CN104860345A - Preparation method for water-soluble tin-monosulfide quantum dot - Google Patents

Abstract

The invention discloses a method for preparing water-soluble stannous sulfide quantum dots. Mix and react under stirring conditions to form a precursor; (2) Add the formed precursor to high-purity water, an aqueous solution containing a surfactant or an aqueous solution containing a protein, and then react the above mixture at 4-80°C for 0.5-24h to obtain a water-soluble permanent stannous sulfide quantum dots. The preparation method of the invention is simple and controllable, the reaction conditions are mild, the raw materials are cheap and easy to obtain, and it is environmentally friendly.

Description

A kind of preparation method of water-soluble stannous sulfide quantum dot

technical field

The invention belongs to the technical field of synthesis of inorganic functional material stannous sulfide, and in particular relates to a preparation method of water-soluble stannous sulfide quantum dots.

Background technique

Quantum dots, also known as nanocrystals, generally have a particle size between 1-10nm. Since electrons and holes are quantum-confined, the continuous energy band structure becomes a discrete energy-level structure with molecular characteristics. Can emit fluorescence. Due to the quantum size effect, surface effect, and macroscopic quantum tunneling effect, quantum dots have incomparable photoelectric properties of bulk materials and have become a research hotspot. Based on quantum effects, quantum dots have broad application prospects in the fields of solar cells, light-emitting devices, and optical biomarkers. Tin sulfide quantum dots have good photoelectric properties and are good materials for the absorber layer of solar cell devices. At present, the methods for synthesizing tin sulfide quantum dots mainly include: electrochemical method, thermal injection method, ion exchange method and hydrothermal method, etc. Most of these synthesis methods require high temperature and complex devices, and the operation steps are cumbersome and applied to biology. On the other hand, it needs to be transformed into water-soluble quantum dots. At present, there are few methods for synthesizing water-soluble stannous sulfide quantum dots. The reasons are: (1) the synthesized quantum dots are unstable and easy to agglomerate without surfactant; (2) the crystallinity is not good, which limits Its application; (3) The yield is low and it is difficult to apply to industrial production. Therefore, the synthesis of water-soluble tin sulfide quantum dots is facing a huge challenge, and it is also a research hotspot in recent years.

Contents of the invention

The technical problem solved by the present invention is to provide a preparation method of water-soluble stannous sulfide quantum dots, which adopts a new raw material ratio to prepare stable and better water-soluble stannous sulfide quantum dots. The obtained water-soluble tin sulfide quantum dots have strong fluorescence properties.

In order to solve the above-mentioned technical problems, the present invention adopts the following technical scheme, a preparation method of water-soluble stannous sulfide quantum dots, which is characterized in that it includes the following steps: (1) dissolving tin salts and sulfur-containing compounds in organic solvents as tin Source and sulfur source, the tin source and the sulfur source are mixed under ultrasonic or stirring conditions to form a precursor, wherein the tin salt is tin chloride, the sulfur compound is thioacetamide or thiourea, and the organic solvent is methanol, Ethanol or propanol; (2) Add the precursor formed in step (1) to high-purity water, an aqueous solution containing a surfactant or an aqueous solution containing a protein, wherein the surfactant is sodium dodecylsulfonate, dodecylbenzene Sodium sulfonate, sodium cetyl sulfate, sodium dioctyl sulfosuccinate, cetylpyridinium chloride, cetylpyridinium bromide, potassium stearate, potassium oleate, potassium laurate or poly Ethylene glycol, the protein is bovine serum albumin, the volume ratio of the precursor to high-purity water, an aqueous solution containing a surfactant or an aqueous solution containing a protein is 1:0.5-2, and then the above mixture is reacted at 4-80°C for 0.5-24h After the reaction is finished, place it in a centrifuge and centrifuge at a centrifugal speed of 13000r/min. The product obtained by centrifugation is washed three times alternately with absolute ethanol and high-purity water, and is dried to obtain water-soluble stannous sulfide quantum dots.

Further defined, the molar ratio of the tin salt to the sulfur-containing compound is 0.43:1.

It is further defined that the mass concentration of the aqueous solution containing surfactant is 1-4 g/L, and the mass concentration of the aqueous solution containing protein is 1-4 g/L.

The outstanding advantage of the present invention is the use of cheap and easy-to-obtain raw materials, the use of precursors and high-purity water for hydrolysis reactions at different temperatures and times, and the controllable preparation of water-soluble sulfites with different crystal types and sizes that can exist stably. Tin quantum dots. Compared with the existing preparation method of stannous sulfide quantum dots, the preparation method of the present invention is simple and controllable, has mild reaction conditions, cheap and easy-to-obtain raw materials and is environmentally friendly.

Description of drawings

Fig. 1 is an X-ray diffraction pattern of the sample prepared in Example 1 of the present invention, and Fig. 2 is a transmission electron microscope image of the sample prepared in Example 1 of the present invention.

Detailed ways

The above-mentioned contents of the present invention are described in further detail below through the embodiments, but this should not be interpreted as the scope of the above-mentioned themes of the present invention being limited to the following embodiments, and all technologies realized based on the above-mentioned contents of the present invention all belong to the scope of the present invention.

Example 1

(1) Add 2.051g of stannous chloride to 150mL of absolute ethanol, stir until completely dissolved, add 1.602g of thioacetamide to 200mL of absolute ethanol, stir until completely dissolved, slowly add sulfur In acetamide solution, ultrasonication for 10 minutes forms the precursor;

(2) Take 300mL of precursor, add 300mL of high-purity water under stirring conditions, react the mixture of the two at 40°C for 0.5h, centrifuge at a centrifugal rate of 13000r/min after the reaction, and centrifuge the obtained product with absolute ethanol and High-purity water was alternately washed three times, and water-soluble stannous sulfide quantum dots were obtained after drying.

As can be seen from Fig. 1, no obvious sharp peak occurs, indicating that the crystallization type of the stannous sulfide quantum dot synthesized by this method is amorphous. It can be seen from Fig. 2 that the particle size of the obtained water-soluble tin sulfide quantum dots is very small, about 10nm.

Example 2

(1) Add 2.051g of stannous chloride to 200mL of absolute ethanol, stir until completely dissolved, add 1.602g of thioacetamide to 200mL of absolute ethanol, stir until completely dissolved, slowly add sulfur In the acetamide solution, stir for 10 minutes to form a precursor;

(2) Take 300mL of pre-refrigerated precursor, add 300mL of pre-refrigerated high-purity water under stirring conditions, react the mixture of the two at 4°C for 24h, centrifuge at a centrifugal rate of 13000r/min after the reaction, and centrifuge the obtained product The water-soluble stannous sulfide quantum dots were obtained by alternately washing three times with absolute ethanol and high-purity water, and drying.

Example 3

(1) Add 2.051g of stannous chloride to 200mL of absolute ethanol, stir until completely dissolved, add 1.602g of thioacetamide to 200mL of absolute ethanol, stir until completely dissolved, slowly add sulfur In the acetamide solution, stir for 10 minutes to form a precursor;

(2) Take 300mL of the precursor, add 300mL of high-purity water under stirring conditions, and react the mixture of the two at 80°C for 0.5h. High-purity water was alternately washed three times, and water-soluble stannous sulfide quantum dots were obtained after drying.

Example 4

(1) Add 2.051g of stannous chloride to 200mL of absolute ethanol, stir until completely dissolved, add 1.602g of thioacetamide to 200mL of absolute ethanol, stir until completely dissolved, slowly add sulfur In acetamide solution, ultrasonication for 10 minutes forms the precursor;

(2) Take 300mL precursor, add 600mL high-purity water under stirring conditions, react the mixture of the two at 40°C for 0.5h, centrifuge at a centrifugal speed of 13000r/min after the reaction, and centrifuge the obtained product with absolute ethanol and High-purity water was alternately washed three times, and water-soluble stannous sulfide quantum dots were obtained after drying.

Example 5

(1) Add 2.051g of stannous chloride to 200mL of absolute ethanol, stir until completely dissolved, add 1.602g of thioacetamide to 200mL of absolute ethanol, stir until completely dissolved, slowly add sulfur In acetamide solution, ultrasonication for 10 minutes forms the precursor;

(2) Take 300mL of the precursor, add 150mL of high-purity water under stirring conditions, and react the mixture of the two at 40°C for 0.5h. High-purity water was alternately washed three times, and water-soluble stannous sulfide quantum dots were obtained after drying.

Example 6

(1) Add 2.051g of stannous chloride to 200mL of absolute ethanol, stir until completely dissolved, add 1.623g of thiourea to 200mL of absolute ethanol, stir until completely dissolved, slowly add the stannous chloride solution to the thiourea solution , ultrasonic 10min to form the precursor;

(2) Take 300mL of precursor, add 300mL of high-purity water under stirring conditions, react the mixture of the two at 40°C for 0.5h, centrifuge at a centrifugal rate of 13000r/min after the reaction, and centrifuge the obtained product with absolute ethanol and High-purity water was alternately washed three times, and water-soluble stannous sulfide quantum dots were obtained after drying.

Example 7

(1) Add 2.051g of stannous chloride to 200mL of methanol, stir until completely dissolved, add 1.602g of thioacetamide to 200mL of methanol, stir until completely dissolved, slowly add the stannous chloride solution into the thioacetamide solution , ultrasonic 10min to form the precursor;

(2) Take 300mL of precursor, add 300mL of high-purity water under stirring conditions, react the mixture of the two at 40°C for 0.5h, centrifuge at a centrifugal rate of 13000r/min after the reaction, and centrifuge the obtained product with absolute ethanol and High-purity water was alternately washed three times, and water-soluble stannous sulfide quantum dots were obtained after drying.

Example 8

(1) Add 2.051g stannous chloride to 200mL propanol, stir until completely dissolved, add 1.602g thioacetamide to 200mL propanol, stir until completely dissolved, slowly add stannous chloride solution to thioethyl In the amide solution, ultrasonication for 10 minutes forms the precursor;

(2) Take 300mL of precursor, add 300mL of high-purity water under stirring conditions, react the mixture of the two at 40°C for 0.5h, centrifuge at a centrifugal rate of 13000r/min after the reaction, and centrifuge the obtained product with absolute ethanol and High-purity water was alternately washed three times, and water-soluble stannous sulfide quantum dots were obtained after drying.

Example 9

(1) Add 2.051g of stannous chloride to 200mL of absolute ethanol, stir until completely dissolved, add 1.602g of thioacetamide to 200mL of absolute ethanol, stir until completely dissolved, slowly add sulfur In acetamide solution, ultrasonication for 10 minutes forms the precursor;

(2) Take 300mL precursor, add 300mL sodium dodecylsulfonate solution (1g/L) under stirring conditions, react the mixture of the two at 40°C for 0.5h, and centrifuge at 13000r/min after the reaction Speed centrifugation, the product obtained by centrifugation is alternately washed three times with absolute ethanol and high-purity water, and dried to obtain water-soluble stannous sulfide quantum dots.

Example 10

(1) Add 2.051g of stannous chloride to 200mL of absolute ethanol, stir until completely dissolved, add 1.602g of thioacetamide to 200mL of absolute ethanol, stir until completely dissolved, slowly add sulfur In acetamide solution, ultrasonication for 10 minutes forms the precursor;

(2) Take 300mL precursor, add 300mL sodium dodecylbenzenesulfonate solution (1g/L) under the condition of stirring, react the mixture of the two at 40℃ for 0.5h, after the reaction is completed, use 13000r/min The centrifugation speed is centrifuged, and the product obtained by centrifugation is alternately washed three times with absolute ethanol and high-purity water, and the water-soluble stannous sulfide quantum dots are obtained after drying.

Example 11

(1) Add 2.051g of stannous chloride to 200mL of absolute ethanol, stir until completely dissolved, add 1.602g of thioacetamide to 200mL of absolute ethanol, stir until completely dissolved, slowly add sulfur In acetamide solution, ultrasonication for 10 minutes forms the precursor;

(2) Take 300mL precursor, add 300mL cetyl sodium sulfate solution (1g/L) under stirring conditions, react the mixture of the two at 40°C for 0.5h, after the reaction is completed, use a centrifugal speed of 13000r/min Centrifuging, the product obtained by centrifuging is alternately washed three times with absolute ethanol and high-purity water, and dried to obtain water-soluble stannous sulfide quantum dots.

Example 12

(1) Add 2.051g of stannous chloride to 200mL of absolute ethanol, stir until completely dissolved, add 1.602g of thioacetamide to 200mL of absolute ethanol, stir until completely dissolved, slowly add sulfur In acetamide solution, ultrasonication for 10 minutes forms the precursor;

(2) Take 300mL precursor, add 300mL sodium dioctyl succinic acid sulfonate solution (1g/L) under stirring conditions, react the mixture of the two at 40°C for 0.5h, after the reaction is completed, use 13000r/min The centrifugation speed is centrifuged, and the product obtained by centrifugation is alternately washed three times with absolute ethanol and high-purity water, and the water-soluble stannous sulfide quantum dots are obtained after drying.

Example 13

(1) Add 2.051g of stannous chloride to 200mL of absolute ethanol, stir until completely dissolved, add 1.602g of thioacetamide to 200mL of absolute ethanol, stir until completely dissolved, slowly add sulfur In acetamide solution, ultrasonication for 10 minutes forms the precursor;

(2) Take 300mL precursor, add 300mL cetylpyridinium chloride solution (1g/L) under stirring conditions, react the mixture of the two at 40°C for 0.5h, and centrifuge at 13000r/min after the reaction Speed centrifugation, the product obtained by centrifugation is alternately washed three times with absolute ethanol and high-purity water, and dried to obtain water-soluble stannous sulfide quantum dots.

Example 14

(1) Add 2.051g of stannous chloride to 200mL of absolute ethanol, stir until completely dissolved, add 1.602g of thioacetamide to 200mL of absolute ethanol, stir until completely dissolved, slowly add sulfur In acetamide solution, ultrasonication for 10 minutes forms the precursor;

(2) Take 300mL precursor, add 300mL cetylpyridinium bromide solution (1g/L) under stirring conditions, react the mixture of the two at 40°C for 0.5h, and centrifuge at 13000r/min after the reaction Speed centrifugation, the product obtained by centrifugation is alternately washed three times with absolute ethanol and high-purity water, and dried to obtain water-soluble stannous sulfide quantum dots.

Example 15

(1) Add 2.051g of stannous chloride to 200mL of absolute ethanol, stir until completely dissolved, add 1.602g of thioacetamide to 200mL of absolute ethanol, stir until completely dissolved, slowly add sulfur In acetamide solution, ultrasonication for 10 minutes forms the precursor;

(2) Take 300mL precursor, add 300mL potassium stearate solution (1g/L) under stirring conditions, react the mixture of the two at 40°C for 0.5h, centrifuge at 13000r/min after the reaction, The centrifuged product was alternately washed three times with absolute ethanol and high-purity water, and dried to obtain water-soluble stannous sulfide quantum dots.

Example 16

(1) Add 2.051g of stannous chloride to 200mL of absolute ethanol, stir until completely dissolved, add 1.602g of thioacetamide to 200mL of absolute ethanol, stir until completely dissolved, slowly add sulfur In acetamide solution, ultrasonication for 10 minutes forms the precursor;

(2) Take 300mL precursor, add 300mL potassium oleate solution (1g/L) under stirring conditions, react the mixture of the two at 40°C for 0.5h, centrifuge at 13000r/min after the reaction, and centrifuge The obtained product is alternately washed three times with absolute ethanol and high-purity water, and dried to obtain water-soluble stannous sulfide quantum dots.

Example 17

(1) Add 2.051g of stannous chloride to 200mL of absolute ethanol, stir until completely dissolved, add 1.602g of thioacetamide to 200mL of absolute ethanol, stir until completely dissolved, slowly add sulfur In acetamide solution, ultrasonication for 10 minutes forms the precursor;

(2) Take 300mL precursor, add 300mL potassium laurate solution (1g/L) under stirring conditions, react the mixture of the two at 40°C for 0.5h, centrifuge at 13000r/min after the reaction, and centrifuge The obtained product is alternately washed three times with absolute ethanol and high-purity water, and dried to obtain water-soluble stannous sulfide quantum dots.

Example 18

(1) Add 2.051g of stannous chloride to 200mL of absolute ethanol, stir until completely dissolved, add 1.602g of thioacetamide to 200mL of absolute ethanol, stir until completely dissolved, slowly add sulfur In acetamide solution, ultrasonication for 10 minutes forms the precursor;

(2) Take 300mL precursor, add 300mL polyethylene glycol solution (1g/L) under stirring conditions, react the mixture of the two at 40°C for 0.5h, centrifuge at 13000r/min after the reaction, The centrifuged product was alternately washed three times with absolute ethanol and high-purity water, and dried to obtain water-soluble stannous sulfide quantum dots.

Example 21

(1) Add 2.051g of stannous chloride to 200mL of absolute ethanol, stir until completely dissolved, add 1.602g of thioacetamide to 200mL of absolute ethanol, stir until completely dissolved, slowly add sulfur In acetamide solution, ultrasonication for 10 minutes forms the precursor;

(2) Take 300mL precursor, add 300mL bovine serum albumin solution (1g/L) under stirring conditions, react the mixture of the two at 40°C for 0.5h, centrifuge at 13000r/min after the reaction, The centrifuged product was alternately washed three times with absolute ethanol and high-purity water, and dried to obtain water-soluble stannous sulfide quantum dots.

Example 22

(1) Add 2.051g of stannous chloride to 200mL of absolute ethanol, stir until completely dissolved, add 1.602g of thioacetamide to 200mL of absolute ethanol, stir until completely dissolved, slowly add sulfur In acetamide solution, ultrasonication for 10 minutes forms the precursor;

(2) Take 300mL precursor, add 300mL sodium dodecylsulfonate solution (4g/L) under stirring conditions, react the mixture of the two at 40°C for 0.5h, and centrifuge at 13000r/min after the reaction Speed centrifugation, the product obtained by centrifugation is alternately washed three times with absolute ethanol and high-purity water, and dried to obtain water-soluble stannous sulfide quantum dots.

The above embodiments have described the basic principles, main features and advantages of the present invention. Those skilled in the art should understand that the present invention is not limited by the above embodiments. What are described in the above embodiments and description are only to illustrate the principles of the present invention. Without departing from the scope of the principle of the present invention, there will be various changes and improvements in the present invention, and these changes and improvements all fall within the protection scope of the present invention.

Claims (4)

1. the preparation method of a water-soluble stannous sulfide quantum dot, it is characterized in that comprising the following steps: pink salt and sulfocompound are dissolved in organic solvent as Xi Yuan and sulphur source by (1) respectively, by Xi Yuan and sulphur source, mixing under condition that is ultrasonic or that stir is carried out reaction and is formed presoma, wherein pink salt is tin chloride, sulfocompound is thioacetamide or thiocarbamide, and organic solvent is methyl alcohol, ethanol or propyl alcohol, (2) presoma that step (1) is formed is added high purity water, the aqueous solution containing tensio-active agent or the aqueous solution containing protein, wherein tensio-active agent is sodium laurylsulfonate, Sodium dodecylbenzene sulfonate, Sodium palmityl sulfate, dioctyl succinate disulfonate acid, cetylpyridinium chloride, brocide, potassium stearate, potassium oleate, potassium laurate or polyoxyethylene glycol, protein is bovine serum albumin, presoma and high purity water, the volume ratio of the aqueous solution containing tensio-active agent or the aqueous solution containing protein is 1:0.5-2, then said mixture is reacted 0.5-24h in 4-80 DEG C, the centrifugation rate that reaction terminates to be placed on 13000r/min in whizzer is centrifugal, the product dehydrated alcohol of centrifugal gained and high purity water replace washing three times, water-soluble stannous sulfide quantum dot is obtained after drying.

2. the preparation method of water-soluble stannous sulfide quantum dot according to claim 1, is characterized in that: described pink salt and the mol ratio of sulfocompound are 0.43:1.

3. the preparation method of water-soluble stannous sulfide quantum dot according to claim 1, is characterized in that: the mass concentration of the described aqueous solution containing tensio-active agent is 1-4g/L.

4. the preparation method of water-soluble stannous sulfide quantum dot according to claim 1, is characterized in that: the mass concentration of the described aqueous solution containing protein is 1-4g/L.