阅读说明：本技术 一种花状CuS亚微米球及其离子液体微乳液热合成方法 (Flower-shaped CuS submicron sphere and thermal synthesis method of ionic liquid microemulsion thereof ) 是由 陈砺 李俞俊杰 严宗诚 于 2019-07-18 设计创作，主要内容包括：本发明公开了一种花状CuS亚微米球及其离子液体微乳液热合成方法。该合成方法主要包括以下步骤：(1)将硫源加入离子液体中,加热搅拌溶解,得混合物A；(2)将二价铜盐与表面活性剂、助表面活性剂及植物油混合搅拌均匀,得混合物B；(3)将混合物A和混合物B混合搅拌均匀得到微乳液C；(4)将微乳液C转移至聚四氟乙烯内衬的水热反应釜中,密闭后置于60~160℃下反应2~24h,室温自然冷却,得黑色溶液；(5)将黑色溶液经分离、洗涤、干燥后,得最终产物黑色粉末。本发明采用离子液体微乳液辅助热合成制得的CuS粒子为花状亚微米球结构、比表面积大、形貌规整、尺寸均一、结晶度高、光催化效率高且稳定。(The invention discloses a flower-shaped CuS submicron sphere and a thermal synthesis method of ionic liquid microemulsion thereof, wherein the synthesis method mainly comprises the following steps of (1) adding a sulfur source into ionic liquid, heating and stirring for dissolving to obtain a mixture A, (2) mixing and stirring divalent copper salt, a surfactant, a cosurfactant and vegetable oil uniformly to obtain a mixture B, (3) mixing and stirring the mixture A and the mixture B uniformly to obtain a microemulsion C, (4) transferring the microemulsion C into a hydrothermal reaction kettle with a polytetrafluoroethylene lining, sealing, placing the hydrothermal reaction kettle at 60 ~ 160 ℃ for 2 ~ 24 hours, naturally cooling at room temperature to obtain a black solution, and (5) separating, washing and drying the black solution to obtain a final product, namely black powder.)

1. A thermal synthesis method of ionic liquid microemulsion of flower-shaped CuS submicron spheres is characterized by comprising the following steps:

(1) Weighing the following raw materials in percentage by weight:

cupric salt 0.156% ~ 2.141%

sulfur source 0.234% ~ 2.293%

8.636% of ionic liquid ~ 32.092%

vegetable oil 0.478% ~ 1.913%

Surfactant 15 ~ 60%

8% of cosurfactant ~ 15%;

(2) adding a sulfur source into the ionic liquid under the condition of stirring, heating, stirring and dissolving to obtain a mixture A;

(3) Under the condition of stirring, mixing and stirring the cupric salt, the surfactant, the cosurfactant and the vegetable oil uniformly to obtain a mixture B;

(4) Under the condition of stirring, uniformly mixing and stirring the mixture A and the mixture B to obtain a microemulsion C;

(5) Transferring the microemulsion C into a hydrothermal reaction kettle with a polytetrafluoroethylene lining, sealing, placing the kettle at the constant temperature of 60 ~ 160 ℃ and normal pressure for reaction for 2 ~ 24h, and naturally cooling at room temperature to obtain a black solution;

(6) And separating, washing and drying the black solution to obtain a black powder product flower-shaped CuS submicron sphere.

2. The method of claim 1, wherein: the cupric salt in the step (1) is one or more of cupric nitrate, cupric chloride and cupric naphthenate.

3. The method of claim 1, wherein: the sulfur source in the step (1) is one or more of thiourea and thioacetamide.

4. the method of claim 1, wherein: the ionic liquid in the step (1) is 1-butyl-3-methylimidazolium tetrafluoroborate ionic liquid.

5. The method of claim 1, wherein: the vegetable oil in the step (1) is one or more of castor oil, epoxidized soybean oil and soybean oil.

6. The method of claim 1, wherein: the surfactant in the step (1) is one or more of octyl phenyl polyoxyethylene ether, 1-octyl-3-methylimidazole chloride ionic liquid and hexadecyl trimethyl ammonium bromide.

7. the method of claim 1, wherein: the cosurfactant in the step (1) is one or more of n-butyl alcohol, isobutyl alcohol and n-propyl alcohol.

8. the method of claim 1, wherein:

the stirring condition in the step (2) is that the stirring is carried out for 5 ~ 10 minutes at the temperature of 30 ~ 50 ℃ and 300 ~ 1200 rpm;

The stirring condition in the step (3) is that the stirring is carried out for 5 ~ 10 minutes at the temperature of 20 ~ 60 ℃ and at the speed of 300 ~ 1200 rpm;

the stirring condition in the step (4) is that the stirring is carried out for 60 ~ 120 minutes at the temperature of 20 ~ 60 ℃ and at the speed of 300 ~ 1200 rpm.

9. The method of claim 1, wherein:

The separation in the step (6) is centrifugal separation, the centrifugal speed is 10000 r/min, and the centrifugal time is 10 ~ 30 min;

The washing in the step (6) refers to washing with water and absolute ethyl alcohol;

The drying in the step (6) refers to oven drying at 60 ~ 90 ℃ for 12 ~ 48 h.

10. The flower-like CuS submicron spheres obtained by the method of claim 1 ~ 9, wherein the crystal structure of the flower-like CuS submicron spheres is pure hexagonal phase.

Technical Field

the invention relates to the field of preparation of CuS submicron spheres, in particular to a flower-shaped CuS submicron sphere and a thermal synthesis method of ionic liquid microemulsion thereof.

background

With the rapid development of industrial technologies, the treatment of industrial wastewater is a focus problem in the current environmental protection field, wherein organic matters occupy a large proportion in the industrial wastewater, how to radically realize the thorough degradation of the organic matters is widely concerned at home and abroad, and the photocatalysis technology is widely applied in numerous fields of organic matter degradation, heavy metal degradation, hydrogen production by hydrolysis and the like due to the characteristics of high efficiency, energy saving and environmental protection, so the photocatalysis technology is one of important means for solving the industrial wastewater, and the synthesis of a photocatalyst with simple process, environmental protection, high efficiency and stability becomes a current research hotspot.

copper sulfide is a good semiconductor photocatalyst, and the forbidden band width of the copper sulfide is 1.2 ~ 2.0.0 2.0 eV., and is widely applied to the field of photocatalysis due to unique photoelectric effect and catalytic capability.

The traditional preparation method of copper sulfide materials mainly comprises a water/solvent thermal method, a template method, a microwave method and the like. The copper sulfide material synthesized by adopting the water/solvothermal method and the microwave method has controllable shape and high crystallinity, but has the problems of uneven particle size distribution, easy agglomeration and the like. The copper sulfide material synthesized by the template method has uniform size, is not easy to agglomerate, but the appearance is not controlled, and a large amount of organic solvent is used in the preparation process, so that the environment is easily polluted.

the ionic liquid microemulsion method is characterized in that ionic liquid is used for replacing a polar phase or a non-polar phase in the traditional microemulsion to form the microemulsion, nanoparticles are obtained through the processes of nucleation, growth and the like in the ionic liquid serving as a liquid drop kernel or an oil kernel, and the ionic liquid has the advantages of high solubilizing capacity, low viscosity, recoverability and the like, is used as a novel green solvent, can reduce the use of volatile organic solvents, and can accurately control the particle size of a synthetic material. Compared with the traditional aliphatic hydrocarbon, the vegetable oil adopted as the oil phase of the microemulsion system has the advantages of strong solubilizing capability, high phase forming speed, small interfacial tension and the like, and simultaneously has the characteristics of rich resources, biodegradability, environmental friendliness and the like as a renewable energy source. Therefore, the preparation of inorganic nano-materials by taking the ionic liquid microemulsion as a 'microreactor' is a current research hotspot. The method adopts an ionic liquid microemulsion method as a reaction system, and adopts a hydrothermal method to assist in controlling the morphology of the material, so that the flower-shaped CuS submicron spheres with large specific surface area, regular morphology, uniform size, high crystallinity, high photocatalytic efficiency and stability are synthesized from the ionic liquid microemulsion.

disclosure of Invention

in order to overcome the defects of the prior art, the invention aims to provide a flower-shaped CuS submicron sphere and a thermal synthesis method of ionic liquid microemulsion thereof. The invention adopts the ionic liquid microemulsion as a reaction system to accurately control the particle size of the CuS material, reduces the use of organic solvents in the traditional synthetic method, and improves the crystallinity of the CuS material by controlling the morphology of the material in an auxiliary way through a hydrothermal method. The product is a flower-shaped CuS submicron sphere which has large specific surface area, regular appearance, uniform size, high crystallinity and high and stable photocatalytic efficiency.

The invention also aims to provide a flower-shaped CuS submicron sphere photocatalyst with catalytic activity, which is obtained by the preparation method.

The object of the present invention is achieved by the following means.

A thermal synthesis method of ionic liquid microemulsion of flower-shaped CuS submicron spheres comprises the following steps:

(1) Weighing the following raw materials in percentage by weight:

cupric salt 0.156% ~ 2.141%

Sulfur source 0.234% ~ 2.293%

8.636% of ionic liquid ~ 32.092%

Vegetable oil 0.478% ~ 1.913%

Surfactant 15 ~ 60%

8% of cosurfactant ~ 15%;

(2) Adding a sulfur source into the ionic liquid under the condition of stirring, heating, stirring and dissolving to obtain a mixture A;

(3) Under the condition of stirring, mixing and stirring the cupric salt, the surfactant, the cosurfactant and the vegetable oil uniformly to obtain a mixture B;

(4) Under the condition of stirring, uniformly mixing and stirring the mixture A and the mixture B to obtain a microemulsion C;

(5) Transferring the microemulsion C into a hydrothermal reaction kettle with a polytetrafluoroethylene lining, sealing, placing the kettle at the constant temperature of 60 ~ 160 ℃ and normal pressure for reaction for 2 ~ 24h, and naturally cooling at room temperature to obtain a black solution;

(6) And separating, washing and drying the black solution to obtain a black powder product flower-shaped CuS submicron sphere.

Preferably, the cupric salt in step (1) is one or more of cupric nitrate, cupric chloride and cupric naphthenate.

Preferably, the sulfur source in step (1) is one or more of thiourea and thioacetamide.

Preferably, the ionic liquid in the step (1) is 1-butyl-3-methylimidazolium tetrafluoroborate ionic liquid.

preferably, the vegetable oil in step (1) refers to one or more of soybean oil, epoxidized soybean oil and castor oil.

preferably, the surfactant in the step (1) is one or more of octyl phenyl polyoxyethylene ether, 1-octyl-3-methylimidazole chloride ionic liquid and hexadecyl trimethyl ammonium bromide.

Preferably, the cosurfactant in step (1) is one or more of n-butanol, isobutanol and n-propanol.

preferably, the stirring conditions in step (2) are 30 ~ 50 ℃ and 300 ~ 1200 rpm/min for 5 ~ 10 minutes, the stirring conditions in step (3) are 20 ~ 60 ℃ and 300 ~ 1200 rpm/min for 5 ~ 10 minutes, and the stirring conditions in step (4) are 20 ~ 60 ℃ and 300 ~ 1200 rpm/min for 60 ~ 120 minutes.

Preferably, the separation in step (6) is centrifugal separation with a centrifugal speed of 10000 rpm and a centrifugal time of 10 ~ 30 minutes, the washing in step (6) is washing with water and absolute ethyl alcohol, and the drying in step (6) is oven drying at 60 ~ 90 ℃ for 12 ~ 48 hours.

The flower-shaped CuS submicron spheres obtained by the method have the crystal structures of pure hexagonal crystal phases.

Compared with the prior art, the invention has the following advantages and beneficial effects:

(1) The invention adopts the ionic liquid microemulsion as a reaction system, adopts the vegetable oil as the oil phase of the microemulsion, accords with the concept of environmental protection, and can accurately control the particle size of the synthetic material.

(2) The invention adopts a hydrothermal auxiliary microemulsion method to ensure that unstable and loose nano particles synthesized in the ionic liquid microemulsion carry out secondary growth of crystal grains, the product appearance is regular, and the crystallinity is high.

(3) The flower-shaped CuS submicron sphere material prepared by the method has the advantages of large specific surface area, regular appearance, uniform size, high crystallinity and high and stable photocatalytic efficiency.

Drawings

FIG. 1 is an X-ray diffraction pattern of flower-like CuS submicron sphere material prepared in example 3 of this invention.

FIGS. 2a and 2b are SEM images of flower-like CuS submicron spheres prepared in example 3 of the present invention.

FIG. 3 is a UV-VISIBLE Diffuse reflectance spectrum of a flower-like CuS submicron sphere material prepared in example 3 of the present invention.

FIG. 4 is a graph showing the relationship between (. alpha.hv) ² and h v of the flower-like CuS submicron sphere material prepared in example 3 of the present invention.

FIG. 5 is a UV-Vis spectrum of a flower-like CuS submicron sphere material prepared in example 3 of the present invention catalyzing the degradation of methylene blue.

FIG. 6 is a graph showing the relationship between the degradation rate of methylene blue catalyzed and degraded by the flower-like CuS submicron sphere material prepared in example 3 of the present invention and time.

FIG. 7 is a graph showing the relationship between the degradation rate of methylene blue catalyzed and degraded by the flower-like CuS submicron sphere material prepared in example 3 of the present invention and the number of recycling times.

FIG. 8 is a graph showing the adsorption and desorption curves of the flower-shaped CuS submicron sphere material N ₂ prepared in example 3 of the present invention.

Detailed Description

the present invention will be described in further detail with reference to examples and drawings, but the present invention is not limited thereto.