CN102942213A - Preparation method of quaternary solid solution CuxInxZn2(1-x)S2 nanobelt - Google Patents
Preparation method of quaternary solid solution CuxInxZn2(1-x)S2 nanobelt Download PDFInfo
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- CN102942213A CN102942213A CN201210484313XA CN201210484313A CN102942213A CN 102942213 A CN102942213 A CN 102942213A CN 201210484313X A CN201210484313X A CN 201210484313XA CN 201210484313 A CN201210484313 A CN 201210484313A CN 102942213 A CN102942213 A CN 102942213A
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Abstract
The invention provides a preparation method of a quaternary solid solution CuxInxZn2(1-x)S2 nanobelt. The method includes the following steps: (1) adding reaction precursors of copper thiocarbamate, indium thiocarbamate and zinc thiocarbamate and a surface ligand mixture sequentially into a reaction container; (2) placing the reaction container into a constant temperature oil bath, and injecting amine quickly into the reaction container with magnetic stirring when the color of a reaction solution is changed into light yellow, continuing reacting for 30-120min with the magnetic stirring when the color of the reaction solution is changed into reddish black, and cooling to the room temperature when the reaction is finished; (3) taking out the original solution, diluting with ethanol, performing ultrasonic oscillation and centrifugation, removing supernatant, and obtaining the CuxInxZn2(1-x)S2 nanobelt. According to the method, the quaternary solid solution CuxInxZn2(1-x)S2 nanobelt is synthetized through the simple solution method for the first time, the defect that reaction conditions such as inert gas shielding are complex and cumbersome to control is overcome completely, the control for shape and structure of the quaternary solid solution CuxInxZn2(1-x)S2 nanobelt can be achieved under a normal pressure, and the yield can reach above 90%.
Description
Technical field
The present invention relates to the nano material preparing technical field, specifically relate to a kind of quaternary sosoloid Cu
xIn
xZn
2 (1-x)S
2The preparation method of nano belt.
Background technology
Because the discovery of conductor oxidate nano belt, multiple inorganic materials and inorganic/organic composite nano belt have been synthesized and have attracted the lasting concern of people.The latest Progress of solid solution semiconductor nanocrystal and film shows, by changing the composition of sosoloid, its band gap and optical property can adjusted in the scope widely, and this is very important for the continuous adjustable nano-electron of character and photoelectronics physical device.Although the preparation of ternary solid solution nano belt and ternary solid solution nanocrystal and nano wire has been described in many reports, seldom report the preparation of high-quality quaternary sosoloid nano belt.And up to the present, the most successful synthetic method of quaternary sosoloid nano belt is vapor phase growth, and solution method is synthetic then not to be related to.
In addition, at I – III – VI
2And the solid solution compound between the II – VI may have very special performance, for example CuInS
2Shown very strong photocatalytic activity in the process of – ZnS photodissociation aquatic products hydrogen under radiation of visible light, and AgInS
2– ZnS solid solution compound all has very strong photoluminescence from green to red in visible-range, and can be applied to Optochemical sensor.Therefore, quaternary I – II – III – VI compound should be paid close attention to widely.
Summary of the invention
The present invention is directed to above-mentioned the deficiencies in the prior art, the quaternary sosoloid Cu that a kind of method is easy, productive rate is high, suitability for industrialized is produced is provided
xIn
xZn
2 (1-x)S
2The preparation method of nano belt.
The present invention is achieved through the following technical solutions:
A kind of quaternary sosoloid Cu
xIn
xZn
2 (1-x)S
2The preparation method of nano belt may further comprise the steps:
(1) will be as thiocarbamate copper, thiocarbamate indium and the zinc thiocarbamate of precursors, and the surface ligand mixture joins in the reaction vessel successively;
(2) reaction vessel is put into constant temperature oil bath, question response liquid color become light yellow after, under magnetic agitation, be injected into rapidly amine in the reaction vessel; After question response liquid color becomes reddish black, continue reaction 30～120 minutes under magnetic agitation, reaction is cooled to room temperature after finishing;
(3) take out original solution, use alcohol dilution, sonic oscillation, centrifugation, abandoning supernatant obtains Cu
xIn
xZn
2 (1-x)S
2Nano belt.
The further setting of the present invention is that the molar ratio of thiocarbamate copper, thiocarbamate indium, zinc thiocarbamate is (0.01～0.99): (0.01～0.99): (1.98～0.02).
The further setting of the present invention is, the thiocarbamate class under thiocarbamate copper, thiocarbamate indium and the zinc thiocarbamate comprise N,N-Diethyldithiocarbamic Acid, dibutyl dithiocaarbamate salt, diisopropyl disulfide for carbaminate and dipropyl disulfide for carbaminate.
The further setting of the present invention is that the molar ratio of reaction precursor, amine and surface ligand mixture is 1:(10～600): (60～1200).
The further setting of the present invention is that the temperature range of described constant temperature oil bath is 120 ℃～240 ℃.
The further setting of the present invention is that described surface ligand mixture is one or more in hexylmercaptan, Dodecyl Mercaptan, stearylmercaptan, oleic acid, 3-thiohydracrylic acid, positive trioctyl phosphine oxide and the positive tri octyl phosphine.
The further setting of the present invention is that described amine is one or more in octylame, decyl amine, amino dodecane, cetylamine, stearylamine, oleyl amine and the oleylamide.
Characteristics of the present invention are the Cu that adopt presoma thiocarbamate copper at high temperature to be decomposed to form
1.75The S particle is catalyzer, and the product that zinc thiocarbamate, thiocarbamate indium pyrolytic decomposition form is dissolved in Cu
1.75In the S catalyzer, under the effect of amine and surface ligand from Cu
1.75Slowly separate out in the S particle, form quaternary sosoloid Cu
xIn
xZn
2 (1-x)S
2Nano belt.This preparation method is for the first time by the synthetic quaternary sosoloid Cu of simple solution method
xIn
xZn
2 (1-x)S
2Nano belt has overcome in the bibliographical information shortcomings such as the reaction conditions such as protection of inert gas is complicated, control is loaded down with trivial details fully, only needs laboratory plant and instrument commonly used, such as flask, agitator and oil bath pan etc., can realize under normal pressure quaternary sosoloid Cu
xIn
xZn
2 (1-x)S
2The shape of nano belt and structure control, productive rate can reach more than 90%.And this simple preparation method may become a kind of novel method of synthetic other quaternary semiconductor nano materials, for example: Cu (In
xGa
1-x) Se
2
Description of drawings
Fig. 1 is quaternary sosoloid Cu
xIn
xZn
2 (1-x)S
2The scanning transmission electron microscope figure of nano belt;
Fig. 2 is quaternary sosoloid Cu
xIn
xZn
2 (1-x)S
2The transmission electron microscope picture of nano belt;
Fig. 3 is quaternary sosoloid Cu
xIn
xZn
2 (1-x)S
2The high-resolution-ration transmission electric-lens figure of nano belt;
Fig. 4 is quaternary sosoloid Cu
xIn
xZn
2 (1-x)S
2The EDS of nano belt can spectrogram.
Embodiment
The present invention will be further described in detail below in conjunction with the drawings and specific embodiments.
Embodiment 1:
With the 0.01mmol copper dibutyldithiocarbamate, 0.01mmol diethyldithiocar bamic acid indium, 1.98mmol zinc dibutyl dithiocarbamate precursors and 60mmol Dodecyl Mercaptan join in the round-bottomed flask of 250mL successively, then flask is put into 180 ℃ constant temperature oil bath, color becomes light yellowly after the several minutes, fast the 600mmol stearylamine is injected in the flask under magnetic agitation.Solution becomes reddish black very soon, continues reaction 30 minutes under magnetic agitation, and reaction is cooled to room temperature after finishing, and takes out original solution, use alcohol dilution, sonic oscillation 5min, centrifugation 5min under the 8000rpm rotating speed, product is sunken to container bottom, and abandoning supernatant obtains sosoloid Cu
0.01In
0.01Zn
1.98S
2Nano belt.The molar ratio of above-mentioned thiocarbamate copper, thiocarbamate indium, zinc thiocarbamate is 0.01:0.01:1.98, and the molar ratio of reaction precursor, amine and surface ligand mixture is 1:600:60.
Embodiment 2:
With the 0.1mmol diisopropyl disulfide for carboxylamine copper, 0.1mmol dibutyl dithiocaarbamate indium, 1.8mmol zinc dibutyl dithiocarbamate precursors and 60mmol stearylmercaptan join in the round-bottomed flask of 250mL successively, then flask is put into 180 ℃ constant temperature oil bath, color becomes light yellowly after the several minutes, fast the 10mmol amino dodecane is injected in the flask under magnetic agitation.Solution becomes reddish black very soon, continues reaction 30 minutes under magnetic agitation, and reaction is cooled to room temperature after finishing, and takes out original solution, use alcohol dilution, sonic oscillation 5min, centrifugation 5min under the 8000rpm rotating speed, product is sunken to container bottom, and abandoning supernatant obtains sosoloid Cu
0.1In
0.1Zn
1.8S
2Nano belt.The molar ratio of above-mentioned thiocarbamate copper, thiocarbamate indium, zinc thiocarbamate is 0.1:0.1:1.8, and the molar ratio of reaction precursor, amine and surface ligand mixture is 1:10:60.
Embodiment 3:
With the 0.6mmol copper dibutyldithiocarbamate, 0.6mmol diisopropyl disulfide is for the carboxylamine indium, 0.8mmol zinc dibutyl dithiocarbamate precursors and 1200mmol hexylmercaptan join in the round-bottomed flask of 250mL successively, then flask is put into 180 ℃ constant temperature oil bath, color becomes light yellowly after the several minutes, fast the 200mmol oleylamide is injected in the flask under magnetic agitation.Solution becomes reddish black very soon, continues reaction 30 minutes under magnetic agitation, and reaction is cooled to room temperature after finishing, and takes out original solution, use alcohol dilution, sonic oscillation 5min, centrifugation 5min under the 8000rpm rotating speed, product is sunken to container bottom, and abandoning supernatant obtains sosoloid Cu
0.6In
0.6Zn
0.8S
2Nano belt.The molar ratio of above-mentioned thiocarbamate copper, thiocarbamate indium, zinc thiocarbamate is 0.6:0.6:0.8, and the molar ratio of reaction precursor, amine and surface ligand mixture is 1:200:1200.
Embodiment 4:
With the 0.99mmol diisopropyl disulfide for carboxylamine copper, 0.99mmol diisopropyl disulfide is for the carboxylamine indium, 0.02mmol zinc diethyldithiocarbamate precursors and 600mmol 3-thiohydracrylic acid join in the round-bottomed flask of 250mL successively, then flask is put into 240 ℃ constant temperature oil bath, color becomes light yellowly after the several minutes, fast the 300mmol oleyl amine is injected in the flask under magnetic agitation.Solution becomes reddish black very soon, continues reaction 120 minutes under magnetic agitation, and reaction is cooled to room temperature after finishing, and takes out original solution, use alcohol dilution, sonic oscillation 5min, centrifugation 5min under the 8000rpm rotating speed, product is sunken to container bottom, and abandoning supernatant obtains sosoloid Cu
0.99In
0.99Zn
0.02S
2Nano belt.The molar ratio of above-mentioned thiocarbamate copper, thiocarbamate indium, zinc thiocarbamate is 0.99:0.99:0.02, and the molar ratio of reaction precursor, amine and surface ligand mixture is 1:300:600.
Embodiment 5:
With the 0.4mmol copper dibutyldithiocarbamate, 0.4mmol dipropyl disulfide is for the carboxylamine indium, 1.2mmol dipropyl disulfide joins in the round-bottomed flask of 250mL successively for carbaminate precursors and the positive trioctyl phosphine oxide of 120mmol, then flask is put into 120 ℃ constant temperature oil bath, color becomes light yellowly after the several minutes, fast the 20mmol oleyl amine is injected in the flask under magnetic agitation.Solution becomes reddish black very soon, continues reaction 30 minutes under magnetic agitation, and reaction is cooled to room temperature after finishing, and takes out original solution, use alcohol dilution, sonic oscillation 5min, centrifugation 5min under the 8000rpm rotating speed, product is sunken to container bottom, and abandoning supernatant obtains sosoloid Cu
0.4In
0.4Zn
1.2S
2Nano belt.The molar ratio of above-mentioned thiocarbamate copper, thiocarbamate indium, zinc thiocarbamate is 0.4:0.4:1.2, and the molar ratio of reaction precursor, amine and surface ligand mixture is 1:20:120.
Shown in Fig. 1-4, adopt the quaternary sosoloid Cu of aforesaid method preparation
xIn
xZn
2 (1-x)S
2Material be shaped as nano belt, the width of band is very even, Cu
xIn
xZn
2 (1-x)S
2The head of nano belt is Catalysts Cu
1.75The S particle.
Claims (7)
1. quaternary sosoloid Cu
xIn
xZn
2 (1-x)S
2The preparation method of nano belt is characterized in that, may further comprise the steps:
(1) will be as thiocarbamate copper, thiocarbamate indium and the zinc thiocarbamate of precursors, and the surface ligand mixture joins in the reaction vessel successively;
(2) reaction vessel is put into constant temperature oil bath, question response liquid color become light yellow after, under magnetic agitation, be injected into rapidly amine in the reaction vessel; After question response liquid color becomes reddish black, continue reaction 30～120 minutes under magnetic agitation, reaction is cooled to room temperature after finishing;
(3) take out original solution, use alcohol dilution, sonic oscillation, centrifugation, abandoning supernatant obtains Cu
xIn
xZn
2 (1-x)S
2Nano belt.
2. a kind of quaternary sosoloid Cu according to claim 1
xIn
xZn
2 (1-x)S
2The preparation method of nano belt is characterized in that, the molar ratio of thiocarbamate copper, thiocarbamate indium, zinc thiocarbamate is (0.01～0.99): (0.01～0.99): (1.98～0.02).
3. a kind of quaternary sosoloid Cu according to claim 1
xIn
xZn
2 (1-x)S
2The preparation method of nano belt, it is characterized in that, the thiocarbamate class under thiocarbamate copper, thiocarbamate indium and the zinc thiocarbamate comprise N,N-Diethyldithiocarbamic Acid, dibutyl dithiocaarbamate salt, diisopropyl disulfide for carbaminate and dipropyl disulfide for carbaminate.
4. a kind of quaternary sosoloid Cu according to claim 1
xIn
xZn
2 (1-x)S
2The preparation method of nano belt is characterized in that, the molar ratio of reaction precursor, amine and surface ligand mixture is 1:(10～600): (60～1200).
5. quaternary sosoloid Cu according to claim 1
xIn
xZn
2 (1-x)S
2The preparation method of nano belt is characterized in that, the temperature range of described constant temperature oil bath is 120 ℃～240 ℃.
6. quaternary sosoloid Cu according to claim 1
xIn
xZn
2 (1-x)S
2The preparation method of nano belt is characterized in that, described surface ligand mixture is one or more in hexylmercaptan, Dodecyl Mercaptan, stearylmercaptan, oleic acid, 3-thiohydracrylic acid, positive trioctyl phosphine oxide and the positive tri octyl phosphine.
7. quaternary sosoloid Cu according to claim 1
xIn
xZn
2 (1-x)S
2The preparation method of nano belt is characterized in that, described amine is one or more in octylame, decyl amine, amino dodecane, cetylamine, stearylamine, oleyl amine and the oleylamide.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103212426A (en) * | 2013-03-25 | 2013-07-24 | 温州大学 | Nano heterojunction and preparation method thereof |
| CN104263362A (en) * | 2014-09-17 | 2015-01-07 | 重庆大学 | Ag-In-Zn-S quaternary alloy nanorod and preparation method thereof |
| CN106833610A (en) * | 2017-01-20 | 2017-06-13 | 深圳天吉新创科技有限公司 | A kind of nuclear shell structure quantum point and preparation method thereof |
| CN112058254A (en) * | 2020-09-29 | 2020-12-11 | 西安建筑科技大学 | Bimetallic oxide solid solution ZnxIn2Ox+3Preparation method of (1) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102764661A (en) * | 2012-07-26 | 2012-11-07 | 上海交通大学 | Sosoloid nanoparticle of photocatalyst and preparation method of sosoloid nanoparticle |
-
2012
- 2012-11-22 CN CN201210484313XA patent/CN102942213A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102764661A (en) * | 2012-07-26 | 2012-11-07 | 上海交通大学 | Sosoloid nanoparticle of photocatalyst and preparation method of sosoloid nanoparticle |
Non-Patent Citations (2)
| Title |
|---|
| CHAO ZOU ET AL.: "Solution-based synthesis of quaternary Cu–In–Zn–S nanobelts with tunable composition and band gap", 《CHEM. COMMUN.》, no. 47, 4 March 2011 (2011-03-04), pages 5256 - 5258 * |
| CHEN YE ET AL.: "Alloyed (ZnS)x(CuInS2)1-x Semiconductor Nanorods: Synthesis, Bandgap Tuning and Photocatalytic Properties", 《CHEM. EUR. J.》, vol. 18, 2 August 2012 (2012-08-02), pages 11258 - 11263 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103212426A (en) * | 2013-03-25 | 2013-07-24 | 温州大学 | Nano heterojunction and preparation method thereof |
| CN103212426B (en) * | 2013-03-25 | 2015-09-23 | 温州大学 | A kind of nano heterojunction and preparation method thereof |
| CN104263362A (en) * | 2014-09-17 | 2015-01-07 | 重庆大学 | Ag-In-Zn-S quaternary alloy nanorod and preparation method thereof |
| CN104263362B (en) * | 2014-09-17 | 2016-04-27 | 重庆大学 | A kind of Ag-In-Zn-S quad alloy nanometer rod and preparation method thereof |
| CN106833610A (en) * | 2017-01-20 | 2017-06-13 | 深圳天吉新创科技有限公司 | A kind of nuclear shell structure quantum point and preparation method thereof |
| CN106833610B (en) * | 2017-01-20 | 2020-04-10 | 深圳天吉新创科技有限公司 | Core-shell structure quantum dot and preparation method thereof |
| CN112058254A (en) * | 2020-09-29 | 2020-12-11 | 西安建筑科技大学 | Bimetallic oxide solid solution ZnxIn2Ox+3Preparation method of (1) |
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Application publication date: 20130227 |