CN104845608B - A kind of CdTe quantum/SiO being self-assembly of2/ TGA complex three-dimensional nano material and preparation method thereof - Google Patents
A kind of CdTe quantum/SiO being self-assembly of2/ TGA complex three-dimensional nano material and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a kind of CdTe quantum/SiO being self-assembly of2/ TGA complex three-dimensional nano material and preparation method thereof, complex three-dimensional nano material is by CdTe quantum, SiO2With TGA composition, as ligand modified on CdTe quantum surface, the CdTe quantum Surface coating that TGA modifies has SiO to TGA2Layer, TGA is located at CdTe quantum and SiO2Between layer；It is shaped as straw bundle shape, length is 200～300 m, a diameter of 50～120 m in center.Its preparation method is that the CdTe quantum that TGA modifies coats one layer of SiO with sol-gal process at room temperature2Layer, is subsequently dispersed CdTe quantum/SiO that PBS self assembly obtains having high brightness2/ TGA complex three-dimensional nano material, has wide practical use in fields such as sensor, light-emitting device, solaodes.
Description
Technical field
The invention belongs to nano-functional material field, it is related to three wieners that a kind of water-soluble CdTe quantum dots are self-assembly of
Rice structure, especially a kind of CdTe quantum/SiO being self-assembly of2/ TGA complex three-dimensional nano material and preparation method thereof.
Background technology
Due to the little size of quantum dot, big specific surface area, very sensitive to solution environmental, the change of surface nature can be led
Cause many new phenomenons to occur although the decades of research experience with regard to quantum dot, but still have many unknown fields
Await further exploring, these imaginations have important meaning to the basic research of quantum dot and application.For water solublity
Quantum dot, CdTe received much concern due to its excellent property, and particularly these water-soluble quantum dots are in bioprobe, luminous
There is important application in the fields such as device, solaode.Water miscible CdTe quantum generally uses TGA（TGA）As work
Property agent, to avoid quantum dot reunion in aqueous, and TGA molecule is per se with sulfydryl and carboxyl Liang Ge functional group, these
Functional group adds new content also to the research of quantum dot.Collosol and gel SiO2Due to its good biocompatibility with stably
Property, there is critically important application in quantum dot field, due to collosol and gel SiO2Containing a lot of hydroxyls, run into the amount of surface-sensitive
Sub- point can produce a series of interaction, is therefore buffered in PBS using the ligand modified quantum dot of sol-gel technique and TGA
In liquid, the three dimensional composite structure of high brightness is prepared in self assembly, not only contributes to the property that research worker explores various quantum dots
Matter, and due to the high stability in PBS and three dimensional structure of quantum dot and strong lighting, before there is good application
Scape.
Content of the invention
It is an object of the invention to provide a kind of CdTe quantum/SiO being self-assembly of2/TGA complex three-dimensional nanometer material
Material, is shaped as straw bundle shape, and structure is novel, and has high stability and fluorescent brightness, can be widely applied to sensor, lights
Device and solaode etc..
Present invention also offers above-mentioned CdTe quantum/SiO2The preparation method of/TGA complex three-dimensional nano material, TGA
The CdTe quantum modified coats one layer of SiO with sol-gal process at room temperature2Layer, is subsequently dispersed in PBS, from group
Dress obtains the CdTe quantum/SiO with high brightness2/ TGA complex three-dimensional nano material.
The present invention is realized by following measures：
A kind of CdTe quantum/SiO being self-assembly of2/ TGA complex three-dimensional nano material it is characterised in that：By CdTe
Quantum dot, SiO2With TGA composition, TGA is as the ligand modified CdTe quantum surface modified on CdTe quantum surface, TGA
It is coated with SiO2Layer, TGA is located at CdTe quantum and SiO2Between layer；Described complex three-dimensional nano material is shaped as straw bundle
Shape, length is 200～300 m, a diameter of 50～120 m in center；A diameter of 2～10nm of described CdTe quantum；Institute
The CdTe quantum stated and SiO2, TGA mol ratio be (5 ~ 8): (1~4) : 11.
A kind of CdTe quantum/SiO being self-assembly of2The preparation method of/TGA complex three-dimensional nano material, including with
Lower step：
1）Water-soluble CdTe quantum dots Surface coating SiO2Layer：It is 10 that silane reagent and ammonia are added to quantum dot concentration-4～10-5In the CdTe quantum aqueous solution that the TGA of M modifies, stir 1～10h, obtain clear solution；
2）It is self-assembly of complex three-dimensional nano material：To step 1）In the solution of preparation, add 0.5～0.6 times of volume
Concentration be 1M PBS, mix, sealing, under room temperature stand 2～12 months, centrifugation goes out the nanometer after self assembly
Composite, washing, in water, the dispersion concentration of wherein quantum dot is 10 to redispersion-4～10-5M, obtains being self-assembly of
CdTe quantum/SiO2/ TGA complex three-dimensional nano material.
Step 1) described in silane reagent and ammonia, the CdTe quantum aqueous solution volume ratio modified of TGA be（1～4）：
100：2000；
Step 1) described in ammoniacal liquor mass concentration be 25%；
Step 1) described in silane reagent be methyl silicate, tetraethyl orthosilicate, positive silicic acid propyl ester or butyl silicate；
Step 2）Described in PBS pH be 7.4.
In preparation method of the present invention, CdTe quantum need to be modified with TGA first, obtain step 1）Described water-soluble CdTe
Quantum dot, the CdTe quantum that is, TGA modifies, those skilled in the art can be according to the synthesis described in having grasped or document
Method synthesizes, and the present invention repeats no more.Then, the CdTe quantum that TGA modifies is utilized sol-gal process to coat one layer of SiO2
Layer, SiO2Layer can play passivation to the surface of quantum dot, reduce the defect of quantum dot surface, so that quantum dot is had higher
Stability.Finally, modified above-mentioned by TGA, and coated SiO2The water-soluble CdTe quantum dots of layer, by buffering in PBS
It is self-assembly of a kind of new straw bundle shape complex three-dimensional nano material in liquid.By self assembling process in PBS buffer solution,
Not give only the new pattern of complex three-dimensional nano material of the present invention, and due to SiO2Passivation to quantum dot surface,
It is provided with high stability and fluorescent brightness, have wide application prospects in fields such as sensor, light-emitting device, solaodes.
A kind of CdTe quantum/SiO being self-assembly of of the present invention2/ TGA complex three-dimensional nano material and its preparation side
Method, its advantage is：
1）The preparation method of the complex three-dimensional nano material of self assembly of the present invention, is the method using collosol and gel, will
SiO2Layer is coated on the CdTe quantum dot surface of TGA modification, and achieves in PBS buffer solution and coated SiO2CdTe
The self assembly of quantum dot.Pass through self assembly in buffer solution, complex three-dimensional nano material of the present invention is not only provided with new shape
Looks, and maintain higher luminous efficiency and optical stability.
2）CdTe quantum/SiO that the present invention is self-assembly of2/ TGA complex three-dimensional nano material is a kind of new Caulis et Folium Oryzae
Bundle shape structure, structure is novel, and property is better than common aqueous phase quantum point solution, has high stability and fluorescent brightness, is passing
The fields such as sensor, light-emitting device, solaode have wide application prospects.
Brief description
Fig. 1 is the optical microscope photograph of embodiment 1 sample.
Specific embodiment
Below by embodiment, the present invention will be further elaborated, it should be noted that the description below merely to
Explain the present invention, its content is not defined.
Embodiment 1
1.1 adopt Aqueous phase to synthesize CdTe quantum dot：NaHTe needed for synthetically prepared first CdTe quantum dot, by Te
Powder and NaBH4According to mol ratio 1:5 mixing, add a certain amount of water, and nitrogen is protected lower 60 DEG C of heating in water bath and stirred to molten
Liquid is changed into lavender.CdCl by 0.4 mmol2·2.5H2O is dissolved in 25 mL water, adds 0.6 mmol TGA
（TGA）, stirring, it is subsequently adding the NaOH solution that concentration is 1M until the PH value of solution is adjusted to 11.2.By this solution nitrogen
Deoxygenation 30 minutes, is then injected into the NaHTe solution of above-mentioned preparation, is heated to reflux 0.5 h at 100 DEG C, obtain final product water miscible greening
The CdTe quantum dot of coloured light（Particle diameter is 2.6 nm）.Using ethanol and isopropanol, quantum dot precipitated from solution, be centrifuged and divide
From, and the quantum dot obtaining is distributed in water.
The 25% of the tetraethyl orthosilicate of 1.5 μ L and 100 μ L ammonia is added to the CdTe quantum of 2mL TGA modification by 1.2
In aqueous solution, a diameter of 2.8nm of quantum dot, the concentration of quantum dot is 1 × 10-5M, stirring 5h obtains the solution of homogeneous transparent.
1.3 1mL 1M pH are that 7.4 PBS is added in the solution of step 1.2, stir 30min, proceed to afterwards
Add a cover in vial, place standing at room temperature and preserve 6 months, solution is centrifuged out the nano combined material after self assembly
Material, washing, redispersion in water, wherein quantum dot dispersion concentration be 4 × 10-5M, obtains what the present embodiment was self-assembly of
CdTe quantum/SiO2/ TGA complex three-dimensional nano material, is straw bundle shape, and its average-size is length 230 m, and center is straight
Footpath is 80 m；
Fig. 1 is the optical microscope photograph of embodiment 1 complex three-dimensional nano material, fluoresced green, and fluorescence intensity is former
Come the 99% of fluorescence intensity, luminous efficiency can reach 50%, can store 12 months at room temperature, and keep original luminous efficiency.
Embodiment 2
2.1 adopt Aqueous phase to synthesize CdTe quantum dot：With 1.1.
The 25% of the methyl silicate of 2 μ L and 100 μ L ammonia is added to the CdTe quantum of 2mL TGA modification by 2.2
In, a diameter of 8nm of quantum dot, the concentration of quantum dot is 5 × 10-5M, stirring 3h obtains the solution of homogeneous transparent.
2.3 1mL 1M pH are that 7.4 PBS is added in the solution of step 2.1, stir 30min, proceed to afterwards
Add a cover in vial, place standing at room temperature and preserve 3 months, solution is centrifuged out the nano combined material after self assembly
Material, washing, redispersion in water, wherein quantum dot dispersion concentration be 4 × 10-5M, obtains what the present embodiment was self-assembly of
CdTe quantum/SiO2/ TGA complex three-dimensional nano material, is straw bundle shape three dimensional composite structure, and its average-size is length
200 m, a diameter of 50 m in center；Send out crimson fluorescent, fluorescence intensity is the 90% of original fluorescence intensity, and luminous efficiency can reach
To 60%, can store 8 months at room temperature, and keep original luminous efficiency.
Embodiment 3
3.1 adopt Aqueous phase to synthesize CdTe quantum dot：With 1.1.
The 25% of the positive silicic acid propyl ester of 1 μ L and 100 μ L ammonia is added to the CdTe quantum of 2mL TGA modification by 3.2
In, a diameter of 4.5nm of quantum dot, the concentration of quantum dot is 10-4M, stirring 5h obtains the solution of homogeneous transparent.
3.3 1mL pH are that the PBS of 7.4 1M is added in the solution of step 3.1, stir 30min, proceed to afterwards
Add a cover in vial, place standing at room temperature and preserve 12 months, solution is centrifuged out the nano combined material after self assembly
Material, washing, redispersion in water, wherein quantum dot dispersion concentration be 1 × 10-4M, obtains what the present embodiment was self-assembly of
CdTe quantum/SiO2/ TGA complex three-dimensional nano material, is the three dimensional composite structure of straw bundle shape, and its average-size is length
300 m, a diameter of 120 m in center；Send out red fluorescence, fluorescence intensity is the 90% of original fluorescence intensity, and luminous efficiency can reach
58%, can store 6 months at room temperature, and keep original luminous efficiency.
Embodiment 4
4.1 adopt Aqueous phase to synthesize CdTe quantum dot：With 1.1.
The 25% of the butyl silicate of 1.5 μ L and 100 μ L ammonia is added to the CdTe quantum of 2mL TGA modification by 4.2
In, a diameter of 10 nm of quantum dot, the concentration of quantum dot is 10-4M, stirring 5h obtains the solution of homogeneous transparent.
4.3 1mL 1M pH are that 7.4 PBS is added in the solution of step 4.1, stir 30min, proceed to afterwards
Add a cover in vial, place standing at room temperature and preserve 8 months, solution is centrifuged out the nano combined material after self assembly
Material, washing, redispersion in water, wherein quantum dot dispersion concentration be 4.5 × 10-5M, obtains the present embodiment and is self-assembly of
CdTe quantum/SiO2/ TGA complex three-dimensional nano material, is the three dimensional composite structure of straw bundle shape, and its average-size is length
Spend 260 m, a diameter of 100 m in center；Kermesinus fluorescence, fluorescence intensity is the 80% of original fluorescence intensity, and luminous efficiency can reach
To 50%, October can be stored at room temperature, and keep original luminous efficiency.
Embodiment 5
5.1 adopt Aqueous phase to synthesize CdTe quantum dot：With 1.1.
The 25% of the tetraethyl orthosilicate of 1 μ L and 100 μ L ammonia is added to the CdTe quantum of 2mL TGA modification by 5.2
In, a diameter of 2.7nm of quantum, the concentration of quantum dot is 4 × 10-5M, stirs 5h, obtains the solution of homogeneous transparent.
5.3 1mL 1M pH are that 7.4 PBS is added in the solution of step 5.1, stir 30min, proceed to afterwards
Add a cover in vial, place standing at room temperature and preserve 6 months, solution is centrifuged out the nano combined material after self assembly
Material, washing, redispersion in water, wherein quantum dot dispersion concentration be 4.5 × 10-5M, obtains the present embodiment self assembly shape
CdTe quantum/the SiO becoming2/ TGA complex three-dimensional nano material, is the three dimensional composite structure of straw bundle shape, and its average-size is
Length 210 m, a diameter of 60 m in center；Fluorescence intensity is the 95% of original fluorescence intensity, and luminous efficiency can reach 58%, in room
Can store 10 months under temperature, and keep original luminous efficiency.
Embodiment 6
6.1 adopt Aqueous phase to synthesize CdTe quantum dot：With 1.1.
The 25% of the tetraethyl orthosilicate of 4 μ L and 100 μ L ammonia is added to the CdTe quantum of 2mL TGA modification by 6.2
In, a diameter of 2.7 nm of quantum, the concentration of quantum dot is 4 × 10-5M, stirs 4h, obtains the solution of homogeneous transparent.
6.3 1mL 1M pH are that 7.4 PBS is added in the solution of step 5.1, stir 30min, proceed to afterwards
Add a cover in vial, place standing at room temperature and preserve 2 months, solution is centrifuged out the nano combined material after self assembly
Material, washing, in water, the dispersion concentration of wherein quantum dot is 5 × 10 to redispersion-5M, obtains what the present embodiment was self-assembly of
CdTe quantum/SiO2/ TGA complex three-dimensional nano material, is the three dimensional composite structure of straw bundle shape, and its average-size is length
220 m, a diameter of 61 m in center；Fluorescence intensity is the 90% of original fluorescence intensity, and luminous efficiency can reach 55%, at room temperature
Can store 12 months, and keep original luminous efficiency.
Comparative example：Without self assembling process in buffer solution.
CdTe quantum dot is synthesized using Aqueous phase：With 1.1.
The 25% of the tetraethyl orthosilicate of 4 μ L and 100 μ L ammonia is added in the CdTe quantum of 2mL TGA modification, amount
A diameter of 2.6 nm of son, the concentration of quantum dot is 4 × 10-5M, stirs 4h, obtains the solution of homogeneous transparent.
Above-mentioned solution is loaded in bottle and adds a cover, place standing at room temperature and preserve 2 months, solution is centrifuged, washing,
To in water, dispersion concentration is 5 × 10 to redispersion-5M, does not obtain the three dimensional composite structure of straw bundle shape of the present invention, obtains
To 1-dimention nano composite fibre, fluoresced green, luminous efficiency only has 10%, stores 12 months at room temperature, and luminous efficiency reduces
To 5%.
Claims (5)
1. a kind of CdTe quantum/SiO being self-assembly of2The preparation method of/TGA complex three-dimensional nano material, its feature exists
In comprising the following steps：
1）Water-soluble CdTe quantum dots Surface coating SiO2Layer：It is 10 that silane reagent and ammonia are added to quantum dot concentration-4~
10-5In the CdTe quantum aqueous solution that the TGA of M modifies, stir 1～10h, obtain clear solution；
2）It is self-assembly of complex three-dimensional nano material：To step 1）In the solution of preparation, add the dense of 0.5～0.6 times of volume
Spend the PBS for 1M, mix, sealing, stand 2～12 months under room temperature, centrifugation goes out nano combined after self assembly
Material, washing, in water, the dispersion concentration of wherein quantum dot is 10 to redispersion-4～10-5M, obtains the CdTe being self-assembly of
Quantum dot/SiO2/ TGA complex three-dimensional nano material；
Described CdTe quantum/the SiO being self-assembly of2/ TGA complex three-dimensional nano material：By CdTe quantum, SiO2With
TGA forms, and as ligand modified on CdTe quantum surface, the CdTe quantum Surface coating that TGA modifies has SiO to TGA2Layer,
TGA is located at CdTe quantum and SiO2Between layer；Described complex three-dimensional nano material is shaped as straw bundle shape, and length is 200
～300 m, a diameter of 50～120 m in center；A diameter of 2～10nm of described CdTe quantum；Described CdTe quantum
Point and SiO2, TGA mol ratio be (5～8):(1～4): 11；Described TGA is TGA.
2. preparation method according to claim 1 it is characterised in that：Step 1) described in silane reagent and ammonia, TGA
Modify CdTe quantum aqueous solution volume ratio be（1～4）：100：2000.
3. preparation method according to claim 1 it is characterised in that：Step 1) described in ammoniacal liquor mass concentration be
25%.
4. preparation method according to claim 1 it is characterised in that：Step 1) described in silane reagent be positive silicic acid first
Ester, tetraethyl orthosilicate, positive silicic acid propyl ester or butyl silicate.
5. preparation method according to claim 1 it is characterised in that：Step 2）Described in PBS pH be 7.4.
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