CN102107904A - Method for preparing cadmium sulfide or zinc sulfide hollow nano diamonds by using non-template method - Google Patents
Method for preparing cadmium sulfide or zinc sulfide hollow nano diamonds by using non-template method Download PDFInfo
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Abstract
The invention relates to a method for preparing cadmium sulfide or zinc sulfide hollow nano diamonds by using a non-template method. The method comprises the following steps of: adding inorganic cadmium source or inorganic zinc power and sulfur powder in a molar ratio of 1:1 into tetrahydrofuran solution, and performing ultrasonic dispersion; weighing sodium borohydride in the same molar content as the sulfur powder, adding the sodium borohydride into the tetrahydrofuran solution, and performing ultrasonic dispersion; dripping the obtained solution into the solution formed by adding the inorganic cadmium source and the sulfur powder into the tetrahydrofuran solution, and performing ultrasonic reaction; performing centrifugal separation on the obtained reaction products by using absolute ethanol; and performing vacuum drying to obtain a final yellow product, namely the cadmium sulfide hollow nano diamonds. The preparation reaction conditions are mild; the method is simple and feasible, has strong operability, good repeatability and low cost, and has certain universality; the cadmium sulfide or zinc sulfide hollow nano diamonds prepared by the method have high specific surface area and regular hollow square shape, and can be applied to medicament transportation more effectively; and meanwhile, cadmium sulfide or zinc sulfide is a good photocatalyst, the hollow nano structure is favorable for improving the photocatalysis performance, and the cadmium sulfide or the zinc sulfide has broad application prospect on the aspects of photocatalytic decomposition of toxic or harmful substances and photocatalytic water decomposition for preparing hydrogen.
Description
Technical field
The present invention relates to the method that a kind of non-template legal system is equipped with Cadmium Sulfide, zinc sulphide hollow Nano square, belong to field of nanometer technology.
Background technology
Preparation has the nano material of special construction, the nano material that especially has a hollow structure to improve material property, to widen the material Application Areas significant.Wherein, Cadmium Sulfide, zinc sulphide hollow structure become the research focus because its special structure and performance all have broad application prospects at photoelectricity, the energy and medical field.On the one hand, Cadmium Sulfide, zinc sulphide hollow structure have high-specific surface area, hollow structure is suitable as pharmaceutical carrier, and the distinctive photoluminescent property of material can carry out the original position spike to whole drug delivery and metabolic process simultaneously, has potential application foreground at the nano biological medical field; On the other hand, Cadmium Sulfide, zinc sulphide are good photocatalysts, hollow nanostructuredly help improving its photocatalysis performance, have broad application prospects aspect, objectionable impurities poisonous in photocatalysis Decomposition and the photocatalytic hydrogen production by water decomposition.At present, the preparation hollow nano-material especially prepares the hollow square nanostructure and need adopt template (comprising soft template and hard template) usually, and preparation condition harshness, process complexity, output are limited.Therefore, invent a kind of non-template, simply to prepare hollow square nanostructure method all significant for material preparation and Application Areas.
Summary of the invention
Defective at the existing method for preparing the hollow square nanostructure exists the purpose of this invention is to provide the method that a kind of non-template legal system is equipped with Cadmium Sulfide, zinc sulphide hollow Nano square.
The non-template legal system that the present invention proposes is equipped with the method for Cadmium Sulfide, zinc sulphide hollow Nano square, and concrete steps are as follows:
(1) be that the inorganic cadmium source of 1:1 or inorganic zinc source and sulphur powder join in the tetrahydrofuran solution of 5-500 ml ultra-sonic dispersion with mol ratio;
(2) take by weighing the molar content sodium borohydride identical, join in the tetrahydrofuran solution of 5-500 ml ultra-sonic dispersion with the sulphur powder;
(3) drips of solution that step (2) is obtained is added in the solution that step (1) obtains, ultrasonic reaction;
(4) with the dehydrated alcohol centrifugation of step (3) reaction products resulting;
(5) with the resulting centrifugal substrate vacuum-drying of step (4), obtain final yellow product and be Cadmium Sulfide hollow Nano square.
Among the present invention, inorganic cadmium source described in the step (1) can be in Cadmium chloride fine powder, cadmium nitrate, Cadmium Sulphate or the cadmium acetate etc. any, the inorganic zinc source can be any in zinc chloride, zinc nitrate, zinc sulfate or the zinc acetate etc.
Among the present invention, the ultra-sonic dispersion time is 1-120 min in step (1), step (2) and the step (3), and ultrasonic power is 100-400 W.
Among the present invention, centrifugal 1-10 time of dehydrated alcohol of the gained reaction product of step (3) described in the step (4), centrifugal rotational speed is controlled between the 1000-10000 rpm.
Among the present invention, the vacuum-drying temperature is 20-200 ℃ described in the step (5), and the time is 1-24 h.
The invention provides a kind of preparation and have the Nano cadmium sulphide of hollow square pattern, the technology of zinc sulphide, under the tetrahydrofuran solution condition, by ultrasonic reaction, need not any template and prepare Cadmium Sulfide, the zinc sulphide hollow Nano square of size below 100 nanometers.This method have the reaction conditions gentleness, simple to operate, need not to adopt any template, repeatable characteristics such as strong, the hollow square pattern that Cadmium Sulfide, the zinc sulfide nano structure of this method preparation has very high specific surface area and rule can be effectively applied to drug delivery more; Simultaneously Cadmium Sulfide, zinc sulphide are good photocatalysts, hollow nanostructuredly help improving its photocatalysis performance, have broad application prospects aspect, objectionable impurities poisonous in photocatalysis Decomposition and the photocatalytic hydrogen production by water decomposition.
Description of drawings
Fig. 1 is the transmission electron microscope photo of Cadmium Sulfide hollow Nano square.
Fig. 2 is the stereoscan photograph of Cadmium Sulfide hollow Nano square.
Fig. 3 is the transmission electron microscope photo of zinc sulphide hollow Nano square.
Fig. 4 is the stereoscan photograph of zinc sulphide hollow Nano square.
Embodiment
The present invention is further illustrated below in conjunction with embodiment.
Embodiment 1:
(1) takes by weighing the Cadmium chloride fine powder of 2 mmol and the sulphur powder of 2 mmol, join in the tetrahydrofuran (THF) of 500 ml, ultra-sonic dispersion 120 min, ultrasonic power 400 W; (2) take by weighing the sodium borohydride of 2 mmol, join in the tetrahydrofuran (THF) of 500 ml ultra-sonic dispersion 120 min, ultrasonic power 400 W; (3) drips of solution that step (2) is obtained is added in the solution that step (1) obtains, and continues ultrasonic reaction 120 min, ultrasonic power 400 W; (4) centrifugal 5 times of dehydrated alcohol of the throw out that step (3) is obtained, products therefrom is at 20 ℃ of following vacuum-drying 24 h.
Fig. 1 and Fig. 2 are respectively the transmission electron microscope photo and the stereoscan photographs of the resulting Cadmium Sulfide of preparation, and as can be seen from the figure Cadmium Sulfide is the hollow Nano box structure, and particle size is below 100 nm.
Embodiment 2:
(1) takes by weighing the cadmium nitrate of 2 mmol and the sulphur powder of 2 mmol, join in the tetrahydrofuran (THF) of 500 ml, ultra-sonic dispersion 120 min, ultrasonic power 100 W; (2) take by weighing the sodium borohydride of 2 mmol, join in the tetrahydrofuran (THF) of 500 ml ultra-sonic dispersion 120 min, ultrasonic power 100 W; (3) drips of solution that step (2) is obtained is added in the solution that step (1) obtains, and continues ultrasonic reaction 120 min, ultrasonic power 100 W; (4) centrifugal 5 times of dehydrated alcohol of the throw out that step (3) is obtained, products therefrom is at 200 ℃ of following vacuum-drying 1 h.Its result is similar with embodiment 1.
Embodiment 3:
(1) takes by weighing the cadmium acetate of 2 mmol and the sulphur powder of 2 mmol, join in the tetrahydrofuran (THF) of 300 ml, ultra-sonic dispersion 60 min, ultrasonic power 200 W; (2) take by weighing the sodium borohydride of 2 mmol, join in the tetrahydrofuran (THF) of 300 ml ultra-sonic dispersion 60 min, ultrasonic power 200 W; (3) drips of solution that step (2) is obtained is added in the solution that step (1) obtains, and continues ultrasonic reaction 60 min, ultrasonic power 200 W; (4) centrifugal 5 times of dehydrated alcohol of the throw out that step (3) is obtained, products therefrom is at 100 ℃ of following vacuum-drying 12 h.Its result is similar with embodiment 1.
Embodiment 4:
(1) takes by weighing the Cadmium chloride fine powder of 4 mmol and the sulphur powder of 4 mmol, join in the tetrahydrofuran (THF) of 500 ml, ultra-sonic dispersion 120 min, ultrasonic power 400 W; (2) take by weighing the sodium borohydride of 4 mmol, join in the tetrahydrofuran (THF) of 300 ml ultra-sonic dispersion 120 min, ultrasonic power 400 W; (3) drips of solution that step (2) is obtained is added in the solution that step (1) obtains, and continues ultrasonic reaction 120 min, ultrasonic power 400 W; (4) centrifugal 5 times of dehydrated alcohol of the throw out that step (3) is obtained, products therefrom is at 60 ℃ of following vacuum-drying 24 h.Its result is similar with embodiment 1.
Embodiment 5:
(1) takes by weighing the Cadmium chloride fine powder of 1 mmol and the sulphur powder of 1 mmol, join in the tetrahydrofuran (THF) of 250 ml, ultra-sonic dispersion 60 min, ultrasonic power 400 W; (2) take by weighing the sodium borohydride of 1 mmol, join in the tetrahydrofuran (THF) of 150 ml ultra-sonic dispersion 60 min, ultrasonic power 400 W; (3) drips of solution that step (2) is obtained is added in the solution that step (1) obtains, and continues ultrasonic reaction 120 min, ultrasonic power 400 W; (4) centrifugal 5 times of dehydrated alcohol of the throw out that step (3) is obtained, products therefrom is at 100 ℃ of following vacuum-drying 24 h.Its result is similar with embodiment 1.
Embodiment 6:
(1) takes by weighing the Cadmium chloride fine powder of 0.01 mmol and the sulphur powder of 0.01 mmol, join in the tetrahydrofuran (THF) of 5 ml, ultra-sonic dispersion 1 min, ultrasonic power 400 W; (2) take by weighing the sodium borohydride of 2 mmol, join in the tetrahydrofuran (THF) of 5 ml ultra-sonic dispersion 1 min, ultrasonic power 400 W; (3) drips of solution that step (2) is obtained is added in the solution that step (1) obtains, and continues ultrasonic reaction 1 min, ultrasonic power 400 W; (4) centrifugal 5 times of dehydrated alcohol of the throw out that step (3) is obtained, products therefrom is at 20 ℃ of following vacuum-drying 24 h.Its result is similar with embodiment 1.
Embodiment 7:
(1) takes by weighing the zinc chloride of 2 mmol and the sulphur powder of 2 mmol, join in the tetrahydrofuran (THF) of 500 ml, ultra-sonic dispersion 120 min, ultrasonic power 100 W; (2) take by weighing the sodium borohydride of 2 mmol, join in the tetrahydrofuran (THF) of 500 ml ultra-sonic dispersion 120 min, ultrasonic power 100 W; (3) drips of solution that step (2) is obtained is added in the solution that step (1) obtains, and continues ultrasonic reaction 120 min, ultrasonic power 100 W; (4) centrifugal 5 times of dehydrated alcohol of the throw out that step (3) is obtained, products therefrom is at 100 ℃ of following vacuum-drying 24 h, can obtain white zinc sulphide hollow Nano square powder, Fig. 3 and Fig. 4 are respectively the transmission electron microscope photo and the stereoscan photographs of the resulting zinc sulphide of preparation, as can be seen from the figure Cadmium Sulfide is the hollow Nano box structure, and particle size is below 100 nm.
Embodiment 8:
(1) takes by weighing the zinc nitrate of 1 mmol and the sulphur powder of 1 mmol, join in the tetrahydrofuran (THF) of 250 ml, ultra-sonic dispersion 60 min, ultrasonic power 400 W; (2) take by weighing the sodium borohydride of 1 mmol, join in the tetrahydrofuran (THF) of 150 ml ultra-sonic dispersion 60 min, ultrasonic power 400 W; (3) drips of solution that step (2) is obtained is added in the solution that step (1) obtains, and continues ultrasonic reaction 120 min, ultrasonic power 400 W; (4) centrifugal 5 times of dehydrated alcohol of the throw out that step (3) is obtained, products therefrom is at 100 ℃ of following vacuum-drying 24 h.Its result is similar with embodiment 7.
Claims (5)
1. a non-template legal system is equipped with the method for Cadmium Sulfide, zinc sulphide hollow Nano square, it is characterized in that concrete steps are as follows:
(1) be that the inorganic cadmium source of 1:1 or inorganic zinc source and sulphur powder join in the tetrahydrofuran solution of 5-500 ml ultra-sonic dispersion n with mol ratio;
(2) take by weighing the molar content sodium borohydride identical, join in the tetrahydrofuran solution of 5-500 ml ultra-sonic dispersion with the sulphur powder;
(3) drips of solution that step (2) is obtained is added in the solution that step (1) obtains, ultrasonic reaction;
(4) with the dehydrated alcohol centrifugation of step (3) reaction products resulting;
(5) with the resulting centrifugal substrate vacuum-drying of step (4), obtain final yellow product and be Cadmium Sulfide hollow Nano square.
2. a kind of non-template legal system according to claim 1 is equipped with the method for Cadmium Sulfide, zinc sulphide hollow Nano square, it is characterized in that described in the step (1) reaction cadmium source be in Cadmium chloride fine powder, cadmium nitrate, Cadmium Sulphate or the cadmium acetate any, described reaction zinc source be in zinc chloride, zinc nitrate, zinc sulfate or the zinc acetate any.
3. a kind of non-template legal system according to claim 1 is equipped with the method for Cadmium Sulfide, zinc sulphide hollow Nano square, it is characterized in that the ultra-sonic dispersion time is 1-120 min in step (1), step (2) and the step (3), and ultrasonic power is 100-400 W.
4. a kind of non-template legal system according to claim 1 is equipped with the method for Cadmium Sulfide, zinc sulphide hollow Nano square, it is characterized in that centrifugal 1-10 time of dehydrated alcohol of the gained reaction product of step (3) described in the step (4), centrifugal rotational speed is controlled between the 1000-10000 rpm.
5. a kind of non-template legal system according to claim 1 is equipped with the method for Cadmium Sulfide, zinc sulphide hollow Nano square, it is characterized in that the vacuum-drying temperature is 20-200 ℃ described in the step (5), and the time is 1-24 h.
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Cited By (5)
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| CN104229870A (en) * | 2014-09-01 | 2014-12-24 | 浙江师范大学 | Method for preparing ZnxCd1-xS nano hollow brick |
| WO2016119481A1 (en) * | 2015-01-30 | 2016-08-04 | 浙江工业大学 | Preparation method of lithium sulfide powder |
| CN106629818A (en) * | 2016-12-30 | 2017-05-10 | 东华大学 | Method for preparing hollow zinc sulfide microspheres in ordinary-pressure, low-temperature and template-free mode |
| CN109772365A (en) * | 2017-11-14 | 2019-05-21 | 天津大学 | A kind of double-layer porous nanometer tube composite materials of zinc sulphide-cadmium sulfide and its preparation method and application |
| CN110003892A (en) * | 2019-05-15 | 2019-07-12 | 齐鲁工业大学 | A kind of sol-gal process preparation CdS/ZnS quantum dot of modification and its photocatalysis liberation of hydrogen application |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104229870A (en) * | 2014-09-01 | 2014-12-24 | 浙江师范大学 | Method for preparing ZnxCd1-xS nano hollow brick |
| CN104229870B (en) * | 2014-09-01 | 2016-03-16 | 浙江师范大学 | One prepares Zn xcd 1-xthe method of S nano-hollow brick |
| WO2016119481A1 (en) * | 2015-01-30 | 2016-08-04 | 浙江工业大学 | Preparation method of lithium sulfide powder |
| CN106629818A (en) * | 2016-12-30 | 2017-05-10 | 东华大学 | Method for preparing hollow zinc sulfide microspheres in ordinary-pressure, low-temperature and template-free mode |
| CN106629818B (en) * | 2016-12-30 | 2018-05-25 | 东华大学 | A kind of method that atmospheric low-temperature prepares hollow zinc sulfide microballoon without template |
| CN109772365A (en) * | 2017-11-14 | 2019-05-21 | 天津大学 | A kind of double-layer porous nanometer tube composite materials of zinc sulphide-cadmium sulfide and its preparation method and application |
| CN109772365B (en) * | 2017-11-14 | 2021-08-24 | 天津大学 | Zinc sulfide-cadmium sulfide double-layer porous nanotube composite material and preparation method and application thereof |
| CN110003892A (en) * | 2019-05-15 | 2019-07-12 | 齐鲁工业大学 | A kind of sol-gal process preparation CdS/ZnS quantum dot of modification and its photocatalysis liberation of hydrogen application |
| CN110003892B (en) * | 2019-05-15 | 2022-03-04 | 齐鲁工业大学 | CdS/ZnS quantum dot prepared by modified sol-gel method and application thereof in photocatalytic hydrogen evolution |
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