CN109721095B

CN109721095B - Preparation method of stannous sulfide nano-particles

Info

Publication number: CN109721095B
Application number: CN201910204117.4A
Authority: CN
Inventors: 李道金; 李冠峰; 刘向慧
Original assignee: Luoyang Normal University
Current assignee: Luoyang Normal University
Priority date: 2019-03-18
Filing date: 2019-03-18
Publication date: 2021-09-10
Anticipated expiration: 2039-03-18
Also published as: CN109721095A

Abstract

The invention provides a preparation method of stannous sulfide nano particles, and relates to the technical field of preparation of non-ferrous metal materials. Under the heating condition, dropwise adding a stannous chloride aqueous solution into a sulfur source aqueous solution for reflux reaction to obtain stannous sulfide nanoparticles; the sulfur source is thioacetamide or L-cysteine. The method takes stannous chloride as a tin source, takes thioacetamide or L-cysteine as a sulfur source, adopts a liquid phase precipitation method to prepare the stannous sulfide nano particles under the reflux condition of normal pressure, has simple process and mild condition, and is convenient to control and operate; in addition, the stannous chloride aqueous solution is dripped into the sulfur source aqueous solution, so that stannous ions can be prevented from being oxidized into stannic ions, and the purity of the prepared stannous sulfide nano particles is ensured.

Description

Preparation method of stannous sulfide nano-particles

Technical Field

The invention relates to the technical field of non-ferrous metal material preparation, in particular to a preparation method of stannous sulfide nano particles.

Background

As a novel inorganic semiconductor, the metal sulfide is widely applied to a plurality of fields such as photocatalysis, biomedicine, solar cells and the like due to the special effect and the unique hollow structure of the metal sulfide. SnS is an important semiconductor material, has a narrow energy band gap (1.3eV), is between Si (1.12eV) and GaAs (1.43eV), and has unique photoelectric characteristics to enable the SnS to be in good spectral matching with solar radiation. The SnS has a band gap close to an ideal width, and the raw materials of tin and sulfur have abundant reserves on the earth, are non-toxic and become the preferred materials for solar energy conversion.

There are many methods for preparing nano SnS, and the physical method comprises the following steps: evaporation condensation method, physical crushing method, mechanical ball milling method and novel electrolysis method. Most of them are low in productivity, complicated in equipment and high in cost. The chemical method comprises the following steps: the methods of gas phase, precipitation, hydrothermal synthesis, sol-gel method and microemulsion method have the problems of harsh synthesis conditions, high reaction temperature, calcination and the like. For example, the hydrothermal reaction usually adopted requires high temperature and high pressure, some precursors are toxic and the synthesis is very complex, and the morphology of the obtained product is difficult to control.

Disclosure of Invention

In view of the above, the present invention is directed to a method for preparing stannous sulfide nanoparticles. The preparation method provided by the invention has the advantages of simple process, mild conditions and convenience in control and operation.

In order to achieve the above object, the present invention provides the following technical solutions:

the invention provides a preparation method of stannous sulfide nano particles, which comprises the following steps:

under the heating condition, dropwise adding a stannous chloride aqueous solution into a sulfur source aqueous solution for reflux reaction to obtain stannous sulfide nanoparticles; the sulfur source is thioacetamide or L-cysteine.

Preferably, the heating temperature is 85-100 ℃.

Preferably, the concentration of the stannous chloride aqueous solution is 0.01-0.20 mol/L, and the concentration of the sulfur source aqueous solution is 0.01-0.20 mol/L.

Preferably, the molar ratio of the stannous chloride in the stannous chloride aqueous solution to the sulfur source in the sulfur source aqueous solution is 1: 1.

Preferably, the dropping speed of the stannous chloride aqueous solution is 1-2 mL/min.

Preferably, the dropwise addition is carried out under the stirring condition, and the stirring rotating speed is 500-800 r/min.

Preferably, the time of the reflux reaction is 5-10 h.

Preferably, the method further comprises the step of carrying out post-treatment on the obtained reflux reaction liquid after the reflux reaction; the post-treatment comprises the following steps:

and sequentially carrying out centrifugal separation, washing, drying and grinding on the reflux reaction liquid to obtain the stannous sulfide nano particles.

Preferably, the drying temperature is 50-60 ℃, and the drying time is 40-60 hours; the drying is carried out under vacuum.

The invention provides a preparation method of stannous sulfide nano particles, which comprises the following steps: under the heating condition, dropwise adding a stannous chloride aqueous solution into a sulfur source aqueous solution for reflux reaction to obtain stannous sulfide nanoparticles; the sulfur source is thioacetamide or L-cysteine. The method takes stannous chloride as a tin source, takes thioacetamide or L-cysteine as a sulfur source, adopts a liquid phase precipitation method to prepare the stannous sulfide nano particles under the reflux condition of normal pressure, has simple process and mild condition, and is convenient to control and operate; in addition, the stannous chloride aqueous solution is dripped into the sulfur source aqueous solution, so that stannous ions can be prevented from being oxidized into stannic ions, and the purity of the prepared stannous sulfide nano particles is ensured. The embodiment result shows that the product prepared by the preparation method provided by the invention is an SnS nano particle with an orthorhombic structure.

Drawings

Figure 1 is the XRD spectrum of the product prepared in example 1.

Detailed Description

In the invention, the heating temperature is preferably 85-100 ℃, and more preferably 90-95 ℃. The invention preferably controls the heating temperature by means of oil bath heating.

In the invention, the concentration of the stannous chloride aqueous solution is preferably 0.01-0.20 mol/L, and more preferably 0.05-0.15 mol/L; the concentration of the sulfur source water solution is preferably 0.01-0.20 mol/L, and more preferably 0.05-0.15 mol/L. In the present invention, the molar ratio of the stannous chloride in the stannous chloride aqueous solution to the sulfur source in the sulfur source aqueous solution is preferably 1: 1. The invention has no special requirements on the sources of the stannous chloride and the sulfur source, and corresponding products sold in the market are adopted.

In the invention, the dripping speed of the stannous chloride aqueous solution is preferably 1-2 mL/min, and more preferably 1.5 mL/min. In the embodiment of the present invention, it is preferable that the sulfur source aqueous solution is placed in a three-neck flask, then the three-neck flask is heated, and when the sulfur source aqueous solution reaches the heating temperature, the stannous chloride aqueous solution is added dropwise. In the present invention, the dropping is preferably performed under stirring conditions; the stirring is preferably magnetic stirring, and the rotating speed of the stirring is preferably 500-800 r/min, and more preferably 600-700 r/min. The invention adds the stannous chloride aqueous solution into the sulfur source aqueous solution dropwise, can prevent stannous ions from being oxidized into stannic ions, ensures the purity of the prepared stannous sulfide nano particles, and can ensure that the chemical reaction is slowly carried out in the dropwise adding mode, thereby being not easy to generate the local over-concentration phenomenon.

After the dropwise addition is finished, under the heating condition, the stannous chloride aqueous solution and the sulfur source aqueous solution are subjected to reflux reaction. In the invention, the time of the reflux reaction is preferably 5-10 h, and more preferably 6-8 h. The apparatus for the reflux reaction of the present invention is not particularly limited, and a reflux apparatus well known in the art may be used. In the invention, the stannous chloride aqueous solution and the sulfur source aqueous solution generate brownish black precipitate through reflux reaction. The method takes stannous chloride as a tin source, takes thioacetamide or L-cysteine as a sulfur source, adopts a liquid phase precipitation method to prepare the stannous sulfide nano particles under the reflux condition of normal pressure, has simple process and mild condition, and is convenient to control and operate. In the invention, the reaction of divalent tin ions and thioacetamide or L-cysteine belongs to homogeneous reaction, and the sulfur ions are slowly generated in the chemical reaction, so that the local over-concentration phenomenon is not easy to generate, and the stannous sulfide nano particles in regular arrangement are easy to generate.

In the present invention, after the reflux reaction, the method preferably further comprises post-treating the obtained reflux reaction solution; the post-treatment preferably comprises the steps of:

In the present invention, it is preferable that the refluxing reaction solution is cooled before the centrifugal separation; the invention has no special requirement on the cooling method, and the cooling method can be carried out naturally to room temperature. The method of centrifugation is not particularly required in the present invention, and a method well known in the art may be used. In the present invention, the washing detergent is preferably distilled water. The invention preferably repeats the centrifugation and washing alternately until the centrifugate is Ag-containing⁺The solution was checked until no white flocculent precipitate appeared. In the invention, the drying temperature is preferably 50-60 ℃, more preferably 55-60 ℃, and the time is preferably 40-60 hours, more preferably 45-55 hours; the drying is preferably carried out in a vacuum drying oven. The invention is to said grindingThe method is not particularly limited, and a method known in the art may be used. The invention has no special requirement on the grinding degree, and corresponding grinding can be carried out according to actual requirements.

The following examples are provided to illustrate the preparation method of the stannous sulfide nanoparticles provided by the present invention, but they should not be construed as limiting the scope of the present invention.

Example 1

Accurately weigh 0.45g SnCl with an electronic balance₂·2H₂O solids and 0.16g thioacetamide C₂H₅Dissolving NS solid in 20mL of distilled water respectively, and dissolving thioacetamide C₂H₅The NS solution is completely transferred into a three-neck flask, and then SnCl is added dropwise in an oil bath at 100 ℃ while magnetic stirring₂The solution was added dropwise at a rate of 1mL/min until the whole was put into a three-necked flask to react with thioacetamide C₂H₅Refluxing NS, reacting for 7 hr, cooling, centrifuging the brown-black precipitate, washing, repeating for ten times, pouring the centrifugate into test tube, and adding Ag⁺The solution of (2) is tested. If no white flocculent precipitate appears, the solid precipitate is washed clean, if white flocculent precipitate appears, the solid precipitate is not washed clean, and the washing with distilled water is continued until the precipitate is washed with the solution containing Ag⁺When the solution is tested, white flocculent precipitate does not appear in the washing liquid. Then, the washed solid precipitate was dried in a vacuum drying oven at 55 ℃ for 48 hours and then ground into powder to obtain the product.

The obtained product was characterized by X-ray powder diffraction method to obtain its XRD spectrum, the result is shown in fig. 1. As can be seen from FIG. 1, the prepared product is an orthorhombic SnS nano-particle.

Example 2

Accurately weigh 0.90g SnCl with an electronic balance₂·2H₂O solids and 0.32g C₂H₅The NS solids were dissolved in 20mL of distilled water, respectively, and C was added₂H₅The NS solution is completely transferred into a three-neck flask and then subjected to oil bath at 90 DEG CDropwise adding SnCl while magnetically stirring₂The solution was added dropwise at a rate of 1.5mL/min until the whole was added to a three-necked flask and allowed to react with C₂H₅NS is refluxed for 8 hours, then cooled, the generated brownish black precipitate is centrifugally separated, washed and repeated for ten times, the centrifugate is poured into a test tube and is treated with Ag⁺The solution of (2) is tested. If no white flocculent precipitate appears, the solid precipitate is washed clean, if white flocculent precipitate appears, the solid precipitate is not washed clean, and the washing with distilled water is continued until the precipitate is washed with the solution containing Ag⁺When the solution is tested, white flocculent precipitate does not appear in the washing liquid. Then, the washed solid precipitate was dried in a vacuum drying oven at 55 ℃ for 48 hours and then ground into powder to obtain the product.

The XRD spectrum of the obtained product is similar to that of example 1, namely the obtained product is SnS nano particles with an orthorhombic structure.

Example 3

0.7932g of SnCl were accurately weighed with an electronic balance₂·2H₂O solids and 0.4018gC₃H₇NO₂S (L-cysteine) solids were dissolved in 15mL of distilled water, respectively, and C was added₃H₇NO₂Transferring the S solution into a three-neck flask, and then dropwise adding SnCl while magnetically stirring in an oil bath at 100 DEG C₂The solution was added dropwise at a rate of 2mL/min until the whole was added to a three-necked flask and allowed to react with C₃H₇NO₂S, carrying out reflux reaction, cooling after 7 hours of reaction, carrying out centrifugal separation on the generated brownish black precipitate, washing, repeating for ten times, pouring the centrifugate into a test tube, and using the solution containing Ag⁺The solution of (2) is tested. If no white flocculent precipitate appears, the solid precipitate is washed clean, if white flocculent precipitate appears, the solid precipitate is not washed clean, and the washing with distilled water is continued until the precipitate is washed with the solution containing Ag⁺When the solution is tested, white flocculent precipitate does not appear in the washing liquid. Then, the washed solid precipitate is put into a vacuum drying oven to be dried for 48 hours at the temperature of 55 ℃, and then is ground into powder to obtain the productAnd (5) preparing the product.

As can be seen from the above examples, the preparation method provided by the invention has the advantages of simple process, mild conditions and convenience in control and operation.

The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims

1. A preparation method of stannous sulfide nanoparticles is characterized by comprising the following steps:

under the heating condition, dropwise adding a stannous chloride aqueous solution into a sulfur source aqueous solution for reflux reaction to obtain stannous sulfide nanoparticles; the sulfur source is L-cysteine; the heating temperature is 100 ℃; the concentration of the stannous chloride aqueous solution is 0.01-0.20 mol/L; the concentration of the sulfur source water solution is 0.01-0.20 mol/L; the dropping speed of the stannous chloride aqueous solution is 1-2 mL/min; the time of the reflux reaction is 6-8 h.

2. The method according to claim 1, wherein the molar ratio of the stannous chloride in the stannous chloride aqueous solution to the sulfur source in the sulfur source aqueous solution is 1: 1.

3. The preparation method according to claim 1, wherein the dropwise addition is performed under stirring conditions, and the rotation speed of the stirring is 500 to 800 r/min.

4. The preparation method according to claim 1, further comprising, after the reflux reaction, post-treating the obtained reflux reaction solution; the post-treatment comprises the following steps:

5. The preparation method according to claim 4, wherein the drying temperature is 50-60 ℃ and the drying time is 40-60 h; the drying is carried out under vacuum.