CN106978182A - A kind of preparation method of the quick water-soluble silver selenide quantum dot for preparing size tunable - Google Patents
A kind of preparation method of the quick water-soluble silver selenide quantum dot for preparing size tunable Download PDFInfo
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Abstract
The invention discloses a kind of preparation method of the quick water-soluble silver selenide quantum dot for preparing size tunable, under heating water bath and magnetic agitation, stabilizer stirring is added in silver nitrate solution, dispersant stirring is added, the pH value of regulation reaction solution is alkalescence, add sodium thiosulfate solution, 5~8min is reacted, products therefrom is precipitated using centrifugal process, supernatant is abandoned, bottom precipitation is collected, that is, the water-soluble silver selenide quantum dot of size tunable is made.The present invention uses relatively inexpensive, nontoxic raw material, and the reaction time is short, it is only necessary to 10~15min, is handled without inert gas shielding and postorder, purification is simple.Ag prepared by the present invention2Se quantum dots can adjust without toxic heavy-metal elements, water-soluble good, size tunable, band gap, and its excellent physicochemical properties can be applied in terms of biomarker, bio-sensing, photoelectronics and photoelectric device.
Description
Technical field
The invention belongs to chemical material scientific domain, more particularly to a kind of quick water-soluble silver selenide for preparing size tunable
The preparation method of quantum dot.
Background technology
Quantum dot is 1~10nm quasi-zero dimension nano materials, due to quantum size effect, with the electricity different from bulk material
Son and luminosity, thus it is widely used in biomarker, the field such as light emitting diode and solar cell.Wherein quantum dot
Size there is material impact to its performance, such as can be by controlling size to adjust the position of emission spectrum.
What application was most at present is II-VI race and IV-VI race's quantum dot, CdS, CdSe, PdS, PdSe etc., such amount
Son point has the advantages that narrow fluorescence spectrum, high quantum production rate, oxidation resistance are strong.But simultaneously as toxic heavy metal lead or cadmium
Presence also limit its development with application.Silver-colored race's quantum dot (such as Ag2Se etc.) there is narrower band gap, wider photoresponse model
Enclose with excellent biocompatibility, there is larger application prospect in terms of bioanalysis, biological imaging, photoelectric device.
At present, the preparation of quantum dot mainly passes through two kinds of approach：It is prepared by organic synthesis and aqueous phase.Organic synthesis is usual
Need under the conditions of anhydrous and oxygen-free carry out, synthesized quantum dot have higher fluorescence quantum yield, preferable monodispersity and
Stability；But selected reagent toxicity is strong simultaneously, experimental cost is high, processing safety is poor, synthesis quantum dot needs further
Aqueous phase is transferred to by organic phase, complex steps, the stability of quantum is obtained after treatment also corresponding to yield to be reduced.Aqueous phase system
Standby quantum dot has superior biocompatibility, and reaction condition is gentle, simple to operate, required low in raw material price is easy to get, water
Mutually preparation is the main preparation methods of mesh quantum dot.
The A of China Patent No. publication number CN 101555000, a kind of open preparation method of silver selenide nanometer material of knowing clearly,
Silver selenide nanometer material is successfully prepared, but this method uses argyrol liquid for silver-colored source, and preparation cost is higher, and needs 12~96h
Standing reaction, the reaction time is longer, is unfavorable for a large amount of preparations.
As known from the above, quantum dot has unique optics, characteristic electron, but toxic metals, preparation process are complicated, reaction
The factors such as condition harshness, reaction time length limit the development of its technology of preparing.Therefore, research and development one kind be readily synthesized, cost it is low
The honest and clean, reaction time is short, size tunable quantum dot, is necessary.
The content of the invention
The technical problems to be solved by the invention are to overcome the shortcomings of to mention with defect that there is provided one in background above technology
Plant the preparation method of the water-soluble silver selenide quantum dot of be readily synthesized, size tunable.
In order to solve the above technical problems, technical scheme proposed by the present invention is：
A kind of preparation method of the quick water-soluble silver selenide quantum dot for preparing size tunable：Water-bath state magnetic force is stirred
Under, stabilizer stirring is added in silver nitrate solution, dispersant stirring is added, the pH value of regulation reaction solution is alkalescence, then
The sodium thiosulfate solution obtained by step (1) is added, 5~8min is reacted, products therefrom is precipitated using centrifugal process, supernatant is abandoned,
Bottom precipitation is collected, that is, the water-soluble silver selenide quantum dot of size tunable is made.
Above-mentioned preparation method, it is preferred that the stabilizer is mercaptopropionic acid (3-MPA), dispersant is selected from polyethylene pyrrole
Any of pyrrolidone (PVP) and Triammonium citrate are several.
Above-mentioned preparation method, it is preferred that the concentration control of the silver nitrate is 2~10mmol/L, and sodium thiosulfate is molten
NaSeSO in liquid3With the AgNO in silver nitrate solution3Mol ratio be 1:(2~5).
Above-mentioned preparation method, it is preferred that the addition of the dispersant is (0.15 with the mass ratio of silver nitrate addition
~1.7)：1, (0.05~0.15) of the addition of stabilizer and the volume ratio of silver nitrate solution：1.
Above-mentioned preparation method, it is preferred that the specific operation process for preparing the water-soluble silver selenide quantum dot of size tunable is：
In adding stabilizer under 15~25 DEG C of water bath conditions into silver nitrate deionized water solution, 3~5min is stirred；Add dispersant
And 1~2min is stirred, it is 10.1~10.8 to adjust pH to pH value of solution by ammoniacal liquor, adds sodium thiosulfate deionized water solution simultaneously
5~8min of stirring reaction.
Above-mentioned preparation method, it is preferred that the sodium thiosulfate solution is to enter in aqueous phase selenium powder with sodium sulfite
The backflow of row oil bath heating is obtained.
Above-mentioned preparation method, it is preferred that the mol ratio of the selenium powder and sodium sulfite is 1:1.
Above-mentioned preparation method, it is preferred that the temperature of the oil bath is 85~95 DEG C；The time of heating is 8~12h.
The present invention from polyvinylpyrrolidone or Triammonium citrate as dispersant, mercaptopropionic acid as stabilizer, by
In surface ligand of the mercaptopropionic acid as nano-particle, Ag can be made2Se quantum dots have good water solubility, polyvinylpyrrolidine
The addition of ketone or Triammonium citrate, contributes to Ag2The rapid forming core of Se quantum dots, shortens the preparation time of quantum dot, meanwhile, hair
A person of good sense is had found by studying, and by controlling the addition of dispersant in silver-colored selenium system effectively to control the particle diameter of quantum dot, is changed
Reaction condition, obtains the Ag of different-grain diameter2Se quantum dots, corresponding band gap will also change.Point employed in the present invention
Powder is macromolecule dispersing agent, forms adsorption layer on the surface of solid particle, making the electric charge of solid particles surface increases, and improves shape
Into the intergranular reaction force of steric hindrance, while by the consumption of dispersant, can effectively it control between quantum dot core
Absorption Growth, so as to control quantum point grain diameter.
Compared with prior art, the advantage of the invention is that：
(1) present invention uses relatively inexpensive, nontoxic raw material, and the reaction time is short, it is only necessary to 10~15min, without indifferent gas
Body is protected and postorder processing, and purification is simple.
(2) Ag prepared by the present invention2Se quantum dots are without toxic heavy-metal elements, water-soluble good, size tunable, band
Gap can adjust, and its excellent physicochemical properties can be applied to the side such as biomarker, bio-sensing, photoelectronics and photoelectric device
Face.
Brief description of the drawings
Fig. 1 is the process chart of the quick water-soluble silver selenide quantum dot for preparing size tunable of the invention.
Fig. 2 is the water-soluble silver selenide (Ag that the embodiment of the present invention 3 is prepared2Se) the transmission electron microscope of quantum dot
Figure.
Fig. 3 is the water-soluble silver selenide (Ag that the embodiment of the present invention 3 is prepared2Se) quantum dot is applied to the quantum dot sun
The UV-Vis absorption spectrums of light anode in energy cell manufacturing process.
Embodiment
For the ease of understanding the present invention, do more complete to inventing herein below in conjunction with Figure of description and preferred embodiment
Face, meticulously describe, but protection scope of the present invention is not limited to specific examples below.
Unless otherwise defined, all technical terms used hereinafter are generally understood that implication phase with those skilled in the art
Together.Technical term used herein is intended merely to describe the purpose of specific embodiment, is not intended to the limitation present invention's
Protection domain.
Unless otherwise specified, various raw material, reagent, instrument and equipment used in the present invention etc. can be by city
Field is commercially available or can prepared by existing method.
Embodiment 1：
A kind of preparation method of the quick water-soluble silver selenide quantum dot for preparing size tunable of the invention, its technological process
Figure is as shown in figure 1, comprise the following steps：
(1) 1.260g Na is weighed respectively at room temperature2SO3(0.01mol) is dissolved in 50mL with 0.789g selenium (0.01mol) powder
In deionized water, flow back 8h under 85 DEG C of oil bath states, treats that selenium powder is completely dissolved, is fully converted to colourless transparent liquid, obtains
0.2mol/L NaSeSO3Solution；
(2) take 0.170g silver nitrates (0.001mol) to be dissolved in 250mL deionized waters, obtain 4mmol/L silver nitrate solutiones；
(3) by gained 0.2mol/L NaSeSO in step (1)3Solution deionized water dilutes 100 times to 2mmol/L；
(4) bath temperature be 23 DEG C under conditions of, into there-necked flask add 5mL 4mmol/L silver nitrate solutiones and
0.5mL 3-MPA, magnetic agitation 3min, are adding 4mg PVP, are stirring 1min；Add ammoniacal liquor and adjust solution ph to 10.1,
Add 5mL 2mmol/L NaSeSO3In solution brown bottle, 5min is reacted；
(5) reaction product obtained by step (4) is precipitated using centrifugal process, abandons supernatant, collect bottom precipitation, particle diameter is made
About 6.7nm water solubility silver selenides (Ag2Se) quantum dot.
Embodiment 2：
A kind of preparation method of the quick water-soluble silver selenide quantum dot for preparing size tunable of the invention, its technological process
Figure is as shown in figure 1, comprise the following steps：
(1) 1.260g Na is weighed respectively at room temperature2SO3(0.01mol) is dissolved in 50mL with 0.789g selenium powders (0.01mol)
In deionized water, flow back 10h under 90 DEG C of oil bath states, treats that selenium powder is completely dissolved, is fully converted to colourless transparent liquid, obtains
0.2mol/L NaSeSO3Solution；
(2) take 0.170g silver nitrates (0.001mol) to be dissolved in 166mL deionized waters, obtain 6mmol/L silver nitrate solutiones；
(3) by gained 0.2mol/L NaSeSO in step (1)3Solution dilutes 100 times to 2mmol/L；
(4) bath temperature be 20 DEG C under conditions of, into there-necked flask add 5mL 6mmol/L silver nitrate solutiones with
0.7mL 3-MPA, magnetic agitation 4min, add 3mg Triammonium citrates, stir 1min；Add ammoniacal liquor regulation solution ph
To 10.7,5mL 2mmol/L NaSeSO are added3In solution brown bottle, 7min is reacted；
(5) reaction product obtained by step (4) is precipitated using centrifugal process, abandons supernatant, collect bottom precipitation, particle diameter is made
About 8.2nm water solubility silver selenides (Ag2Se) quantum dot.
Embodiment 3：
A kind of preparation method of the quick water-soluble silver selenide quantum dot for preparing size tunable of the invention, its technological process
Figure is as shown in figure 1, comprise the following steps：
(1) 1.260g Na is weighed respectively at room temperature2SO3(0.01mol) is dissolved in 50mL with 0.789g selenium powders (0.01mol)
In deionized water, flow back 12h under 95 DEG C of oil bath states, treats that selenium powder is completely dissolved, is fully converted to colourless transparent liquid, obtains
0.2mol/L NaSeSO3Solution.
(2) take 0.170g silver nitrates (0.001mol) to be dissolved in 125mL deionized waters, obtain 8mmol/L silver nitrate solutiones；
(3) by gained 0.2mol/L NaSeSO in step (1)3Solution dilutes 100 times to 2mmol/L；
(4) bath temperature be 18 DEG C under conditions of, into there-necked flask add 5mL 6mmol/L silver nitrate solutiones with
0.7mL 3-MPA, magnetic agitation 5min, add 2mg PVP, stir 2min；Add ammoniacal liquor and adjust solution ph to 10.7,
Add 5mL 2mmol/L NaSeSO3In solution brown bottle, 8min is reacted；
(5) reaction product obtained by step (4) is precipitated using centrifugal process, abandons supernatant, collect bottom precipitation, particle diameter is made
About 9.1nm water solubility silver selenides (Ag2Se) quantum dot, its transmission electron microscope figure is as shown in Figure 2.
Silver selenide quantum dot manufactured in the present embodiment is prepared into quantum dot solar cell, its light anode part extinction light
Spectrum as shown in figure 3, the battery photoelectric efficiency η be 2.31%,
In summary, the preparation method of water-soluble silver selenide quantum dot of the invention is simple, and extensively, cost is low for raw material sources
Honest and clean, homogeneous controllable using the water-soluble silver selenide quantum dot prepared by this method, quality is higher, with narrower band gap, wider
Photoresponse scope and excellent biocompatibility, have in terms of bioanalysis, biological imaging, photoelectric device it is larger should
Use prospect.
Claims (8)
1. a kind of preparation method of the quick water-soluble silver selenide quantum dot for preparing size tunable, it is characterised in that in water-bath plus
Under heat and magnetic agitation, stabilizer stirring is added in silver nitrate solution, dispersant stirring is added, adjusts the pH of reaction solution
It is worth for alkalescence, adds sodium thiosulfate solution, react 5~8min, products therefrom is precipitated using centrifugal process, supernatant is abandoned, collection
Bottom precipitation, that is, be made the water-soluble silver selenide quantum dot of size tunable.
2. preparation method as claimed in claim 1, it is characterised in that the stabilizer is mercaptopropionic acid, dispersant is selected from poly-
Any of vinylpyrrolidone and Triammonium citrate are several.
3. preparation method as claimed in claim 1, it is characterised in that the concentration control of the silver nitrate is 2~10mmol/L,
NaSeSO in sodium thiosulfate solution3With the AgNO in silver nitrate solution3Mol ratio be 1:(2~5).
4. preparation method as claimed in claim 1, it is characterised in that the addition of the dispersant and the mass ratio of silver nitrate
For (0.15~1.7)：1, (0.05~0.15) of the addition of stabilizer and the volume ratio of silver nitrate solution：1.
5. preparation method as claimed in claim 1, it is characterised in that prepare the tool of the water-soluble silver selenide quantum dot of size tunable
Body operating process is：In adding stabilizer under 15~25 DEG C of water bath conditions into silver nitrate deionized water solution, stirring 3~
5min；Add dispersant and stir 1~2min, by ammoniacal liquor adjust pH to 10.1~10.8, add sodium thiosulfate go from
The sub- aqueous solution and 5~8min of stirring reaction.
6. the preparation method as described in claim any one of 1-5, it is characterised in that the sodium thiosulfate solution is by selenium powder
Carry out what oil bath heating backflow was obtained in aqueous phase with sodium sulfite.
7. preparation method as claimed in claim 6, it is characterised in that the mol ratio of the selenium powder and sodium sulfite is 1:1.
8. preparation method as claimed in claim 6, it is characterised in that the temperature of the oil bath is 85~95 DEG C；Heating when
Between be 8~12h.
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| CN113340866A (en) * | 2021-06-28 | 2021-09-03 | 上海应用技术大学 | Method for detecting sulfite ions based on yellow fluorescent carbon quantum dots |
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| CN103145105B (en) * | 2013-04-09 | 2014-07-16 | 吉林大学 | Preparation method of metal selenide nanocrystals |
| CN103484121B (en) * | 2013-09-07 | 2015-01-07 | 桂林理工大学 | Method for preparing near infrared fluorescent Ag2Se colloid semiconductor nanocrystals by adopting normal-temperature aqueous phase process |
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| CN113340866A (en) * | 2021-06-28 | 2021-09-03 | 上海应用技术大学 | Method for detecting sulfite ions based on yellow fluorescent carbon quantum dots |
| CN113340866B (en) * | 2021-06-28 | 2023-03-31 | 上海应用技术大学 | Method for detecting sulfite ions based on yellow fluorescent carbon quantum dots |
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