CN104045105A - Process for preparing cadmium sulfide quantum dots by low temperature two-phase synthesis method - Google Patents
Process for preparing cadmium sulfide quantum dots by low temperature two-phase synthesis method Download PDFInfo
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Abstract
The invention discloses a process for preparing cadmium sulfide quantum dots by a low temperature two-phase synthesis method. The process is as follows: a cadmium source is dissolved in oleylamine at room temperature, oleic acid is added for dilution to prepare a cadmium solution as an oil phase; the cadmium source is one of cadmium chloride, cadmium sulfate and cadmium nitrate, the volume ratio of oleylamine to oleic acid is 1:4; sublimated sulfur powder is ultrasonically dissolved in dimethyl sulfoxide containing tri-n-octylphosphine at room temperature to prepare a sulfur solution, or a sulfur compound is directly dissolved in the dimethyl sulfoxide containing the tri-n-octylphosphine to prepare a sulfur solution; the sublimated sulfur powder or the sulfur compound is used as a sulfur source, the sulfur compound is thiourea or sodium sulfide, the tri-n-octylphosphine is used as a wrapping agent, the molar ratio of sulfur source to wrapping agent is 2:1; the cadmium solution is mixed with the sulfur solution for reaction for 30 minutes under the condition of water bath at 70 DEG C, and the cadmium sulfide quantum dots are produced in the oil phase. The process has the advantages of wide raw material sources and low reaction temperature, the prepared cadmium sulfide quantum dots are uniform in particle size and narrow in size distribution, the absorption peak position can be adjusted between 396 to 445 nm, and the fluorescence is strong.
Description
Technical field
The invention belongs to inorganic nano material synthesis technical field, particularly a kind of low temperature two phase synthesis are prepared the method for cadmiumsulfide quantum dot.
Background technology
Cadmium Sulfide is a kind of important II-VI family direct band-gap semicondictor material, and body phase band gap 2.42eV has good receptivity in visible-range.The Cadmium Sulfide that size reaches quantum dot level produces multiple electronics (many exciton effects) because quantum effect can absorb a photon, and its optical property changes with size is different, and these features make cadmiumsulfide quantum dot have more wide application prospect in the fields such as catalysis, nonlinear optics, magneticsubstance, opto-electronic device, solar energy converting, biology and communication.Therefore synthetic particle diameter is controlled, and the cadmiumsulfide quantum dot material of narrow diameter distribution has important practical significance.At present, preparing the controlled cadmiumsulfide quantum dot of particle diameter is mainly to adopt solvent-thermal method.Early stage solvent-thermal method mainly adopts the organism compound of cadmium as cadmium source, not only toxicity is large, and there is the danger of blast (referring to document: C. B. Murray, D. J. Norris, M. G. Bawendi, J. Am. Chem. Soc., 1993,115 (19): 9706-8715).After this, this method is improved, and can adopt more stable Cadmium oxide as raw material (referring to document: L. Qu, Z. A. Peng, X. Peng, Nano Letters, 2001,1 (6): 333-337).But from the whole preparation process of solvent-thermal method, Ji Liu source, cadmium source need to be mixed under hot conditions, and nanocrystalline nucleation and growth need be controlled under different high temperature to be carried out, the control of these conditions has all strengthened synthetic difficulty, makes this method be difficult to realize large-scale industrial production.Therefore need to look for a kind of raw material to stablize, easily obtain and comparatively close friend of relative environment, the simple synthetic method of preparation process is very important.
Summary of the invention
The object of this invention is to provide a kind of raw material is safer, cost is lower, simple to operate low temperature two phase synthesis and prepare the method for cadmiumsulfide quantum dot.
Thinking of the present invention: adopt two kinds of immiscible liquid systems respectively as the solvent that dissolves He Liu source, cadmium source, the two-phase system of formation reacts at low temperatures, prepares cadmiumsulfide quantum dot.
Concrete steps are:
(1) cadmium source is at room temperature dissolved in to oleyl amine, adds afterwards oleic acid dilution, make cadmium solution, be oil phase; Described cadmium source is the one in Cadmium chloride fine powder, Cadmium Sulphate and cadmium nitrate, and the volume ratio of described oleyl amine and oleic acid is 1:4.
(2) by sublimed sulphur powder at ambient temperature ultrasonic dissolution in the dimethyl sulfoxide (DMSO) that contains tri octyl phosphine, make sulphur solution or sulfocompound be directly dissolved in and in the dimethyl sulfoxide (DMSO) that contains tri octyl phosphine, make sulphur solution; Described sublimed sulphur powder or sulfocompound are sulphur source, and described sulfocompound is thiocarbamide or sodium sulphite, and described tri octyl phosphine is coating agent, and the mol ratio of sulphur source and coating agent is 2:1.
(3) cadmium solution step (1) being made mixes with the sulphur solution that step (2) makes, under 70 degree water bath condition, react 30 minutes, in oil phase, have cadmiumsulfide quantum dot to generate, then the oil phase in abstraction reaction system, adds ethanol, centrifugal, by the yellow mercury oxide toluene wash obtaining, then add ethanol, centrifugal, finally, taking toluene as solvent dispersion, make cadmiumsulfide quantum dot colloidal sol.
The mol ratio in He Liu source, described cadmium source is 1:7 ~ 5:3.The mol ratio that changes Yu Liu source, cadmium source can make the quantum dot of different size.
The inventive method raw material sources are wide, and temperature of reaction is low, only need the material rate in change Yu Liu source, cadmium source can obtain the cadmiumsulfide quantum dot of different-grain diameter.Adopting on the basis of same materials proportioning, changing temperature of reaction and can not produce significantly impact to particle size were.The particle diameter of the cadmiumsulfide quantum dot making is even, and distribution of sizes is narrower, and extinction peak position is adjustable between 396 ~ 445 nanometers, and fluorescence is stronger.
Brief description of the drawings
Fig. 1 is the transmission electron microscope picture of the cadmiumsulfide quantum dot that makes of embodiment of the present invention 1-4, wherein A is the transmission electron microscope picture of the cadmiumsulfide quantum dot that makes of embodiment 1, B is the transmission electron microscope picture of the cadmiumsulfide quantum dot that makes of embodiment 2, C is the transmission electron microscope picture of the cadmiumsulfide quantum dot that makes of embodiment 3, and D is the transmission electron microscope picture of the cadmiumsulfide quantum dot that makes of embodiment 4.
Fig. 2 is the ultraviolet-visible light spectrogram of the cadmiumsulfide quantum dot that makes of embodiment of the present invention 1-5, wherein Cd:S=1:7 line is the ultraviolet-visible light spectrogram of the cadmiumsulfide quantum dot that makes of embodiment 1, Cd:S=1:5 line is the ultraviolet-visible light spectrogram of the cadmiumsulfide quantum dot that makes of embodiment 2, Cd:S=1:2 line is the ultraviolet-visible light spectrogram of the cadmiumsulfide quantum dot that makes of embodiment 3, Cd:S=1:1 line is the ultraviolet-visible light spectrogram of the cadmiumsulfide quantum dot that makes of embodiment 4, and Cd:S=5:3 line is the ultraviolet-visible light spectrogram of the cadmiumsulfide quantum dot that makes of embodiment 5.
The fluorescence spectrum figure of the cadmiumsulfide quantum dot that Fig. 3 embodiment of the present invention 1-5 makes, wherein Cd:S=1:7 line is the fluorescence spectrum figure of the cadmiumsulfide quantum dot that makes of embodiment 1, Cd:S=1:5 line is the fluorescence spectrum figure of the cadmiumsulfide quantum dot that makes of embodiment 2, Cd:S=1:2 line is the fluorescence spectrum figure of the cadmiumsulfide quantum dot that makes of embodiment 3, Cd:S=1:1 line is the fluorescence spectrum figure of the cadmiumsulfide quantum dot that makes of embodiment 4, and Cd:S=5:3 line is the fluorescence spectrum figure of the cadmiumsulfide quantum dot that makes of embodiment 5.
Embodiment
embodiment 1:
(1) 0.025 mmole cadmium nitrate is dissolved in 1.25 milliliters of oleyl amines, then adds 5 milliliters of oleic acid dilutions, make cadmium solution.
(2) 0.0056 gram of (0.175 mmole) sublimed sulphur powder and 0.0324 gram of (0.0875 mmole) tri octyl phosphine are joined in 5 milliliters of dimethyl sulfoxide (DMSO), ultrasonicly at ambient temperature sublimed sulphur powder is dissolved make sulphur solution.
(3) cadmium solution step (1) being made mixes with the sulphur solution that step (2) makes, and under 70 degree water-baths, reacts 30 minutes, after reaction finishes, has cadmiumsulfide quantum dot to generate in oil phase.Then the oil phase in abstraction reaction system, adds ethanol, centrifugal, by the yellow mercury oxide toluene wash obtaining, then adds ethanol, centrifugal, finally taking toluene as solvent dispersion, makes cadmiumsulfide quantum dot colloidal sol.
The cadmiumsulfide quantum dot that the present embodiment is made characterizes, transmission electron microscope picture is shown in the A in Fig. 1, the cadmiumsulfide quantum dot making is class point-like, particle diameter is 5.5nm, the extinction peak position of its toluene solution is (Cd:S=1:7 line in seeing Fig. 2) near 445 nm, and fluorescence peak position is (Cd:S=1:7 line in seeing Fig. 3) near 470 nm.
embodiment 2:
(1) 0.025 mmole Cadmium Sulphate is dissolved in 1.25 milliliters of oleyl amines, then adds 5 milliliters of oleic acid dilutions, make cadmium solution.
(2) 0.004 gram of (0.125 mmole) sublimed sulphur powder and 0.0232 gram of (0.0625 mmole) tri octyl phosphine are joined in 5 milliliters of dimethyl sulfoxide (DMSO), ultrasonicly at ambient temperature sublimed sulphur powder is dissolved make sulphur solution.
(3) cadmium solution step (1) being made mixes with the sulphur solution that step (2) makes, and under 70 degree water-baths, reacts 30 minutes, after reaction finishes, has cadmiumsulfide quantum dot to generate in oil phase.Then the oil phase in abstraction reaction system, adds ethanol, centrifugal, by the yellow mercury oxide toluene wash obtaining, then adds ethanol, centrifugal, finally taking toluene as solvent dispersion, makes cadmiumsulfide quantum dot colloidal sol.
The cadmiumsulfide quantum dot that the present embodiment is made characterizes, transmission electron microscope picture is shown in the B in Fig. 1, the cadmiumsulfide quantum dot making is that class is spherical, particle diameter is 3.8 nm, the extinction peak position of its toluene solution is (Cd:S=1:5 line in seeing Fig. 2) near 436 nm, and fluorescence peak position is (Cd:S=1:5 line in seeing Fig. 3) near 464 nm.
embodiment 3:
(1) 0.025 mmole Cadmium chloride fine powder is dissolved in 1.25 milliliters of oleyl amines, then adds 5 milliliters of oleic acid dilutions, make cadmium solution.
(2) 0.0016 gram of (0.05 mmole) sublimed sulphur powder and 0.0093 gram of (0.025 mmole) tri octyl phosphine are joined in 5 milliliters of dimethyl sulfoxide (DMSO), ultrasonicly at ambient temperature sublimed sulphur powder is dissolved make sulphur solution.
(3) cadmium solution step (1) being made mixes with the sulphur solution that step (2) makes, and under 70 degree water-baths, reacts 30 minutes, after reaction finishes, has cadmiumsulfide quantum dot to generate in oil phase.Then the oil phase in abstraction reaction system, adds ethanol, centrifugal, by the yellow mercury oxide toluene wash obtaining, then adds ethanol, centrifugal, finally taking toluene as solvent dispersion, makes cadmiumsulfide quantum dot colloidal sol.
The cadmiumsulfide quantum dot that the present embodiment is made characterizes, transmission electron microscope picture is shown in the C in Fig. 1, the cadmiumsulfide quantum dot making is that class is spherical, particle diameter is 2.6 nm, the extinction peak position of its toluene solution is (Cd:S=1:2 line in seeing Fig. 2) near 420 nm, and fluorescence peak position is (Cd:S=1:2 line in seeing Fig. 3) near 460 nm.
embodiment 4:
(1) 0.025 mmole cadmium nitrate is dissolved in 1.25 milliliters of oleyl amines, then adds 5 milliliters of oleic acid dilutions, make cadmium solution.
(2) 0.002 gram of (0.025 mmole) thiocarbamide and 0.0046 gram of (0.0125 mmole) tri octyl phosphine are dissolved in 5 milliliters of dimethyl sulfoxide (DMSO).
(3) cadmium solution step (1) being made mixes with the sulphur solution that step (2) makes, and under 70 degree water-baths, reacts 30 minutes, after reaction finishes, has cadmiumsulfide quantum dot to generate in oil phase.Then the oil phase in abstraction reaction system, adds ethanol, centrifugal, by the yellow mercury oxide toluene wash obtaining, then adds ethanol, centrifugal, finally taking toluene as solvent dispersion, makes cadmiumsulfide quantum dot colloidal sol.
The cadmiumsulfide quantum dot that the present embodiment is made characterizes, transmission electron microscope picture is shown in the D in Fig. 1, the cadmiumsulfide quantum dot making is that class is spherical, particle diameter is 2.1 nm, the extinction peak position of its toluene solution is (Cd:S=1:1 line in seeing Fig. 2) near 405 nm, and fluorescence peak position is (Cd:S=1:1 line in seeing Fig. 3) near 440 nm.
embodiment 5:
(1) 0.025 mmole cadmium nitrate is dissolved in 1.25 milliliters of oleyl amines, then adds 5 milliliters of oleic acid dilutions, make cadmium solution.
(2) 0.001 gram of (0.015 mmole) sodium sulphite and 0.0028 gram of (0.0075 mmole) tri octyl phosphine are dissolved in 5 milliliters of dimethyl sulfoxide (DMSO).
(3) cadmium solution step (1) being made mixes with the sulphur solution that step (2) makes, and reacts after reaction in 30 minutes finishes and in oil phase, have cadmiumsulfide quantum dot to generate under 70 degree water-baths.Then the oil phase in abstraction reaction system, adds ethanol, centrifugal, by the yellow mercury oxide toluene wash obtaining, then adds ethanol, centrifugal, finally taking toluene as solvent dispersion, makes cadmiumsulfide quantum dot colloidal sol.
The cadmiumsulfide quantum dot that the present embodiment is made characterizes, in transmission electron microscope picture, can find out that the cadmiumsulfide quantum dot that the present embodiment makes is that class is spherical, particle diameter is 1.8 nm, the extinction peak position of its toluene solution is (Cd:S=5:3 line in seeing Fig. 2) near 390 nm, and fluorescence peak position is (Cd:S=5:3 line in seeing Fig. 3) near 430 nm.
Claims (1)
1. low temperature two phase synthesis are prepared a method for cadmiumsulfide quantum dot, it is characterized in that concrete steps are:
(1) cadmium source is at room temperature dissolved in to oleyl amine, adds afterwards oleic acid dilution, make cadmium solution, be oil phase; Described cadmium source is the one in Cadmium chloride fine powder, Cadmium Sulphate and cadmium nitrate, and the volume ratio of described oleyl amine and oleic acid is 1:4;
(2) by sublimed sulphur powder at ambient temperature ultrasonic dissolution in the dimethyl sulfoxide (DMSO) that contains tri octyl phosphine, make sulphur solution or sulfocompound be directly dissolved in and in the dimethyl sulfoxide (DMSO) that contains tri octyl phosphine, make sulphur solution; Described sublimed sulphur powder or sulfocompound are sulphur source, and described sulfocompound is thiocarbamide or sodium sulphite, and described tri octyl phosphine is coating agent, and the mol ratio of sulphur source and coating agent is 2:1;
(3) cadmium solution step (1) being made mixes with the sulphur solution that step (2) makes, under 70 degree water bath condition, react 30 minutes, in oil phase, have cadmiumsulfide quantum dot to generate, then the oil phase in abstraction reaction system, adds ethanol, centrifugal, by the yellow mercury oxide toluene wash obtaining, then add ethanol, centrifugal, finally, taking toluene as solvent dispersion, make cadmiumsulfide quantum dot colloidal sol;
Mol ratio 1:7 ~ the 5:3 in He Liu source, described cadmium source.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111710754A (en) * | 2020-05-11 | 2020-09-25 | 桂林理工大学 | Bi preparation by two-phase one-step solvothermal method2S3Method for preparing-graphene-ZnS photoelectric composite material |
| CN113755164A (en) * | 2021-10-14 | 2021-12-07 | 汕头职业技术学院 | Green and environment-friendly cadmium sulfide quantum dot preparation and manufacturing process |
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| CN102516995A (en) * | 2011-11-22 | 2012-06-27 | 武汉因诺维生物科技有限公司 | Method for preparing water-phase CdS quantum dots in oil phase |
| CN103361066A (en) * | 2013-06-28 | 2013-10-23 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method for synthesizing CdSe/CdS core-shell structure quantum dots through one step |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102516995A (en) * | 2011-11-22 | 2012-06-27 | 武汉因诺维生物科技有限公司 | Method for preparing water-phase CdS quantum dots in oil phase |
| CN103361066A (en) * | 2013-06-28 | 2013-10-23 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method for synthesizing CdSe/CdS core-shell structure quantum dots through one step |
Non-Patent Citations (2)
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| NA LI, ET AL.: "Synthesis and optical properties of CdS nanorods and CdSe nanocrystals using oleylamine as both solvent and stabilizer", 《MATERIALS SCIENCE AND ENGINEERING B》, vol. 176, 31 December 2011 (2011-12-31), pages 688 - 691, XP028194882, DOI: 10.1016/j.mseb.2011.02.016 * |
| SHUTANG CHEN, ET AL.: "Trioctylphosphine as Both Solvent and Stabilizer to Synthesize CdS Nanorods", 《NANOSCALE RESEARCH LETTERS》, vol. 4, 17 June 2009 (2009-06-17), pages 1159 - 1165 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111710754A (en) * | 2020-05-11 | 2020-09-25 | 桂林理工大学 | Bi preparation by two-phase one-step solvothermal method2S3Method for preparing-graphene-ZnS photoelectric composite material |
| CN111710754B (en) * | 2020-05-11 | 2023-01-06 | 桂林理工大学 | Two-phase one-step solvothermal preparation of Bi 2 S 3 Method for preparing-graphene-ZnS photoelectric composite material |
| CN113755164A (en) * | 2021-10-14 | 2021-12-07 | 汕头职业技术学院 | Green and environment-friendly cadmium sulfide quantum dot preparation and manufacturing process |
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