CN1785816A - Preparation method of star shaped copper sulfide - Google Patents

Preparation method of star shaped copper sulfide Download PDF

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Publication number
CN1785816A
CN1785816A CN 200510111375 CN200510111375A CN1785816A CN 1785816 A CN1785816 A CN 1785816A CN 200510111375 CN200510111375 CN 200510111375 CN 200510111375 A CN200510111375 A CN 200510111375A CN 1785816 A CN1785816 A CN 1785816A
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tensio
active agent
preparation
copper sulfide
shaped copper
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CN100406389C (en
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刘洪来
陈立飞
尚亚卓
徐建
彭昌军
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East China University of Science and Technology
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East China University of Science and Technology
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Abstract

The present invention belongs to the field of inorganic metal nano material technology, and relates to a method for synthesizing star cupric sulfide by means of reaction in microemulsion. It mainly includes the following steps: using new-type microemulsion formed from quaternary cationic Gemini surfactant as template, controlling emulsion synthesis condition, making centrifugal separation and drying so as to obtain the star cupric sulfide with narrow size distribution. The prepared cupric sulfide has extensive application in the fields of pigment, catalyst, color indicator of aniline black and semiconductor material, etc.

Description

A kind of preparation method of star shaped copper sulfide
Technical field
The invention belongs to technical field of inorganic nanometer material, be specifically related to the preparation method of a kind of cupric sulfide of new pattern star, narrow size distribution.
Background technology
The electroconductibility of the metalloid of cupric sulfide, chemosensitivity and make it become a kind of extremely interested material that makes us to the ideal behavior of solar absorption.Cupric sulfide is not only a kind of good semiconductor material, and at the aspects such as color indicator of pigment, catalyzer, nigrosine application is very widely arranged also.The special property that nano-scale structure is given it will make cupric sulfide be applied in field widely.
At present synthetic copper sulphide nano crystal mainly contains following method: solid state reaction [I.P.Parkin, Chem.Soc.Rev.1996,15,199], high-temperature decomposition [P.P.Paul, T.B.Rauchfuss, S.R.Wilson, J.Am.Chem.Soc.1993,115,3316], reduction method [X.Jiang, Y.Xie, J.Lu, W.He, L.Zhu, Y.Qian, J.Mater.Chem.2000,10,2193], hydrothermal synthesis method [Q.Lu, F.Gao, D.Zhao, Nanotechnology.2002,13,741] etc.There is deficiency to a certain extent in these methods, such as product size, pattern are restive; Pyroreaction condition harshness or preparation process more complicated, cost are more high relatively.And emulsion synthesis method [M.P.Pileni, Nature Mater.2003,2,145] is owing to the favor advantage enjoys investigator such as the size of control material and the validity aspect the pattern, temperature of reaction be low.Yet what adopt in emulsion in the past is synthetic all is conventional surfactant, has defectives such as dosage of surfactant is many, the distribution of sizes of product is wide, pattern disunity mostly.At present nano material synthetic aspect, key is to guarantee high yield, cheaply under the situation, adopting a kind of synthetic method of reaction conditions gentleness to synthesize that pattern is controlled, the nano material of narrow size distribution.And the appearance of novel pattern investigator's continuous pursuit especially.
Summary of the invention
Purpose of the present invention is exactly the preparation method that a kind of star shaped copper sulfide is provided for the defective that overcomes above-mentioned prior art existence, can obtain a kind of form stable by implementing this method, be uniformly dispersed, the star shaped copper sulfide of narrow size distribution, this method is at room temperature to carry out simultaneously, the reaction conditions gentleness, used tensio-active agent can be recycled, do not pollute the environment and cost is reduced greatly, need not use the direct centrifugation of emulsion splitter to get final product.
Purpose of the present invention can be achieved through the following technical solutions: a kind of preparation method of star shaped copper sulfide, it is characterized in that, this method is that the microemulsion that forms with quaternary ammonium salt cationic (Gemini) tensio-active agent is that template prepares, and this method may further comprise the steps:
(1) the mixing percentage composition of selected quaternary ammonium salt cationic (Gemini) tensio-active agent and alcohol, preparation comprises the Cu of 0.1～0.5mol/L 2+And water and tensio-active agent mol ratio ω 0Be 5～30 microemulsion A;
(2) the mixing percentage composition of selected quaternary ammonium salt cationic (Gemini) tensio-active agent and alcohol, preparation comprises and Cu 2+Mol ratio is 7.5～35 S 2-And water and tensio-active agent mol ratio be 5～30 microemulsion B;
(3) under stirring state, mix corresponding microemulsion A and B;
Stop when (4) liquid to be mixed presents deep yellow stirring, sealing, at room temperature placing response is 2～48 hours;
(5) the reaction solution centrifugation that step (4) is obtained, washing, drying, recovery tensio-active agent obtain the star shaped copper sulfide product.
The model of described quaternary ammonium salt cationic (Gemini) tensio-active agent is 12-3-12.
The mixing quality percentage composition of described tensio-active agent and alcohol is 20～40%.At this moment, the microemulsion maximum water content of formation can reach 25～50%, can form large-area microemulsion, and remaining is an oil phase content.
The Cu of described microemulsion A 2+Volumetric molar concentration be 0.2～0.3mol/L.Find in the experiment, along with Cu 2+Concentration increases, and the maximum water content that the formation microemulsion can reach descends to some extent, and low water content will reduce the output of product; The water-content of microemulsion height directly influences the microtexture of microemulsion in addition, closely influences the pattern of product.
The mol ratio ω of water and tensio-active agent in described step (1), (2) 0Be 22～30.Can under the prerequisite that guarantees the formation microemulsion, make the output of product high as much as possible like this.
S in the described step (2) 2-With Cu 2+Mol ratio be 25～30.Be difficult to form cupric sulfide when the mol ratio of the two is 1, two emulsions are mixed the long-time nondiscoloration in back, also are seldom to measure even formed cupric sulfide this moment.This may be the reason of selected new type of Gemini surfactant, and this tensio-active agent can form microemulsion fast, and because the microemulsion that the characteristics of tensio-active agent self structure make formation very stable again.It is very slow to carry out exchange of substance like this when two emulsions are mixed between them, and the brilliant unit that closely forms cupric sulfide is very slow.But the mol ratio of the two again can not be too high, comprises S otherwise just can not form 2-Microemulsion.
The reaction times of described step (4) is 12～15 hours.Reaction times is too short, and crystallinity is relatively poor, and the reaction times is long, and pattern there is no too big variation, considers that preferred reaction time production cycle is 12 hours.The star shaped copper sulfide consistent appearance that obtains, narrow size distribution.
The reaction times of described step (4) be 12～13 hours more excellent.
Compared with prior art, the present invention has following characteristics:
1. the cupric sulfide among the present invention is formed in the water nuclear of microemulsion, by regulating Cu 2+Concentration control the maximum water content of microemulsion, and then the water nuclear structure of control microemulsion obtains the copper sulphide nano crystal of desired pattern.
2. pass through control S among the present invention 2-With Cu 2+The mole maximum water content of reaction speed and microemulsion recently, near and control reaction time and very high product yield.
3. the reaction among the present invention is at room temperature carried out, and mild condition is easily controlled, noenergy consumption, and cost is low.
4. select novel Gemini tensio-active agent as template among the present invention, this template just can form stable microemulsion liquid under very low content, be easy to obtain the cupric sulfide of desired pattern, narrow size distribution; Tensio-active agent is recyclable, reduces cost, and environmentally safe.
Description of drawings
Fig. 1 is the needle-like CuS TEM figure of the embodiment of the invention 1 preparation;
Fig. 2 is the star CuS TEM figure of the embodiment of the invention 2 preparations;
Fig. 3 is the star CuS TEM figure of the embodiment of the invention 3 preparations;
Fig. 4 is the star CuS TEM figure of the embodiment of the invention 4 preparations;
Fig. 5 is the star CuS TEM figure of the embodiment of the invention 5 preparations.
Embodiment
The invention will be further described below in conjunction with specific embodiment, and the description of embodiment is only for ease of understanding the present invention, but not limiting the scope of the invention.
Embodiment 1
Preparation comprises 0.1mol/L Cu 2+Microemulsion A, wherein tensio-active agent (12-3-12) and alcohol mixing quality content be 25%, the mol ratio ω of water and tensio-active agent 0Be 5, all the other are oil phase content; Make comprising and Cu of each component concentration of respective emulsion 2+Mol ratio is 7.5 S 2-Microemulsion B.Under stirring state, emulsion B is joined in the latex A, stop when waiting brown to occur stirring, deposited under the room temperature 24 hours.Centrifugation, the dry needle-like copper sulphide nano crystal that gets of washing.As Fig. 1.Restriction owing to emulsion structure under this condition does not also obtain star shaped copper sulfide.
Embodiment 2
Preparation comprises 0.2mol/L Cu 2+Microemulsion A, wherein tensio-active agent (12-3-12) and alcohol mixing quality content be 25%, the mol ratio ω of water and tensio-active agent 0Be 30, all the other are oil phase content; Make comprising and Cu of each component concentration of respective emulsion 2+Mol ratio is 30 S 2-Microemulsion B.Under stirring state, emulsion B is joined in the latex A, stop when waiting brown to occur stirring, deposited under the room temperature 4 hours.Centrifugation, the dry star shaped copper sulfide nanocrystal that gets of washing.As Fig. 2.As seen water-content raises and has changed emulsion structure, closely influence the product pattern, but because the time is too short, crystallinity is bad.
Embodiment 3
Preparation comprises 0.2mol/L Cu 2+Microemulsion A, wherein tensio-active agent (12-3-12) and alcohol mixing quality content be 25%, the mol ratio ω of water and tensio-active agent 0Be 30, all the other are oil phase content; Make comprising and Cu of each component concentration of respective emulsion 2+Mol ratio is 25 S 2-Microemulsion B.Under stirring state, emulsion B is joined in the latex A, stop when waiting brown to occur stirring, deposited under the room temperature 12 hours.Centrifugation, the dry star shaped copper sulfide nanocrystal that gets of washing.As Fig. 3.As seen during the digestion time sufficiently long, crystallinity is intact.
Embodiment 4
Preparation comprises 0.5mol/L Cu 2+Microemulsion A, wherein tensio-active agent (12-4-12) and alcohol mixing quality content be 40%, the mol ratio ω of water and tensio-active agent 0Be 30, all the other are oil phase content; Make comprising and Cu of each component concentration of respective emulsion 2+Mol ratio is 35 S 2-Microemulsion B.Under stirring state, emulsion B is joined in the latex A, stop when waiting brown to occur stirring, deposited under the room temperature 13 hours.Centrifugation, the dry star shaped copper sulfide nanocrystal that gets of washing.As Fig. 4.The linking group of tensio-active agent increases the pattern that does not influence product a little.
Embodiment 5
Preparation comprises 0.3mol/L Cu 2+Microemulsion A, wherein tensio-active agent (12-3-12) and alcohol mixing quality content be 25%, the mol ratio ω of water and tensio-active agent 0Be 30, all the other are oil phase content; Make comprising and Cu of each component concentration of respective emulsion 2+Mol ratio is 30 S 2-Microemulsion B.Under stirring state, emulsion B is joined in the latex A, stop when waiting brown to occur stirring, deposited under the room temperature 48 hours.Centrifugation, the dry star shaped copper sulfide nanocrystal that gets of washing.As Fig. 5.Too big variation does not take place in the prolongation along with the time behind the star shaped copper sulfide complete crystallization, illustrates that the Gemini tensio-active agent of selecting for use has the better controlled effect to product pattern and size.

Claims (8)

1. the preparation method of a star shaped copper sulfide is characterized in that, this method is that the microemulsion that forms with quaternary ammonium salt cationic (Gemini) tensio-active agent is that template prepares, and this method may further comprise the steps:
(1) the mixing percentage composition of selected quaternary ammonium salt cationic (Gemini) tensio-active agent and alcohol, preparation comprises the Cu of 0.1～0.5mol/L 2+And water and tensio-active agent mol ratio ω 0Be 5～30 microemulsion A;
(2) the mixing percentage composition of selected quaternary ammonium salt cationic (Gemini) tensio-active agent and alcohol, preparation comprises and Cu 2+Mol ratio is 7.5～35 S 2-And water and tensio-active agent mol ratio be 5～30 microemulsion B;
(3) under stirring state, mix corresponding microemulsion A and B;
Stop when (4) liquid to be mixed presents deep yellow stirring, sealing, at room temperature placing response is 2～48 hours;
(5) the reaction solution centrifugation that step (4) is obtained, washing, drying, recovery tensio-active agent obtain the star shaped copper sulfide product.
2. the preparation method of star shaped copper sulfide according to claim 1 is characterized in that, the model of described quaternary ammonium salt cationic (Gemini) tensio-active agent is 12-3-12.
3. the preparation method of star shaped copper sulfide according to claim 1 is characterized in that, the mixing quality percentage composition of described tensio-active agent and alcohol is 20～40%.
4. the preparation method of star shaped copper sulfide according to claim 1 is characterized in that, the Cu of described microemulsion A 2+Volumetric molar concentration be 0.2～0.3mol/L.
5. the preparation method of star shaped copper sulfide according to claim 1 is characterized in that, the mol ratio ω of water and tensio-active agent in described step (1), (2) 0Be 22～30.
6. the preparation method of star shaped copper sulfide according to claim 1 is characterized in that, S in the described step (2) 2-With Cu 2+Mol ratio be 25～30.
7. the preparation method of star shaped copper sulfide according to claim 1 is characterized in that, the reaction times of described step (4) is 12～15 hours.
8. the preparation method of star shaped copper sulfide according to claim 7 is characterized in that, the reaction times of described step (4) is 12～13 hours.
CNB2005101113756A 2005-12-12 2005-12-12 Preparation method of star shaped copper sulfide Expired - Fee Related CN100406389C (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100424017C (en) * 2006-11-23 2008-10-08 上海交通大学 Method for preparing hexagonal Nano slices of copper sulphide
CN102863006A (en) * 2012-09-25 2013-01-09 镇江市高等专科学校 Preparation method of copper sulfide ultra-long micro-wire
CN102910667A (en) * 2012-10-23 2013-02-06 中科院广州化学有限公司 Hydrophilic vermiform CuS (copper sulphide) agglomerate and preparation method and usage thereof
CN106861598A (en) * 2015-12-10 2017-06-20 上海交通大学 Application in nanocrystalline adsorbents of CuS and preparation method thereof and electro-coppering wastewater treatment
CN108940376A (en) * 2018-07-25 2018-12-07 广州大学 A kind of surface organic complex copper sulfide fenton catalyst and its synthetic method and application

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2636001B2 (en) * 1988-06-03 1997-07-30 三菱化学株式会社 Method for producing ultrafine particles of metal sulfide, metal selenide or a mixed crystal thereof
CN1191115C (en) * 2003-08-08 2005-03-02 陕西师范大学 Process for preparing sulfide-polymer composite micro sphere with surface pattern

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100424017C (en) * 2006-11-23 2008-10-08 上海交通大学 Method for preparing hexagonal Nano slices of copper sulphide
CN102863006A (en) * 2012-09-25 2013-01-09 镇江市高等专科学校 Preparation method of copper sulfide ultra-long micro-wire
CN102910667A (en) * 2012-10-23 2013-02-06 中科院广州化学有限公司 Hydrophilic vermiform CuS (copper sulphide) agglomerate and preparation method and usage thereof
CN106861598A (en) * 2015-12-10 2017-06-20 上海交通大学 Application in nanocrystalline adsorbents of CuS and preparation method thereof and electro-coppering wastewater treatment
CN106861598B (en) * 2015-12-10 2020-06-19 上海交通大学 CuS nanocrystalline adsorbent, preparation method thereof and application thereof in copper electroplating wastewater treatment
CN108940376A (en) * 2018-07-25 2018-12-07 广州大学 A kind of surface organic complex copper sulfide fenton catalyst and its synthetic method and application
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

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