CN107955611A - A kind of quantum dot complex microsphere containing higher fatty acids and preparation method thereof - Google Patents
A kind of quantum dot complex microsphere containing higher fatty acids and preparation method thereof Download PDFInfo
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- CN107955611A CN107955611A CN201711112032.0A CN201711112032A CN107955611A CN 107955611 A CN107955611 A CN 107955611A CN 201711112032 A CN201711112032 A CN 201711112032A CN 107955611 A CN107955611 A CN 107955611A
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- C09K11/88—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing selenium, tellurium or unspecified chalcogen elements
- C09K11/881—Chalcogenides
- C09K11/883—Chalcogenides with zinc or cadmium
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- C09K11/88—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing selenium, tellurium or unspecified chalcogen elements
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Abstract
The invention discloses a kind of quantum dot complex microsphere containing higher fatty acids and preparation method thereof.The quantum dot complex microsphere includes quantum dot and silicon dioxide nanosphere, and on the surface of the silicon dioxide nanosphere, the silicon dioxide nanosphere includes shell and kernel for the quantum dot self assembly, and the shell is SiO2, the kernel is higher fatty acids.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
The application is application number 2015109809637,22 days December 2015 applying date, " one kind is containing height for denomination of invention
The divisional application of quantum dot complex microsphere of level aliphatic acid and preparation method thereof ".
Technical field
It is compound micro- more specifically to a kind of quantum dot containing higher fatty acids the present invention relates to a kind of quantum dot
Ball and preparation method thereof.
Background technology
When scantling is reduced to nanometer scale, due to its nano effect, material will produce many novel and uniqueness
Better than the various functional characteristics of traditional material, valency is had a wide range of applications in fields such as microelectronics, bioengineering, chemical industry, medicine
Value.
In recent years, the nano luminescent material using transition metal as active ions, due to its excellent optical characteristics, such as absorbs
Wavelength is wide and continuous, and fluorescence emission peak is tunable, fluorescence lifetime length etc., in luminescent device, fluorescence imaging, solar cell, glimmering
Light is detected shows wide application prospect with fields such as biomarkers.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 light political affairs luminescent spectrum wavelength occur is generally individually smaller than
10nm.Furthermore although luminous intensity has certain linear relationship with temperature, varying with temperature, 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, the prior art
The very high quantum dot of temperature sensitivity cannot be prepared.
The content of the invention
In order to overcome shortcoming of the prior art, contain height the present invention provides a kind of temperature sensitivity is very high
The quantum dot complex microsphere of level aliphatic acid.
A kind of quantum dot complex microsphere containing higher fatty acids provided by the invention, it is characterised in that it includes quantum
Point and silicon dioxide nanosphere, the quantum dot self assembly is in the surface of the silicon dioxide nanosphere, the titanium dioxide
Silicon nanoparticle includes shell and kernel, and the shell is SiO2, the kernel is higher fatty acids.
The quantum dot is the quantum dot of mercaptan carboxylic acid's modification；Triamido is passed through on the surface of the silicon dioxide nanosphere
Silane and aluminium polychloride modification, wherein, the chemical formula of triamido silane is H2N-CH2-CH2-NH-CH2-CH2-NH-
(CH2)3-Si-(OCH3)3。
In the quantum dot complex microsphere, the SiO2Part by weight with the higher fatty acids is (0.2~1.2)
∶1.There are the 1-20 layers of quantum dot in the surface self-organization of the silicon dioxide nanosphere.
The average grain diameter of the quantum dot complex microsphere is 55nm~600nm, is preferably 65nm~500nm.The dioxy
The average grain diameter of SiClx nanoparticle is 50nm~600nm, is preferably 60nm~500nm.
The quantum dot for CdTe, CdSe, InP, InAs, CdSe/CdS, CdSe/ZnS, CdSe/ZnSe, CdTe/ZnS,
One or more in CdHgTe/ZnS, HgTe/HgCdS quantum dot.
The higher fatty acids is C9~C18Higher fatty acids, be preferably capric acid, laurate, myristic acid, palmitic acid,
One or more in palmitic acid, pearly-lustre ester acid, stearic acid, oleic acid, linoleic acid.
The present invention also provides the above-mentioned quantum dot complex microsphere containing higher fatty acids preparation method, this method includes
Following steps：
(1) higher fatty acids and surfactant are added in ethanol water, then heating melts higher fatty acids
Melt and stir evenly, the emulsion containing higher fatty acids is made, ethyl orthosilicate is then added in the emulsion, add
Aqueous slkali adjusting pH to 9~12, is then hydrolyzed reaction, after stirring, ageing, filtering, washing, drying, that is, obtains titanium dioxide
Silicon coats the silicon dioxide nanosphere of higher fatty acids；
(2) silicon dioxide nanosphere is immersed in the aqueous solution of quantum dot, then filtered, washed and do
It is dry, you can quantum dot complex microsphere is made.
In (1) step, the higher fatty acids, surfactant and ethanol water part by weight are 10: (0.1~
3.0): (20~100), the weight ratio of ethanol and water is (1~5) in the ethanol water: 1；The higher fatty acids with just
Silester part by weight is 10: (5~40).
The surfactant is polyethylene glycol, sucrose ester, polysorbate, octadecyl benzenesulfonic acid, dodecyl sulphate
One or more in sodium, sodium tetradecyl sulfate, sodium hexadecyl sulfate, are preferably lauryl sodium sulfate and/or 14
Sodium alkyl sulfate.
In (2) step, the aqueous solution of the quantum dot is the aqueous solution of the quantum dot of mercaptan carboxylic acid's modification.The immersion
Time be 5min~240min.
Before the silicon dioxide nanosphere is added to the aqueous solution of quantum dot, with polymeric aluminum chlorides solution and three
Amino silane solution modification handles silicon dioxide nanosphere, comprises the following steps that：By the silicon dioxide nanosphere enter to
In the solution of aluminium polychloride, then filter and dry, be then then added in triamido solution of silane, stirring, filter and do
It is dry.Wherein, concentration 0.20wt%~0.01wt% of polymeric aluminum chlorides solution, the triamido solution of silane be containing
The ethanol solution of 0.5wt%~2.0wt% triamido silane.The dosage of polymeric aluminum chlorides solution and triamido solution of silane submerges
Titanium dioxide silication nanoparticle, but it is not restricted to this.Silicon dioxide nanosphere and triamido solution of silane mass ratio
Can be 1: (5~20).Silicon dioxide nanosphere 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 of mercaptan carboxylic acid's modification, and its preparation method is as follows：By tellurium powder
Mixed with sodium borohydride with water, inert ambient environment and constant temperature are reacted, quantum dot precursor liquid is made；By caddy
It is dissolved in water, then sequentially adds thin yl carboxylic acid and sodium hydroxide solution, obtain mixed liquor, whole mixed liquor is moved into high pressure
Kettle inside liner, the quantum dot precursor liquid, is then added in the mixed liquor by letting nitrogen in and deoxidizing, and it is anti-to carry out hydro-thermal in autoclave
Should, obtain the water-soluble quantum dot of mercaptan carboxylic acid's modification.The tellurium powder, sodium borohydride, caddy and mercaptan carboxylic acid rub
Your ratio is 1: (20~60): (15~45): (6~15).Mercaptan carboxylic acid is preferably thioacetic acid, 2 mercaptopropionic acid and 3- sulfydryls
Propionic acid.
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 are 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 the phase transition temperature of environment temperature rise higher fatty acids, in quantum dot complex microsphere
Higher fatty acids undergo phase transition, transparent liquid, the printing opacity of such silicon dioxide nanosphere are become by lighttight solid-state
Property is significantly increased, and the intensity (luminous intensity) of its light political affairs luminescent spectrum can be significantly increased；When environment temperature is less than advanced fat
During the phase transition temperature of fat acid, lighttight solid-state is become by transparent liquid, the translucency of such silicon dioxide nanosphere is big
Width reduces, and the intensity (luminous intensity) of its light political affairs luminescent spectrum can decline to a great extent.Therefore, quantum dot is compounded in phase transition temperature
Point nearby 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
Fluorescence is abnormal the place of change, 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 suitable for the close sample monitoring with the phase transformation temperature points of higher fatty acids,
, can be by selecting the higher aliphatics of different phase transition temperatures since different higher fatty acids have many different phase transition temperature values
Acid, to change the temperature sensitivity value of quantum dot complex microsphere Fatty Acids, so that the real-time monitoring of different samples can be realized.
(2) present invention is in the preparation process of quantum dot complex microsphere, in the higher aliphatic yogurt containing surfactant
Change in liquid, when ethyl orthosilicate is hydrolyzed in alkaline environment, silica is grown on the surface of emulsion droplet, two obtained
Silica nanoparticle has neat appearance, the SiO that surface flatness is higher and surface silanol group is very more2Shell, then
SiO2Shell aggregated aluminium chloride and triamido solution of silane processing again, so that improved silica surface charge, and three
The multidigit that the polyamino of amino silane combines to form three-dimensional with thin yl carboxylic acid presses branch, is so grafted in surface charge and more sites
Double action under, quantum dot is very strongly assembled in the surface of titanium dioxide nanoparticle, can effectively prevent quantum dot table
Face sulfydryl class ligand comes off, and quantum dot sheet has extraordinary time stability, and in certain acid, alkali, oxidation environment
Acid, alkaline stability and antioxidative stabilizer, at the same time also maintain the good bio-compatibility of quantum dot, so as to greatly improve
The stability of quantum dot in a particular application.
(3) quantum dot complex microsphere of the invention, can be used in quantum dot in luminescent device, fluorescence imaging, solar energy
Battery, fluoroscopic examination and biomarker etc..
Embodiment
The preparation of the quantum dot complex microsphere of the invention containing higher fatty acids 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 the complexing generation of thin yl carboxylic acid
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 is simultaneously grown, so that the quantum dot solution of mercaptan carboxylic acid's modification be made.The temperature being heated to reflux is 60~90 DEG C, the time for 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 CN102786037A,
The preparation method of the ZnS quantum dots solution of mercaptan carboxylic acid's modification may be referred to CN103242829A.Quantum dot can also be by mercapto
Cadmium sulfide, zinc selenide or the telluride zinc solution self-chambering of yl carboxylic acid modification form.Sulfydryl carboxylic is described in detail in the following each embodiment of the present invention
The preparation method of the cadmium telluride of acid modification.
Embodiment 1
(1) 100g phase transition temperatures are taken to be added to 700g second for 52~54 DEG C of myristic acid and 20g lauryl sodium sulfate
In alcohol solution, wherein the mass ratio of absolute ethyl alcohol and water is 4: 1.Heated in 60 DEG C of water-baths, the machine after myristic acid melting
Tool stirs 30 minutes, obtains finely dispersed emulsion；80g ethyl orthosilicates are added dropwise in above-mentioned emulsion, it is molten to add NaOH
Liquid adjusts pH to 10, micro- up to silica nanometer after ageing, filtering, washing, drying at room temperature when continuation constant temperature stirring 3 is small
Ball.Characterized by electron scanning micrograph：Silicon dioxide nanosphere particle diameter is 80nm~110nm, particle diameter distribution
Uniformly, and silicon dioxide nanosphere shape it is more 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 produces in bottle.Will be whole small bottled
Put in water-bath, reaction temperature is 32 DEG C, is taken out after 2h, is 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 thioacetic acid
(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
In cadmium chloride solution (tellurium powder, sodium borohydride, the molar ratio of caddy and thioacetic acid are 1: 41: 33: 9), hydroxide is added
Sodium solution adjusts PH to 10, covers, assembles autoclave, 80 DEG C of hydro-thermal reaction 12h, obtain the quantum of thioacetic acid modification
Point aqueous solution.
(3) 10g silicon dioxide nanospheres are added in 100mL polymeric aluminum chlorides solutions, polymeric aluminum chlorides solution
Concentration 0.05wt%, after stirring 10min, is filtered and is dried, silicon dioxide nanosphere then is added to 100mL tri- again
Amino silane solution, the solvent absolute ethyl alcohol of the solution, the concentration of triamido solution of silane is 0.5wt%, triamido silane
Chemical formula is H2N-CH2-CH2-NH-CH2-CH2-NH-(CH2)3-Si-(OCH3)3, 30min is stirred at 20 DEG C, then refilter,
Wash and be dried to obtain modified silicon dioxide nanosphere.
(4) silicon dioxide nanosphere for being modified 10g is soaked in the quantum dot aqueous solution of above-mentioned thioacetic acid modification, in
15min is reacted at room temperature, is filtered, is washed with water, is dry, up to composite quantum dot microballoon.
(5) 10g composite quantum dot microballoons are added in 20mL phosphate-buffereds mixed solution (pH value 6.8), used
Mixed solution system under sepectrophotofluorometer detection different temperatures, the excitation wavelength 400nm of quantum dot, fluorescence spectrophotometry
It is included under conditions of penetrating and being 5nm with exit slit spectral band-width, measures the fluorescence spectrum of system, obtain relative intensity of fluorescence.
Table 1
| 30℃ | 40℃ | 50℃ | 56℃ | 60℃ | 65℃ | |
| Relative intensity of fluorescence (a.u.) | 205 | 203 | 214 | 825 | 836 | 835 |
Embodiment 2
(1) 100g phase transition temperatures are taken to be added to 500g ethanol for 62~63 DEG C of palmitic acid and 20g sodium tetradecyl sulfates
In aqueous solution, wherein the mass ratio of absolute ethyl alcohol and water is 4: 1.Heated in 70 DEG C of water-baths, machinery stirs after palmitic acid melting
Mix 30 minutes, obtain finely dispersed emulsion；160g ethyl orthosilicates are added dropwise in above-mentioned emulsion, add NaOH solution tune
PH to 10 is saved, when continuation constant temperature stirring 4 is small, at room temperature up to silicon dioxide nanosphere after ageing, filtering, washing, drying.It is logical
Electron micrograph characterization is over-scanned to understand：Silicon dioxide nanosphere particle diameter is 80nm~120nm, and particle diameter distribution is uniform,
And the shape of silicon dioxide nanosphere is more 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 produces in bottle.Will be whole small bottled
Put in water-bath, reaction temperature is 32 DEG C, is taken out after 2h, is prepared into the fresh precursor liquid of purple bag.
100mg caddies are added in 100mL water, and glass bar is stirred to caddy particle and is completely dissolved, and add thioacetic acid
(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
In cadmium chloride solution (selenium powder, sodium borohydride, the molar ratio of caddy and thioacetic acid are 1: 41: 33: 9), hydroxide is added
Sodium solution adjusts PH to 10, covers, assembles autoclave, 80 DEG C of hydro-thermal reaction 12h, obtain the quantum of thioacetic acid modification
Point aqueous solution.
(3) in the quantum dot aqueous solution that 10g silicon dioxide nanospheres are soaked to above-mentioned thioacetic acid modification, at room temperature
15min is reacted, filters, be washed with water, is dry, up to composite quantum dot microballoon.
(4) 10g composite quantum dots microballoon is added in 20mL phosphate-buffereds mixed solution (pH value 6.8), and use is glimmering
Mixed solution system under light spectrophotometer detection different temperatures, the excitation wavelength of quantum dot is 540nm.Fluorescence spectrophotometry
It is included under conditions of penetrating and being 5nm with exit slit spectral band-width, measures the fluorescence spectrum of system, it is strong to obtain maximum relative fluorescence
Degree.
Table 2
| 40℃ | 50℃ | 60℃ | 65℃ | 68℃ | 72℃ | |
| Relative intensity of fluorescence (a.u.) | 98 | 95 | 207 | 622 | 640 | 638 |
Embodiment 3
(1) 100g phase transition temperatures are taken to be added to 900g ethanol for 43~45 DEG C of laurate and 30g octadecyl benzenesulfonic acids
In aqueous solution, wherein the mass ratio of absolute ethyl alcohol and water is 3: 1.Heated in 50 DEG C of water-baths, machinery stirs after laurate melting
Mix 30 minutes, obtain finely dispersed emulsion；240g ethyl orthosilicates are added dropwise in above-mentioned emulsion, add NaOH solution tune
PH to 10 is saved, when continuation constant temperature stirring 4 is small, at room temperature up to silicon dioxide nanosphere after ageing, filtering, washing, drying.Two
Silica nanoparticle particle diameter is 80nm~140nm, and distribution is more uniform.
(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 produces in bottle.Will be whole small bottled
Put in water-bath, reaction temperature is 32 DEG C, is taken out after 2h, is prepared into the fresh precursor liquid of purple bag.
100mg zinc nitrates are added in 100mL water, and glass bar is stirred to zinc nitrate particle and is completely dissolved, and add thioacetic acid
(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
In zinc nitrate solution (selenium powder, sodium borohydride, the molar ratio of zinc nitrate and thioacetic acid are 1: 41: 33: 9), hydroxide is added
Sodium solution adjusts PH to 10, covers, assembles autoclave, 80 DEG C of hydro-thermal reaction 12h, obtain the quantum of thioacetic acid modification
Point aqueous solution.
(3) 10g silicon dioxide nanospheres are added in 100mL polymeric aluminum chlorides solutions, polymeric aluminum chlorides solution
Concentration 0.08wt%, after stirring 10min, is filtered and is dried, silicon dioxide nanosphere then is added to 100mL tri- again
Amino silane solution, the solvent absolute ethyl alcohol of the solution, the concentration of triamido solution of silane are 1wt%, the change of triamido silane
Learn as H2N-CH2-CH2-NH-CH2-CH2-NH-(CH2)3-Si-(OCH3)3), 30min is stirred at 20 DEG C, is filtered, washed and dried
Obtain modified silicon dioxide nanosphere.
(4) modified 10g silicon dioxide nanospheres are added in the quantum dot aqueous solution of above-mentioned thioacetic acid modification, stirred
Mix scattered, react 15min at room temperature, filter, be washed with water, is dry, up to composite quantum dot microballoon.
(5) 10g composite quantum dots microballoon is added in 20mL phosphate-buffereds mixed solution (pH value 6.8), and use is glimmering
Mixed solution system under light spectrophotometer detection different temperatures, the excitation wavelength of quantum dot is 470nm.Fluorescence spectrophotometry
It is included under conditions of penetrating and being 5nm with exit slit spectral band-width, measures the fluorescence spectrum of system, it is strong to obtain maximum relative fluorescence
Degree.
Table 3
| 25℃ | 35℃ | 41℃ | 46℃ | 50℃ | 55℃ | |
| Relative intensity of fluorescence (a.u.) | 149 | 142 | 163 | 704 | 724 | 719 |
Comparative example 1
(1) 20g lauryl sodium sulfate is taken to be added in 700g ethanol waters, wherein the mass ratio of absolute ethyl alcohol and water
For 4: 1.Heated in 50 DEG C of water-baths, mechanical agitation 30 minutes, 80g ethyl orthosilicates are then added dropwise again, add NaOH solution tune
PH to 10 is saved, when continuation constant temperature stirring 3 is small, at room temperature up to silicon dioxide nanosphere after ageing, filtering, washing, drying.It is logical
Electron micrograph characterization is over-scanned to understand：Silicon dioxide nanosphere particle diameter is 80nm~110nm.
(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 produces in bottle.Will be whole small bottled
Put in water-bath, reaction temperature is 32 DEG C, is taken out after 2h, is prepared into the fresh precursor liquid of purple bag.
100mg caddies are added in 100mL water, and glass bar is stirred to caddy particle and is completely dissolved, and add thioacetic acid
(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
In cadmium chloride solution (tellurium powder, sodium borohydride, the molar ratio of caddy and thioacetic acid are 1: 41: 33: 9), hydroxide is added
Sodium solution adjusts PH to 10, covers, assembles autoclave, 80 DEG C of hydro-thermal reaction 12h, obtain the quantum of thioacetic acid modification
Point aqueous solution.
(3) 10g silicon dioxide nanospheres are added in the quantum dot aqueous solution of thioacetic acid modification, be dispersed with stirring, in
15min is reacted at room temperature, is filtered, is washed with water, is dry, up to composite quantum dot microballoon.
(4) 10g composite quantum dots microballoon is added in 20mL phosphate-buffereds mixed solution (pH value 6.8), and use is glimmering
Mixed solution system under light spectrophotometer detection different temperatures, the excitation wavelength 400nm of quantum dot, sepectrophotofluorometer
Under conditions of incident and exit slit spectral band-width is 5nm, the fluorescence spectrum of system is measured, obtains relative intensity of fluorescence.
Table 4
| 30℃ | 40℃ | 50℃ | 56℃ | 60℃ | 65℃ | |
| Relative intensity of fluorescence (a.u.) | 990 | 987 | 975 | 970 | 969 | 967 |
Pass through the data of table 1-3：The environment temperature of the composite quantum dot microballoon of each embodiment is once slightly above advanced
The phase transition temperature of aliphatic acid, the higher fatty acids in quantum dot complex microsphere have occurred and that phase transformation, are become by lighttight solid-state
Transparent liquid, the translucency of such quantum dot complex microsphere are significantly increased, the intensity (luminous intensity) of its light political affairs luminescent spectrum
It can be significantly increased, such quantum dot, which is compounded in phase transformation temperature points annex, has very strong temperature sensitivity.And comparative example 1
Composite quantum dot microballoon environment temperature in elevation process, fluorescence intensity change is very small, under the influence of fluorescence makes an uproar production, no
It is monitored beneficial to instrument, temperature sensitivity is poor.
Test case 1
The composite quantum dot microballoon of Example 1-3 and comparative example 1, then using spin-coating film technology commonly used in the art
Form a film respectively on electro-conductive glass, so that different fluorescence membrane sensing materials be made.The repetition of fluorescence membrane sensing material makes
Contain 0.5 μ g/L copper ion solutions with test.The result shows that：The fluorescence membrane sensing composite material of embodiment 1-3 uses 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 passes
Feel composite material, after using 5 times, fluorescence drops to original 90%, drops to less than 80% using fluorescence after 7 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 (8)
1. a kind of preparation method of the quantum dot complex microsphere containing higher fatty acids, it is characterised in that described containing is advanced
The quantum dot complex microsphere of aliphatic acid, it includes quantum dot and silicon dioxide nanosphere, and the quantum dot self assembly is described
The surface of silicon dioxide nanosphere, the silicon dioxide nanosphere include shell and kernel, and the shell is SiO2, described
Kernel is higher fatty acids, and described is C9~C18Higher fatty acids；In the quantum dot complex microsphere, the SiO2 and institute
The part by weight for stating higher fatty acids is (0.2~1.2)：1；The quantum dot for CdTe, CdSe, InP, InAs, CdSe/CdS,
One kind in CdSe/ZnS, CdSe/ZnSe, CdTe/ZnS, CdHgTe/ZnS, HgTe/HgCdS quantum dot；
The preparation method of the quantum dot complex microsphere containing higher fatty acids, includes the following steps：
(1) higher fatty acids and surfactant are added in ethanol water, then heating makes higher fatty acids melting simultaneously
Stir evenly, the emulsion containing higher fatty acids is made, ethyl orthosilicate is then added in the emulsion, add alkali soluble
Liquid adjusting pH to 9~12, is then hydrolyzed reaction, after stirring, ageing, filtering, washing, drying, that is, obtains silica bag
Cover the silicon dioxide nanosphere of higher fatty acids；
(2) silicon dioxide nanosphere is immersed in the aqueous solution of quantum dot, then filtered, washed and dry, you can
Quantum dot complex microsphere is made.
2. the preparation method of quantum dot complex microsphere described in accordance with the claim 1, it is characterised in that：The quantum dot is sulfydryl
The quantum dot of carboxylic acid modification；The surface of the silicon dioxide nanosphere is passed through at triamido silane and aluminium polychloride modification
Reason, the chemical formula of the triamido silane is H2N-CH2-CH2-NH-CH2-CH2-NH-(CH2)3-Si-(OCH3)3。
3. according to the preparation method of the quantum dot complex microsphere described in claim 1 or 2, it is characterised in that：The quantum dot is answered
The average grain diameter for closing microballoon is 55nm~600nm.
4. the preparation method of quantum dot complex microsphere described in accordance with the claim 1, it is characterised in that：The higher fatty acids is
One kind in capric acid, laurate, myristic acid, palmitic acid, pearly-lustre ester acid, stearic acid, oleic acid, linoleic acid.
5. the preparation method of the quantum dot complex microsphere described in accordance with the claim 1 containing higher fatty acids, it is characterised in that：
The higher fatty acids, surfactant and ethanol water part by weight are 10：(0.1~3.0)：(20~100), the second
The weight ratio of ethanol and water is (1~5) in alcohol solution:1；The part by weight of the higher fatty acids and ethyl orthosilicate is
10：(5~40), the surfactant is polyethylene glycol, sucrose ester, polysorbate, octadecyl benzenesulfonic acid, dodecyl sulphur
One or more in sour sodium, sodium tetradecyl sulfate, sodium hexadecyl sulfate.
6. according to the preparation method of the quantum dot complex microsphere containing higher fatty acids described in claim 1 or 5, its feature exists
In：The aqueous solution for the quantum dot that the aqueous solution of the quantum dot is modified for mercaptan carboxylic acid.
7. according to the preparation method of the quantum dot complex microsphere containing higher fatty acids described in claim 1 or 5, its feature exists
In：Before the silicon dioxide nanosphere is added to the aqueous solution of quantum dot, with polymeric aluminum chlorides solution and triamido
Solution of silane modification silicon dioxide nanosphere, comprises the following steps that：The silicon dioxide nanosphere is entered to polymerization
In the solution of aluminium chloride, then filter and dry, be then then added in triamido solution of silane, stirring, filtering and drying.
8. according to the preparation method of the quantum dot complex microsphere containing higher fatty acids described in claim 7, it is characterised in that：
Concentration 0.20wt%~0.01wt% of the polymeric aluminum chlorides solution, the triamido solution of silane be containing 0.5wt%~
The ethanol solution of 2.0wt% triamido silane.
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