CN100424017C - Method for preparing hexagonal Nano slices of copper sulphide - Google Patents
Method for preparing hexagonal Nano slices of copper sulphide Download PDFInfo
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- CN100424017C CN100424017C CNB2006101186709A CN200610118670A CN100424017C CN 100424017 C CN100424017 C CN 100424017C CN B2006101186709 A CNB2006101186709 A CN B2006101186709A CN 200610118670 A CN200610118670 A CN 200610118670A CN 100424017 C CN100424017 C CN 100424017C
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- copper sulphide
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- mantoquita
- nanoflakes
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Abstract
This invention relates to a method for preparing hexagonal CuS nanoflakes. The method utilizes long-chain alkyl amine as the surfactant, CS2 as the sulfur source and toluene as the solvent, and adopts chemical solution method to prepare hexagonal CuS nanoflakes. The method comprises: dissolving Cu salt, sulfur source and long-chain alkyl amine in toluene to prepare reactive solution, and performing solvent thermal treatment at a certain temperature for a certain time to obtain regular hexagonal CuS nanoflakes. The method is simple and low cost. The obtained hexagonal CuS nanoflakes have diameters of 26 plus and minus 1.5 nm, and thickness of 8 plus and minus 1.2 nm. The hexagonal CuS nanoflakes can self-assemble into nanoscale cylindrical, raft and lamellar superstructures.
Description
Technical field
The present invention relates to a kind of preparation method of hexagonal Nano slices of copper sulphide, is tensio-active agent with chain alkyl amine, adopts the chemical solution method preparation to have the Nano slices of copper sulphide of regular hexagonal shape.Belong to the nano material preparation technical field.
Background technology
Nano material's structure and pattern have very big influence for the performance of nano material with application, and the uniform nano material of shape is self-assembled into two dimension or three-dimensional superstructure has great significance in fields such as nanoelectronics, magnetics, photoelectronics, dephasign catalysis for it, so the synthetic increasing attention that has stood of the control of nano material.In numerous nano materials, nano-copper sulfide is a kind of important semiconductor material, and this bill of material reveals the characteristic of metal and be converted into superconductor when 1.6k, shows the characteristic of fast-ionic conductor when high temperature; Simultaneously, the cupric sulfide with covellite structure all has important use at aspects such as thermoelectric-cooled material, fiber optics, optical recording material, solar cells.In present copper sulfide nano material synthetic method, relatively Chang Yong method has that hydro-thermal is synthetic, microemulsion method, sonochemistry are synthetic, gamma-ray irradiation method etc.As: preparation such as hydrothermal method, sonochemical method, gamma-ray irradiation method cupric sulfide, all obtain having erose product or serious material of reuniting, be unfavorable for the product morphology control; And microemulsion method synthetic output seldom, is unfavorable for the practical application of material; By contrast, the organic solvent process for thermosynthesizing has simple to operate, controllable product shape, is easy to realize the characteristics such as serialization production of material.
Summary of the invention
The object of the invention is at the deficiencies in the prior art, and a kind of preparation method of hexagonal Nano slices of copper sulphide is provided, and technology is simple, production cost is low, and the Nano slices of copper sulphide pattern rule of preparation is controlled.
For realizing such purpose, in technical scheme of the present invention, be tensio-active agent with chain alkyl amine, be the sulphur source with dithiocarbonic anhydride, with toluene reaction solvent, adopt the chemical solution method preparation to have the Nano slices of copper sulphide of regular hexagonal shape.At first mantoquita, sulphur source and chain alkyl amine are dissolved in the toluene, preparation feedback liquid carries out solvent heat treatment with the reaction solution for preparing then, controlled temperature and reaction times, can obtain the hexagonal Nano slices of copper sulphide of pattern rule.
Preparation method of the present invention comprises following concrete steps:
1) preparation of chemical reaction liquid: mantoquita, tensio-active agent chain alkyl amine, dithiocarbonic anhydride mixing are dissolved in the toluene, are mixed with reaction solution; Wherein the concentration of mantoquita is 0.01～0.1moll
-1, tensio-active agent and mantoquita mol ratio be 4～20, the mol ratio of dithiocarbonic anhydride and mantoquita is 20～40.
2) hexagonal Nano slices of copper sulphide is synthetic: reaction solution is moved into the autoclave that has the 50ml polytetrafluoroethylliner liner, under 120 ℃ of conditions, react, reaction times is 24-48 hour, after reaction finished, reactor naturally cooled to about 60 ℃, added the methyl alcohol of reaction solution cumulative volume 20～30%, product is filtered, with absolute ethanol washing for several times, vacuum is drained, and promptly obtains to have the Nano slices of copper sulphide of hexagonal configuration.
In the inventive method, described mantoquita is a neutralized verdigris, and described tensio-active agent chain alkyl amine is amino dodecane, cetylamine or stearylamine.
Excellent results of the present invention is:
1. be tensio-active agent owing to having adopted chain alkyl amine; make the nanocrystal of cupric sulfide in the process of growth, reach the better controlled growth; this anisotropic growth for hexagonal Nano slices of copper sulphide provides good guide effect; and hexagonal Nano slices of copper sulphide played the better protecting effect, make it to have good homogeneity.
2. because the present invention has adopted the chemical solution method reaction, raw material is cheap, simple to operate, cost is low, efficient is high, the cupric sulfide of preparation is the hexagonal nano sheet, about 26 ± the 1.5nm of the diameter of sheet, about 8 ± the 1.2nm of thickness, and this hexagonal nanometer sheet can be self-assembled into column, raft shape or lamellated nano-superstructure.
Description of drawings
Fig. 1 is the X-ray diffracting spectrum of the hexagonal Nano slices of copper sulphide of the embodiment of the invention 1 gained.(embodiment 1-4 has identical x-ray diffraction pattern).
Fig. 2 is the transmission electron microscope photo of the different amplification with column, raft-shaped structure hexagonal Nano slices of copper sulphide of the embodiment of the invention 1 gained.
Fig. 3 has a stratiform Nano slices of copper sulphide transmission electron microscope photo for the embodiment of the invention 2 gained.
Fig. 4 is the transmission electron microscope photo of the hexagonal Nano slices of copper sulphide of the embodiment of the invention 3 gained.
Fig. 5 is the transmission electron microscope photo of the hexagonal Nano slices of copper sulphide of the embodiment of the invention 4 gained.
Embodiment
The following examples are to further specify of the present invention, and do not limit the scope of the invention.
Embodiment 1
1. in the flask of a 100ml, the neutralized verdigris of 0.4mmol, the cetylamine of 8mmol are joined in the toluene of 39.5ml, be heated to 60 ℃ and keep adding the 0.5ml dithiocarbonic anhydride to whole dissolving backs in 30 minutes, continue magnetic agitation in the time of adding, be prepared into the reaction solution of cupric sulfide.
2. will move into according to the reaction solution that 1. step prepares and have in the autoclave of 50ml polytetrafluoroethylliner liner, 120 ℃ the reaction 24 hours after, reactor naturally cools to 60 ℃, add 10ml methyl alcohol, after the centrifugation, with absolute ethanol washing for several times, vacuum is drained sample, can obtain to have the Nano slices of copper sulphide of hexagonal configuration.
The x-ray diffraction pattern of the Nano slices of copper sulphide of resulting hexagonal configuration such as Fig. 1.Prepared as seen from Figure 1 material is the cupric sulfide of hexagonal structure covellite structure.Fig. 2 is the transmission electron microscope photo that obtains the Nano slices of copper sulphide self-assembled structures of hexagonal configuration.As seen from the figure, the about 26 ± 1.5nm of diameter of this cupric sulfide hexagonal nanometer sheet, the about 8 ± 1.2nm of thickness, and this hexagonal nanometer sheet can be self-assembled into the nano super-lattice of two-dimentional column, raft shape.
Embodiment 2
1. in the flask of a 100ml, the neutralized verdigris of 4mmol, the cetylamine of 2.4mmol are joined in the toluene of 39ml, be heated to 60 ℃ and keep adding the 1ml dithiocarbonic anhydride to whole dissolving backs in 30 minutes, continue magnetic agitation in the time of adding, be prepared into the reaction solution of cupric sulfide.
2. will move into according to the reaction solution that 1. step prepares and have in the autoclave of 50ml polytetrafluoroethylliner liner, in 120 ℃ of solvent thermal after 48 hours, reactor naturally cools to 60 ℃, add 10ml methyl alcohol, after the centrifugation, with absolute ethanol washing for several times, vacuum is drained sample, promptly can obtain to have the Nano slices of copper sulphide of hexagonal configuration
Fig. 3 is the transmission electron microscope photo of resulting hexagonal Nano slices of copper sulphide self-assembled structures.As seen from the figure, the about 26 ± 1.5nm of diameter of this cupric sulfide hexagonal nanometer sheet, the about 8 ± 1.2nm of thickness, and can be self-assembled into lamellated three-dimensional manometer superlattice.
Embodiment 3
1. in the flask of a 100ml, the neutralized verdigris of 0.4mmol, the stearylamine of 1.6mmol are joined in the toluene of 39.5ml, be heated to 60 ℃ and keep adding the 0.5ml dithiocarbonic anhydride to whole dissolving backs in 30 minutes, continue magnetic agitation in the time of adding, be prepared into the reaction solution of cupric sulfide.
2. will move into according to the reaction solution that 1. step prepares and have in the autoclave of 50ml polytetrafluoroethylliner liner, in 120 ℃ of solvent thermal after 24 hours, reactor naturally cools to 60 ℃, add 10ml methyl alcohol, after the centrifugation, with absolute ethanol washing for several times, vacuum is drained sample, promptly can obtain the hexagonal Nano slices of copper sulphide.
Fig. 4 is the transmission electron microscope photo of resulting hexagonal Nano slices of copper sulphide self-assembled structures.As seen from the figure, the pattern of the product of this embodiment, size and embodiment 1 and can be self-assembled into two-dimentional column similar to Example 1, the nano super-lattice of raft shape much at one.
Embodiment 4
1. in the flask of a 100ml, the neutralized verdigris of 0.4mmol, the amino dodecane of 4mmol are joined in the toluene of 39.5ml, be heated to 60 ℃ and keep adding the 0.5ml dithiocarbonic anhydride to whole dissolving backs in 30 minutes, continue magnetic agitation in the time of adding, be prepared into the reaction solution of cupric sulfide.
2. will move into according to the reaction solution that 1. step prepares and have in the autoclave of 50ml polytetrafluoroethylliner liner, in 120 ℃ of solvent thermal after 24 hours, reactor naturally cools to 60 ℃, add 10ml methyl alcohol, after the centrifugation, with absolute ethanol washing for several times, vacuum is drained sample, promptly can obtain to have the Nano slices of copper sulphide of hexagonal configuration.
Fig. 5 is the transmission electron microscope photo of resulting hexagonal Nano slices of copper sulphide self-assembled structures.As seen from the figure, this cupric sulfide hexagonal nanometer sheet is similar to the Nano slices of copper sulphide of embodiment 1 gained.
Claims (2)
1. the preparation method of a hexagonal Nano slices of copper sulphide is characterized in that may further comprise the steps:
1) preparation of chemical reaction liquid: mantoquita, tensio-active agent chain alkyl amine, dithiocarbonic anhydride mixing are dissolved in the toluene, are mixed with reaction solution; Wherein the concentration of mantoquita is 0.01～0.1moll
-1, tensio-active agent and mantoquita mol ratio be 4～20, the mol ratio of dithiocarbonic anhydride and mantoquita is 20～40;
2) hexagonal Nano slices of copper sulphide is synthetic: reaction solution is moved into the autoclave that has the 50ml polytetrafluoroethylliner liner, under 120 ℃ of conditions, react, reaction times is 24-48 hour, after reaction finished, reactor naturally cooled to 60 ℃, added the methyl alcohol of reaction solution cumulative volume 20～30%, product is filtered, with absolute ethanol washing for several times, vacuum is drained, and promptly obtains to have the Nano slices of copper sulphide of hexagonal configuration.
2. according to the preparation method of the hexagonal Nano slices of copper sulphide of claim 1, it is characterized in that described mantoquita is a neutralized verdigris, described tensio-active agent chain alkyl amine is amino dodecane, cetylamine or stearylamine.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101844799A (en) * | 2010-06-17 | 2010-09-29 | 安阳师范学院 | Preparation method of hexagon stannic disulphide nano slice |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101580266B (en) * | 2009-03-23 | 2010-12-01 | 哈尔滨工程大学 | Preparation method of CuS hierarchical structure nano material |
| CN101851010B (en) * | 2010-06-08 | 2011-08-31 | 南开大学 | Synthesizing method for transition metal sulfide |
| CN102219251B (en) * | 2011-03-30 | 2014-04-16 | 东华大学 | Copper sulfide superstructure and its application in improving near infrared thermal conversion efficiency |
| CN103359770A (en) * | 2012-03-28 | 2013-10-23 | 华东师范大学 | Synthesis method of metal sulfide nano-structure material |
| CN109867306B (en) * | 2017-12-05 | 2022-02-15 | 中国科学院大连化学物理研究所 | Low-temperature preparation method of mesoporous manganese dioxide nanosheets |
| CN108217713B (en) * | 2018-01-25 | 2019-08-02 | 北京化工大学 | A kind of method that polishing prepares Nano slices of copper sulphide |
| CN108529661B (en) * | 2018-05-18 | 2020-07-03 | 中北大学 | Preparation method of hexagonal copper sulfide nanosheet |
| CN108940376B (en) * | 2018-07-25 | 2021-06-25 | 广州大学 | Surface organic complexing copper sulfide Fenton catalyst and synthetic method and application thereof |
| TWI698507B (en) * | 2018-12-06 | 2020-07-11 | 財團法人工業技術研究院 | Modified metal nanoplate and conductive paste comprising the same |
| CN109954888B (en) * | 2019-04-10 | 2021-10-26 | 延边大学 | Triangular-plate-shaped elemental copper nanosheet and preparation method thereof |
| CN111892079B (en) * | 2020-06-23 | 2021-07-20 | 华南理工大学 | Metal ion doped copper sulfide nanosheet with near-infrared shielding function and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060039850A1 (en) * | 2004-04-20 | 2006-02-23 | Samsung Electronics Co., Ltd. | Method for manufacturing metal sulfide nanocrystals using thiol compound as sulfur precursor |
| CN1785816A (en) * | 2005-12-12 | 2006-06-14 | 华东理工大学 | Preparation method of star shaped copper sulfide |
| JP2006240900A (en) * | 2005-03-01 | 2006-09-14 | Nagoya Institute Of Technology | Synthetic method for copper sulfide nanoparticle |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060039850A1 (en) * | 2004-04-20 | 2006-02-23 | Samsung Electronics Co., Ltd. | Method for manufacturing metal sulfide nanocrystals using thiol compound as sulfur precursor |
| JP2006240900A (en) * | 2005-03-01 | 2006-09-14 | Nagoya Institute Of Technology | Synthetic method for copper sulfide nanoparticle |
| CN1785816A (en) * | 2005-12-12 | 2006-06-14 | 华东理工大学 | Preparation method of star shaped copper sulfide |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101844799A (en) * | 2010-06-17 | 2010-09-29 | 安阳师范学院 | Preparation method of hexagon stannic disulphide nano slice |
| CN101844799B (en) * | 2010-06-17 | 2012-05-09 | 安阳师范学院 | Preparation method of hexagon stannic disulphide nano slice |
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