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 PDFInfo
- Publication number
- 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
- Authority
- CN
- China
- Prior art keywords
- water
- solution
- preparation
- soluble
- silver nitrate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/88—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing selenium, tellurium or unspecified chalcogen elements
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- Crystallography & Structural Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- General Physics & Mathematics (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
- Hybrid Cells (AREA)
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
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.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201710161283.1A CN106978182B (en) | 2017-03-17 | 2017-03-17 | A kind of preparation method for the water-soluble selenizing silver content point quickly preparing size tunable |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201710161283.1A CN106978182B (en) | 2017-03-17 | 2017-03-17 | A kind of preparation method for the water-soluble selenizing silver content point quickly preparing size tunable |
Publications (2)
Publication Number | Publication Date |
---|---|
CN106978182A CN106978182A (en) | 2017-07-25 |
CN106978182B true CN106978182B (en) | 2019-04-19 |
Family
ID=59338116
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201710161283.1A Active CN106978182B (en) | 2017-03-17 | 2017-03-17 | A kind of preparation method for the water-soluble selenizing silver content point quickly preparing size tunable |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN106978182B (en) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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 |
Citations (4)
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 |
-
2017
- 2017-03-17 CN CN201710161283.1A patent/CN106978182B/en active Active
Patent Citations (4)
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 |
Also Published As
Publication number | Publication date |
---|---|
CN106978182A (en) | 2017-07-25 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Sun et al. | Fe-doped g-C3N4 derived from biowaste material with Fe-N bonds for enhanced synergistic effect between photocatalysis and Fenton degradation activity in a broad pH range | |
Das et al. | Synthetic developments of nontoxic quantum dots | |
Kadam et al. | Template free synthesis of ZnO/Ag2O nanocomposites as a highly efficient visible active photocatalyst for detoxification of methyl orange | |
Shen et al. | All-solid-state Z-scheme system of RGO-Cu2O/Bi2O3 for tetracycline degradation under visible-light irradiation | |
Su et al. | Recent advances in quantum dot catalysts for hydrogen evolution: Synthesis, characterization, and photocatalytic application | |
Misra et al. | Synthesis and visible photocatalytic activities of a Au@ Ag@ ZnO triple layer core–shell nanostructure | |
CN105195144B (en) | A kind of method of the bar-shaped heterojunction photocatalysts of synthesis Au/ZnO | |
You et al. | Preparation, visible light-driven photocatalytic activity, and mechanism of multiphase CdS/C3N4 inorganic-organic hybrid heterojunction | |
Zhang et al. | Size effects of Ag nanoparticles on plasmon-induced enhancement of photocatalysis of Ag-α-Fe2O3 nanocomposites | |
Yang et al. | One step solvothermal synthesis of Bi/BiPO4/Bi2WO6 heterostructure with oxygen vacancies for enhanced photocatalytic performance | |
Wang et al. | Facile construction of 3D hierarchical flake ball-shaped γ-AgI/Bi2WO6 Z-scheme heterojunction towards enhanced visible-light photocatalytic performance | |
JP2005343782A (en) | Method for producing bismuth telluride nanoparticle and method for producing tellurium nanoparticle | |
Wang et al. | Environmentally benign chitosan as reductant and supporter for synthesis of Ag/AgCl/chitosan composites by one-step and their photocatalytic degradation performance under visible-light irradiation | |
Yang et al. | Facile surface engineering of Ag–In–Zn–S quantum dot photocatalysts by mixed-ligand passivation with improved charge carrier lifetime | |
KR101701762B1 (en) | Multi-branched star-shaped Au nanoparticles and synthesizing method thereof | |
Chen et al. | Multi-component (Cu, Mn)(Se, S) nanosheet catalysts for redox reactions in the dark | |
Amaral-Júnior et al. | Tunable luminescence of Cu-In-S/ZnS quantum dots-polysaccharide nanohybrids by environmentally friendly synthesis for potential solar energy photoconversion applications | |
Basaleh et al. | Novel visible light heterojunction CdS/Gd2O3 nanocomposites photocatalysts for Cr (VI) photoreduction | |
Huang et al. | Bi 2 O 2 CO 3/Bi 2 O 3 Z-scheme photocatalyst with oxygen vacancies and Bi for enhanced visible-light photocatalytic degradation of tetracycline | |
CN107282071B (en) | A kind of spherical AgInS2/Bi2S3Heterojunction photocatalysis material and its preparation method and application | |
CN102786037A (en) | CdX quantum dot and preparation method thereof | |
US20140158021A1 (en) | Electrochemical Synthesis of Selenium Nanoparticles | |
Liu et al. | Surfactants-assisted morphological regulation of BiVO4 nanostructures for photocatalytic degradation of organic pollutants in wastewater | |
Bharti et al. | Green synthesis of luminescent gold-zinc oxide nanocomposites: Cell imaging and visible light–induced dye degradation | |
CN106978182B (en) | A kind of preparation method for the water-soluble selenizing silver content point quickly preparing size tunable |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |