CN106978182B - A kind of preparation method for the water-soluble selenizing silver content point quickly preparing size tunable - Google Patents

A kind of preparation method for the water-soluble selenizing silver content point quickly preparing size tunable Download PDF

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CN106978182B
CN106978182B CN201710161283.1A CN201710161283A CN106978182B CN 106978182 B CN106978182 B CN 106978182B CN 201710161283 A CN201710161283 A CN 201710161283A CN 106978182 B CN106978182 B CN 106978182B
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silver nitrate
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CN106978182A (en
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田庆华
张政
郭学益
杨英
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Central South University
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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 preparation methods of water-soluble selenizing silver content point for quickly preparing size tunable, under heating water bath and magnetic agitation, stabilizer stirring is added in silver nitrate solution, adds dispersing agent stirring, adjusts the pH value of reaction solution as alkalinity, sodium thiosulfate solution is added, 5~8min is reacted, products therefrom is precipitated using centrifugal process, abandons supernatant, bottom precipitation is collected, the sub- point of size tunable water solubility selenizing silver content is obtained.The present invention uses relatively inexpensive, nontoxic raw material, and the reaction time is short, it is only necessary to which 10~15min is handled without inert gas shielding and postorder, and purification is simple.Ag prepared by the present invention2Se quantum dot is adjusted without toxic heavy-metal elements, water-soluble good, size tunable, band gap, and excellent physicochemical properties can be applied to biomarker, bio-sensing, photoelectronics and photoelectric device etc..

Description

A kind of preparation method for the water-soluble selenizing silver content point quickly preparing size tunable
Technical field
The invention belongs to chemical material scientific domains, more particularly to a kind of water-soluble silver selenide for quickly preparing size tunable The preparation method of quantum dot.
Background technique
Quantum dot is 1~10nm quasi-zero dimension nano material, due to quantum size effect, has the electricity different from bulk material Son and luminosity, thus it is widely used in biomarker, the fields such as light emitting diode and solar battery.Wherein quantum dot Size to its performance have great influence, such as can pass through control the adjustable emission spectrum of size position.
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 many advantages, such as 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 and application.Silver-colored race's quantum dot (such as Ag2Se etc.) there is relatively narrow band gap, wider photoresponse model Enclose with excellent biocompatibility, bioanalysis, biological imaging, in terms of there is biggish application prospect.
Currently, the preparation of quantum dot mainly passes through two kinds of approach: organic synthesis and water phase preparation.Organic synthesis is usual Need to carry out under the conditions of anhydrous and oxygen-free, synthesized quantum dot fluorescence quantum yield with higher, preferable monodispersity and Stability；But selected simultaneously reagent toxicity is strong, experimental cost is high, operational safety is poor, and synthesis quantum dot needs further Water phase is transferred to by organic phase, complex steps, obtain after treatment the stability of quantum to yield is also corresponding reduces.Water phase system Standby quantum dot has superior biocompatibility, and mild, easy to operate, the required low in raw material price of reaction condition is easy to get, water Mutually preparation is the main preparation methods of mesh quantum dot.
101555000 A of China Patent No. publication number CN, has disclosed a kind of preparation method of silver selenide nanometer material, It is successfully prepared silver selenide nanometer material, but this method uses argyrol liquid for silver-colored source, preparation cost is higher, and needs 12~96h Standing reaction, the reaction time is longer, is unfavorable for largely preparing.
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 is harsh, the reaction time is long limit the development of its technology of preparing.Therefore, one kind is researched and developed to be readily synthesized, is at low cost It is honest and clean, the reaction time is short, the quantum dot of size tunable, be necessary.
Summary of the invention
The technical problem to be solved by the present invention is to overcome the shortcomings of to mention in background above technology and defect, provide one Preparation method that kind is readily synthesized, size tunable water solubility selenizing silver content sub- point.
In order to solve the above technical problems, technical solution proposed by the present invention are as follows:
A kind of preparation method for the water-soluble selenizing silver content point quickly preparing size tunable: water-bath state magnetic force stirring Under, stabilizer stirring is added in silver nitrate solution, adds dispersing agent stirring, adjusts the pH value of reaction solution as alkalinity, then Step (1) resulting sodium thiosulfate solution is added, reacts 5~8min, products therefrom is precipitated using centrifugal process, abandons supernatant, Bottom precipitation is collected, the sub- point of size tunable water solubility selenizing silver content is obtained.
Above-mentioned preparation method, it is preferred that the stabilizer is mercaptopropionic acid (3-MPA), and dispersing agent is selected from polyethylene pyrrole Any one or more of pyrrolidone (PVP) and Triammonium citrate.
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 solution3Molar ratio be 1:(2~5).
Above-mentioned preparation method, it is preferred that the mass ratio of the additional amount of the dispersing agent and silver nitrate additional amount is (0.15 ~1.7): 1, (0.05~0.15) of the volume ratio of the additional amount and silver nitrate solution of stabilizer: 1.
Above-mentioned preparation method, it is preferred that prepare the specific operation process of size tunable water solubility selenizing silver content sub- point are as follows: Stabilizer is added into silver nitrate deionized water solution under 15~25 DEG C of water bath conditions, stirs 3~5min；Add dispersing agent And 1~2min is stirred, adjusting pH to pH value of solution by ammonium hydroxide is 10.1~10.8, and sodium thiosulfate deionized water solution is added simultaneously It is stirred to react 5~8min.
Above-mentioned preparation method, it is preferred that the sodium thiosulfate solution be by selenium powder and sodium sulfite in water phase into Row oil bath heating flows back.
Above-mentioned preparation method, it is preferred that the molar 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 selects polyvinylpyrrolidone or Triammonium citrate as dispersing agent, mercaptopropionic acid as stabilizer, by In surface ligand of the mercaptopropionic acid as nanoparticle, Ag can be made2Se quantum dot has good water solubility, polyvinylpyrrolidine The addition of ketone or Triammonium citrate, facilitates Ag2The rapid forming core of Se quantum dot shortens the preparation time of quantum dot, meanwhile, hair Bright people passes through the study found that the partial size of quantum dot, change can be effectively controlled by the additional amount for controlling dispersing agent in silver-colored selenium system Reaction condition obtains the Ag of different-grain diameter2Se quantum dot, corresponding band gap will also change.Employed in the present invention point Powder is macromolecule dispersing agent, forms adsorption layer on the surface of solid particle, increases the charge of solid particles surface, improve shape At the intergranular reaction force of steric hindrance, while by the dosage of dispersing agent, can effectively control between quantum dot core Absorption Growth, to control quantum point grain diameter.
Compared with the prior art, the advantages of the present invention are as follows:
(1) present invention uses relatively inexpensive, nontoxic raw material, and the reaction time is short, it is only necessary to which 10~15min is not necessarily to indifferent gas Body protection and postorder processing, purification are simple.
(2) Ag prepared by the present invention2Se quantum dot is without toxic heavy-metal elements, water-soluble good, size tunable, band Gap is adjustable, and excellent physicochemical properties can be applied to the side such as biomarker, bio-sensing, photoelectronics and photoelectric device Face.
Detailed description of the invention
Fig. 1 is the process flow chart of the water-soluble selenizing silver content point of the invention for quickly preparing size tunable.
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 spectrum of light anode in energy cell manufacturing process.
Specific embodiment
To facilitate the understanding of the present invention, invention herein is done below in conjunction with Figure of description and preferred embodiment more complete Face meticulously describes, but protection scope of the present invention is not limited to following specific embodiments.
Unless otherwise defined, all technical terms used hereinafter are generally understood meaning phase with those skilled in the art Together.Technical term used herein is intended merely to the purpose of description specific embodiment, and it is of the invention to be not intended to limitation Protection scope.
Unless otherwise specified, various raw material, reagent, the instrument and equipment etc. used in the present invention can pass through city Field is commercially available or can be prepared by existing method.
Embodiment 1:
A kind of preparation method of the water-soluble selenizing silver content point for quickly preparing size tunable of the invention, process flow Figure is as shown in Figure 1, comprising the following steps:
(1) Na of 1.260g is weighed respectively at room temperature2SO3(0.01mol) and 0.789g selenium (0.01mol) powder are dissolved in 50mL In deionized water, flow back 8h under 85 DEG C of oil bath states, is completely dissolved to selenium powder, is fully converted to colourless transparent liquid, obtains 0.2mol/L NaSeSO3Solution；
(2) it takes 0.170g silver nitrate (0.001mol) to be dissolved in 250mL deionized water, obtains 4mmol/L silver nitrate solution；
(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 be added 5mL 4mmol/L silver nitrate solution and The 3-MPA of 0.5mL, magnetic agitation 3min are being added 4mg PVP, are stirring 1min；Ammonium hydroxide is added and adjusts solution ph to 10.1, Add the 2mmol/L NaSeSO of 5mL3In solution brown bottle, 5min is reacted；
(5) step (4) resulting reaction product is precipitated using centrifugal process, abandons supernatant, collect bottom precipitation, partial size is made About 6.7nm water solubility silver selenide (Ag2Se) quantum dot.
Embodiment 2:
A kind of preparation method of the water-soluble selenizing silver content point for quickly preparing size tunable of the invention, process flow Figure is as shown in Figure 1, comprising the following steps:
(1) Na of 1.260g is weighed respectively at room temperature2SO3(0.01mol) and 0.789g selenium powder (0.01mol) is dissolved in 50mL In deionized water, flow back 10h under 90 DEG C of oil bath states, is completely dissolved to selenium powder, is fully converted to colourless transparent liquid, obtains The NaSeSO of 0.2mol/L3Solution；
(2) it takes 0.170g silver nitrate (0.001mol) to be dissolved in 166mL deionized water, obtains 6mmol/L silver nitrate solution；
(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 be added 5mL 6mmol/L silver nitrate solution with The 3-MPA of 0.7mL, magnetic agitation 4min add 3mg Triammonium citrate, stir 1min；It adds ammonium hydroxide and adjusts solution ph To 10.7, the 2mmol/L NaSeSO of 5mL is added3In solution brown bottle, 7min is reacted；
(5) step (4) resulting reaction product is precipitated using centrifugal process, abandons supernatant, collect bottom precipitation, partial size is made About 8.2nm water solubility silver selenide (Ag2Se) quantum dot.
Embodiment 3:
A kind of preparation method of the water-soluble selenizing silver content point for quickly preparing size tunable of the invention, process flow Figure is as shown in Figure 1, comprising the following steps:
(1) Na of 1.260g is weighed respectively at room temperature2SO3(0.01mol) and 0.789g selenium powder (0.01mol) is dissolved in 50mL In deionized water, flow back 12h under 95 DEG C of oil bath states, is completely dissolved to selenium powder, is fully converted to colourless transparent liquid, obtains 0.2mol/L NaSeSO3Solution.
(2) it takes 0.170g silver nitrate (0.001mol) to be dissolved in 125mL deionized water, obtains 8mmol/L silver nitrate solution；
(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 be added 5mL 6mmol/L silver nitrate solution with The 3-MPA of 0.7mL, magnetic agitation 5min add 2mg PVP, stir 2min；Ammonium hydroxide is added and adjusts solution ph to 10.7, Add the 2mmol/L NaSeSO of 5mL3In solution brown bottle, 8min is reacted；
(5) step (4) resulting reaction product is precipitated using centrifugal process, abandons supernatant, collect bottom precipitation, partial size is made About 9.1nm water solubility silver selenide (Ag2Se) quantum dot, transmission electron microscope figure are as shown in Figure 2.
Silver selenide quantum dot manufactured in the present embodiment is prepared into quantum dot solar cell, 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 selenizing silver content point of the invention is simple, and raw material sources are extensive, at low cost Honest and clean, uniform controllable using water-soluble selenizing silver content point prepared by this method, quality is higher, has relatively narrow band gap, wider Optical response range and excellent biocompatibility, bioanalysis, biological imaging, in terms of there is biggish answer Use prospect.

Claims (4)

1. a kind of preparation method for the water-soluble selenizing silver content point for quickly preparing size tunable, which is characterized in that in 15~25 Stabilizer is added under DEG C water bath condition and magnetic agitation into silver nitrate deionized water solution, stirs 3~5min；Add dispersion Agent simultaneously stirs 1~2min, adjusts pH to 10.1~10.8 by ammonium hydroxide, and sodium thiosulfate deionized water solution is added and stirs anti- 5~8min is answered, products therefrom is precipitated using centrifugal process, supernatant is abandoned, collects bottom precipitation, obtain size tunable water soluble selenium Change silver-colored quantum dot；The stabilizer is mercaptopropionic acid, any of dispersing agent in polyvinylpyrrolidone and Triammonium citrate Kind is several；The concentration control of the silver nitrate is 2~10mmol/L, the NaSeSO in sodium thiosulfate solution3With silver nitrate AgNO in solution3Molar ratio be 1:(2~5)；The mass ratio of the additional amount of the dispersing agent and silver nitrate be (0.15~ 1.7): 1, (0.05~0.15) of the volume ratio of the additional amount and silver nitrate solution of stabilizer: 1.
2. preparation method as described in claim 1, which is characterized in that the sodium thiosulfate solution is by selenium powder and sulfurous acid Sodium carries out what oil bath heating flowed back in water phase.
3. preparation method as claimed in claim 2, which is characterized in that the molar ratio of the selenium powder and sodium sulfite is 1:1.
4. preparation method as claimed in claim 2, which is characterized in that the temperature of the oil bath is 85~95 DEG C；Heating when Between be 8~12h.
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1995273A (en) * 2007-01-09 2007-07-11 南开大学 Synthesis method of core/shell type cadmium telluride/cadmium sulfide water-soluble quantum dot
CN103145105A (en) * 2013-04-09 2013-06-12 吉林大学 Preparation method of metal selenide nanocrystals
CN103484121A (en) * 2013-09-07 2014-01-01 桂林理工大学 Method for preparing near infrared fluorescent Ag2Se colloid semiconductor nanocrystals by adopting normal-temperature aqueous phase process
CN105036092A (en) * 2015-08-07 2015-11-11 中南大学 Preparation method of spherical silver selenide particles

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1995273A (en) * 2007-01-09 2007-07-11 南开大学 Synthesis method of core/shell type cadmium telluride/cadmium sulfide water-soluble quantum dot
CN103145105A (en) * 2013-04-09 2013-06-12 吉林大学 Preparation method of metal selenide nanocrystals
CN103484121A (en) * 2013-09-07 2014-01-01 桂林理工大学 Method for preparing near infrared fluorescent Ag2Se colloid semiconductor nanocrystals by adopting normal-temperature aqueous phase process
CN105036092A (en) * 2015-08-07 2015-11-11 中南大学 Preparation method of spherical silver selenide particles

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