CN105482821B - A kind of quantum dot complex microsphere with bi-component shell and preparation method thereof - Google Patents
A kind of quantum dot complex microsphere with bi-component shell and preparation method thereof Download PDFInfo
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- CN105482821B CN105482821B CN201510995510.1A CN201510995510A CN105482821B CN 105482821 B CN105482821 B CN 105482821B CN 201510995510 A CN201510995510 A CN 201510995510A CN 105482821 B CN105482821 B CN 105482821B
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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Abstract
The invention discloses a kind of quantum dot complex microsphere with bi-component shell and preparation method thereof.The quantum dot complex microsphere includes quantum dot and microcapsules, and the quantum dot self assembly is on the surface of the microcapsules, and the microcapsules include shell and kernel, and the shell contains polystyrene and silica, and the kernel is paraffin.The quantum dot complex microsphere of the present invention, quantum dot of the invention is not only able to keep the excellent properties such as general quantum dot luminous efficiency height, photochemical stability, and luminous intensity also has specific temperature sensitivity value, is associated available for specific temperature.The quantum dot of the present invention also has good reusability, and quantum dot will not fall off problem.
Description
Technical field
The present invention relates to a kind of quantum dot, it is combined more specifically to a kind of quantum dot with bi-component shell micro-
Ball and preparation method thereof.
Background technology
When scantling is reduced to nanometer scale, due to its nano effect, it is many novel and unique that material will be produced
Better than the various functions characteristic of traditional material, valency is had a wide range of applications in fields such as microelectronics, bioengineering, chemical industry, medical science
Value.
In recent years, using transition metal as the nano luminescent material of active ions, due to its excellent optical characteristics, such as absorb
Wavelength is wide and continuous, and fluorescence emission peak is tunable, fluorescence lifetime length etc., in luminescent device, fluorescence imaging, solar cell, glimmering
The field such as light detection and biomarker shows wide application prospect.But when quantum dot is used for luminescent device or fluoroscopic examination
When, in the range of 25-100 DEG C, the red shift that quantum dot absworption peak wavelength and photoluminescence spectra wavelength occur is generally individually smaller than
10nm.Furthermore, although luminous intensity has certain linear relationship with temperature, but varies with temperature, and its luminous intensity is very small,
At a temperature of less than thermal quenching, less temperature change will not cause luminous intensity significantly to strengthen or weaken.Therefore, prior art
Temperature sensitivity very high quantum dot can not be prepared.
The content of the invention
In order to overcome weak point of the prior art, the invention provides a kind of temperature sensitivity very it is high have it is double
The quantum dot complex microsphere of component shell.
The invention provides a kind of quantum dot complex microsphere with bi-component shell, it includes quantum dot and microcapsules,
The quantum dot self assembly includes shell and kernel in the surface of the microcapsules, the microcapsules, and the shell contains polyphenyl
Ethene and silica, the kernel are paraffin.
The quantum dot is the quantum dot that mercaptan carboxylic acid modifies；Triamido silane and polymerization are passed through in the surface of the microcapsules
Aluminum chloride modified processing, the chemical formula of the triamido silane is H2N-CH2-CH2-NH-CH2-CH2-NH-(CH2)3-Si-
(OCH3)3。
In the quantum dot complex microsphere, the part by weight of the paraffin, polystyrene and silica is (2~6):
(2~10):0.29.There are the 1-20 layers of quantum dot in the surface self-organization of the microcapsules.
The average grain diameter of the quantum dot complex microsphere is 55nm~600nm, preferably 65nm~500nm.Micro- glue
The particle diameter of capsule is 50nm~600nm, preferably 60nm~500nm.The particle diameter of the quantum dot be 2~150nm, preferably 5~
100nm；
The quantum dot be CdTe, CdSe, InP, InAs, CdSe/CdS, CdSe/ZnS, CdSe/ZnSe, CdTe/ZnS,
One or more in CdHgTe/ZnS, HgTe/HgCdS quantum dot.
Paraffin is preferably 18#Paraffin, 20#Paraffin, 25#Paraffin, 30#Paraffin, 35#Paraffin, 45#Paraffin, 58#One in paraffin
Plant or a variety of.
The preparation method there is provided the above-mentioned quantum dot complex microsphere with bi-component shell of the present invention, its feature exists
In this method comprises the following steps：
(1) will be (2~6) by weight proportion:(2~10):1 blended wax, styrene and tetraethyl orthosilicate, are then heated
Paraffin is melted and is stirred, mixture is made, then aqueous surfactant solution is added to and added in the mixture
Enter, dispersed with stirring uniformly obtains emulsion, the aqueous solution of ammonium persulfate is then added dropwise in the emulsion, at 60~95 DEG C
React after 0.5~6h, be down to after room temperature, be then demulsified, stood, vacuum is filtered, is washed and is dried, finally given with paraffin
For core, polystyrene and the microcapsules that silica is shell,
(2) microcapsules are immersed in the aqueous solution of quantum dot, then filtered, washed and dry, you can amount is made
Son point complex microsphere.
The quality of surfactant in the aqueous surfactant solution and paraffin, styrene and tetraethyl orthosilicate
The ratio of quality sum is 1:(10~30), the concentration of the aqueous solution of the surfactant is 0.5wt%~5wt%；It is described
The ratio of the quality of ammonium persulfate in ammonium persulfate solution and the quality sum of paraffin, styrene and tetraethyl orthosilicate is 1:
(10~50), the concentration of the ammonium persulfate solution is 1wt%~10wt%；The surfactant is polyethylene glycol, sucrose
Ester, polysorbate, octadecyl benzenesulfonic acid, lauryl sodium sulfate, sodium tetradecyl sulfate, sodium hexadecyl sulfate, 12
One or more in sodium alkyl benzene sulfonate.
In (2) step, the aqueous solution of the quantum dot is the aqueous solution for the quantum dot that mercaptan carboxylic acid modifies.The immersion
Time be 5min~240min.
It is molten with polymeric aluminum chlorides solution and triamido silane before the microcapsules are added into the aqueous solution of quantum dot
Liquid modification microcapsules, are comprised the following steps that：The microcapsules are entered into the solution of aluminium polychloride, then filtered and dry
It is dry, then it is then added in triamido solution of silane, stirs, filters and dry.The concentration of the polymeric aluminum chlorides solution
0.20wt%~0.01wt%, the triamido solution of silane is that the ethanol containing 0.5wt%~2.0wt% triamido silane is molten
Liquid.The consumption submergence microcapsules of polymeric aluminum chlorides solution and triamido solution of silane, but it is not restricted to this.Microcapsules and three
Amino silane solution quality ratio can be 1：(5~20).Microcapsules can be 1 with polymeric aluminum chlorides solution mass ratio：(5
~20).
The aqueous solution of the quantum dot is the water-soluble quantum dot that mercaptan carboxylic acid modifies, and is that conventional use of mercaptan carboxylic acid repaiies
The water-soluble quantum dot of decorations, the solution of conventional concentration.Its preparation method is as follows：Tellurium powder and sodium borohydride are mixed with water,
Inert ambient environment and constant temperature are reacted, quantum dot precursor liquid is made；Caddy is dissolved in water, then successively
Mercaptan carboxylic acid and sodium hydroxide solution are added, mixed liquor is obtained, whole mixed liquor is moved into autoclave inside liner, letting nitrogen in and deoxidizing,
Then the quantum dot precursor liquid is added in the mixed liquor, carries out hydro-thermal reaction in autoclave, obtain the sulfydryl carboxylic
The water-soluble quantum dot of acid modification.The tellurium powder, sodium borohydride, caddy and the molar ratio of mercaptan carboxylic acid are 1:(20~
60):(15~45):(6~15).Mercaptan carboxylic acid is preferably TGA, 2 mercaptopropionic acid and 3- mercaptopropionic acids.
Compared with prior art, it is of the invention to have the following advantages that：
(1) quantum dot complex microsphere of the invention, quantum dot of the invention is not only able to keep general quantum dot light emitting to imitate
The excellent properties such as rate height, photochemical stability, and luminous intensity also has specific temperature sensitivity value, available for specific
Temperature is associated.It is embodied in：When environment temperature raises the phase transition temperature of paraffin, the paraffin in quantum dot complex microsphere
Undergo phase transition, transparent liquid is become by lighttight solid-state, the translucency of such microcapsules is significantly increased, its luminescence generated by light light
The intensity (luminous intensity) of spectrum can be significantly increased；When environment temperature is less than the phase transition temperature of paraffin, by transparent liquid
Become lighttight solid-state, the translucency of such microcapsules is greatly reduced, intensity (luminous intensity) meeting of its photoluminescence spectra
Decline to a great extent.Therefore, quantum dot, which is compounded near phase transformation temperature pointses, has very strong temperature sensitivity.
, can be by on-line real time monitoring integral system when the quantum dot complex microsphere of the present invention is applied to fluoroscopic examination
The place of anomalous variation occurs for fluorescence, can detect the temperature minor variations near temperature sensitivity value.When for quantum dot
, can be by adjusting temperature value, to regulate and control the significantly change of quantum dot light emitting intensity during device.
The quantum dot complex microsphere of the present invention is applied to the close sample monitoring with the phase transformation temperature pointses of paraffin, due to stone
Wax has the unusual multi-temperature trade mark, can be by selecting the paraffin of the different temperatures trade mark, to change stone in quantum dot complex microsphere
The temperature sensitivity value of wax, so that the real-time monitoring of different samples can be realized.
(2) quantum dot complex microsphere of the invention, the polystyrene cladding shell thicker with silica formation, and polyphenyl
Ethene has stronger impact strength, is conducive to improving the heat endurance and structural stability of the microcapsules, and can be well
The elasticity and the poor shortcoming of compactness of silica are made up, the shell of densification is advantageously formed and avoids phase-change material from leaking,
Improve stability.
Silica has the characteristic such as high structural strength, thermally-stabilised, mechanically stable, chemically stable, high heat conduction, can be very
It is good to make up that polystyrene is thermally-stabilised and chemical stability is relatively poor, mechanical property is relatively poor and heat conductivility is relatively poor
Shortcoming.
Polystyrene and silicon dioxide composite material combine the advantage of polystyrene and silica, and can mutually more
The shortcoming being individually present is mended, is had complementary advantages, so as to improve the heat endurance, chemical stability, mechanically stable of the microcapsules
Property and structural stability, so that the stability of microcapsules is higher.
(3) present invention is in the preparation process of quantum dot complex microsphere, and ammonium persulfate draws as the initiator of polymerisation
The poly- polystyrene of polystyrene polymerization generation is sent out, while generating dioxy as ester-type hydrolysis catalyst teos hydrolysis
SiClx, so makes the interface polymerization reaction of polystyrene and the interface hydrolysis of tetraethyl orthosilicate carry out simultaneously, interfacial polymerization
Synergy between reaction and hydrolysis, controls the W-response speed of reaction system, makes preparation well
Microcapsules have good structural homogeneity and stability, so as to realize even particle size distribution, constitutionally stable microcapsules
Preparation.
The microcapsules of preparation aggregated aluminium chloride and triamido solution of silane processing again, so that modified microcapsule surface is electric
Lotus, and be grafted in many sites that the polyamino of triamido silane and mercaptan carboxylic acid combine to form three-dimensional, so in surface charge
Under the double action being grafted with many sites, quantum dot is very strongly assembled in the surface of microcapsules, can effectively prevent quantum
Coming off for surface sulfydryl class part is put, quantum dot originally has extraordinary time stability, and in certain acid, alkali, oxidation ring
Acid, alkaline stability and antioxidative stabilizer in border, at the same time also maintain the good biological compatibility of quantum dot, so that significantly
Improve the stability of quantum dot in a particular application.
(4) quantum dot complex microsphere of the invention, can be used in quantum dot in luminescent device, fluorescence imaging, solar energy
In terms of battery, fluoroscopic examination and biomarker.
Embodiment
The preparation of quantum dot complex microsphere of the present invention with bi-component shell is further illustrated below by embodiment
Process, but invention should not be deemed limited in following embodiment, wherein wt% is mass fraction.
The preparation method of the quantum dot solution of mercaptan carboxylic acid's modification uses preparation method commonly used in the art.The present invention
By the metal salt containing quantum dot cation, (cation for example can be Zn2+、Cd2+Or Hg2+) positive with mercaptan carboxylic acid's complexing generation
Ion precursor, then (anion for example can be S with anion precursor2-、Se2-Or Te2-) be heated to reflux so that quantum dot into
Core simultaneously grows, so that the quantum dot solution of mercaptan carboxylic acid's modification is made.The temperature being heated to reflux be 60~90 DEG C, the time be 3~
12h.For example, the cadmium telluride of mercaptan carboxylic acid's modification, the preparation method of CdSe quantum dots solution may be referred to CN
102786037A, the preparation method of the ZnS quantum dots solution of mercaptan carboxylic acid's modification may be referred to the A of CN 103242829.Amount
Cadmium sulfide, zinc selenide or the telluride zinc solution self-chambering that son point can also be modified by mercaptan carboxylic acid are formed.The following each reality of the present invention
Apply the preparation method that the cadmium telluride of mercaptan carboxylic acid's modification is described in detail in example.
Embodiment 1
(1) it is 6 in mass ratio:9:1 combined phase-change temperature is the 25 of 25 DEG C#Paraffin, styrene and tetraethyl orthosilicate, are obtained
Mixture；
Said mixture is added in 500mL round-bottomed flasks, is stirred using sheet stainless steel, in 1500 turns/min
Mixing speed under heating water bath to 60 DEG C, 1g neopelex is added in 100mL water, is uniformly dispersed, and
It is added in round-bottomed flask and emulsifies after 20min, 80 DEG C are then warming up to again, continues to emulsify under 1500 turns/min mixing speed
10min, obtains uniform microemulsion, wherein, quality and paraffin, styrene and the tetraethyl orthosilicate of neopelex
The ratio of quality sum is 1:13；
After the completion of emulsification, by the temperature adjustment of water-bath to 85 DEG C.1g ammonium persulfate is dissolved in 7.5mL deionized water
In, and be slowly added dropwise into round-bottomed flask completely.After 1500 turns/min mixing speed stirring 30min, machinery is stirred
The speed mixed is adjusted to 1000 turns/min, and the temperature of water-bath is adjusted to after 80 DEG C, reaction 1.5h, and hydrolysis and polymerisation are entered
Row is complete.Reaction solution is down to after room temperature, and the NaCl aqueous solution 10mL that saturation is added into the reaction solution of room temperature is demulsified, and is stood
After 30min, there is lamination, the emulsion of layering by way of vacuum is filtered with distillation water washing 6 times, and with being dried in vacuo
Case is dried in vacuo 6h under conditions of 45 DEG C, finally gives using phase-change material as core, and polystyrene and silica are the micro- of shell
Capsule, wherein, the ratio of the quality of ammonium persulfate and the quality sum of paraffin, styrene and tetraethyl orthosilicate is 1:16.
Characterized by electron scanning micrograph：Microcapsules Size is 160nm~200nm, and particle diameter distribution is uniform,
And the shape matching of microcapsules is regular, surface is smooth.
(2) 2mg telluriums powder and 24mg sodium borohydrides are weighed, is moved among the bottle with bottle stopper, leads to nitrogen 5min, covers bottle
Plug.Syringe extracts high purity water 2mL, is expelled in bottle, is then then exhausted from the gas that reaction is produced in bottle.Will be whole small bottled
Put in water-bath, reaction temperature is 32 DEG C, taken out after 2h, be prepared into the fresh precursor liquid of purple.
100mg caddies are added in 100mL water, and glass bar is stirred to caddy particle and is completely dissolved, and add TGA
(TGA) whole liquid is moved into autoclave inside liner again, letting nitrogen in and deoxidizing 30min obtains mixed liquor.
Good seal removes the cadmium chloride solution of peroxide, and syringe extracts the fresh precursor liquids prepared of 1mL and is quickly moved to
(tellurium powder, sodium borohydride, the molar ratio of caddy and TGA are 1 in cadmium chloride solution：41：33：9) hydroxide, is added
Sodium solution adjusts PH to 10, covers, and assembles autoclave, and 80 DEG C of hydro-thermal reaction 12h obtain the quantum of TGA modification
The point aqueous solution.
(3) 5g microcapsules are added in 50mL polymeric aluminum chlorides solutions, the concentration 0.05wt% of polymeric aluminum chlorides solution,
Stir after 10min, filtered and dried, microcapsules are then added to 50mL triamido solution of silane again, the solution it is molten
Agent absolute ethyl alcohol, the concentration of triamido solution of silane is 0.5wt%, and the chemical formula of triamido silane is H2N-CH2-CH2-NH-
CH2-CH2-NH-(CH2)3-Si-(OCH3)3, 30min are stirred at 20 DEG C, then refilters, wash and is dried to obtain and be modified micro-
Capsule.
(4) in the quantum dot aqueous solution that the microcapsules of the modification obtained by step (3) are soaked to above-mentioned TGA modification, in
15min is reacted at room temperature, is filtered, is washed with water, drying, producing quantum dot complex microsphere.
(5) the quantum dot complex microsphere obtained by step (4) is added to 20mL phosphate-buffereds mixed solution (pH value is
6.8) in, using sepectrophotofluorometer detect different temperatures under mixed solution system, the excitation wavelength 400nm of quantum dot,
Under conditions of sepectrophotofluorometer is incident and exit slit spectral band-width is 5nm, the fluorescence spectrum of system is determined, phase is obtained
To fluorescence intensity.
Table 1
| 10℃ | 20℃ | 23℃ | 26℃ | 30℃ | 40℃ | |
| Relative intensity of fluorescence (a.u.) | 164 | 173 | 187 | 806 | 824 | 827 |
Embodiment 2
(1) it is 10 in mass ratio:15:4 combined phase-change temperature are the 35 of 35 DEG C#Paraffin, styrene and tetraethyl orthosilicate, are obtained
To mixture；
Said mixture is added in 500mL round-bottomed flasks, is stirred using sheet stainless steel, in 1500 turns/min
Mixing speed under heating water bath to 60 DEG C, by 1g neopelex be added in 100mL deionized water disperse
Uniformly, and be added in round-bottomed flask emulsify 10min after, 80 DEG C are then warming up to again, under 1500 turns/min mixing speed
Continue to emulsify 20min, obtain uniform milky microemulsion, wherein, the quality of sodium tetradecyl sulfate and paraffin, styrene and
The ratio of the quality sum of tetraethyl orthosilicate is 1:25；
After the completion of emulsification, by the temperature adjustment of water-bath to 85 DEG C.1g ammonium persulfate is dissolved in 7.5mL deionized water
In, and be slowly added dropwise into round-bottomed flask completely.After 1500 turns/min mixing speed stirring 15min, machinery is stirred
The speed mixed is adjusted to 1000 turns/min, and the temperature of water-bath is adjusted to after 85 DEG C, reaction 1h, and hydrolysis and polymerisation are carried out
Completely.Reaction solution is down to after room temperature, and the NaCl aqueous solution 10mL that saturation is added into the reaction solution of room temperature is demulsified, and is stood
After 30min, there is lamination, the emulsion of layering by way of vacuum is filtered with distillation water washing 5 times, and with being dried in vacuo
Case is dried in vacuo 4h under conditions of 50 DEG C, finally gives using phase-change material as core, and polystyrene and silica are the micro- of shell
Capsule, wherein, the ratio of the quality of ammonium persulfate and the quality sum of paraffin, styrene and tetraethyl orthosilicate is 1:25.
Characterized by electron scanning micrograph：Microcapsules Size is 100nm~140nm, and particle diameter distribution is uniform,
And the shape matching of microcapsules is regular, surface is smooth.
(2) 2mg selenium powders and 24mg sodium borohydrides are weighed, is moved among the bottle with bottle stopper, leads to nitrogen 5min, covers bottle
Plug.Syringe extracts high purity water 2mL, is expelled in bottle, is then then exhausted from the gas that reaction is produced in bottle.Will be whole small bottled
Put in water-bath, reaction temperature is 32 DEG C, taken out after 2h, be prepared into the fresh precursor liquid of purple.
100mg caddies are added in 100mL water, and glass bar is stirred to caddy particle and is completely dissolved, and add TGA
(TGA) whole liquid is moved into autoclave inside liner again, letting nitrogen in and deoxidizing 30min obtains mixed liquor.
Good seal removes the cadmium chloride solution of peroxide, and syringe extracts the fresh precursor liquids prepared of 1mL and is quickly moved to
(selenium powder, sodium borohydride, the molar ratio of caddy and TGA are 1 in cadmium chloride solution：41：33：9) hydroxide, is added
Sodium solution adjusts PH to 10, covers, and assembles autoclave, and 80 DEG C of hydro-thermal reaction 12h obtain the quantum of TGA modification
The point aqueous solution.
(3) in the quantum dot aqueous solution that 5g microcapsules are soaked to above-mentioned TGA modification, 15min is reacted at room temperature,
Filter, be washed with water, drying, producing quantum dot complex microsphere.
(4) the quantum dot complex microsphere obtained by step (3) is added to 20mL phosphate-buffereds mixed solution (pH value is
6.8) in, the mixed solution system under different temperatures is detected using sepectrophotofluorometer, the excitation wavelength of quantum dot is
540nm.Under conditions of sepectrophotofluorometer is incident and exit slit spectral band-width is 5nm, the fluorescence spectrum of system is determined,
Obtain maximum relative intensity of fluorescence.
Table 2
| 20℃ | 30℃ | 33℃ | 36℃ | 40℃ | 50℃ | |
| Relative intensity of fluorescence (a.u.) | 167 | 163 | 161 | 740 | 748 | 742 |
Embodiment 3
(1) it is 8 in mass ratio:12:2 combined phase-change temperature are the 58 of 58 DEG C#Paraffin, styrene and tetraethyl orthosilicate are obtained
Mixture；
Said mixture is added in 500mL round-bottomed flasks, is stirred using sheet stainless steel, in 1500 turns/min
Mixing speed under heating water bath to 65 DEG C, 1g lauryl sodium sulfate is added in 42.5mL deionized water and disperses equal
It is even, and be added in round-bottomed flask emulsify 15min after, 80 DEG C are then warming up to again, under 1500 turns/min mixing speed after
Continuous emulsification 15min, obtains uniform milky microemulsion, wherein, the quality of neopelex and paraffin, styrene and
The ratio of the quality sum of tetraethyl orthosilicate is 1:20；
After the completion of emulsification, by the temperature adjustment of water-bath to 85 DEG C.1g initiator and catalyst ammonium persulfate are dissolved in
In 7.5mL deionized water, and slowly it is added dropwise into round-bottomed flask completely.Stirred with 1500 turns/min mixing speed
After 25min, churned mechanically speed is adjusted to 1000 turns/min, and the temperature of water-bath is adjusted to after 82 DEG C, reaction 5h, hydrolysis is anti-
It should be carried out with polymerisation complete.Reaction solution is down to after room temperature, and the NaCl aqueous solution of saturation is added into the reaction solution of room temperature
10mL is demulsified, and stands after 30min, there is lamination, and the emulsion of layering is washed by way of vacuum is filtered with distillation
Wash 4 times, and 5h is dried in vacuo under conditions of 48 DEG C with vacuum drying chamber, finally give using phase-change material as core, polystyrene
With the microcapsules that silica is shell, wherein, the quality of ammonium persulfate and the quality sum of paraffin, styrene and tetraethyl orthosilicate
Ratio be 1:20.
Characterized by electron scanning micrograph：Microcapsules Size is 80nm~110nm, and particle diameter distribution is uniform,
And the shape matching of microcapsules is regular, surface is smooth.
(2) 2mg selenium powders and 24mg sodium borohydrides are weighed, is moved among the bottle with bottle stopper, leads to nitrogen 5min, covers bottle
Plug.Syringe extracts high purity water 2mL, is expelled in bottle, is then then exhausted from the gas that reaction is produced in bottle.Will be whole small bottled
Put in water-bath, reaction temperature is 32 DEG C, taken out after 2h, be prepared into the fresh precursor liquid of purple.
100mg zinc nitrates are added in 100mL water, and glass bar is stirred to zinc nitrate particle and is completely dissolved, and add TGA
(TGA) whole liquid is moved into autoclave inside liner again, letting nitrogen in and deoxidizing 30min obtains mixed liquor.
Good seal removes the zinc nitrate solution of peroxide, and syringe extracts the fresh precursor liquids prepared of 1mL and is quickly moved to
(selenium powder, sodium borohydride, the molar ratio of zinc nitrate and TGA are 1 in zinc nitrate solution：41：33：9) hydroxide, is added
Sodium solution adjusts PH to 10, covers, and assembles autoclave, and 80 DEG C of hydro-thermal reaction 12h obtain the quantum of TGA modification
The point aqueous solution.
(3) 5g microcapsules are added in 50mL polymeric aluminum chlorides solutions, the concentration 0.08wt% of polymeric aluminum chlorides solution,
Stir after 10min, filtered and dried, microcapsules are then added to 50mL triamido solution of silane again, the solution it is molten
Agent absolute ethyl alcohol, the concentration of triamido solution of silane is 1wt%, and the chemistry of triamido silane is H2N-CH2-CH2-NH-CH2-
CH2-NH-(CH2)3-Si-(OCH3)3), 30min is stirred at 20 DEG C, is filtered, washed and dried and obtains modified microcapsules.
(4) microcapsules of the modification obtained by step (3) are added in the quantum dot aqueous solution of above-mentioned TGA modification, stirred
Mix scattered, 15min is reacted at room temperature, filter, be washed with water, drying, producing quantum dot complex microsphere.
(5) the quantum dot complex microsphere obtained by step (4) is added to 20mL phosphate-buffereds mixed solution (pH value is
6.8) in, the mixed solution system under different temperatures is detected using sepectrophotofluorometer, the excitation wavelength of quantum dot is
470nm.Under conditions of sepectrophotofluorometer is incident and exit slit spectral band-width is 5nm, the fluorescence spectrum of system is determined,
Obtain maximum relative intensity of fluorescence.
Table 3
| 40℃ | 50℃ | 56℃ | 59℃ | 65℃ | 70℃ | |
| Relative intensity of fluorescence (a.u.) | 163 | 159 | 157 | 724 | 726 | 723 |
Comparative example 1
(1) tetraethyl orthosilicate is added in 500mL round-bottomed flasks, is stirred using sheet stainless steel, 1500 turns/
1g neopelex is added in 100mL water, is uniformly dispersed to 60 DEG C by heating water bath under min mixing speed,
And be added in round-bottomed flask after emulsification 20min, 80 DEG C are then warming up to again, continue breast under 1500 turns/min mixing speed
Change 10min, obtain uniform microemulsion, wherein, the quality of neopelex and the ratio of tetraethyl orthosilicate are 1:13；
After the completion of emulsification, by the temperature adjustment of water-bath to 85 DEG C.1g ammonium persulfate is dissolved in 7.5mL deionized water
In, and be slowly added dropwise into round-bottomed flask completely.After 1500 turns/min mixing speed stirring 30min, machinery is stirred
The speed mixed is adjusted to 1000 turns/min, and the temperature of water-bath is adjusted to after 80 DEG C, reaction 1.5h, and hydrolysis and polymerisation are entered
Row is complete.Reaction solution is down to after room temperature, and the NaCl aqueous solution 10mL that saturation is added into the reaction solution of room temperature is demulsified, and is stood
After 30min, there is lamination, the emulsion of layering by way of vacuum is filtered with distillation water washing 6 times, and with being dried in vacuo
Case is dried in vacuo 6h under conditions of 45 DEG C, obtains silicon dioxide particles, wherein, the quality of ammonium persulfate and silica
Ratio is 1:16.Characterized by electron scanning micrograph：Particle diameter is 110nm~150nm.
(2) 2mg telluriums powder and 24mg sodium borohydrides are weighed, is moved among the bottle with bottle stopper, leads to nitrogen 5min, covers bottle
Plug.Syringe extracts high purity water 2mL, is expelled in bottle, is then then exhausted from the gas that reaction is produced in bottle.Will be whole small bottled
Put in water-bath, reaction temperature is 32 DEG C, taken out after 2h, be prepared into the fresh precursor liquid of purple.
100mg caddies are added in 100mL water, and glass bar is stirred to caddy particle and is completely dissolved, and add TGA
(TGA) whole liquid is moved into autoclave inside liner again, letting nitrogen in and deoxidizing 30min obtains mixed liquor.
Good seal removes the cadmium chloride solution of peroxide, and syringe extracts the fresh precursor liquids prepared of 1mL and is quickly moved to
(tellurium powder, sodium borohydride, the molar ratio of caddy and TGA are 1 in cadmium chloride solution：41：33：9) hydroxide, is added
Sodium solution adjusts PH to 10, covers, and assembles autoclave, and 80 DEG C of hydro-thermal reaction 12h obtain the quantum of TGA modification
The point aqueous solution.
(3) 5g silicon dioxide particles are added in the quantum dot aqueous solution of TGA modification, dispersed with stirring, in room temperature
Lower reaction 15min, filters, is washed with water, drying, producing quantum dot complex microsphere.
(4) the quantum dot complex microsphere obtained by step (3) is added to 20mL phosphate-buffereds mixed solution (pH value is
6.8) in, using sepectrophotofluorometer detect different temperatures under mixed solution system, the excitation wavelength 400nm of quantum dot,
Under conditions of sepectrophotofluorometer is incident and exit slit spectral band-width is 5nm, the fluorescence spectrum of system is determined, phase is obtained
To fluorescence intensity.
Table 4
| 10℃ | 20℃ | 23℃ | 26℃ | 30℃ | 40℃ | |
| Relative intensity of fluorescence (a.u.) | 891 | 888 | 887 | 883 | 882 | 878 |
Pass through table 1-4 data：Once the environment temperature of the quantum dot complex microsphere of each embodiment is slightly above paraffin
Phase transition temperature, the paraffin in quantum dot complex microsphere has occurred and that phase transformation, transparent liquid become by lighttight solid-state, this
The translucency of sample quantum dot complex microsphere is significantly increased, and the intensity (luminous intensity) of its photoluminescence spectra can occur significantly to increase
Plus, such quantum dot, which is compounded in phase transformation temperature pointses annex, has very strong temperature sensitivity.And the quantum dot of comparative example 1 is combined
The environment temperature of microballoon is in elevation process, and fluorescence intensity change is very small, under the influence of fluorescent noise, is unfavorable for instrument progress
Monitoring, temperature sensitivity is poor.
Test case 1
Example 1-3 and comparative example 1 quantum dot complex microsphere, then using spin-coating film technology commonly used in the art
The film forming on electro-conductive glass respectively, so that different fluorescence membrane sensing materials is made.The repetition of fluorescence membrane sensing material makes
Contain 0.5 μ g/L copper ion solutions with test.As a result show：Embodiment 1-3 fluorescence membrane sensing composite material is used 10 times
Afterwards, fluorescence can return to original more than 95%, quantum dot do not occur and come off problem；And the fluorescence membrane of comparative example 1 is passed
Feel composite, after using 5 times, fluorescence drops to original 90%, drops to less than 80% using fluorescence after 8 times, and go out
, after using 10 times, there is severe detachment problem, it is impossible to be further continued for using in existing quantum dot obscission.
Claims (11)
1. a kind of quantum dot complex microsphere with bi-component shell, it is characterised in that it includes quantum dot and microcapsules, described
Quantum dot self assembly includes shell and kernel in the surface of the microcapsules, the microcapsules, and the shell contains polystyrene
And silica, the kernel is paraffin.
2. according to the quantum dot complex microsphere described in claim 1, it is characterised in that：The quantum dot is what mercaptan carboxylic acid modified
Quantum dot；Triamido silane and aluminium polychloride modification, the change of the triamido silane are passed through in the surface of the microcapsules
Formula is H2N-CH2-CH2-NH-CH2-CH2-NH-(CH2)3-Si-(OCH3)3。
3. according to the quantum dot complex microsphere described in claim 1 or 2, it is characterised in that：In the quantum dot complex microsphere,
The part by weight of the paraffin, polystyrene and silica is (2~6):(2~10):0.29.
4. according to the quantum dot complex microsphere described in claim 1 or 2, it is characterised in that：The quantum dot complex microsphere it is flat
Equal particle diameter is 55nm~600nm.
5. according to the quantum dot complex microsphere described in claim 4, it is characterised in that：The average grain of the quantum dot complex microsphere
Footpath is 65nm~500nm.
6. according to the quantum dot complex microsphere described in claim 1 or 2, it is characterised in that：The quantum dot be CdTe, CdSe,
In InP, InAs, CdSe/CdS, CdSe/ZnS, CdSe/ZnSe, CdTe/ZnS, CdHgTe/ZnS, HgTe/HgCdS quantum dot
It is one or more of.
7. a kind of preparation side of the quantum dot complex microsphere with bi-component shell in 1-6 such as claim as described in any one
Method, it is characterised in that this method comprises the following steps：
(1) will be (2~6) by weight proportion:(2~10):1 blended wax, styrene and tetraethyl orthosilicate, then heating make stone
Wax is melted and stirred, and mixture is made, and is then added to aqueous surfactant solution and is added in the mixture, is stirred
Mix to be uniformly dispersed and obtain emulsion, the aqueous solution of ammonium persulfate is then added dropwise in the emulsion, reacted at 60~95 DEG C
After 0.5~6h, be down to after room temperature, be then demulsified, stood, vacuum is filtered, is washed and is dried, finally give using paraffin as
Core, polystyrene and silica are the microcapsules of shell,
(2) microcapsules are immersed in the aqueous solution of quantum dot, then filtered, washed and dry, you can quantum dot is made
Complex microsphere.
8. in accordance with the method for claim 7, it is characterised in that：Surfactant in the aqueous surfactant solution
The ratio of quality sum of quality and paraffin, styrene and tetraethyl orthosilicate be 1:(10~30), the surfactant
The concentration of the aqueous solution is 0.5wt%~5wt%；The quality of ammonium persulfate in the ammonium persulfate solution and paraffin, styrene
Ratio with the quality sum of tetraethyl orthosilicate is 1:(10~50), the concentration of the ammonium persulfate solution for 1wt%~
10wt%；The surfactant is polyethylene glycol, sucrose ester, polysorbate, octadecyl benzenesulfonic acid, dodecyl sulphate
One or more in sodium, sodium tetradecyl sulfate, sodium hexadecyl sulfate, neopelex.
9. according to the method described in claim 7 or 8, it is characterised in that：The aqueous solution of the quantum dot is modified for mercaptan carboxylic acid
Quantum dot the aqueous solution.
10. according to the method described in claim 7 or 8, it is characterised in that：The microcapsules are being added to the water-soluble of quantum dot
Before liquid, with polymeric aluminum chlorides solution and triamido solution of silane modification microcapsules, comprise the following steps that：By micro- glue
Capsule enters into the solution of aluminium polychloride, then filters and dries, is then then added in triamido solution of silane, stirring, mistake
Filter and dry.
11. in accordance with the method for claim 10, it is characterised in that：The concentration 0.20wt% of the polymeric aluminum chlorides solution~
0.01wt%, the triamido solution of silane is the ethanol solution containing 0.5wt%~2.0wt% triamido silane.
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