CN104624179B - Nano-ZnO transparent photo-catalytic emulsion of quantum dot modification and preparation method thereof - Google Patents

Abstract

The invention discloses a kind of nano-ZnO transparent photo-catalytic emulsion of quantum dot modification, the 50wt% of nano-ZnO 0.05, the 6wt% of carboxylic acid 0.1, the 10wt% of emulsifying agent 1, the 10wt% of hydrogen peroxide 0.1 and water surplus that it contains quantum dot modification；Wherein, the quantum dot is II VI race's semiconductor-quantum-points.Emulsion prepared by the present invention, under visible region, or even under weaker fluorescent lamp, realize in the degradable of the organic pollutions such as agricultural chemicals, formaldehyde, benzene class, microorganism, dyestuff, the speed and efficiency of photocatalytic degradation organic matter are improve, so as to realize the purification to environment.The invention also discloses the preparation method of the nano-ZnO transparent photo-catalytic emulsion of quantum dot modification, it is comprised the following steps：a）Carboxylic acid is added in the nano-ZnO of quantum dot modification, water mashing is subsequently adding, hydrogen peroxide is added and is stirred 20 70 hours, be subsequently adding emulsifying agent, heating stirring backflow obtains emulsion.Using the photo-catalytic emulsion good stability prepared by the method for the present invention, place does not have deposited phenomenon in 1 year at room temperature.

Description

Nano-ZnO transparent photo-catalytic emulsion of quantum dot modification and preparation method thereof

Technical field

The present invention relates to nano zine oxide photocatalyst, specifically a kind of transparent light of nano-ZnO of quantum dot modification is touched Matchmaker's emulsion and preparation method thereof.

Background technology

In recent years, it is waste water that various industry, agricultural and daily lifes are produced, useless with society and economic fast development Gas, waste residue make environment deteriorate increasingly, meanwhile, a large amount of synthesis toxic materials in household, work, life increasingly affect people's Physical and mental health, in various toxic pollutant Study on degradation fields, photocatalysis technology is just gradually showing its incomparable advantage. Macromolecule pollutant can be finally decomposed to inorganic molecules by catalysis material under light illumination, and treatment effeciency is high, and operating condition is easy Control, and non-secondary pollution.

TiO is found first from the clear professor in rattan island of Nihon University₂Since photo-catalysis function, photocatalysis technology starts extensively It is general to apply in the depollution of environment field such as degraded, antifouling, sterilized, deodorant.Nano-ZnO is after TiO₂Another kind afterwards extensively should Used in the material of photocatalysis field, itself and TiO₂Band-gap energy it is similar, all can effectively absorb ultraviolet light, have been reported show drop The toxic pollutant aspect of bio-refractory is solved, nano-ZnO photocatalysis performance and quantum yield are better than TiO₂。

But the Related product of nano-ZnO photocatalyst at present not yet can be by large-scale development and application, and its reason is ZnO As a kind of wide-band gap material（3.37eV）It is only capable of absorbing the sunshine less than below 368nm, the utilization rate to sunshine only has 4%, and electron-hole pair is easily compound, photo-generated carrier interfacial migration rate is low, and these unfavorable factors greatly affected ZnO light and touch The development of matchmaker.In order to develop can be by excited by visible light, the ZnO photocatalyst with high catalytic activity, people are permitted Many good tries, are modified ZnO using various methods, it is intended to improve its photocatalysis performance.Lu et al. passes through noble metal Deposition, three-dimensional Ag/ZnO hollow microspheres are prepared for using one step hydro thermal method, and experiment shows that the Ag of ZnO surfaces deposition can not only make Promote the separation in light induced electron and hole for electronic library, and also improve the amount of surface hydroxyl, show light higher and urge Change activity, but noble metal loading method raw material are costly, are unfavorable for large-scale production.Guan Wei provinces et al. use hydro-thermal method The ZnO photocatalyst of Fe, Co, Ni dopant Fe-Co, Fe-Ni codope is prepared for, experiment shows that the doping of metal cations Fe is carried Photocatalytic activity high, but the doping of metal Co and Ni but inhibits its photocatalysis performance.Lahiri et al. is deposited on ZnO One layer of ZnS film, makes the overall forbidden band of material be reduced to 2.8eV, makes the Absorption edge red shift of material, improves its photocatalysis Performance, but the polar orientation of strict control of material is wanted in its preparation for using, and preparation technology is complicated, is difficult to realize industrialization.

Although the above method improves the photocatalytic activity of ZnO photocatalysts to a certain extent, gained ZnO light is touched The photocatalytic activity of matchmaker can not still meet the demand of industrialization, and these methods are also substantially all because that can not be kept away in the presence of some Defect or the problem exempted from and cannot commercial application.

The content of the invention

It is an object of the invention to provide a kind of photocatalytic activity, the nano-ZnO of high, good stability quantum dot modification is transparent Photo-catalytic emulsion, to solve the problems, such as that ZnO photocatalyst product photocatalytic activities prepared by existing method are bad, stability is poor. It is a further object to provide a kind of preparation method of the nano-ZnO transparent photo-catalytic emulsion of quantum dot modification, to solve Certainly the existing method prices of raw materials are expensive or because preparation technology complicated difficult is with the problem of industrialization.

First purpose of the invention is realized by following technical scheme：

A kind of nano-ZnO transparent photo-catalytic emulsion of quantum dot modification, it contains following components：

Nano-ZnO 0.05-50wt%, carboxylic acid 0.1-6wt%, emulsifying agent 1-10wt%, the hydrogen peroxide 0.1- of quantum dot modification 10wt% and water surplus；

Wherein, in the nano-ZnO of the quantum dot modification, quantum dot is 0.1-20%, the amount with nano-ZnO mol ratio Son point is II-VI race's semiconductor-quantum-point；The hydrogen peroxide is the hydrogen peroxide of mass concentration 25-35%.

Preferably, the nano-ZnO transparent photo-catalytic emulsion of quantum dot modification of the present invention, contains receiving for quantum dot modification Rice ZnO 0.05-0.5wt%, carboxylic acid 1-4wt%, emulsifying agent 1-4wt%, the hydrogen peroxide 1-4wt% and water surplus of mass concentration 30%； It is more highly preferred to, the carboxylic acid, the emulsifying agent and the hydrogen peroxide content are equal.

Preferably, in the nano-ZnO of the quantum dot modification, quantum dot is 0.1-10% with nano-ZnO mol ratio.

Described II-VI race's semiconductor-quantum-point is cadmium sulfide, cadmium selenide, cadmium telluride, vulcanized lead, lead selenide, lead telluride, sulphur Change magnesium, magnesium selenide, telluride magnesium, calcium sulfide, calcium selenide, telluride calcium, barium sulphide, barium selenide, telluride barium, zinc sulphide, zinc selenide, tellurium Change in zinc, strontium sulfide, selenizing strontium or strontium telluride any one or it is any two or more.

The carboxylic acid is C_1-4Aliphatic carboxylic acid, it is preferred that the C_1-4Aliphatic carboxylic acid be formic acid, acetic acid, butyric acid, malic acid or Any one in tartaric acid.

The emulsifying agent be D-glucitol, Arlacel-20, Arlacel-40, Arlacel-60, Arlacel-80, Tween-20, tween -21, It is any one in Tween-40, Tween-60, tween -61, Tween-80, Tween-81, Tween-85, OP-9, OP-10 or OP-15 Kind；Preferably, emulsifying agent used is D-glucitol.

Second object of the present invention is realized by following technical scheme：

A kind of preparation method of the nano-ZnO transparent photo-catalytic emulsion of quantum dot modification, it is comprised the following steps：

a）1-60g carboxylic acids are added in the nano-ZnO of 0.5-500g quantum dots modification, suitable quantity of water mashing is subsequently adding, beaten The hydrogen peroxide 1-100g of mass concentration 25-35% is added after slurry, is then stirred 20-70 hours, obtain transparent complex compound molten Liquid；

The nano-ZnO of the quantum dot modification is the nano-ZnO of II-VI race semiconductor-quantum-point modification, described II-VI race The preparation method of nano-ZnO of semiconductor-quantum-point modification is：Zinc acetate is slowly added in water and is fully dissolved, then massaged Ratio of that than Cu Suan Xin ︰ quantum dot Yang Li Yuan ︰ quantum dots negative ion source=︰ 1 of 5-1000 ︰ 1, successively in zinc acetate solution Quantum dot cationic source and quantum dot negative ion source are added while stirring, obtain mixed solution；To slowly being dripped in gained mixed solution Plus the ammoniacal liquor of mass concentration 30-50%, adjust pH value to 8-9, make to produce complex precipitate in the mixed solution, then vacuum is taken out Filter, washing, obtain final product the nano-ZnO of II-VI race semiconductor-quantum-point modification；

b）Emulsifying agent 10-100g is added in the transparent complex solution of gained, is then heated under the conditions of 70-100 DEG C and is stirred Mix backflow 0.5-20h and decompose complex compound, obtain the nano-ZnO transparent photo-catalytic emulsion of quantum dot modification；

Wherein, step a）The amount added water during middle mashing is with step b）Gained photo-catalytic emulsion quality is reached on the basis of 1000g.

Step a）The stirring is carried out for 20-70 hours under the conditions of 2-7 DEG C.

Preferably, the preparation method of the nano-ZnO transparent photo-catalytic emulsion of quantum dot modification of the present invention, the quantum The consumption of the nano-ZnO of point modification is 0.5-5g, and the consumption of the carboxylic acid is 10-40g, and the consumption of the hydrogen peroxide is 10- 40g, the consumption of the emulsifying agent is 10-40g, and the hydrogen peroxide is the hydrogen peroxide of mass concentration 30%；It is more highly preferred to, it is described Carboxylic acid, the hydrogen peroxide and the emulsifier are equal.

Preferably, step a）In, zinc acetate, quantum dot cationic source, quantum dot negative ion source consumption mol ratio are 100- The ︰ 1 of 1000 ︰ 1.

The quantum dot cationic source is cadmium nitrate, plumbi nitras, magnesium sulfate, calcium nitrate, barium nitrate, zinc nitrate or strontium chloride In any one or it is any two or more；The quantum dot negative ion source is in vulcanized sodium, sodium selenide or telluride sodium Any one or it is any two or more.

The carboxylic acid is C_1-4Aliphatic carboxylic acid, it is preferred that the C_1-4Aliphatic carboxylic acid be formic acid, acetic acid, butyric acid, malic acid or Any one in tartaric acid.

The emulsifying agent be D-glucitol, Arlacel-20, Arlacel-40, Arlacel-60, Arlacel-80, polysorbas20, tween -21, It is any one in Tween-40, Tween-60, tween -61, Tween-80, Tween-81, Tween-85, OP-9, OP-10 or OP-15 Kind；Preferably, emulsifying agent used is D-glucitol.

Used OP-9, OP-10 or OP-15 belong to OP class emulsifying agents in the present invention, and it is alkylphenol-polyethenoxy The trade name of ethers emulsifying agent.

II-VI race's semiconductor-quantum-point due to characteristics such as its quantum size effect, skin effects, in light, electricity, magnetic, heat etc. Aspect shows excellent performance.Quantum dot can adjust the wavelength of radiating light by simply changing its grain size, obtain Excitation launching light higher.Its spectral line of emission is narrow, PLE line width, wavelength of fluorescence are steady with change of size continuously adjustabe, performance Performance in terms of many physicochemical properties such as fixed makes it in cell imaging, DNA sequencing, immune detection, TEMP, white light LEDs etc. Field has broad application prospects.Quick et al. the reporting using pamam dendrimer molecule of Cong is that template prepares CdS quantum dot, is made Its avtive spot on quantum dot surface is difficult passivation, and is degraded object with methyl orange, improves photocatalysis efficiency, but This mode that quantum dot photocatalyst is used alone has to strictly control the size of quantum dot, complex manufacturing technology, no It is market-oriented beneficial to realizing.The present invention is modified nano ZnO particles using II-VI race's semiconductor-quantum-point of low energy gap, can Regulation and control photochemical catalyst absorbs the light of different wavelength range, and realization expands spectral response in the case where nano-ZnO structure is not destroyed Interval, two or more semiconductor-quantum-point modifications are capable of achieving the cooperative effect between semiconductor, effectively reduce light induced electron-sky The recombination rate in cave, is conducive to the separation in light induced electron and hole, produces more activating oxides, extends the spectrum of nano-ZnO Response, expands the active face of nano-ZnO, and enhance the photostability of catalyst.II-VI race's semiconductor-quantum-point is because of its amount Sub- dimensional effect makes its conduction band and valence-band level more discrete, meanwhile, it has highly excited conduction band, and electronics is several with hole-recombination Rate reduction, is widely used in photocatalysis field.Its catalysis activity is easily reduced, can be used repeatedly, high stability the advantages of.

Emulsion prepared by the present invention, under visible region, or even under weaker fluorescent lamp, realizes in agricultural chemicals, first The organic pollutions such as aldehyde, benzene class, microorganism, dyestuff it is degradable, improve the speed and efficiency of photocatalytic degradation organic matter, So as to realize the purification to environment.

Emulsion prepared by the present invention, range of application is fairly widespread.Such as in automotive interior：Can be widely used for automotive interior each Kind of the part such as table such as carpet, steering wheel cover for automobile, sunshading board, roof flannelette, vehicle door interior trim and other in-car articles for use, ornaments Face forms one layer of nano protective film, resolving harmful gas, eliminates peculiar smell, mould proof.Exterior decoration：Ceramics, construction equipment, illuminating lamp Deng.In household room：Upholstery, purification of air etc..Working environment：Office, workshop, factory building, meeting can be widely applied to Room.Public place：Hotel, hospital, public place of entertainment, megastore, school, public lavatory, station etc..Sewage disposal：Can be extensive For processing sanitary sewage, benzene class sewage, dye wastewater, microorganism sewage water etc..Strong mechanical property of the invention, without secondary dirt Dye, is capable of achieving 100% depollution of environment, and the catalysis material of this quantum dot modification has efficient practical value.

The present invention is complexed-controls the nano-ZnO that precipitation reaction prepares the semiconductor-quantum-point modification of II-VI race using low temperature, Prepared semiconductor-quantum-point is that radius is less than or close to the quantum dot of Exciton Bohr Radius, be semi-conducting material between point Transition state between son and crystal, it is various with unique skin effect, quantum confined effect and macro quanta tunnel effect etc. Novel effect, with the optical property different from bulk material.Using receiving that the quantum dot prepared by the method for the present invention is modified The characteristics of rice ZnO has small particle, light absorption range wide with its material prepared.

In addition, using the photo-catalytic emulsion good stability prepared by the method for the present invention, place does not have precipitation in 1 year at room temperature Phenomenon occurs.

Figure of description

Fig. 1 is the Particle Size of Nanometer ZnO distribution map of the quantum dot modification prepared by the embodiment of the present invention 3.

Fig. 2 is the present invention and other photocatalyst samples to degradation of organic dyes rate result.

In Fig. 2：Sample 1 is transparent photo-catalytic emulsion prepared by embodiment 1, and sample 2 is the ZnO of Jing Rui Co., Ltds production Photocatalyst, sample 3 is that Shanghai Kai Rui bio tech ltd produces ZnO photocatalysts, and sample 4 has for the sub- chemical products of Shanghai show The ZnO photocatalysts of limit company production, sample 5 is commercially available nano-ZnO white powder.

Specific embodiment

In terms of mass concentration, its concentration range is 30-50wt% to ammoniacal liquor used in example 1 below -14；Hydrogen peroxide used In terms of mass concentration, its concentration is 30%.

Embodiment 1

（1）At room temperature, 100mL water is taken to stand-by in beaker with graduated cylinder, take the zinc acetate of 0.01moL（Zn(CH₃COO)₂） It is slowly added into water, stirs to being completely dissolved, obtains transparent zinc acetate solution；

（2）The cadmium nitrate of zinc acetate mole 0.3% is sequentially added in zinc acetate solution（Cd(NO₃)₂）Sulphur with 0.3% Change sodium（Na₂S）, stir to whole dissolvings, the ammoniacal liquor of concentration 30% is then slowly added into, regulation pH value is 8-9, produces compound Precipitation；

（3）Then vacuum filtration and with distillation water washing gained complex precipitate, that is, it is 0.3% to obtain with ZnO mol ratios Cadmium sulfide（CdS）The nano-ZnO filter cake of quantum dot modification；

（4）12.5g formic acid, the ad pond om 967.5g that then adds water mashing, in gained after mashing are added in gained filter cake 20g hydrogen peroxide is added in slurries, is then stirred for 40 hours with magnetic rotation agitator at 3 DEG C, obtain transparent complex compound molten Liquid；

（5）The D-glucitol of 12.5g is added in above-mentioned transparent complex solution, then the heating stirring at 100 DEG C Backflow 20h decomposes complex compound, obtains the nano-ZnO transparent photo-catalytic emulsion of CdS quantum dot modification.

Embodiment 2

（1）At room temperature, 100mL water is taken to stand-by in beaker with graduated cylinder, take the Zn (CH of 0.02moL₃COO)₂It is slowly added to To in water, stir to being completely dissolved, obtain transparent zinc acetate solution；

（2）The calcium nitrate of zinc acetate mole 0.1% is sequentially added in zinc acetate solution（Ca(NO₃)₂）Sulphur with 0.1% Change sodium, stir to whole dissolvings, be then slowly added into the ammoniacal liquor of concentration 30%, regulation pH value is 8 ~ 9, produces complex precipitate；

（3）Then vacuum filtration and with distillation water washing gained complex precipitate, that is, it is 0.1% to obtain with ZnO mol ratios Calcium sulfide（CaS）The nano-ZnO filter cake of quantum dot modification；

（4）20g formic acid, the ad pond om 965g that then adds water mashing, in gained slurries after mashing are added in gained filter cake Middle addition 15g hydrogen peroxide, is then stirred for 10 hours at 3 DEG C with magnetic rotation agitator, obtains transparent complex solution；

（5）The D-glucitol of 20g is added in above-mentioned transparent complex solution, then heating stirring is returned at 100 DEG C Stream 20h decomposes complex compound, obtains the nano-ZnO transparent photo-catalytic emulsion of CaS quantum dots modification.

Embodiment 3

（1）At room temperature, 200mL water is taken to stand-by in beaker with graduated cylinder, take the Zn (CH of 0.03moL₃COO)₂It is slowly added to To in water, stir to being completely dissolved, obtain transparent zinc acetate solution；

（2）Barium nitrate, 0.5% vulcanized sodium of zinc acetate mole 1% are sequentially added in the solution of resulting zinc acetate Sodium selenide with 0.5%, stirs to whole dissolvings, is then slowly added into the ammoniacal liquor of concentration 30%, and regulation pH value is 8 ~ 9, is produced multiple Compound is precipitated；

（3）Then vacuum filtration and with distillation water washing gained complex precipitate, that is, obtain being 0.5% with ZnO mol ratios Barium sulphide（BaS）Quantum dot and barium selenide（BaSe）The nano-ZnO filter cake of quantum dot modification；

（4）20g formic acid is added in gained filter cake, the ad pond om 960g that then adds water mashing is added in gained slurries 20g hydrogen peroxide, is then stirred for 30 hours at 3 DEG C with magnetic rotation agitator, obtains transparent complex solution；

（5）20g D-glucitols are added in above-mentioned transparent complex solution, the then heating stirring backflow at 80 DEG C 20h decomposes complex compound, obtains the nano-ZnO transparent photo-catalytic emulsion of BaS quantum dots and the modification of BaSe quantum dots.

The particle diameter of the nano-ZnO of quantum dot modification in the prepared photo-catalytic emulsion of detection, as a result as shown in figure 1, by Fig. 1 As can be seen that the nano particle prepared by the inventive method has the advantages that particle diameter is small, centralized particle diameter is in 3.8-14.5nm Between.

Embodiment 4

（1）At room temperature, 200mL water is taken to stand-by in beaker with graduated cylinder, take the Zn (CH of 0.03moL₃COO)₂It is slowly added to To in water, stir to being completely dissolved, obtain transparent zinc acetate solution；

（2）Calcium nitrate, 0.5% chlorine of zinc acetate mole 1% will be sequentially added in above-mentioned resulting zinc acetate solution Change strontium and 1.5% vulcanized sodium, stirring to whole dissolvings, then to the ammoniacal liquor that concentration 30% is added in gained mixed solution, regulation PH value is 8 ~ 9, produces complex precipitate；

（3）Vacuum filtration and by above-mentioned precipitation distilled water washes clean, obtains and the calcium sulfide that ZnO mol ratios are 1% （CaS）Quantum dot and 0.5% strontium sulfide（SrS）The nano-ZnO filter cake of quantum dot modification；

（4）10g acetic acid is added in gained filter cake, the ad pond om 970g that then adds water mashing is added in gained slurries 30g hydrogen peroxide, is then being stirred for 40 hours at 4 DEG C with magnetic rotation agitator, obtains transparent complex solution；

（5）10g Tween-40s are added in above-mentioned transparent complex solution, then the heating stirring backflow 15h at 70 DEG C Complex compound is decomposed, the nano-ZnO transparent photo-catalytic emulsion of CaS and SrS quantum dots modification is obtained.

Embodiment 5

（1）At room temperature, 200mL water is taken to stand-by in beaker with graduated cylinder, take the Zn (CH of 0.01moL₃COO)₂It is slowly added to To in water, stir to being completely dissolved, obtain transparent zinc acetate solution；

（2）To be added in above-mentioned resulting zinc acetate solution the cadmium nitrate of zinc acetate mole 1%, 1% strontium chloride and 2% sodium selenide, stirs to whole dissolvings, then to the ammoniacal liquor of concentration 30% is added in gained mixed solution, regulation pH value is 8 ~ 9, Produce complex precipitate；

（3）Vacuum filtration and by above-mentioned precipitation distilled water washes clean, obtains and the cadmium selenide that ZnO mol ratios are 1% （CdSe）Quantum dot and 1% selenizing strontium（SrSe）The nano-ZnO filter cake of quantum dot modification；

（4）10g acetic acid is added in gained filter cake, the ad pond om 972g that then adds water mashing is added in gained slurries 18g hydrogen peroxide, is then stirred for 30 hours at 7 DEG C with magnetic rotation agitator, obtains transparent complex solution；

（5）10g Arlacel-20s are added in above-mentioned transparent complex solution, the then heating stirring backflow at 100 DEG C 15h decomposes complex compound, obtains the nano-ZnO transparent photo-catalytic emulsion of CdSe and SrSe quantum dots modification；

Step（4）The amount added water during middle mashing by the quality of gained photo-catalytic emulsion in 1000g on the basis of.

Embodiment 6

（1）At room temperature, 100mL water is taken to stand-by in beaker with graduated cylinder, take the Zn (CH of 0.01moL₃COO)₂It is slowly added to To in water, stir to being completely dissolved, obtain transparent zinc acetate solution；

（2）The % chlorinations of zinc acetate mole 1 will be successively slowly added in above-mentioned resulting zinc acetate solution while stirring Strontium, 1% vulcanized sodium, 1% zinc nitrate and 1% telluride sodium, then to the ammoniacal liquor that concentration 40% is added in resulting solution, adjust pH It is 8 ~ 9 to be worth, and produces complex precipitate；

（3）Vacuum filtration, by gained complex precipitate filter cake distilled water washes clean, that is, obtain be with ZnO mol ratios 1% strontium sulfide（SrS）Quantum dot and 1% zinc telluridse（ZnTe）The nano-ZnO filter cake of quantum dot modification；

（4）12.5g formic acid, the ad pond om 957.5g that then adds water mashing, in gained slurries are added in gained filter cake 30g hydrogen peroxide is added, is then stirred for 40 hours with magnetic rotation agitator at 4 DEG C, obtain transparent complex solution；

（5）12.5g Arlacel-80s are added in resulting transparent complex solution, then the heating stirring at 100 DEG C Backflow 15h decomposes complex compound, obtains the nano-ZnO transparent photo-catalytic emulsion of SrS and ZnTe quantum dots modification.

Embodiment 7

（1）At room temperature, 200mL water is taken to stand-by in beaker with graduated cylinder, take the Zn (CH of 0.03moL₃COO)₂It is slowly added to To in water, stir to being completely dissolved, obtain transparent zinc acetate solution；

（2）To successively be added while stirring in above-mentioned resulting zinc acetate solution zinc acetate mole 1 % strontium chlorides, 1% vulcanized sodium, 1% zinc nitrate and 1% telluride sodium, stir to whole dissolvings, then to the ammonia of addition concentration 40% in the solution Water, regulation pH value is 8 ~ 9, produces complex precipitate；

（3）Vacuum filtration, by gained complex precipitate filter cake distilled water washes clean, that is, obtain be with ZnO mol ratios 1%SrS quantum dots and the ZnO filter cakes of 1%ZnTe quantum dots modification；

（4）12.5g formic acid is added in gained filter cake, the ad pond om 957.5g that then adds water mashing adds in gained slurries Enter 30g hydrogen peroxide, be then stirred for 40 hours with magnetic rotation agitator at 4 DEG C, obtain transparent complex solution；

（5）The transparent complex solution of gained is taken, 12.5gD- sorbierites are added, then 12h is heated to reflux at 100 DEG C Complex compound is decomposed, the nano-ZnO transparent photo-catalytic emulsion of SrS and ZnTe quantum dots modification is obtained.

Embodiment 8

（1）At room temperature, 200mL water is taken to stand-by in beaker with graduated cylinder, take the Zn (CH of 0.01moL₃COO)₂It is slowly added to To in water, stir to being completely dissolved, obtain transparent zinc acetate solution；

（2）The plumbi nitras and 1% vulcanized sodium of zinc acetate mole 1% will be added in above-mentioned resulting zinc acetate solution, To whole dissolvings, then to the ammoniacal liquor of concentration 40% is added in the solution, regulation pH value is 8 ~ 9, produces complex precipitate for stirring；

（3）Vacuum filtration and by gained complex precipitate filter cake distilled water washes clean, that is, obtain be with ZnO mol ratios 1% vulcanized lead（PbS）The nano-ZnO filter cake of quantum dot modification；

（4）32.5g butyric acid is added in gained filter cake, the ad pond om 937.5g that then adds water mashing adds in gained slurries Enter 30g hydrogen peroxide, be then stirred for 70 hours with magnetic rotation agitator at 5 DEG C, obtain transparent complex solution；

（5）Above-mentioned transparent complex solution is taken, 32.5g emulsifier op-10s are added, is then heated to reflux at 100 DEG C 10h decomposes complex compound, obtains the nano-ZnO transparent photo-catalytic emulsion of PbS quantum modification.

Embodiment 9

（1）At room temperature, 100mL water is taken to stand-by in beaker with graduated cylinder, take the Zn (CH of 0.02moL₃COO)₂It is slowly added to To in water, stir to being completely dissolved, obtain transparent zinc acetate solution；

（2）Plumbi nitras, 0.5% nitric acid of zinc acetate mole 0.5% will be added in above-mentioned resulting zinc acetate solution Zinc and 1% vulcanized sodium, stir to whole dissolvings, then to the ammoniacal liquor of concentration 40% is added in the solution, regulation pH value is 8 ~ 9, is produced Raw complex precipitate；

（3）Vacuum filtration and by gained complex precipitate distilled water washes clean, that is, it is 0.5% to obtain with ZnO mol ratios PbS quantum and the nano-ZnO filter cake of 0.5%ZnS quantum dots modification；

（4）25g butyric acid is added in gained filter cake, the ad pond om 955g that then adds water mashing adds 30g in gained slurries Hydrogen peroxide, is then stirred for 30 hours at 5 DEG C with magnetic rotation agitator, obtains transparent complex solution；

（5）Above-mentioned transparent complex solution is taken, 25g Arlacel-20s are added, 5h decomposition is then heated to reflux at 100 DEG C Complex compound, obtains the nano-ZnO transparent photo-catalytic emulsion of PbS and ZnS quantum dot modification.

Embodiment 10

（1）At room temperature, 100mL water is taken to stand-by in beaker with graduated cylinder, by 30mL（2.0moL/L）Zn (CH₃COO)₂ The aqueous solution is slowly added into water, obtains transparent zinc acetate solution；

（2）To successively be added while stirring in above-mentioned resulting zinc acetate solution zinc acetate mole 3% cadmium nitrate, 3% sodium selenide, 3% zinc nitrate and 3% vulcanized sodium, finally stir to whole dissolvings, then to addition concentration 50% in the solution Ammoniacal liquor, regulation pH value be 8 ~ 9, produce complex precipitate；

（3）Vacuum filtration and by gained complex precipitate distilled water washes clean, it is 3% to obtain with zinc oxide mol ratio CdSe quantum dot and the nano-ZnO filter cake of 3%ZnS quantum dots modification；

（4）Add 12.5g malic acid, the ad pond om 457.5 that then adds water to be beaten in gained filter cake, added in gained slurries 30g hydrogen peroxide, is then stirred for 40 hours at 6 DEG C with magnetic rotation agitator, obtains transparent complex solution；

（5）Above-mentioned transparent complex solution is taken, 12.5g emulsifier op-10s are added, 15h points is heated to reflux at 100 DEG C Solution complex compound, obtains the nano-ZnO transparent photo-catalytic emulsion of CdSe and ZnS quantum dot modification.

Embodiment 11

（1）At room temperature, 200mL water is taken to stand-by in beaker with graduated cylinder, take the Zn (CH of 0.03moL₃COO)₂It is slowly added to To in water, stir to being completely dissolved, obtain transparent SAS；

（2）To be added in above-mentioned resulting SAS the plumbi nitras of sodium acetate mole 1%, 1% magnesium sulfate and 2% vulcanized sodium, stirs to whole dissolvings, then to the ammoniacal liquor of concentration 50% is added in the solution, regulation pH value is 8 ~ 9, is produced multiple Compound is precipitated；

（3）Vacuum filtration and by the complex precipitate of gained distilled water washes clean, that is, obtain and ZnO mol ratios difference It is the nano-ZnO filter cake of 1%PbS and 1%MgS quantum dots modification；

（4）10g malic acid is added in gained filter cake, the ad pond om 457.5g that then adds water mashing adds in gained slurries Enter 30g hydrogen peroxide, be then stirred for 40 hours with magnetic rotation agitator at 4 DEG C, obtain transparent complex solution；

（5）The transparent complex solution of gained is taken, 12.5g polyoxyethylene nonylphenol ether -15 are added, is then heated to reflux at 100 DEG C 15h decomposes complex compound, obtains the nano-ZnO transparent photo-catalytic emulsion of PbS and MgS quantum dots modification.

Embodiment 12

（1）At room temperature, 100mL water is taken to stand-by in beaker with graduated cylinder, take the Zn (CH of 0.03moL₃COO)₂It is slowly added to To in water, stir to being completely dissolved, obtain transparent zinc acetate solution；

（2）To successively be added while stirring in above-mentioned resulting zinc acetate solution zinc acetate mole 1% cadmium nitrate, 1% sodium selenide, 0.5% magnesium sulfate, 0.5% vulcanized sodium, 1% barium nitrate and 1% telluride sodium, finally stir molten to whole Solution, then to the ammoniacal liquor of concentration 50% is added in the solution, regulation pH value is 8 ~ 9, produces complex precipitate；

（3）Vacuum filtration and by the complex precipitate filter cake distilled water washes clean of gained, that is, obtain and ZnO mol ratios The nano-ZnO filter cake of respectively 1% CdSe, 0.5%MgS and 1%BaTe quantum dot modification；

（4）10g tartaric acid is added in gained filter cake, the ad pond om 475g that then adds water mashing adds 15g in gained slurries Hydrogen peroxide, is then stirred for 20 hours at 6 DEG C with magnetic rotation agitator, obtains transparent complex solution；

（5）Above-mentioned transparency complex solution is taken, 10g Tween-85s are added, 12h is heated to reflux at 100 DEG C and is decomposed complexing Thing, obtains the nano-ZnO transparent photo-catalytic emulsion of CdSe, MgS and BaTe quantum dot modification.

Embodiment 13

（1）At room temperature, 100mL water is taken to stand-by in beaker with graduated cylinder, take the Zn (CH of 0.01moL₃COO)₂It is slowly added to To in water, stir to being completely dissolved, obtain transparent zinc acetate solution；

（2）To successively be added while stirring in above-mentioned resulting zinc acetate solution zinc acetate mole 3% barium nitrate, 3% sodium selenide, 0.5% calcium nitrate, 2% strontium chloride, 2.5% telluride sodium, 1% plumbi nitras and 1% vulcanized sodium, stirring is extremely All dissolvings, then to the ammoniacal liquor of concentration 50% is added in the solution, regulation pH value is 8 ~ 9, produces complex precipitate；

（3）Vacuum filtration and by gained complex precipitate distilled water washes clean, that is, obtain being respectively with ZnO mol ratios The nano-ZnO filter cake of 1% PbS, 0.5%CaTe, 2%SrTe and 3%BaSe quantum dot modification；

（4）12.5g tartaric acid is added in gained filter cake, 482.5g mashing is then added water to, 5g is added in gained slurries Hydrogen peroxide, is stirred for 40 hours at 5 DEG C with magnetic rotation agitator, obtains transparent complex solution；

（5）Above-mentioned transparent complex solution is taken, 12.5g Arlacel-80s are added, 12h is heated to reflux at 100 DEG C and is decomposed network Compound, obtains the nano-ZnO transparent photo-catalytic emulsion of PbS, CaTe, SrTe and BaSe quantum dot modification.

Experimental example 1：Emulsion intercalation method experiment prepared by embodiment 1-13

1-2 will be placed under emulsion room temperature state prepared by embodiment 1-13, see whether deposited phenomenon occur, counted The results are shown in Table 1.

Table 1：Precipitation status statistics

In table 1, "None" expression thing precipitation occurs, and it is total that " a small amount of " quality for representing sediment in emulsion accounts for dry in emulsion Amount ＜ 50%, " a large amount of " quality for representing sediment in emulsion account for dry substance mixture >=50% in emulsion.

Experimental example 2：Emulsion prepared by embodiment 1-13 is tested degradation of organic dyes under fluorescent light

It is parallel to take the Acid Red B solution that 28 parts of concentration is 20 mg/L and be placed in beaker, every part of 15mL, with contained ZnO= 0.1 mol is counted, after the freshly prepd transparent photo-catalytic emulsion samples of Example 1-13 are distinguished at the lucifuge, placing 1 year respectively Photo-catalytic emulsion prepared by sample and embodiment 3 places 1.5 years, the sample after 2 years respectively, is added separately to above-mentioned beaker In, 400 mL are then added water to, then be 3 with the pH value of watery hydrochloric acid regulation reaction system, magnetic agitation 40-50min, makes in the dark Holding absorption and desorption balance are fully contacted between photo-catalytic emulsion and organic dyestuff, are then sampled with test tube, then will sampling Test tube put under fluorescent light（400 nm~750 nm）Light-catalyzed reaction is carried out, at regular intervals sampling and testing, in UV- Its A ~ λ curve is carried out into the scanning of 200 ~ 1200nm wave bands on 4100 ultraviolet-visible spectrophotometers, the dye solution is recorded maximum Extinction wavelength（507nm）The absorbance and its concentration at place, calculate its degradation rate maximum and reach the time of maximum.

Degradation rate statistics shows that transparent photo-catalytic emulsion of the invention is after about 90 ~ 100 min to Acid Red B Degradation rate reaches maximum, and average degradation rate is up to 97 ~ 98% or so.In addition, table 2 gives photocatalyst of the invention in 50min When specific degradation rate data, can be seen that what the co-modified sample of multi layered quantum dots was modified compared with single quantum dot by the data in table 2 Sample faster, and after all samples place 1-2, declines to the degradation effect of Acid Red B and fails to understand to the degradation rate of Acid Red B It is aobvious.

Table 2：Acid Red B degradation rate

Experimental example 3：Degradation experiment of the nano-ZnO of difference doping to different organic pollutions

Doped transition metal ionses nano-ZnO photocatalyst：

Prepare the nano-ZnO photocatalyst of 3%Fe-1%Ni codopes and the pure nano-ZnO photocatalyst sample of undoped p transition metal Product, it is standby.Its preparation method reference《The preparation of modified form ZnO photocatalyst and its research of photocatalytic degradation antibiotic waste water》 （Author：Song Younan, Chang An University's master thesis, delivers the time：2013-06-05）, chapter 2 is transient metal doped The preparation of ZnO and photocatalysis performance, the method and step that 2.2 experimental sections are provided are carried out.

The nano-ZnO photocatalyst of precious metal ion doping：

The preparation of three-dimensional Ag/ZnO hollow microspheres sample：Its preparation method reference《The preparation of three-dimensional Ag/ZnO hollow microspheres And its anti-microbial property》（Lu Weiwei etc., University Of Science and Technology Of He'nan's journal：Natural science edition, in October, 2011 volume 32 the 5th phase, P89- 93）The method and step for being provided is carried out.

By pure nano-ZnO photocatalyst, the nano-ZnO light of 3%Fe-1%Ni codopes above by reference to prepared by existing method Catalyst and the nano-ZnO photocatalyst of precious metals ag doping and the quantum dot-doped nano-ZnO light prepared by the embodiment of the present invention 3 Catalyst, is respectively compared it under fluorescent light to different organic pollutions（Acephatemet, formaldehyde, toluene, Escherichia coli, Acid Red B） Degradation effect, specific experiment process is as follows：

It is parallel to take agricultural chemicals, formaldehyde, toluene, Escherichia coli, Acid Red B solution that 4 parts of concentration is 20 mg/L respectively and be placed in burning In cup, every part of 15mL in terms of contained ZnO=0.1 mol, distinguishes photocatalyst, the 3%Fe- prepared by Example 3 at lucifuge The nano-ZnO photocatalyst of 1%Ni codopes, three-dimensional Ag/ZnO hollow microspheres, the freshly prepd transparent light of pure nano-ZnO photocatalyst are touched Matchmaker's samples of latex is added separately in above-mentioned beaker, then adds water to 400 mL, then the pH value of reaction system is adjusted with watery hydrochloric acid It is 3, magnetic agitation 40-50 min, make to be fully contacted holding absorption between photo-catalytic emulsion and organic dyestuff and desorb in the dark Balance, is then sampled with test tube, then puts under fluorescent light the test tube of sampling（400 nm~750 nm）Carry out photocatalysis anti- Should, sampling and testing at regular intervals, its A ~ λ curve is carried out 200 on UV-4100 ultraviolet-visible spectrophotometers ~ 1200nm wave bands are scanned, and record dye solution maximum extinction wavelength（507nm）The absorbance and its concentration at place, calculate its degraded Rate maximum.

Result is as shown in table 3：

Table 3：Degradation rate of the nano-ZnO photocatalyst of difference doping to different organic pollutions

Experimental example 4：New material of the invention and comparing of other samples to degradation of organic dyes rate

It is parallel to take 5 parts of concentration for the Acid Red B solution of 20mg/L is placed in beaker, every part of 15mL；With contained ZnO=0.1 Mol is counted, and separately sampled 1 ~ sample of product 5, is added separately in above-mentioned beaker at lucifuge, then adds water to 400 mL, then with dilute The pH value of hydrochloric acid regulation reaction system is 3, and magnetic agitation 40-50min, makes to be filled between photo-catalytic emulsion and organic dyestuff in the dark Tap is touched and keeps absorption and desorption balance, is then sampled with test tube, then puts under fluorescent light the test tube of sampling（400 nm~ 750 nm）Light-catalyzed reaction is carried out, at regular intervals sampling and testing, by it on UV-4100 ultraviolet-visible spectrophotometers A ~ λ curves carry out the scanning of 200 ~ 1200nm wave bands, record dye solution maximum extinction wavelength（507nm）The absorbance at place and its Concentration, calculates its degradation rate maximum, as a result as shown in Figure 2.

As seen from Figure 2, transparent photo-catalytic emulsion of the invention has reached more than 97% in the degradation rate to Acid Red B, The photocatalyst of Jing Rui Co., Ltds production is up to 81%, the life of Shanghai Kai Rui bio tech ltd to the degradation rate of Acid Red B The ZnO photocatalysts of product are up to 65%, the ZnO photocatalysts pair of Shanghai Xiu Zi chemical products Co., Ltd to the degradation rate of Acid Red B The degradation rate of Acid Red B is up to 78%, and commercially available nano-ZnO white emulsion is only up to 38% to the degradation rate of Acid Red B.

Claims (1)

1. the preparation method of the nano-ZnO transparent photo-catalytic emulsion of a kind of quantum dot modification, it is characterized in that, it includes following step Suddenly：

a）1-60g carboxylic acids are added in the nano-ZnO of 0.5-500g quantum dots modification, suitable quantity of water mashing is subsequently adding, after mashing The hydrogen peroxide 1-100g of mass concentration 25-35% is added, is then stirred 20-70 hours, obtain transparent complex solution；Institute State stirring is carried out for 20-70 hours under the conditions of 2-7 DEG C；

The nano-ZnO of the quantum dot modification is the nano-ZnO of II-VI race semiconductor-quantum-point modification, and described II-VI race partly leads The preparation method of nano-ZnO of body quantum dot modification is：Zinc acetate is slowly added in water and is fully dissolved, then in molar ratio The ratio of Cu Suan Xin ︰ quantum dot Yang Li Yuan ︰ quantum dots negative ion source=︰ 1 of 5-1000 ︰ 1, stirs to side in zinc acetate solution successively Mix side and add quantum dot cationic source and quantum dot negative ion source, obtain mixed solution；To being slowly added dropwise matter in gained mixed solution The ammoniacal liquor of amount concentration 30-50%, adjusts pH value to 8-9, makes to produce complex precipitate in the mixed solution, then vacuum filtration, wash Wash, obtain final product the nano-ZnO of II-VI race semiconductor-quantum-point modification；Wherein, the quantum dot cationic source is cadmium nitrate, nitric acid In lead, magnesium sulfate, calcium nitrate, barium nitrate, zinc nitrate or strontium chloride any one or it is any two or more；The amount Son point negative ion source be in vulcanized sodium, sodium selenide or telluride sodium any one or it is any two or more；

b）Emulsifying agent 10-100g is added in the transparent complex solution of gained, then heating stirring is returned under the conditions of 70-100 DEG C Stream 0.5-20h decomposes complex compound, obtains the nano-ZnO transparent photo-catalytic emulsion of quantum dot modification；

Wherein, step a）The amount added water during middle mashing is with step b）Gained photo-catalytic emulsion quality is reached on the basis of 1000g.