CN111777095A - Synthesis method of tin disulfide microspheres - Google Patents
Synthesis method of tin disulfide microspheres Download PDFInfo
- Publication number
- CN111777095A CN111777095A CN202010697081.0A CN202010697081A CN111777095A CN 111777095 A CN111777095 A CN 111777095A CN 202010697081 A CN202010697081 A CN 202010697081A CN 111777095 A CN111777095 A CN 111777095A
- Authority
- CN
- China
- Prior art keywords
- powder
- sno
- solution
- suspension
- solid precipitate
- 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.)
- Granted
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G19/00—Compounds of tin
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/84—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by UV- or VIS- data
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/50—Agglomerated particles
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Abstract
The invention relates to a SnS2The 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 SnCl4、Zn(OAc)2Mixing the solution, stirring, transferring into a reaction kettle for reaction, separating, washing and drying the obtained reactant to obtain Zn2SnO4Nano powder; 3) zn is added2SnO4Adding 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 SnO2Powder; 4) SnO2Adding 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 SnS2And (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 SnS2A method for synthesizing microspheres.
Background
Tin disulfide (SnS)2) The sulfide 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 of different layers are connected through weaker van der Waals force to form a sandwich structure, and a layered structure is easily formed in the crystal growth process. SnS2The 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, SnS2Has good visible light catalytic activity, can be applied to the degradation of organic pollutants and Cr6+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 2011,196,3650-2The product of the micron sphere 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 SnS2The synthesis method of the micron sphere has simple process and easy operation, and the prepared SnS2The micro-sphere has excellent photocatalytic performance.
The technical scheme of the invention is to synthesize Zn firstly2SnO4Nano powder of Zn synthesized2SnO4Adding the nano powder into a glacial acetic acid aqueous solution, carrying out ultrasonic treatment by using an ultrasonic cleaner, and separating, washing and drying the obtained product to obtain SnO2Powder ofSnO2Adding the powder into a glacial acetic acid aqueous solution, then adding a certain amount of cysteine, and obtaining SnS through hydrothermal reaction2And (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) weighing a certain amount of tetravalent tin salt and divalent zinc salt, adding the tetravalent tin salt and the divalent zinc salt into a solvent, fully stirring the mixture until the tetravalent tin salt and the divalent zinc salt are completely dissolved to obtain Sn4+With Zn2+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 Zn2SnO4Nano powder;
(5) according to each 5-10gZn2SnO4Adding the nano powder into 100ml of glacial acetic acid aqueous solution, and weighing Zn prepared in the step (4)2SnO4Adding 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 SnO2Powder;
(7) according to 5-10g SnO2Adding the powder into 100ml of glacial acetic acid aqueous solution, and weighing the SnO obtained in the step (6)2Adding the powder into glacial acetic acid water solution, and adding a certain amount of halfCystine to obtain 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.
Further, 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, the tetravalent tin salt in the step (2) 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)2The molar ratio of the powder is 3-5: 1.
The final product prepared by the technical scheme of the invention is SnS2The 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 method2The 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 method2The micro-spheres are subjected to a photocatalytic degradation experiment on Methylene Blue (MB) solution under the irradiation of a fluorescent lamp, and show excellent lightCatalytic performance.
Invention SnS2The synthesis method of the micro-spheres has higher practicability and wide industrial utilization value.
Drawings
FIG. 1 shows SnS obtained in example 12A microsphere XRD pattern;
FIG. 2 shows SnS obtained in example 12SEM image of the microsphere;
FIG. 3 shows SnS obtained in example 12Micro-spheres and Zn2SnO4(ii) a UV spectrum;
FIG. 4 shows SnS obtained in example 12Photocatalytic results of microspheres and Zn2SnO4Comparative 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
SnS2The 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 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 Sn4+With Zn2+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 Zn2SnO4Nano powder;
(5) weighing 5g of Zn prepared in the step (4)2SnO4Adding 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 SnO2Powder;
(7) taking 5g of SnO obtained in the step (6)2Adding 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 SnO2The 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 SnS2Is in the shape of micron sphere, and the average grain diameter is about 2-4 μm.
For synthetic SnS2The 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 microspheres2SnO4Compared with SnS2The 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 Zn2SnO4(as control) and SnS synthesized in this example2The microspheres (as a test group) were used as a photocatalyst, Methylene Blue (MB) solution was used as a target degradation product, and the concentration of the MB solution was 1 × 10-5And (3) performing a photocatalytic degradation experiment by using a 60W fluorescent tube as a light source and a sample at a distance of 10cm from the tube, wherein the mol/L is 40ml in volume. After 60min of light irradiation, the results are shown in FIG. 4. As can be seen from the figure, Zn is used2SnO4As a photocatalyst, the concentration of MB can be degraded by 56%; by SnS2The 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 embodiment2The microspheres show excellent photocatalytic performance.
Example 2:
SnS2The 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 Sn4+With Zn2+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 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 19 hours, and then cooling to room temperature 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 Zn2SnO4Nano powder;
(5) weighing 10g of Zn prepared in the step (4)2SnO4Adding 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 SnO2Powder;
(7) taking 10g of SnO obtained in the step (6)2Adding 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 are2The 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 SnS2Is in the shape of micron sphere, and the average grain diameter is about 2-4 μm.
Example 3:
SnS2The 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 Sn4+With Zn2+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 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) to a high-speed centrifugal separator for centrifugal separation to obtain solid precipitate, cleaning the solid precipitate, and drying at 75 ℃ for 12h to obtain Zn2SnO4Nano powder;
(5) weighing 5g of Zn prepared in the step (4)2SnO4Adding 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 SnO2Powder;
(7) taking 5g of SnO obtained in the step (6)2Adding 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 ice vinegarThe volume concentration of acid is 20 percent, and cysteine and SnO2The 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 tests of the product obtained in the example show that the product is SnS2Is in the shape of micron sphere, and the average grain diameter is about 2-4 μm.
Example 4:
SnS2The 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 Sn4+With Zn2+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 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 23h, and then cooling to room temperature 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 Zn2SnO4Nano powder;
(5) weighing 8g of Zn prepared in the step (4)2SnO4Adding 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) 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 SnO2Powder;
(7) taking 8g of SnO obtained in the step (6)2Adding 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 are2The 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 SnS2Is in the shape of micron sphere, and the average grain diameter is about 2-4 μm.
Example 5:
SnS2The 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 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 Sn4+With Zn2+Mixing the solution at concentrations of 0.4mol/L and 0.8mol/L respectivelyThe solution 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 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 11 hours to obtain Zn2SnO4Nano powder;
(5) weighing 7.5g of Zn prepared in the step (4)2SnO4Adding 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 SnO2Powder;
(7) taking 8g of SnO obtained in the step (6)2Adding 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 are2The 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 example show that the product is SnS2Is 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 (7)
1. SnS2The synthesis method of the microspheres is characterized by comprising 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) weighing a certain amount of tetravalent tin salt and divalent zinc salt, adding the tetravalent tin salt and the divalent zinc salt into a solvent, fully stirring the mixture until the tetravalent tin salt and the divalent zinc salt are completely dissolved to obtain Sn4+With Zn2+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 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 Zn2SnO4Nano powder；
(5) According to 5-10g of Zn per unit2SnO4Adding the nano powder into 100ml of glacial acetic acid aqueous solution, and weighing Zn prepared in the step (4)2SnO4Adding 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 SnO2Powder;
(7) according to 5-10g SnO2Adding 100ml of glacial acetic acid aqueous solution into the powder, and weighing the SnO obtained in the step (6)2Adding 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.
2. The SnS of claim 12The synthesis method of the microspheres is characterized in that the solvents used in the steps (1) and (2) are 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. The SnS of claim 12The 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.
4. The SnS of claim 12The 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%.
5. The SnS of claim 12The synthesis method of the micro-spheres 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.
6. The SnS of claim 12The 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%.
7. The SnS of claim 12The synthesis method of the microspheres is characterized in that cysteine and SnO added in the step (7)2The molar ratio of the powder is 3-5: 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010697081.0A CN111777095B (en) | 2020-07-20 | 2020-07-20 | Synthesis method of tin disulfide microspheres |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010697081.0A CN111777095B (en) | 2020-07-20 | 2020-07-20 | Synthesis method of tin disulfide microspheres |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111777095A true CN111777095A (en) | 2020-10-16 |
| CN111777095B CN111777095B (en) | 2022-09-09 |
Family
ID=72764564
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010697081.0A Active CN111777095B (en) | 2020-07-20 | 2020-07-20 | Synthesis method of tin disulfide microspheres |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111777095B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114653382A (en) * | 2022-03-25 | 2022-06-24 | 桂林电子科技大学 | P-n type stannous sulfide-zinc stannate semiconductor material and preparation method and application thereof |
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 (9)
| 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 |
| US20100028236A1 (en) * | 2006-10-02 | 2010-02-04 | Nanomaterials Technology Pte Ltd | 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 |
|---|
| 杜珍妮: ""SnS2和SnS2/SnO2纳米粉的合成与光催化性质"", 《中国优秀博硕士学位论文全文数据库(硕士) 工程科技Ⅰ辑》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114653382A (en) * | 2022-03-25 | 2022-06-24 | 桂林电子科技大学 | P-n type stannous sulfide-zinc stannate semiconductor material and preparation method and application thereof |
| CN114653382B (en) * | 2022-03-25 | 2023-07-04 | 桂林电子科技大学 | P-n type stannous sulfide-zinc stannate semiconductor material and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111777095B (en) | 2022-09-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Wang et al. | Enhancing photocatalytic activity of titania materials by using porous structures and the addition of gold nanoparticles | |
| CN104069844B (en) | Grading three-dimensional porous graphene/titanium dioxide photocatalyst and preparation method thereof | |
| CN108126756B (en) | Bismuth tungstate-MIL-53 (Al) composite material, and preparation method and application thereof | |
| Zhao et al. | Visible light driven photocatalytic hydrogen evolution over CdS incorporated mesoporous silica derived from MCM-48 | |
| CN106040216A (en) | Double-layer ZnO hollow sphere photocatalytic material and preparation method thereof | |
| CN112958061B (en) | Oxygen vacancy promoted direct Z mechanism mesoporous Cu2O/TiO2Photocatalyst and preparation method thereof | |
| CN109331845A (en) | A kind of synthesis and application of high dispersive BiOCl/ diatomite photochemical catalyst | |
| CN112058252A (en) | Hollow core-shell structure ZnO/In2O3Heterogeneous II type photocatalytic material and preparation method thereof | |
| CN110102322A (en) | The preparation method of flower-shaped Ag@AgBr/ZnO catalysis material | |
| CN103007912A (en) | One-dimensional nanometer titania photocatalyst with mica serving as support and preparation method thereof | |
| CN111777095B (en) | Synthesis method of tin disulfide microspheres | |
| Hu et al. | gC 3 N 4/TiO 2 composite microspheres: in situ growth and high visible light catalytic activity | |
| CN114522709B (en) | Three-dimensional porous graphite phase carbon nitride/bismuth oxyiodide/silver nanoparticle composite photocatalyst and preparation method and application thereof | |
| CN106378158A (en) | Preparation method of bismuth sulfide/titanium dioxide/graphene compound with high-catalysis degradation activity under visible light | |
| CN109225217A (en) | A kind of carbonate plant blade ZnO/Au hetero-junctions multilevel structure assembling body catalyst and preparation method thereof | |
| CN108579775B (en) | Silver phosphate/silver/titanium dioxide nanoflower composite material and preparation method and application thereof | |
| CN111054419B (en) | For CO 2 Reduced semiconductor/g-C 3 N 4 Photocatalyst and preparation method thereof | |
| CN111715211B (en) | Active carbon loaded TiO 2 /Bi 2 WO 6 Preparation method of heterojunction composite material | |
| Moniruddin et al. | Nanoassembly of perovskite-based photocatalysts in a nanoconfined system for photocatalytic H2 production under visible light | |
| CN107008337B (en) | Non-stoichiometric copper bismuthate nano material and preparation method and application thereof | |
| CN109999859B (en) | Preparation method of microspherical ZnO-BiOI composite material | |
| CN108940368B (en) | Zeolite-like framework encapsulated metal nanoparticle catalyst and preparation method and application thereof | |
| CN106391008A (en) | Method for loading three-dimensional zinc oxide surface with metal nanoparticles | |
| Yang et al. | Synthesis and photocatalysis of Al doped CdS templated by non-surfactant hypocrellins | |
| CN114904521B (en) | Au/Bi 2 WO 6 Mineral ternary composite material, preparation method and application thereof |
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 |