CN111777095B - Synthesis method of tin disulfide microspheres - Google Patents
Synthesis method of tin disulfide microspheres Download PDFInfo
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Abstract
The invention relates to a SnS 2 The synthesis method of the microsphere mainly comprises the following steps: 1) respectively preparing a sodium hydroxide solution and a mixed solution of stannic chloride and zinc acetate; 2) adding NaOH solution to SnCl 4 、Zn(OAc) 2 Mixing the solution, stirring, transferring into a reaction kettle for reaction, separating, washing and drying the obtained reactant to obtain Zn 2 SnO 4 Nano powder; 3) zn is added 2 SnO 4 Adding the nano powder into a glacial acetic acid aqueous solution, then carrying out ultrasonic treatment, and separating, washing and drying the obtained product to obtain SnO 2 Powder; 4) SnO 2 Adding the powder into a glacial acetic acid aqueous solution, then adding a certain amount of cysteine, and fully stirring to obtain a suspension; 5) transferring the suspension into a reaction kettle, naturally cooling after reaction, separating, washing and drying the product to obtain SnS 2 And (4) micro-spheres. The invention has simple synthesis process, spherical product, mesoporous structure characteristic, large specific surface area and excellent photocatalytic performance under visible light.
Description
Technical Field
The invention relates to a synthesis method of sulfide semiconductor powder, in particular to SnS 2 A method for synthesizing microspheres.
Background
Tin disulfide (SnS) 2 ) Is an important n-type semiconductor sulfide, belongs to a hexagonal system, Sn atoms of each layer are connected with S atoms tightly stacked between an upper layer and a lower layer through stronger Sn-S covalent bonds to form S-Sn-S, but S atoms between different layers are connected through weaker van der Waals force to form a sandwich structure, and crystal growth is realizedThe laminated structure is easy to form in a long process. SnS 2 The band gap width value of the composite material is 2.4-2.5eV, and the composite material has strong adsorption capacity and strong visible light absorption capacity. Thus, SnS 2 Has good visible light catalytic activity, and can be applied to the degradation of organic pollutants and Cr 6+ Reduction of (2).
The photocatalytic performance of the semiconductor catalyst is closely related to the surface area and the morphology, and the increase of the surface area can increase the number of active sites participating in photocatalytic reaction and promote the improvement of the photocatalytic performance. Compared with one-dimensional and two-dimensional structure materials, the three-dimensional structure material has larger specific surface area and more surface active sites, can shorten the migration distance of a photon-generated carrier, accelerates the separation speed of photon-generated electrons and holes, and provides a structural condition for obtaining excellent photocatalytic activity. Zai et al (Journal of Power Sources 2011,196,3650- 2 The product of the micro-spheres has excellent electrochemical performance. Wang et al (Journal of Colloid and Interface Science,2017,507,225- & lt233) synthesized a flower-like three-dimensional structure by a hydrothermal method, and the product had good adsorption performance.
Disclosure of Invention
The invention aims to provide SnS 2 The synthesis method of the micron sphere has simple process and easy operation, and the prepared SnS 2 The micro-sphere has excellent photocatalytic performance.
The technical scheme of the invention is that Zn is firstly synthesized 2 SnO 4 Nano powder of Zn synthesized 2 SnO 4 Adding the nano powder into glacial acetic acid aqueous solution, carrying out ultrasonic treatment by using an ultrasonic cleaner, and separating, washing and drying the obtained product to obtain SnO 2 Powder of SnO 2 Adding the powder into a glacial acetic acid aqueous solution, then adding a certain amount of cysteine, and obtaining SnS through hydrothermal reaction 2 And (4) micro-spheres. The technical scheme of the invention specifically comprises the following steps:
(1) weighing a certain amount of NaOH powder, adding the NaOH powder into a solvent, fully stirring the mixture until the NaOH powder is completely dissolved to prepare a NaOH solution with the concentration of 3.6mol/L, and marking the NaOH solution as a solution A for later use;
(2) weighingAdding a certain amount of tetravalent tin salt and divalent zinc salt into a solvent, fully stirring until the tetravalent tin salt and the divalent zinc salt are completely dissolved to obtain Sn 4+ With Zn 2+ The mixed solution with the concentration of 0.4mol/L and 0.8mol/L is marked as mixed solution B for standby;
(3) respectively taking 2 parts by volume of the solution A prepared in the step (1) and 1 part by volume of the mixed solution B prepared in the step (2), adding the solution A into the mixed solution B under the stirring condition, uniformly stirring, fully reacting to obtain a suspension, transferring the obtained suspension into a reaction kettle, controlling the temperature in the reaction kettle to be 190 ℃, preserving the temperature for 15-25h, and cooling to room temperature to obtain a solvothermal product;
(4) transferring the solvent thermal product prepared in the step (3) to a high-speed centrifugal separator for centrifugal separation to obtain solid precipitate, cleaning the solid precipitate, and drying at the temperature of 75-85 ℃ for 10-12h to obtain Zn 2 SnO 4 Nano powder;
(5) according to each 5-10gZn 2 SnO 4 Adding the nano powder into 100ml of glacial acetic acid aqueous solution, and weighing Zn prepared in the step (4) 2 SnO 4 Adding the nano powder into a glacial acetic acid aqueous solution, fully stirring, and performing ultrasonic treatment for 30min to obtain a suspension;
(6) transferring the suspension obtained in the step (5) into a high-speed centrifugal separator for centrifugal separation to obtain solid precipitate, cleaning the solid precipitate, and drying at 75-85 ℃ for 10-12h to obtain SnO 2 Powder;
(7) according to 5-10g SnO 2 Adding the powder into 100ml of glacial acetic acid aqueous solution, and weighing the SnO obtained in the step (6) 2 Adding the powder into a glacial acetic acid aqueous solution, and then adding a certain amount of cysteine to obtain a suspension; transferring the obtained suspension into a reaction kettle, controlling the temperature in the reaction kettle to be 150-;
(8) and (4) transferring the hydrothermal product prepared in the step (7) to a high-speed centrifugal separator for centrifugal separation to obtain a solid precipitate, cleaning the solid precipitate, and drying the cleaned solid precipitate at 65-75 ℃ for 10-12h to obtain a final product.
Furthermore, the solvent used in the step (1) and the step (2) is a mixture of deionized water and absolute ethyl alcohol, and the volume ratio of the deionized water to the absolute ethyl alcohol is 5-7: 1.
Further, in the step (2), the tetravalent tin salt is tin tetrachloride, and the divalent zinc salt is zinc acetate.
Further, in the step (3) and the step (7), the filling degree of the suspension in the reaction kettle is 80%.
Further, in the steps (4), (6) and (8), the method for cleaning the solid precipitate comprises the following steps: and alternately cleaning the solid precipitate for 3-5 times by sequentially adopting deionized water and absolute ethyl alcohol.
Further, the volume concentration of the glacial acetic acid in the steps (5) and (7) is 5-25%.
Further, the parameters of the ultrasonic cleaner used in the step (5) are as follows: the frequency is 40KHz, and the power is 500W.
Further, cysteine and SnO added in the step (7) 2 The molar ratio of the powder is 3-5: 1.
The final product prepared by the technical scheme of the invention is SnS 2 The diameter of the microsphere is 2-4 μm, and the microsphere is assembled by nano particles.
The invention has the beneficial effects that:
1. SnS (stannum sulfide) synthesized by hydrothermal-ultrasonic-ion exchange hydrothermal method 2 The reaction of the micro-spheres does not need a template, the synthesis process is simple and convenient, the operation is easy, and the purity of the product synthesized by the reaction is high.
2. SnS prepared by the method 2 The microsphere is used for carrying out a photocatalytic degradation experiment on a Methylene Blue (MB) solution under the irradiation of a fluorescent lamp, and shows excellent photocatalytic performance.
Invention SnS 2 The synthesis method of the micro-spheres has higher practicability and wide industrial utilization value.
Drawings
FIG. 1 shows SnS obtained in example 1 2 A microsphere XRD pattern;
FIG. 2 shows SnS obtained in example 1 2 SEM image of the microsphere;
FIG. 3 shows SnS obtained in example 1 2 Micro-spheres and Zn 2 SnO 4 (ii) a UV spectrum;
FIG. 4 shows SnS obtained in example 1 2 Photocatalytic results of microspheres and Zn 2 SnO 4 Comparative figures show the photocatalytic results under the same test conditions.
Detailed Description
The invention will be further described with reference to the following examples for better understanding, but the scope of the invention is not limited to the examples.
Example 1
SnS 2 The synthesis method of the microspheres comprises the following steps:
(1) weighing a certain amount of NaOH powder, adding the NaOH powder into a solvent, fully stirring the NaOH powder until the NaOH powder is completely dissolved to prepare NaOH solution with the concentration of 3.6mol/L, and marking the NaOH solution as solution A for later use; wherein the used solvent is a mixture of deionized water and absolute ethyl alcohol, and the volume ratio of the deionized water to the absolute ethyl alcohol is 5: 1;
(2) weighing a certain amount of stannic chloride and zinc acetate, adding into the solvent, fully stirring until the stannic chloride and the zinc acetate are completely dissolved to obtain Sn 4+ With Zn 2+ The mixed solution with the concentration of 0.4mol/L and 0.8mol/L is marked as mixed solution B for standby; wherein the used solvent is a mixture of deionized water and absolute ethyl alcohol, and the volume ratio of the deionized water to the absolute ethyl alcohol is 5: 1;
(3) respectively taking 2 parts of the solution A prepared in the step (1) and 1 part of the mixed solution B prepared in the step (2) according to the volume parts, adding the measured solution A into the mixed solution B at a dropping speed of 2ml/min under the stirring condition, fully reacting to obtain a suspension, transferring the obtained suspension into a reaction kettle, controlling the filling temperature of the suspension in the reaction kettle to be 80%, controlling the temperature in the reaction kettle to be 190 ℃, preserving the temperature for 17h, and then cooling to room temperature to obtain a solvothermal product;
(4) transferring the solvent thermal product prepared in the step (3) to a high-speed centrifugal separator for centrifugal separation to obtain solid precipitate, cleaning the solid precipitate, and drying at 75 ℃ for 10 hours to obtain Zn 2 SnO 4 Nano powder;
(5) weighing 5g of Zn prepared in the step (4) 2 SnO 4 Adding the nano powder into 100mL of glacial acetic acid aqueous solution, fully stirring, and performing ultrasonic treatment for 30min to obtain a suspension; wherein the volume concentration of the glacial acetic acid is 10 percent;
(6) transferring the suspension obtained in the step (5) into a high-speed centrifugal separator for centrifugal separation to obtain solid precipitate, cleaning the solid precipitate, and drying at 78 ℃ for 10 hours to obtain SnO 2 Powder;
(7) taking 5g of SnO obtained in the step (6) 2 Adding the powder into 100mL of glacial acetic acid aqueous solution, and then adding a certain amount of cysteine to obtain a suspension; transferring the obtained suspension into a reaction kettle, controlling the filling degree of the suspension in the reaction kettle to be 80%, controlling the temperature in the reaction kettle to be 155 ℃, preserving the temperature for 20 hours, and then cooling to room temperature to obtain a hydrothermal reaction product; wherein the volume concentration of the glacial acetic acid is 10 percent, and the cysteine and the SnO are 2 The molar ratio of the powder is 3: 1;
(8) and (4) transferring the hydrothermal product prepared in the step (7) to a high-speed centrifugal separator for centrifugal separation to obtain a solid precipitate, cleaning the solid precipitate, and drying the cleaned solid precipitate at 70 ℃ for 10 hours to obtain a final product.
The XRD and SEM tests of the product obtained in this example are shown in fig. 1 and 2, and it can be seen that: the synthetic product is SnS 2 Is in the shape of micron sphere, and the average grain diameter is about 2-4 μm.
For synthetic SnS 2 The UV-visible diffuse reflectance spectrum of the microspheres was analyzed, and the results are shown in FIG. 3, which shows that Zn is present in the microspheres 2 SnO 4 In contrast, SnS 2 The micro-spheres have stronger absorption in a visible light region, and are beneficial to improving the photocatalytic performance.
Carrying out photocatalytic performance test on the synthesized product, and respectively taking 0.15g of Zn 2 SnO 4 (as control) and SnS synthesized in this example 2 The microspheres (as test group) were used as photocatalyst, Methylene Blue (MB) solution was used as target degradation product, and the concentration of MB solution was 1X 10 -5 mol/L, bodyThe volume is 40ml, a 60W fluorescent tube is used as a light source, the distance between a sample and the fluorescent tube is 10cm, and a photocatalytic degradation experiment is carried out. After 60min of light irradiation, the results are shown in FIG. 4. As can be seen from the figure, Zn is used 2 SnO 4 As a photocatalyst, the concentration of MB can be degraded by 56%; by SnS 2 The concentration of MB can be degraded by 96.5% by using the micron spheres as the photocatalyst, and the result shows that the SnS prepared by the embodiment 2 The micro-spheres show excellent photocatalytic performance.
Example 2:
SnS 2 The synthesis method of the microspheres comprises the following steps:
(1) weighing a certain amount of NaOH powder, adding the NaOH powder into a solvent, fully stirring the mixture until the NaOH powder is completely dissolved to prepare a NaOH solution with the concentration of 3.6mol/L, and marking the NaOH solution as a solution A for later use; wherein the used solvent is a mixture of deionized water and absolute ethyl alcohol, and the volume ratio of the deionized water to the absolute ethyl alcohol is 6: 1;
(2) weighing a certain amount of stannic chloride and zinc acetate, adding into the solvent, fully stirring until the stannic chloride and the zinc acetate are completely dissolved to obtain Sn 4+ With Zn 2+ The mixed solution with the concentration of 0.4mol/L and 0.8mol/L is marked as mixed solution B for standby; wherein the used solvent is a mixture of deionized water and absolute ethyl alcohol, and the volume ratio of the deionized water to the absolute ethyl alcohol is 6: 1;
(3) respectively taking 2 parts of the solution A prepared in the step (1) and 1 part of the mixed solution B prepared in the step (2) according to the volume parts, adding the weighed solution A into the mixed solution B at a dropping speed of 2ml/min under the stirring condition, fully reacting to obtain a suspension, transferring the obtained suspension into a reaction kettle, controlling the filling temperature of the suspension in the reaction kettle to be 80%, keeping the temperature in the reaction kettle to be 190 ℃, and cooling to room temperature after keeping the temperature for 19 hours to obtain a solvothermal product;
(4) transferring the solvothermal product prepared in the step (3) into a high-speed centrifugal separator for centrifugal separation to obtain a solid precipitate, cleaning the solid precipitate, and drying at 80 ℃ for 12 hours to obtain Zn 2 SnO 4 Nano powder;
(5) weighing 10g of Zn prepared in the step (4) 2 SnO 4 Adding the nano powder into 100mL of glacial acetic acid aqueous solution, fully stirring, and performing ultrasonic treatment for 30min to obtain a suspension; wherein the volume concentration of the glacial acetic acid is 15 percent;
(6) transferring the suspension obtained in the step (5) into a high-speed centrifugal separator for centrifugal separation to obtain solid precipitate, cleaning the solid precipitate, and drying at 75 ℃ for 12 hours to obtain SnO 2 Powder;
(7) taking 10g of SnO obtained in the step (6) 2 Adding the powder into 100mL of glacial acetic acid aqueous solution, and then adding a certain amount of cysteine to obtain a suspension; transferring the obtained suspension into a reaction kettle, controlling the filling degree of the suspension in the reaction kettle to be 80%, controlling the temperature in the reaction kettle to be 160 ℃, preserving the heat for 18 hours, and then cooling to room temperature to obtain a hydrothermal reaction product; wherein the volume concentration of the glacial acetic acid is 15 percent, and the cysteine and the SnO are 2 The molar ratio of the powder is 3.5: 1;
(8) and (4) transferring the hydrothermal product prepared in the step (7) to a high-speed centrifugal separator for centrifugal separation to obtain a solid precipitate, cleaning the solid precipitate, and drying the cleaned solid precipitate at 65 ℃ for 10 hours to obtain a final product.
XRD and SEM tests of the product obtained in the example show that the product is SnS 2 Is in the shape of micron sphere, and the average grain diameter is about 2-4 μm.
Example 3:
SnS 2 The synthesis method of the microspheres comprises the following steps:
(1) weighing a certain amount of NaOH powder, adding the NaOH powder into a solvent, fully stirring the mixture until the NaOH powder is completely dissolved to prepare a NaOH solution with the concentration of 3.6mol/L, and marking the NaOH solution as a solution A for later use; wherein the used solvent is a mixture of deionized water and absolute ethyl alcohol, and the volume ratio of the deionized water to the absolute ethyl alcohol is 7: 1;
(2) weighing a certain amount of stannic chloride and zinc acetate, adding into the solvent, fully stirring until the stannic chloride and the zinc acetate are completely dissolved to obtain Sn 4+ With Zn 2+ The mixed solution with the concentration of 0.4mol/L and 0.8mol/L is marked as mixed solution B for standby; wherein the solvent used is deionized water and anhydrous ethyl acetateThe volume ratio of the deionized water to the absolute ethyl alcohol is 7: 1;
(3) respectively taking 2 parts of the solution A prepared in the step (1) and 1 part of the mixed solution B prepared in the step (2) according to the volume parts, adding the measured solution A into the mixed solution B at a dropping speed of 2ml/min under the stirring condition, fully reacting to obtain a suspension, transferring the obtained suspension into a reaction kettle, controlling the filling temperature of the suspension in the reaction kettle to be 80%, controlling the temperature in the reaction kettle to be 190 ℃, preserving the temperature for 20h, and then cooling to room temperature to obtain a solvothermal product;
(4) transferring the solvent thermal product prepared in the step (3) into a high-speed centrifugal separator for centrifugal separation to obtain solid precipitate, cleaning the solid precipitate, and drying at 75 ℃ for 12 hours to obtain Zn 2 SnO 4 Nano powder;
(5) weighing 5g of Zn prepared in the step (4) 2 SnO 4 Adding the nano powder into 100mL of glacial acetic acid aqueous solution, fully stirring, and performing ultrasonic treatment for 30min to obtain a suspension; wherein the volume concentration of the glacial acetic acid is 20 percent;
(6) transferring the suspension obtained in the step (5) into a high-speed centrifugal separator for centrifugal separation to obtain solid precipitate, cleaning the solid precipitate, and drying at 76 ℃ for 12 hours to obtain SnO 2 Powder;
(7) taking 5g of SnO obtained in the step (6) 2 Adding the powder into 100mL of glacial acetic acid aqueous solution, and then adding a certain amount of cysteine to obtain a suspension; transferring the obtained suspension into a reaction kettle, controlling the filling degree of the suspension in the reaction kettle to be 80%, controlling the temperature in the reaction kettle to be 160 ℃, preserving the heat for 18 hours, and then cooling to room temperature to obtain a hydrothermal reaction product; wherein the volume concentration of the glacial acetic acid is 20 percent, and the cysteine and the SnO are 2 The molar ratio of the powder is 4: 1;
(8) and (4) transferring the hydrothermal product prepared in the step (7) to a high-speed centrifugal separator for centrifugal separation to obtain a solid precipitate, cleaning the solid precipitate, and drying the cleaned solid precipitate at 68 ℃ for 11 hours to obtain a final product.
XRD and SEM measurements were carried out on the product obtained in this exampleTest shows that the product is SnS 2 Is in the shape of micron sphere, and the average grain diameter is about 2-4 μm.
Example 4:
SnS 2 The synthesis method of the microspheres comprises the following steps:
(1) weighing a certain amount of NaOH powder, adding the NaOH powder into a solvent, fully stirring the mixture until the NaOH powder is completely dissolved to prepare a NaOH solution with the concentration of 3.6mol/L, and marking the NaOH solution as a solution A for later use; wherein the used solvent is a mixture of deionized water and absolute ethyl alcohol, and the volume ratio of the deionized water to the absolute ethyl alcohol is 6: 1;
(2) weighing a certain amount of stannic chloride and zinc acetate, adding into the solvent, fully stirring until the stannic chloride and the zinc acetate are completely dissolved to obtain Sn 4+ With Zn 2+ The mixed solution with the concentration of 0.4mol/L and 0.8mol/L is marked as mixed solution B for standby; wherein the used solvent is a mixture of deionized water and absolute ethyl alcohol, and the volume ratio of the deionized water to the absolute ethyl alcohol is 6: 1;
(3) respectively taking 2 parts of the solution A prepared in the step (1) and 1 part of the mixed solution B prepared in the step (2) according to the volume parts, adding the weighed solution A into the mixed solution B at a dropping speed of 2ml/min under the stirring condition, fully reacting to obtain a suspension, transferring the obtained suspension into a reaction kettle, controlling the filling temperature of the suspension in the reaction kettle to be 80%, keeping the temperature in the reaction kettle to be 190 ℃, and cooling to room temperature after keeping the temperature for 23 hours to obtain a solvothermal product;
(4) transferring the solvothermal product prepared in the step (3) into a high-speed centrifugal separator for centrifugal separation to obtain solid precipitate, cleaning the solid precipitate, and drying at 76 ℃ for 12 hours to obtain Zn 2 SnO 4 Nano powder;
(5) weighing 8g of Zn prepared in the step (4) 2 SnO 4 Adding the nano powder into 100mL of glacial acetic acid aqueous solution, fully stirring, and performing ultrasonic treatment for 30min to obtain a suspension; wherein the volume concentration of the glacial acetic acid is 12.5%;
(6) transferring the suspension obtained in the step (5) to a high-speed centrifugal separator for centrifugal separation to obtain a solid precipitate, cleaning the solid precipitate, and then carrying outDrying at 76 deg.C for 12h to obtain SnO 2 Powder;
(7) taking 8g of SnO obtained in the step (6) 2 Adding the powder into 100mL of glacial acetic acid aqueous solution, and then adding a certain amount of cysteine to obtain a suspension; transferring the obtained suspension into a reaction kettle, controlling the filling degree of the suspension in the reaction kettle to be 80%, controlling the temperature in the reaction kettle to be 168 ℃, preserving the heat for 15 hours, and then cooling to room temperature to obtain a hydrothermal reaction product; wherein the volume concentration of the glacial acetic acid is 12.5 percent, and the cysteine and the SnO are 2 The molar ratio of the powder is 5: 1;
(8) and (4) transferring the hydrothermal product prepared in the step (7) to a high-speed centrifugal separator for centrifugal separation to obtain a solid precipitate, cleaning the solid precipitate, and drying the cleaned solid precipitate at 72 ℃ for 10 hours to obtain a final product.
XRD and SEM tests of the product obtained in the example show that the product is SnS 2 Is in the shape of micron sphere, and the average grain diameter is about 2-4 μm.
Example 5:
SnS 2 The synthesis method of the microspheres comprises the following steps:
(1) weighing a certain amount of NaOH powder, adding the NaOH powder into a solvent, fully stirring the NaOH powder until the NaOH powder is completely dissolved to prepare NaOH solution with the concentration of 3.6mol/L, and marking the NaOH solution as solution A for later use; wherein the used solvent is a mixture of deionized water and absolute ethyl alcohol, and the volume ratio of the deionized water to the absolute ethyl alcohol is 5: 1;
(2) weighing a certain amount of stannic chloride and zinc acetate, adding into the solvent, fully stirring until the stannic chloride and the zinc acetate are completely dissolved to obtain Sn 4+ With Zn 2+ The mixed solution with the concentration of 0.4mol/L and 0.8mol/L is marked as mixed solution B for standby; wherein the used solvent is a mixture of deionized water and absolute ethyl alcohol, and the volume ratio of the deionized water to the absolute ethyl alcohol is 5: 1;
(3) respectively taking 2 parts of the solution A prepared in the step (1) and 1 part of the mixed solution B prepared in the step (2) according to the volume parts, adding the measured solution A into the mixed solution B at a dropping speed of 2ml/min under the stirring condition, fully reacting to obtain a suspension, transferring the obtained suspension into a reaction kettle, controlling the filling temperature of the suspension in the reaction kettle to be 80%, controlling the temperature in the reaction kettle to be 190 ℃, preserving the temperature for 25h, and then cooling to room temperature to obtain a solvothermal product;
(4) transferring the solvent thermal product prepared in the step (3) into a high-speed centrifugal separator for centrifugal separation to obtain solid precipitate, cleaning the solid precipitate, and drying at 80 ℃ for 11h to obtain Zn 2 SnO 4 Nano powder;
(5) weighing 7.5g of Zn prepared in the step (4) 2 SnO 4 Adding the nano powder into 100mL of glacial acetic acid aqueous solution, fully stirring, and performing ultrasonic treatment for 30min to obtain a suspension; wherein the volume concentration of the glacial acetic acid is 8.5%;
(6) transferring the suspension obtained in the step (5) into a high-speed centrifugal separator for centrifugal separation to obtain solid precipitate, cleaning the solid precipitate, and drying at 76 ℃ for 12 hours to obtain SnO 2 Powder;
(7) taking 8g of SnO obtained in the step (6) 2 Adding the powder into 100mL of glacial acetic acid aqueous solution, and then adding a certain amount of cysteine to obtain a suspension; transferring the obtained suspension into a reaction kettle, controlling the filling degree of the suspension in the reaction kettle to be 80%, controlling the temperature in the reaction kettle to be 163 ℃, preserving the heat for 20 hours, and then cooling to room temperature to obtain a hydrothermal reaction product; wherein the volume concentration of the glacial acetic acid is 8.5 percent, and the cysteine and the SnO are 2 The molar ratio of the powder is 4.5: 1;
(8) and (4) transferring the hydrothermal product prepared in the step (7) to a high-speed centrifugal separator for centrifugal separation to obtain a solid precipitate, cleaning the solid precipitate, and drying the cleaned solid precipitate at 75 ℃ for 10 hours to obtain a final product.
XRD and SEM tests of the product obtained in the embodiment show that the product is SnS 2 Is in the shape of micron sphere, and the average grain diameter is about 2-4 μm.
Although the present invention has been described with reference to a preferred embodiment, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (5)
1. SnS 2 The synthesis method of the microspheres is characterized by comprising the following steps:
(1) weighing NaOH powder, adding the NaOH powder into a solvent, fully stirring the mixture until the NaOH powder is completely dissolved to prepare a NaOH solution with the concentration of 3.6mol/L, and marking the NaOH solution as a solution A for later use; in the step, the solvent is a mixture of deionized water and absolute ethyl alcohol, and the volume ratio of the deionized water to the absolute ethyl alcohol is 5-7: 1;
(2) weighing tetravalent tin salt and divalent zinc salt, adding into solvent, fully stirring to dissolve completely to obtain Sn 4+ With Zn 2+ The mixed solution with the concentration of 0.4mol/L and 0.8mol/L is marked as mixed solution B for standby; in the step, the solvent is a mixture of deionized water and absolute ethyl alcohol, and the volume ratio of the deionized water to the absolute ethyl alcohol is 5-7: 1;
(3) respectively taking 2 parts of the solution A prepared in the step (1) and 1 part of the mixed solution B prepared in the step (2) according to the volume parts, adding the solution A into the mixed solution B, uniformly stirring, fully reacting to obtain a suspension, transferring the obtained suspension into a reaction kettle, controlling the temperature in the reaction kettle to be 190 ℃, preserving the temperature for 15-25h, and then cooling to room temperature to obtain a solvothermal product;
(4) transferring the solvent thermal product prepared in the step (3) to a high-speed centrifugal separator for centrifugal separation to obtain solid precipitate, cleaning the solid precipitate, and drying at the temperature of 75-85 ℃ for 10-12h to obtain Zn 2 SnO 4 Nano powder;
(5) according to 5-10g of Zn per unit 2 SnO 4 Adding the nano powder into 100mL of glacial acetic acid aqueous solution, and weighing Zn prepared in the step (4) 2 SnO 4 Adding the nano powder into a glacial acetic acid aqueous solution, fully stirring, and performing ultrasonic treatment for 30min to obtain a suspension;
(6) transferring the suspension obtained in the step (5) into a high-speed centrifugal separator for centrifugal separation to obtain solid precipitate, cleaning the solid precipitate, and drying at 75-85 ℃ for 10-12h to obtain SnO 2 Powder;
(7) according to 5-10g SnO 2 Adding 100mL of glacial acetic acid aqueous solution into the powder, and weighing the SnO obtained in the step (6) 2 Adding the powder into a glacial acetic acid aqueous solution, and then adding cysteine, cysteine and SnO 2 The mol ratio of the powder is 3-5:1, and suspension is obtained; transferring the obtained suspension into a reaction kettle, controlling the temperature in the reaction kettle to be 150-;
(8) and (4) transferring the hydrothermal product prepared in the step (7) to a high-speed centrifugal separator for centrifugal separation to obtain a solid precipitate, cleaning the solid precipitate, and drying the cleaned solid precipitate at 65-75 ℃ for 10-12h to obtain a final product.
2. The SnS of claim 1 2 The synthesis method of the microspheres is characterized in that the tetravalent tin salt in the step (2) is stannic chloride, and the divalent zinc salt is zinc acetate.
3. The SnS of claim 1 2 The synthesis method of the microspheres is characterized in that in the step (3) and the step (7), the filling degree of suspension in the reaction kettle is 80%.
4. The SnS of claim 1 2 The synthesis method of the microspheres is characterized in that in the steps (4), (6) and (8), the cleaning method of the solid precipitate comprises the following steps: and alternately cleaning the solid precipitate for 3-5 times by sequentially adopting deionized water and absolute ethyl alcohol.
5. The SnS of claim 1 2 The synthesis method of the microspheres is characterized in that the volume concentration of the glacial acetic acid in the steps (5) and (7) is 5-25%.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101523168A (en) * | 2006-10-02 | 2009-09-02 | 新加坡纳米材料科技公司 | Process for making nano-sized and micro-sized precipitate particles |
| CN104310463A (en) * | 2014-10-08 | 2015-01-28 | 吉林大学 | Preparation method of tin dioxide of hollow cube structure |
| CN104891557A (en) * | 2015-05-29 | 2015-09-09 | 吉林大学 | Tin dioxide nanoflower with hollow structure and preparation method of tin dioxide nanoflower |
| CN105366714A (en) * | 2015-12-11 | 2016-03-02 | 暨南大学 | Synthetic method of stannic oxide nanoflower array |
| CN106512978A (en) * | 2016-11-29 | 2017-03-22 | 洛阳理工学院 | Method for preparing visible-light response photocatalyst by utilizing nano Zn2SnO4 |
| CN106629824A (en) * | 2016-12-26 | 2017-05-10 | 吉林大学 | Preparation method for hierarchical hollow cubic stannic oxide nanometer particle |
| CN110887871A (en) * | 2019-11-27 | 2020-03-17 | 哈尔滨师范大学 | Oxygen-enriched defect zinc stannate material, synthesis method thereof and hydrogen sulfide early warning sensor |
| CN111285397A (en) * | 2020-03-09 | 2020-06-16 | 西安工业大学 | Method for hydro-thermal synthesis of ultrathin hexagonal tin disulfide nanosheets |
-
2020
- 2020-07-20 CN CN202010697081.0A patent/CN111777095B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101523168A (en) * | 2006-10-02 | 2009-09-02 | 新加坡纳米材料科技公司 | Process for making nano-sized and micro-sized precipitate particles |
| CN104310463A (en) * | 2014-10-08 | 2015-01-28 | 吉林大学 | Preparation method of tin dioxide of hollow cube structure |
| CN104891557A (en) * | 2015-05-29 | 2015-09-09 | 吉林大学 | Tin dioxide nanoflower with hollow structure and preparation method of tin dioxide nanoflower |
| CN105366714A (en) * | 2015-12-11 | 2016-03-02 | 暨南大学 | Synthetic method of stannic oxide nanoflower array |
| CN106512978A (en) * | 2016-11-29 | 2017-03-22 | 洛阳理工学院 | Method for preparing visible-light response photocatalyst by utilizing nano Zn2SnO4 |
| CN106629824A (en) * | 2016-12-26 | 2017-05-10 | 吉林大学 | Preparation method for hierarchical hollow cubic stannic oxide nanometer particle |
| CN110887871A (en) * | 2019-11-27 | 2020-03-17 | 哈尔滨师范大学 | Oxygen-enriched defect zinc stannate material, synthesis method thereof and hydrogen sulfide early warning sensor |
| CN111285397A (en) * | 2020-03-09 | 2020-06-16 | 西安工业大学 | Method for hydro-thermal synthesis of ultrathin hexagonal tin disulfide nanosheets |
Non-Patent Citations (1)
| Title |
|---|
| "SnS2和SnS2/SnO2纳米粉的合成与光催化性质";杜珍妮;《中国优秀博硕士学位论文全文数据库(硕士) 工程科技Ⅰ辑》;20130415(第04期);46-59 * |
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