organic pollution
Doped transition metal ions nano-ZnO photocatalyst:
The nano-ZnO photocatalyst of preparation 3%Fe-1%Ni codope and the pure nano-ZnO photocatalyst sample of non-containing transition metal, for subsequent use.Its preparation method is with reference to " preparation of modified form ZnO photocatalyst and the research of photocatalytic degradation antibiotic waste water thereof " (author: Song Younan, Chang An University's master thesis, deliver the time: 2013-06-05), chapter 2, the preparation of transient metal doped ZnO and photocatalysis performance, the method step that 2.2 experimental sections provide carries out.
The nano-ZnO photocatalyst of precious metal ion doping:
The preparation of three-dimensional Ag/ZnO hollow microsphere sample: its preparation method is with reference to " preparation of three-dimensional Ag/ZnO hollow microsphere and anti-microbial property thereof " (Lu Weiwei etc., University Of Science and Technology Of He'nan's journal: natural science edition, volume the 5th phase October the 32nd in 2011, P89-93) method step that provides carries out.
The nano-ZnO photocatalyst that the above nano-ZnO photocatalyst with reference to the pure nano-ZnO photocatalyst prepared by existing method, 3%Fe-1%Ni codope and precious metals ag are adulterated and the quantum dot-doped nano-ZnO photocatalyst prepared by the embodiment of the present invention 3, compare it respectively under fluorescent light to the degradation effect of different organic pollution (acephatemet, formaldehyde, toluene, Escherichia coli, Acid Red B), specific experiment process is as follows:
Parallelly get the agricultural chemicals that 4 parts of concentration are 20 mg/L respectively, formaldehyde, toluene, Escherichia coli, Acid Red B solution is placed in beaker, every part of 15mL, in contained ZnO=0.1 mol, photocatalyst at lucifuge place respectively prepared by Example 3, the nano-ZnO photocatalyst of 3%Fe-1%Ni codope, three-dimensional Ag/ZnO hollow microsphere, pure nano-ZnO photocatalyst freshly prepd transparent photo-catalytic emulsion sample joins in above-mentioned beaker respectively, then 400 mL are added water to, the pH value of reaction system is regulated to be 3 with watery hydrochloric acid again, in the dark magnetic agitation 40-50 min, make fully to contact between photo-catalytic emulsion and organic dyestuff to keep sorption and desorption balance, then sample with test tube, then the test tube of sampling is put under fluorescent light (400 nm ~ 750 nm) and carry out light-catalyzed reaction, sampling and testing at set intervals, its A ~ λ curve carries out the scanning of 200 ~ 1200nm wave band by UV-4100 ultraviolet-visible spectrophotometer, record absorbance and the concentration thereof at this dye solution maximum extinction wavelength (507nm) place, calculate its degradation rate maximum.
Result is as shown in table 3:
Table 3: the nano-ZnO photocatalyst of different doping is to the degradation rate of different organic pollution
Experimental example 4: new material of the present invention and other samples comparing degradation of organic dyes rate
It is parallel that to get 5 parts of concentration be that the Acid Red B solution of 20mg/L is placed in beaker, every part of 15mL, in contained ZnO=0.1 mol, at lucifuge place difference sample thief 1 ~ sample 5, join in above-mentioned beaker respectively, then 400 mL are added water to, the pH value of reaction system is regulated to be 3 with watery hydrochloric acid again, in the dark magnetic agitation 40-50min, make fully to contact between photo-catalytic emulsion and organic dyestuff to keep sorption and desorption balance, then sample with test tube, then the test tube of sampling is put under fluorescent light (400 nm ~ 750 nm) and carry out light-catalyzed reaction, sampling and testing at set intervals, its A ~ λ curve carries out the scanning of 200 ~ 1200nm wave band by UV-4100 ultraviolet-visible spectrophotometer, record absorbance and the concentration thereof at this dye solution maximum extinction wavelength (507nm) place, calculate its degradation rate maximum, result as shown in Figure 2.
As seen from Figure 2, transparent photo-catalytic emulsion of the present invention is reaching more than 97% to the degradation rate of Acid Red B, the degradation rate of photocatalyst to Acid Red B that Jing Rui Co., Ltd produces is up to 81%, the degradation rate of ZnO photocatalyst to Acid Red B that Kai Rui bio tech ltd, Shanghai produces is up to 65%, the degradation rate of ZnO photocatalyst to Acid Red B of Shanghai Xiu Zi chemical products Co., Ltd is up to 78%, and commercially available nano-ZnO white emulsion to the degradation rate of Acid Red B only up to 38%.
Claims (3)
1. a nano-ZnO transparent photo-catalytic emulsion for quantum dot modification, is characterized in that, containing following component:
Quantum dot modify nano-ZnO 0.05-50wt%, carboxylic acid 0.1-6wt%, emulsifying agent 1-10wt%, hydrogen peroxide 0.1-10wt% and water surplus;
Wherein, in the nano-ZnO that described quantum dot is modified, quantum dot and nano-ZnO mol ratio are 0.1-20%, and described quantum dot is II-VI race's semiconductor-quantum-point; Described hydrogen peroxide is the hydrogen peroxide of mass concentration 25-35%.
2. a preparation method for the nano-ZnO transparent photo-catalytic emulsion of quantum dot modification, it is characterized in that, it comprises the following steps:
A) in the nano-ZnO of 0.5-500g quantum dot modification, add 1-60g carboxylic acid, then add suitable quantity of water making beating, after making beating, add the hydrogen peroxide 1-100g of mass concentration 25-35% again, then stir 20-70 hour, obtain transparent complex solution;
The nano-ZnO that described quantum dot is modified is the nano-ZnO that II-VI race's semiconductor-quantum-point is modified, the preparation method of the nano-ZnO that described II-VI race's semiconductor-quantum-point is modified is: be slowly added to the water by zinc acetate and fully dissolve, then the ratio of Cu Suan Xin ︰ quantum dot Yang Li Yuan ︰ quantum dot negative ion source=5-1000 ︰ 1 ︰ 1 in molar ratio, in zinc acetate solution, add quantum dot cationic source and quantum dot negative ion source while stirring successively, obtain mixed solution; In gained mixed solution, slowly drip the ammoniacal liquor of mass concentration 30-50%, adjust pH, to 8-9, makes to produce complex precipitate in described mixed solution, then vacuum filtration, washing, obtains the nano-ZnO that II-VI race's semiconductor-quantum-point is modified;
B) in the transparent complex solution of gained, add emulsifying agent 10-100g, then heat stirring and refluxing 0.5-20h under 70-100 DEG C of condition and decompose complex compound, obtain the nano-ZnO transparent photo-catalytic emulsion that quantum dot is modified;
Wherein, the amount added water when pulling an oar in step a) reaches 1000g for benchmark with step b) gained photo-catalytic emulsion quality.
3. the preparation method of the nano-ZnO transparent photo-catalytic emulsion of quantum dot modification according to claim 2, is characterized in that, stir and carry out under 2-7 DEG C of condition for 20-70 hour described in step a).
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