CN104014349A - Quantum dot modified nano titanium dioxide emulsion and preparation method thereof - Google Patents
Quantum dot modified nano titanium dioxide emulsion and preparation method thereof Download PDFInfo
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- CN104014349A CN104014349A CN201410262816.1A CN201410262816A CN104014349A CN 104014349 A CN104014349 A CN 104014349A CN 201410262816 A CN201410262816 A CN 201410262816A CN 104014349 A CN104014349 A CN 104014349A
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Abstract
The invention discloses a preparation method of a quantum dot modified nano titanium dioxide emulsion. The preparation method comprises the following steps: slowly dropwise adding titanium tetrachloride into deionized water to obtain a titanium dioxide precursor solution, then respectively adding a quantum dot positive ion precursor and a quantum dot negative ion precursor and stirring until the quantum dot positive ion precursor and the quantum dot negative ion precursor are all dissolved; and adjusting a pH value to 7-9 by ammonia water while a sediment is generated, performing vacuum filtration to obtain a filter cake, cleaning the filter cake by deionized water, then adding carboxylic acid, an emulsifying agent and deionized water for pulping, then stirring for 10-80 hours to obtain a transparent complex solution, and heating and reflowing the obtained transparent complex solution to obtain the quantum dot modified nano titanium dioxide emulsion. The preparation method disclosed by the invention has the advantages of cheap raw materials, simple preparation process, safety in operation, and the like, and is suitable for mass production; the prepared quantum dot modified nano titanium dioxide emulsion is large in light absorption range, stable in quality, less prone to agglomeration and small in particle size, and has high use value in the preparation of a photocatalytic material.
Description
Technical field
The present invention relates to nano-TiO
2photochemical catalyst and preparation technology thereof, specifically a kind of quantum dot decorated nanometer titanium dioxide emulsion and preparation method thereof.
Background technology
1972, the clear professor in Tokyo Univ Japan rattan island finds that titanium dioxide has light decomposition water performance first, since then, and through the effort of more than 30 years, the also continuous progress of making a breakthrough property of the application study of nano-titania photocatalyst technology: nineteen ninety, Weller etc. by quantum dot sensitized CdS to mesoporous TiO
2on electrode, and apply it in solar cell; 1991, Switzerland professor Gratzel invented DSSC, and this battery is because the features such as its preparation technology is simple, cost is low are by extensive concern, wherein TiO
2be widely used as this battery light anode material; 1993, Fox etc. delivered and have utilized TiO
2the paper of photocatalysis performance degradation of contaminant, causes researcher's extensive concern.As a kind of important inorganic functional material, nano titanium oxide is because having that specific area is large, nontoxic, cost is low and there is wide application the aspect such as the pollutant of the advantage such as long service life in the storage of solar energy and utilization, opto-electronic conversion, the photochromic and large G&W of photocatalytic degradation.
But due to TiO
2poor to visible absorption, quantum efficiency is low, has suppressed its utilization rate to sunshine, thereby also limited its photocatalysis performance, the main path addressing this problem is at present to nano-TiO
2surface is modified.To nano-TiO
2the method that modification is carried out in finishing has a lot, comparatively speaking, uses quantum dot decorated nanometer TiO
2the more effective method of modifying of one, as with cadmium sulfide (CdS) decorated nanometer TiO
2for example, the band-gap energy of CdS is 2.5eV, in the time that the photon energy of irradiating is enough, and CdS and TiO
2electron transition occurs simultaneously, and due to the energy level difference between valence band and conduction band, photohole will concentrate in the valence band of compound CdS, and light induced electron concentrates on TiO
2conduction band on, realize photohole and light induced electron effective separation spatially, widened TiO
2spectral response range, and improved the photocatalysis performance of catalyst; When excitation photon energy is only between CdS and TiO
2band-gap energy between, excitation energy only can excite CdS, is not enough to excite TiO
2, because TiO is compared in CdS conduction band position
2conduction band position is high, and in whole excitation process, only band-to-band transition occurs CdS, makes the electronics being stimulated on CdS more easily transfer to TiO
2conduction band on, and excite the hole of generation still to stay in the valence band of CdS, spatially realize separating of light induced electron and hole, improve photocatalysis efficiency.
At present, quantum dot decorated nanometer TiO
2preparation method a lot, as PbS quantum dot is deposited to TiO by the use chemical depositions such as Ratanatawanate
2on nanotube, improve photocatalysis performance, widened the utilization to solar spectrum.In the same year, Li etc. utilize simple wet chemical method to be compounded with CdS and TiO
2nanotube, under UV-irradiation, has improved the degradation efficiency to methyl orange.The employing infusion processes such as Xu Zhanxia and hydro-thermal combine and have prepared novel CdS/TiO
2nano composite material.Above-mentioned chemical deposition, wet chemical method, infusion process, hydro-thermal method etc. all have the shortcomings such as fabricating technology complexity, raw material toxicity be large, expensive, are unfavorable for realizing industrialization.
Summary of the invention
The object of the present invention is to provide the preparation method of a kind of raw material cheapness and the simple quantum dot decorated nanometer of preparation technology titanium dioxide emulsion, to solve existing preparation method due to fabricating technology complexity, raw material toxicity are large, high in cost of production problem is unfavorable for industrialized implementation problem.
The object of the invention is to realize by following technical scheme:
A preparation method for quantum dot decorated nanometer titanium dioxide emulsion, it comprises the steps:
(1) under room temperature, 1 ~ 7: 10 titanium tetrachloride is slowly dropped in deionized water and fully and mixed by volume, obtain transparent TiO 2 precursor solution; In described TiO 2 precursor solution, add respectively quantum dot cation presoma and quantum dot anion presoma and be stirred to whole dissolvings, pH value to 7 ~ 9 of the ammoniacal liquor regulator solution that then service property (quality) concentration is 10 ~ 40%, produce sediment, suction filtration, gained sediment washs by deionized water, obtains quantum dot decorated nanometer titanium dioxide filter cake;
Described quantum dot cation presoma consumption, described quantum dot anion presoma consumption and described titanium tetrachloride consumption are 1 ︰ 1 ︰ 2 ~ 1000 according to molar ratio computing;
Described quantum dot cation presoma is any one or any two kinds and two or more in cadmium nitrate, plumbi nitras, magnesium sulfate, calcium nitrate, barium nitrate, zinc nitrate or strontium chloride; Described quantum dot anion presoma is any one or any two kinds and two or more in vulcanized sodium, sodium selenide or tellurium sodium;
(2) in gained quantum dot decorated nanometer titanium dioxide filter cake, add carboxylic acid and emulsifying agent, then add deionized water making beating; After making beating, under room temperature, stir 10 ~ 80h, obtain transparent complex solution; Then transparent gained complex solution is heated under 60 ~ 100 DEG C of conditions, stirring and refluxing 1 ~ 30h, obtain quantum dot modify nano titanium oxide emulsion;
Described carboxylic acid consumption and the described titanium tetrachloride consumption of step (1) count 0.5 ~ 10 by mass volume ratio: 1 ~ 7, and the described titanium tetrachloride consumption of described emulsifier and step (1) counts 0.1 ~ 5 by mass volume ratio: 1 ~ 7;
Described carboxylic acid is C
1 ~ 4aliphatic carboxylic acid; Described emulsifying agent is any one in D-glucitol, sapn, tween or OP.
Preferably, described quantum dot cation presoma consumption, described quantum dot anion presoma consumption and described titanium tetrachloride consumption are 1 ︰ 1 ︰ 10 ~ 1000 according to molar ratio computing.
More preferred, described quantum dot cation presoma consumption, described quantum dot anion presoma consumption and described titanium tetrachloride consumption are 1 ︰ 1 ︰ 10 ~ 500 according to molar ratio computing.
Preferably, described carboxylic acid consumption and the described titanium tetrachloride consumption of step (1) count 3 ~ 6 by mass volume ratio: 1 ~ 7, and the described titanium tetrachloride consumption of described emulsifier and step (1) counts 0.5 ~ 1.5 by mass volume ratio: 1 ~ 7.
Preferably, described C
1 ~ 4aliphatic carboxylic acid is any one in formic acid, acetic acid, butyric acid, malic acid or tartaric acid.
Preferably, 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; More preferred, emulsifying agent used is D-glucitol.
The preparation method of quantum dot decorated nanometer titanium dioxide emulsion of the present invention, the amount that adds deionized water in step (2) is described quantum dot decorated nanometer titanium dioxide filter cake, described emulsifying agent and described carboxylic acid volume sum 1 ~ 100 times.
In the present invention, OP-9 used, OP-10 or OP-15 belong to OP class emulsifying agent, and it is the trade name of APES class emulsifying agent.
Method of the present invention has the advantages such as material is cheap, preparation technology simple, handling safety, be applicable to large-scale production, and according to the prepared quantum dot decorated nanometer titanium dioxide emulsion extinction scope large (can reach 550nm) of method of the present invention, even under faint fluorescent lamp, also can realize degradable to organic pollutions such as agricultural chemicals, microorganism, benzene class, formaldehyde, dyestuffs, in addition, it also can be used for automotive interior, office space, exterior decoration etc., and scope has a wide range of applications.In addition, adopt stable, the difficult reunion of the prepared quality of the emulsion of method of the present invention, at room temperature place and within 2 years, also can not produce precipitation, its contained quantum dot decorated nanometer TiO 2 particles particle diameter minimum reaches 2.7nm, in catalysis material preparation, has efficient use value.When for quantum dot sensitized solar cell, this method preparation technology is simple, stable performance, is applicable to large-scale production.
Brief description of the drawings
Fig. 1 is PbS quantum dot decorated nanometer TiO in the emulsion prepared of embodiment 1
2xRD figure.
Fig. 2 is PbS quantum dot decorated nanometer TiO in the emulsion prepared of embodiment 1
2particle diameter distribution map.
Fig. 3 is that quantum dot decorated nanometer titanium dioxide emulsion of the present invention and existing commercially available photo-catalytic emulsion/coating solution are to the comparison of acid red dye degradation rate.
In Fig. 3:
Sample 1 is quantum dot decorated nanometer titanium dioxide emulsion prepared by the embodiment of the present invention 1;
Sample 2 is photo-catalytic emulsions that Henan Huarong Environmental Protection Technology Co., Ltd produces;
Sample 3 is the photocatalyst coating liquid that nano development in science and technology Co., Ltd of Shenzhen produces;
Sample 4 is photo-catalytic emulsions that Guangzhou Yi Meilv key Environmental Protection Technology Co., Ltd produces;
Sample 5 is commercially available common nano-TiOs
2white emulsion.
Detailed description of the invention
In following examples, reagent used all can obtain by commercially available channel, titanium tetrachloride (TiCl used
4) pure for analyzing, content is not less than 99.0%; Ammoniacal liquor mass concentration used is 10 ~ 40%.
In the present invention, OP class emulsifying agent used is the trade name of polyoxyethylene alkylphenol ether class emulsifying agent, can obtain by commercially available channel.
Embodiment 1
(1) under room temperature, measure 100mL deionized water and pour in beaker stand-byly, then slowly drip the TiCl of 30mL
4to deionized water, obtain transparent TiO 2 precursor solution;
(2) in the transparent TiO 2 precursor solution of above-mentioned gained, add respectively TiCl
4the plumbi nitras of mole 1% and 1% vulcanized sodium, be stirred to whole dissolvings, then add ammoniacal liquor (mass concentration 40%) in this solution, and regulating pH value is 7 ~ 9, neutralizes TiCl
4the HCl producing in hydrolytic process, and and Ti
4+reaction produces sediment;
(3) vacuum filtration, washs gained sediment until inspection does not measure Cl by deionized water
-till, obtain vulcanized lead (PbS) the quantum dot decorated nanometer TiO with titanium ion mol ratio 1%
2filter cake;
(4) in gained filter cake, add 50g acetic acid, 8g D-glucitol emulsifying agent, adds deionized water to 1000mL, and then making beating is stirred 36 hours with magnetic rotation agitator at ambient temperature, obtains transparent complex solution;
(5) by transparent gained complex solution, at 100 DEG C, add hot reflux 20h and decompose complex compound, obtain the nano-TiO that PbS quantum dot is modified
2emulsion.
The filter cake of the step that takes a morsel (3) gained is dried at 80 DEG C, and then grind into powder uses X-ray diffractometer (XRD) to detect, and XRD diffraction result shows that gained filter cake is the nano-TiO that PbS quantum dot is modified
2.
Prepared emulsion is carried out to XRD detection, result as shown in Figure 1, in Fig. 1, curve a represents the XRD diffraction curve of pure nano titanium oxide, curve b represents the XRD diffraction curve of pure PbS quantum dot, curve c represents the XRD diffraction curve of nano particle in prepared emulsion, correlation curve c and curve a, b can know, the nano particle in the emulsion obtaining is the nano-TiO that PbS quantum dot is modified
2.
The nano-TiO that prepared PbS quantum dot is modified
2emulsion detects, result shows, in emulsion, the particle diameter of nano particle is at 2.7 ~ 10nm(as shown in Figure 2), light absorption test shows that its light to < 550nm wave-length coverage has light absorption, and this material is at room temperature placed and within 2 years, also can not produced precipitation.
Embodiment 2
(1) under room temperature condition, measure 100mL deionized water and pour in beaker stand-byly, then slowly drip the TiCl of 10mL
4to deionized water, obtain transparent TiO 2 precursor solution;
(2) in the transparent TiO 2 precursor solution of above-mentioned gained, add respectively TiCl
4the cadmium nitrate of mole 0.3% and 0.3% vulcanized sodium, be stirred to whole dissolvings, then adds ammoniacal liquor (mass concentration 10%), and pH to 7 ~ 9 of regulator solution, neutralize TiCl
4the HCl producing in hydrolytic process, and and Ti
4+reaction produces sediment;
(3) vacuum filtration, washs gained sediment until inspection does not measure Cl by deionized water
-till, obtain the CdS quantum dot decorated nanometer TiO with titanium ion mol ratio 0.3%
2filter cake;
(4) in gained filter cake, add 30g butyric acid, 5g D-glucitol emulsifying agent, adds deionized water to 1000mL, and then making beating stirs 40 hours with magnetic rotation agitator under room temperature condition, obtains transparent complex solution;
(5) by transparent gained complex solution, at 100 DEG C, add hot reflux 20h, complex compound is decomposed, obtain the nano-TiO that CdS quantum dot is modified
2emulsion.
In the step that takes a morsel (3), gained filter cake is dried at 80 DEG C, and grind into powder, then uses X-ray diffractometer (XRD) to detect, and XRD testing result shows that gained filter cake is CdS quantum dot decorated nanometer TiO
2.
The nano-TiO that made CdS quantum dot is modified
2emulsion detects, and result shows, in emulsion, the particle diameter of nano particle is at 2.7 ~ 10nm, and light absorption test shows that its light to < 550nm wave-length coverage has light absorption, and this material is at room temperature placed and within 2 years, also can not produced precipitation.
Embodiment 3
(1) at room temperature, get 100mL deionized water to stand-by in beaker at graduated cylinder, then get the TiCl of 40mL with graduated cylinder
4slowly splash in deionized water, obtain transparent TiO 2 precursor solution;
(2) in the transparent TiO 2 precursor solution of above-mentioned gained, add respectively TiCl
4the plumbi nitras of mole 0.5%, 0.5% zinc nitrate, 1% vulcanized sodium, be stirred to whole dissolvings, then add ammoniacal liquor (mass concentration 20%) in this solution, and regulating pH value is 7 ~ 9, neutralizes TiCl
4the HCl producing in hydrolytic process, and and Ti
4+reaction produces sediment;
(3) vacuum filtration, washs gained sediment until inspection does not measure Cl by deionized water
-till, obtain the nano-TiO that PbS/ZnS quantum dot is modified
2filter cake; Wherein, PbS and ZnS quantum dot and titanium ion mol ratio are 0.5%;
(4) in above-mentioned filter cake, add 30g formic acid, 8gD-sorbierite emulsifying agent, adds deionized water to be settled to 1000mL, and then making beating is stirred 48 hours with magnetic rotation agitator at ambient temperature, obtains transparent complex solution;
(5) get above-mentioned transparent complex solution, under 100 degrees Celsius, add hot reflux 20h and decompose complex compound, obtain the nano-TiO that PbS/ZnS quantum dot is modified
2emulsion.
In the step that takes a morsel (3), gained filter cake is dried at 80 DEG C, and grind into powder, then uses X-ray diffractometer (XRD) to detect, and XRD diffraction result shows that gained filter cake is the nano-TiO that PbS/ZnS quantum dot is modified
2.
The nano-TiO that prepared PbS/ZnS quantum dot is modified
2emulsion detects, result demonstration, and in emulsion, the particle diameter of nano particle is at 2.7 ~ 10nm; Light absorption test shows that its light to < 550nm wave-length coverage has light absorption, and this material is at room temperature placed and within 2 years, also can not produced precipitation.
Embodiment 4
(1) at room temperature, get 200mL deionized water to stand-by in beaker at graduated cylinder, then get the TiCl of 50mL with graduated cylinder
4slowly splash in deionized water, obtain transparent TiO 2 precursor solution;
(2) in the transparent TiO 2 precursor solution of above-mentioned gained, add TiCl
4the plumbi nitras of mole 0.5%, 0.5% barium nitrate and 1% vulcanized sodium are also stirred to whole dissolvings, then add ammoniacal liquor (mass concentration 30%) in this solution, and regulating pH value is 7 ~ 9, neutralizes TiCl
4the HCl producing in hydrolytic process, and and Ti
4+reaction produces sediment;
(3) vacuum filtration, washs gained sediment until inspection does not measure Cl by deionized water
-till, obtain the nano-TiO that PbS/BaS quantum dot is modified
2filter cake; Wherein PbS and BaS quantum dot and titanium ion mol ratio are 0.5%;
(4) in above-mentioned filter cake, add 40g acetic acid, 8gD-sorbierite emulsifying agent, adds deionized water to 1000mL, and then making beating is stirred 30 hours with magnetic rotation agitator at ambient temperature, obtains transparent complex solution; Filter cake is dried at 80 DEG C, grind, that use X-ray diffractometer (XRD) can be measured generation is the TiO that PbS and BaS modify
2powder;
(5) get above-mentioned transparent complex solution, under 100 degrees Celsius, add hot reflux 10h and decompose complex compound, obtain the nano-TiO that PbS/BaS quantum dot is modified
2.
The filter cake of the step that takes a morsel (3) gained is dried at 80 DEG C, and grind into powder uses X-ray diffractometer (XRD) to detect, and XRD diffraction result shows that gained filter cake is the nano-TiO that PbS/BaS quantum dot is modified
2.
The nano-TiO that prepared PbS/BaS quantum dot is modified
2emulsion detects, and testing result shows that the particle diameter of nano particle in emulsion is at 2.7 ~ 10nm, and light absorption test shows that its light to < 550nm wave-length coverage has light absorption, and this material is at room temperature placed and within 2 years, also can not produced precipitation.
Embodiment 5
(1) at room temperature, get 100mL deionized water to stand-by in beaker at graduated cylinder, then get the TiCl of 60mL with graduated cylinder
4slowly splash in deionized water, obtain transparent TiO 2 precursor solution;
(2) in the transparent TiO 2 precursor solution of above-mentioned gained, add TiCl
4the cadmium nitrate of mole 2%, 1% sodium selenide and 1% vulcanized sodium, be stirred to whole dissolvings, then add ammoniacal liquor (mass concentration 10 ~ 40%) in this solution, and regulating pH value is 7 ~ 9, neutralizes TiCl
4the HCl producing in hydrolytic process, and and Ti
4+reaction produces sediment;
(3) vacuum filtration, washs gained sediment until inspection does not measure Cl by deionized water
-till, obtain the nano-TiO that CdS/CdSe quantum dot is modified
2filter cake; Wherein, CdS and CdSe quantum dot and titanium ion mol ratio are 1%;
(4) in above-mentioned filter cake, add 30g malic acid, 8g D-glucitol emulsifying agent, adds deionized water to 1000mL, and then making beating is stirred 48 hours with magnetic rotation agitator at ambient temperature, obtains transparent complex solution;
(5) get the above-mentioned transparent complex solution of 400mL, under 100 degrees Celsius, add hot reflux 10h and decompose complex compound, obtain the nano-TiO that CdS/CdSe quantum dot is modified
2.
In the step that takes a morsel (3), the filter cake of gained is dried at 80 DEG C, and grind into powder uses X-ray diffractometer (XRD) to detect, and XRD diffraction result shows that gained filter cake is the nano-TiO that CdS/CdSe quantum dot is modified
2.
The nano-TiO that prepared CdS/CdSe quantum dot is modified
2emulsion detects, and result shows, in emulsion, the particle diameter of nano particle is at 2.7 ~ 10nm, and light absorption test shows that its light to < 550nm wave-length coverage has light absorption, and this material is at room temperature placed and within 2 years, also can not produced precipitation.
Embodiment 6
(1) at room temperature, get 100mL deionized water at graduated cylinder stand-by in pouring beaker into, then get the TiCl of 40mL with graduated cylinder
4slowly splash in deionized water, obtain transparent TiO 2 precursor solution;
(2) in the transparent TiO 2 precursor solution of above-mentioned gained, add TiCl
4the calcium nitrate of mole 0.5%, 1% strontium chloride and 1.5% vulcanized sodium, be stirred to whole dissolvings, then add ammoniacal liquor (mass concentration 30%) in this solution, and regulating pH value is 7 ~ 9, neutralizes TiCl
4the HCl producing in hydrolytic process, and and Ti
4+reaction produces sediment;
(3) vacuum filtration, washs gained sediment until inspection does not measure Cl by deionized water
-till, obtain the nano-TiO that CaS/SrS quantum dot is modified
2filter cake; Wherein, CaS and SrS quantum dot and titanium ion mol ratio are respectively 0.5% and 1%;
(4) add 60g butyric acid at above-mentioned filter cake, 8g Arlacel-20 emulsifying agent, adds deionized water to 1000mL, and then making beating is at room temperature stirred 30 hours with magnetic rotation agitator, obtains transparent complex solution;
(5) get the above-mentioned transparent complex solution of 400mL, under 100 degrees Celsius, add hot reflux 20h and decompose complex compound, obtain the nano-TiO that CaS/SrS quantum dot is modified
2emulsion.
The step that takes a morsel (3) gained filter cake is dried at 80 DEG C, grinds, and uses X-ray diffractometer (XRD) to detect, and result proves that gained filter cake is CaS/SrS quantum dot decorated nanometer TiO
2.
The nano-TiO that prepared CaS/SrS quantum dot is modified
2emulsion detects, and testing result shows that the particle diameter of nano particle in emulsion is at 2.7 ~ 10nm, and light absorption test shows that it has light absorption to the light that is less than 550nm wave-length coverage, and this material is at room temperature placed and within 2 years, also can not produced precipitation.
Embodiment 7
(1) at room temperature, get 100mL deionized water at graduated cylinder stand-by in pouring beaker into, then get the TiCl of 40mL with graduated cylinder
4slowly splash in deionized water, obtain transparent TiO 2 precursor solution;
(2) in the transparent TiO 2 precursor solution of above-mentioned gained, add TiCl
4the cadmium nitrate of mole 3% and 3% sodium selenide, be stirred to whole dissolvings, then add ammoniacal liquor (mass concentration 40%) in this solution, and regulating pH value is 7 ~ 9, neutralizes TiCl
4the HCl producing in hydrolytic process, and and Ti
4+reaction produces sediment;
(3) vacuum filtration, washs gained sediment until inspection does not measure Cl by deionized water
-till, obtain the CdSe quantum dot decorated nanometer TiO with titanium ion mol ratio 3%
2filter cake;
(4) in above-mentioned filter cake, add 30g tartaric acid, 10g Arlacel-60 emulsifying agent, adds deionized water to 1000mL, and then making beating is stirred 40 hours with magnetic rotation agitator at ambient temperature, obtains transparent complex solution;
(5) get the above-mentioned transparent complex solution of 400mL, under 100 degrees Celsius, add hot reflux 20h and decompose complex compound, obtain the nano-TiO that CdSe quantum dot is modified
2.
The step that takes a morsel (3) gained filter cake is dried at 80 DEG C, and grind into powder uses X-ray diffractometer (XRD) to detect, and XRD diffraction result shows that gained filter cake is the nano-TiO that CdSe quantum dot is modified
2.
The nano-TiO that prepared CdSe quantum dot is modified
2emulsion detects, and result shows that the particle diameter of nano particle in emulsion is at 2.7 ~ 10nm, and light absorption test shows that its light to < 550nm wave-length coverage has light absorption, and this material is at room temperature placed and within 2 years, also can not produced precipitation.
Embodiment 8
(1) at room temperature, get 100mL deionized water at graduated cylinder stand-by in pouring beaker into, then get the TiCl of 50mL with graduated cylinder
4slowly splash in deionized water, obtain transparent TiO 2 precursor solution;
(2) in the transparent TiO 2 precursor solution of above-mentioned gained, successively add TiCl
4the strontium chloride of mole 2%, 2% vulcanized sodium, 2% zinc nitrate and 2% tellurium sodium, be stirred to whole dissolvings, then add ammoniacal liquor (mass concentration 40%) in this solution, and regulating pH value is 7 ~ 9, neutralizes TiCl
4the HCl producing in hydrolytic process, and and Ti
4+reaction forms sediment;
(3) vacuum filtration, washs gained sediment until inspection does not measure Cl by deionized water
-till, obtain the nano-TiO that SrS/ZnTe quantum dot is modified
2filter cake; Wherein, SrS, ZnTe quantum dot and titanium ion mol ratio are 2%;
(4) in above-mentioned filter cake, add 30g acetic acid, 5g Tween-20 emulsifying agent, adds deionized water to 1000mL, and then making beating is stirred 30 hours with magnetic rotation agitator at ambient temperature, obtains transparent complex solution;
(5) get the above-mentioned transparent complex solution of 400mL, under 100 degrees Celsius, add hot reflux 20h and decompose complex compound, obtain the nano-TiO that SrS/ZnTe quantum dot is modified
2emulsion.
The step that takes a morsel (3) gained filter cake is dried at 80 DEG C, grinds, and uses X-ray diffractometer (XRD) to detect, and XRD diffraction result proves that gained filter cake is the nano-TiO that SrS/ZnTe quantum dot is modified
2.
The nano-TiO that prepared SrS/ZnTe quantum dot is modified
2emulsion detects, and result shows that the particle diameter of nano particle in emulsion is at 2.7 ~ 10nm, and light absorption test shows that its light to < 550nm wave-length coverage has light absorption, and this material is at room temperature placed and within 2 years, also can not produced precipitation
Embodiment 9
(1) at room temperature, get 100mL deionized water at graduated cylinder stand-by in pouring beaker into, then get the TiCl of 70mL with graduated cylinder
4slowly splash in deionized water, obtain transparent TiO 2 precursor solution;
(2) in the transparent TiO 2 precursor solution of gained, add TiCl
4the zinc nitrate of mole 3% and 3% tellurium sodium, be stirred to whole dissolvings, then add ammoniacal liquor (mass concentration 10 ~ 40%) in this solution, and regulating pH value is 7 ~ 9, neutralizes TiCl
4the HCl producing in hydrolytic process, and and Ti
4+reaction forms sediment;
(3) vacuum filtration, washs gained sediment until inspection does not measure Cl by deionized water
-till, obtain the ZnTe quantum dot decorated nanometer TiO with titanium ion mol ratio 3%
2filter cake;
(4) in above-mentioned filter cake, add 30g malic acid, 15g Tween-40 emulsifying agent, adds deionized water to 1000mL, and then making beating is stirred 36 hours with magnetic rotation agitator at ambient temperature, obtains transparent complex solution;
(5) get the above-mentioned transparent complex solution of 400mL, under 100 degrees Celsius, add hot reflux 15h and decompose complex compound, obtain the nano-TiO that ZnTe quantum dot is modified
2emulsion.
The filter cake of the step that takes a morsel (3) gained is dried at 80 DEG C, and then pulverize uses X-ray diffractometer (XRD) to detect, and XRD testing result shows that the filter cake of gained is the nano-TiO that ZnTe quantum dot is modified
2.
The nano-TiO that the ZnTe quantum dot of preparation is modified
2emulsion detects, and result shows, in emulsion, the particle diameter of nano particle is at 2.7 ~ 10nm, and light absorption test shows that its light to < 550nm wave-length coverage has light absorption, and this material is at room temperature placed and within 2 years, also can not produced precipitation.
Embodiment 10
(1) at room temperature, get 100mL deionized water at graduated cylinder stand-by in pouring beaker into, then get the TiCl of 50mL with graduated cylinder
4slowly splash in deionized water, obtain transparent TiO 2 precursor solution;
(2) in the transparent TiO 2 precursor solution of above-mentioned gained, add TiCl
4the magnesium sulfate of mole 5% and 5% vulcanized sodium, be stirred to whole dissolvings, then add ammoniacal liquor (mass concentration 10 ~ 40%) in this solution, and regulating pH value is 7 ~ 9, neutralizes TiCl
4the HCl producing in hydrolytic process, and and Ti
4+reaction forms sediment;
(3) vacuum filtration, washs gained sediment until inspection does not measure Cl by deionized water
-till, obtain the MgS quantum dot decorated nanometer TiO with titanium ion mol ratio 5%
2filter cake;
(4) in above-mentioned filter cake, add 50g butyric acid, 10g Tween-80 emulsifying agent, adds deionized water to 1000mL, and then making beating is stirred 30 hours with magnetic rotation agitator at ambient temperature, obtains transparent complex solution;
(5) get the above-mentioned transparent complex solution of 400mL, under 100 degrees Celsius, add hot reflux 10h and decompose complex compound, obtain the nano-TiO that MgS quantum dot is modified
2.
The filter cake of the step that takes a morsel (3) is dried at 80 DEG C, grinds, and then uses X-ray diffractometer (XRD) to detect, and XRD diffraction result shows that gained filter cake is the nano-TiO that MgS quantum dot is modified
2.
The nano-TiO that the MgS quantum dot of preparation is modified
2emulsion detects, and result shows that the particle diameter of nano particle in emulsion is at 2.7 ~ 10nm, and light absorption test shows that its light to < 550nm wave-length coverage has light absorption, and this material is at room temperature placed and within 2 years, also can not produced precipitation.
Embodiment 11
(1) at room temperature, get 200mL deionized water at graduated cylinder stand-by in pouring beaker into, then get the TiCl of 30mL with graduated cylinder
4slowly splash in deionized water, obtain transparent TiO 2 precursor solution;
(2) TiCl will successively be added in TiO 2 precursor solution transparent above-mentioned gained
4the strontium chloride of mole 2%, 2% vulcanized sodium, 2% zinc nitrate, 2.5% tellurium sodium and 0.5% cadmium nitrate, be stirred to whole dissolvings, then add ammoniacal liquor (mass concentration 10 ~ 40%) in this solution, and regulating pH value is 7 ~ 9, neutralizes TiCl
4the HCl producing in hydrolytic process, and and Ti
4+reaction forms sediment;
(3) vacuum filtration, washs gained sediment until inspection does not measure Cl by deionized water
-till, obtain the nano-TiO that SrS/ZnTe/CdTe quantum dot is modified
2filter cake; Wherein, SrS/ZnTe/CdTe quantum dot and titanium ion mol ratio are respectively 2%, 2%, 0.5%;
(4) in above-mentioned filter cake, add 50g tartaric acid, 15g Tween-60 emulsifying agent, adds deionized water to 1000mL, and then making beating is stirred 36 hours with magnetic rotation agitator at ambient temperature, obtains transparent complex solution;
(5) get the above-mentioned solution of 400mL, under 100 degrees Celsius, add hot reflux 30h and decompose complex compound, obtain the nano-TiO that SrS/ZnTe/CdTe quantum dot is modified
2emulsion.
The step that takes a morsel (3) gained filter cake is dried at 80 DEG C, and then grind into powder uses X-ray diffractometer (XRD) to detect, and XRD testing result shows that gained filter cake is the nano-TiO that SrS/ZnTe/CdTe quantum dot is modified
2.
The nano-TiO that the SrS/ZnTe/CdTe quantum dot of preparation is modified
2emulsion detects, and result shows that the particle diameter of nano particle in emulsion is at 2.7 ~ 10nm, and light absorption test shows that its light to < 550nm wave-length coverage has light absorption, and this material is at room temperature placed and within 2 years, also can not produced precipitation.
Embodiment 12
(1) at room temperature, get 100mL deionized water at graduated cylinder stand-by in pouring beaker into, then get the TiCl of 40mL with graduated cylinder
4slowly splash in deionized water, obtain transparent TiO 2 precursor solution;
(2) in the transparent TiO 2 precursor solution of above-mentioned gained, add TiCl
4the cadmium nitrate of mole 6%, 2% vulcanized sodium, 2% sodium selenide and 2% tellurium sodium, be stirred to whole dissolvings, then add ammoniacal liquor (mass concentration 10 ~ 40%) in this solution, and regulating pH value is 7 ~ 9, neutralizes TiCl
4the HCl producing in hydrolytic process, and and Ti
4+reaction forms sediment;
(3) vacuum filtration, washs gained sediment until inspection does not measure Cl by deionized water
-till, obtain the nano-TiO that CdS/CdSe/CdTe quantum dot is modified
2filter cake; Wherein, CdS, CdSe, CdTe quantum dot and titanium ion mol ratio are 2%;
(4) in above-mentioned filter cake, add 30g malic acid, 5g OP-9 emulsifying agent, adds deionized water to 1000mL, and then making beating is stirred 48 hours with magnetic rotation agitator at ambient temperature, obtains transparent complex solution;
(5) get the above-mentioned transparent complex solution of 400mL, under 100 degrees Celsius, add hot reflux 15h and decompose complex compound, obtain the nano-TiO that CdS/CdSe/CdTe quantum dot is modified
2emulsion.
The step that takes a morsel (3) gained filter cake is dried at 80 DEG C, grinds, and then uses X-ray diffractometer (XRD) to detect, and XRD testing result shows that gained filter cake is the nano-TiO that CdS/CdSe/CdTe quantum dot is modified
2.
The nano-TiO that the CdS/CdSe/CdTe quantum dot of preparation is modified
2emulsion detects, and result shows that the particle diameter of nano particle in emulsion is at 2.7 ~ 10nm, and light absorption test shows that its light to < 550nm wave-length coverage has light absorption, and this material is at room temperature placed and within 2 years, also can not produced precipitation.
Embodiment 13
(1) at room temperature, get 100mL deionized water at graduated cylinder stand-by in pouring beaker into, then get the TiCl of 50mL with graduated cylinder
4slowly splash in deionized water, obtain transparent TiO 2 precursor solution;
(2) in the transparent TiO 2 precursor solution of above-mentioned gained, successively add cadmium nitrate, 2% vulcanized sodium, 1% zinc nitrate, 3% tellurium sodium and 2% the magnesium sulfate of titanium tetrachloride mole 2%, be stirred to whole dissolvings, in this solution, add ammoniacal liquor (mass concentration 10 ~ 40%) again, regulating pH value is 7 ~ 9, neutralizes TiCl
4the HCl producing in hydrolytic process, and and Ti
4+reaction forms sediment;
(3) vacuum filtration, washs gained sediment until inspection does not measure Cl by deionized water
-till, obtain the nano-TiO that CdS/ZnTe/MgTe quantum dot is modified
2filter cake;
Wherein, CdS, ZnTe, MgTe quantum dot and titanium ion mol ratio are respectively 2%, 1%, 2%;
(4) in above-mentioned filter cake, add 40g tartaric acid, 5g D-glucitol emulsifying agent, adds deionized water to 1000mL, and then making beating is stirred 10 hours with magnetic rotation agitator at ambient temperature, obtains transparent complex solution;
(5) get the above-mentioned transparent complex solution of 400mL, under 100 degrees Celsius, add hot reflux 30h and decompose complex compound, obtain the nano-TiO that CdS/ZnTe/MgTe quantum dot is modified
2emulsion.
Filter cake in the step that takes a morsel (3) is dried at 80 DEG C, and then grind into powder uses X-ray diffractometer (XRD) to detect, and XRD testing result shows that gained filter cake is the nano-TiO that CdS/ZnTe/MgTe quantum dot is modified
2.
The nano-TiO that prepared CdS/ZnTe/MgTe quantum dot is modified
2emulsion detects, and result shows that the particle diameter of nano particle in emulsion is at 2.7 ~ 10nm, and light absorption test shows that its light to < 550nm wave-length coverage has light absorption, and this material is at room temperature placed and within 2 years, also can not produced precipitation.
Embodiment 14
(1) at room temperature, get 100mL deionized water at graduated cylinder stand-by in pouring beaker into, then get the TiCl of 50mL with graduated cylinder
4slowly splash in deionized water, obtain transparent TiO 2 precursor solution;
(2) in the transparent TiO 2 precursor solution of above-mentioned gained, successively add calcium nitrate, 3% vulcanized sodium, 2% zinc nitrate, 5% tellurium sodium and 4% the magnesium sulfate of titanium tetrachloride mole 2%, be stirred to whole dissolvings, in this solution, add ammoniacal liquor (mass concentration 10 ~ 40%) again, regulating pH value is 7 ~ 9, neutralizes TiCl
4the HCl producing in hydrolytic process, and and Ti
4+reaction forms sediment;
(3) vacuum filtration, washs gained sediment until inspection does not measure Cl by deionized water
-till, obtain CaS/ZnS/ZnTe/MgTe quantum dot decorated nanometer TiO
2filter cake;
Gained CaS/ZnS/ZnTe/MgTe quantum dot is modified TiO
2in filter cake, CaS, ZnS, ZnTe, MgTe quantum dot and titanium ion mol ratio are respectively 2%, 1%, 1%, 4%;
(4) in above-mentioned filter cake, add 50g acetic acid, 15g D-glucitol emulsifying agent, adds deionized water to 1000mL, and making beating then at ambient temperature, uses magnetic rotation agitator to be stirred 36 hours, obtains transparent complex solution;
(5) get the above-mentioned transparent complex solution of 400mL, under 100 degrees Celsius, add hot reflux 20h and decompose complex compound, obtain the nano-TiO that CaS/ZnS/ZnTe/MgTe quantum dot is modified
2emulsion.
Filter cake in the step that takes a morsel (3) is dried at 80 DEG C, grinds, and then uses X-ray diffractometer (XRD) to detect, and testing result shows that gained filter cake is the nano-TiO that CaS/ZnS/ZnTe/MgTe quantum dot is modified
2.
The nano-TiO that prepared CaS/ZnS/ZnTe/MgTe quantum dot is modified
2emulsion detects, and testing result shows, in emulsion, the particle diameter of nano particle is at 2.7 ~ 10nm, and light absorption test shows that its light to < 550nm wave-length coverage has light absorption, and this material is at room temperature placed and within 2 years, also can not produced precipitation.
Embodiment 15
(1) at room temperature, get 100mL deionized water at graduated cylinder stand-by in pouring beaker into, then get the TiCl of 40mL with graduated cylinder
4slowly splash in deionized water, obtain transparent TiO 2 precursor solution;
(2) in the transparent TiO 2 precursor solution of above-mentioned gained, successively add TiCl
4the plumbi nitras of mole 2%, 2% vulcanized sodium, 3% magnesium sulfate, 3% sodium selenide, 4% tellurium sodium, 3% zinc nitrate and 1% cadmium nitrate, be stirred to whole dissolvings, in this solution, add ammoniacal liquor (mass concentration 10 ~ 40%) again, regulating pH value is 7 ~ 9, neutralizes TiCl
4the HCl producing in hydrolytic process, and and Ti
4+reaction forms sediment;
(3) vacuum filtration, washs gained sediment until inspection does not measure Cl by deionized water
-till, obtain PbS/MgS/ZnTe/CdTe quantum dot decorated nanometer TiO
2filter cake;
Gained PbS/MgS/ZnTe/CdTe quantum dot is modified TiO
2in filter cake, PbS, MgS, ZnTe, CdTe quantum dot and titanium ion mol ratio are respectively 2%, 3%, 3%, 1%;
(4) in above-mentioned filter cake, add 50g formic acid, 15g OP-15 emulsifying agent, adds deionized water to 1000mL, and then making beating is stirred 36 hours with magnetic rotation agitator at ambient temperature, obtains transparent complex solution;
(5) get the above-mentioned transparent complex solution of 400mL, under 100 degrees Celsius, add hot reflux 20h and decompose complex compound, obtain the nano-TiO that PbS/MgS/ZnTe/CdTe quantum dot is modified
2emulsion.
The step that takes a morsel (3) gained filter cake is dried at 80 DEG C, and then grind into powder uses X-ray diffractometer (XRD) to detect, and XRD diffraction result shows that gained filter cake is the nano-TiO that PbS/MgS/ZnTe/CdTe quantum dot is modified
2.
The nano-TiO that prepared PbS/MgS/ZnTe/CdTe quantum dot is modified
2emulsion detects, and result shows, in emulsion, the particle diameter of nano particle is at 2.7 ~ 10nm, and light absorption test shows that its light to < 550nm wave-length coverage has light absorption, and this material is at room temperature placed and within 2 years, also can not produced precipitation.
Embodiment 16: Acid Red B degradation experiment ()
Parallelly get Acid Red B solution that 5 parts of concentration are 75mg/L to be placed in beaker for subsequent use, every part of 10mL, the quantum dot decorated nanometer TiO at lucifuge place being prepared by the embodiment of the present invention 1
2photo-catalytic emulsion (sample 4) and the commercially available nano-TiO of photo-catalytic emulsion (sample 2) prepared by emulsion (sample 1), Henan Huarong Environmental Protection Technology Co., Ltd, photocatalyst coating liquid (sample 3) prepared by nano development in science and technology Co., Ltd of Shenzhen, Guangzhou Yi Meilv key Environmental Protection Technology Co., Ltd
2the each portion of white solution (sample 5), every part of 10mL, join respectively in the ready beaker that fills Acid Red B solution, then add water to 200mL, regulate with watery hydrochloric acid behind pH value to 6 ~ 7 of reaction system, in the dark magnetic agitation 40-60min, make the abundant sorption and desorption balance that keeps between emulsion and Acid Red B organic dyestuff, then sample and be placed on outdoor sunshine place with test tube and carry out catalytic reaction, after 50min, its A ~ λ curve is carried out to the scanning of 200 ~ 800nm wave band on U-4100 ultraviolet-visible spectrophotometer, record absorbance and concentration thereof that the maximum extinction wavelength of this dye solution (512.5nm) is located, calculate its degradation rate.
Result of the test is added up, and result is as Fig. 3, and as seen from Figure 3, sample 1(is quantum dot decorated nanometer TiO prepared by the embodiment of the present invention 1
2emulsion) degradation rate of Acid Red B has been reached more than 98%, and sample 2(is photo-catalytic emulsion prepared by Henan Huarong Environmental Protection Technology Co., Ltd) be 68% to the degradation rate of Acid Red B, sample 3(is photocatalyst coating liquid prepared by nano development in science and technology Co., Ltd of Shenzhen) be 82% to the degradation rate of Acid Red B, sample 4(is the photo-catalytic emulsion of Guangzhou Yi Meilv key Environmental Protection Technology Co., Ltd) be 85% to the degradation rate of Acid Red B, sample 5(is commercially available nano-TiO
2white emulsion) be 40% to the degradation rate of Acid Red B.
Embodiment 17: Acid Red B degradation experiment (two)
Get the quantum dot decorated nanometer titanium dioxide emulsion of embodiment 2,4,6,8,10,12,14 preparations and photo-catalytic emulsion prepared by Henan Huarong Environmental Protection Technology Co., Ltd, photocatalyst coating liquid prepared by nano development in science and technology Co., Ltd of Shenzhen, the photo-catalytic emulsion of Guangzhou Yi Meilv key Environmental Protection Technology Co., Ltd, commercially available nano-TiO
2white solution, placed after 6 months ~ 2 years, and the method step providing by embodiment 16 detects the degradation rate to Acid Red B, and result is as follows:
| ? | Place after 6 months Acid Red B degradation rate | Place after 1 year Acid Red B degradation rate | Place after 2 years Acid Red B degradation rate |
| Embodiment 2 | 92% | 89% | 83% |
| Embodiment 4 | 94% | 90% | 80% |
| Embodiment 6 | 91% | 90% | 84% |
| Embodiment 8 | 89% | 86% | 80% |
| Embodiment 10 | 91% | 87% | 81% |
| Embodiment 12 | 92% | 89% | 83% |
| Embodiment 14 | 92% | 89% | 82% |
| Photo-catalytic emulsion prepared by Henan Huarong Environmental Protection Technology Co., Ltd | 60% | 40% | 30% |
| Photocatalyst coating liquid prepared by nano development in science and technology Co., Ltd of Shenzhen | 71% | 59% | 39% |
| The photo-catalytic emulsion of Guangzhou Yi Meilv key Environmental Protection Technology Co., Ltd | 79% | 61% | 45% |
| Commercially available nano-TiO 2White solution | 38% | 30% | 26% |
Existing commercially available photo-catalytic emulsion, placing after 2 years, all occur reunion sinkage, and as can be seen from the above results, its degradation rate to Acid Red B reduces greatly, commercially available nano-TiO
2white solution is only 26% to the degradation rate of Acid Red B, even and if the quantum dot decorated nanometer titanium dioxide emulsion of preparing according to the inventive method was placed after 2 years, also do not precipitate generation, and its photocatalytic activity also remains on higher level, reach as high as 84%.
Embodiment 17: different contaminant degradation experiments
Get the quantum dot decorated nanometer titanium dioxide emulsion of embodiment 1,3,5,7,9,11,13 preparations and photo-catalytic emulsion prepared by Henan Huarong Environmental Protection Technology Co., Ltd, photocatalyst coating liquid prepared by nano development in science and technology Co., Ltd of Shenzhen, the photo-catalytic emulsion of Guangzhou Yi Meilv key Environmental Protection Technology Co., Ltd, commercially available nano-TiO
2the method step that white solution provides by embodiment 16, under identical fluorescent lamp, detects the degradation rate to organophosphor (agricultural chemicals), commercially available paint (containing benezene), formalin (35% formalin) and Acid Red B dyestuff, and result is as follows:
| ? | Organophosphor | Commercially available paint | Formalin | Acid Red B dyestuff |
| Embodiment 1 | 90% | 92% | 90% | 95% |
| Embodiment 3 | 91% | 94% | 91% | 96% |
| Embodiment 5 | 94% | 95% | 93% | 97% |
| Embodiment 7 | 89% | 97% | 95% | 98% |
| Embodiment 9 | 91% | 98% | 96% | 99% |
| Embodiment 11 | 92% | 96% | 95% | 98% |
| Embodiment 13 | 91% | 97% | 97% | 98% |
| Photo-catalytic emulsion prepared by Henan Huarong Environmental Protection Technology Co., Ltd | 60% | 70% | 50% | 68% |
| Photocatalyst coating liquid prepared by nano development in science and technology Co., Ltd of Shenzhen | 71% | 76% | 69% | 82% |
| The photo-catalytic emulsion of Guangzhou Yi Meilv key Environmental Protection Technology Co., Ltd | 79% | 80% | 71% | 85% |
| Commercially available nano-TiO 2White solution | 38% | 31% | 30% | 40% |
As can be seen from the above table, even if the nano titanium oxide emulsion that the quantum dot of preparing according to method of the present invention is modified under fluorescent light, organophosphor (agricultural chemicals), commercially available paint (containing benezene), formalin (35% formalin) and the degradation rate of Acid Red B dyestuff have all been reached more than 90%, and existing commercially available nano photo-catalytic liquid is under fluorescent light to the highest ability 85% of the degradation rate of these several pollutants.
Claims (4)
1. a preparation method for quantum dot decorated nanometer titanium dioxide emulsion, is characterized in that, comprises the steps:
(1) under room temperature, 1 ~ 7: 10 titanium tetrachloride is slowly dropped in deionized water and fully and mixed by volume, obtain transparent TiO 2 precursor solution; In described TiO 2 precursor solution, add respectively quantum dot cation presoma and quantum dot anion presoma and be stirred to whole dissolvings, pH value to 7 ~ 9 of the ammoniacal liquor regulator solution that then service property (quality) concentration is 10 ~ 40%, produce sediment, suction filtration, gained sediment washs by deionized water, obtains quantum dot decorated nanometer titanium dioxide filter cake;
Described quantum dot cation presoma consumption, described quantum dot anion presoma consumption and described titanium tetrachloride consumption are 1 ︰ 1 ︰ 2 ~ 1000 according to molar ratio computing;
Described quantum dot cation presoma is any one or any two kinds and two or more in cadmium nitrate, plumbi nitras, magnesium sulfate, calcium nitrate, barium nitrate, zinc nitrate or strontium chloride; Described quantum dot anion presoma is any one or any two kinds and two or more in vulcanized sodium, sodium selenide or tellurium sodium;
(2) in gained quantum dot decorated nanometer titanium dioxide filter cake, add carboxylic acid and emulsifying agent, then add deionized water making beating; After making beating, under room temperature, stir 10 ~ 80h, obtain transparent complex solution; Then transparent gained complex solution is heated under 60 ~ 100 DEG C of conditions, stirring and refluxing 1 ~ 30h, obtain quantum dot modify nano titanium oxide emulsion;
Described carboxylic acid consumption and the described titanium tetrachloride consumption of step (1) count 0.5 ~ 10 by mass volume ratio: 1 ~ 7, and the described titanium tetrachloride consumption of described emulsifier and step (1) counts 0.1 ~ 5 by mass volume ratio: 1 ~ 7;
Described carboxylic acid is C
1 ~ 4aliphatic carboxylic acid; Described emulsifying agent is any one in D-glucitol, sapn, tween or OP.
2. the preparation method of quantum dot decorated nanometer titanium dioxide emulsion according to claim 1, it is characterized in that, described quantum dot cation presoma consumption, described quantum dot anion presoma consumption and described titanium tetrachloride consumption are 1 ︰ 1 ︰ 10 ~ 1000 according to molar ratio computing.
3. the preparation method of quantum dot decorated nanometer titanium dioxide emulsion according to claim 2, it is characterized in that, described quantum dot cation presoma consumption, described quantum dot anion presoma consumption and described titanium tetrachloride consumption are 1 ︰ 1 ︰ 10 ~ 500 according to molar ratio computing.
4. the preparation method of quantum dot decorated nanometer titanium dioxide emulsion according to claim 1, it is characterized in that, described carboxylic acid consumption and the described titanium tetrachloride consumption of step (1) count 3 ~ 6 by mass volume ratio: 1 ~ 7, and the described titanium tetrachloride consumption of described emulsifier and step (1) counts 0.5 ~ 1.5 by mass volume ratio: 1 ~ 7.
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