CN1762820A - Method for preparing sulfide nanometer particle - Google Patents

Method for preparing sulfide nanometer particle Download PDF

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Publication number
CN1762820A
CN1762820A CN 200510103028 CN200510103028A CN1762820A CN 1762820 A CN1762820 A CN 1762820A CN 200510103028 CN200510103028 CN 200510103028 CN 200510103028 A CN200510103028 A CN 200510103028A CN 1762820 A CN1762820 A CN 1762820A
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particle
reaction
sulfide
metal ion
polar solvent
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CN100383048C (en
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王训
庄京
李亚栋
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Tsinghua University
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Tsinghua University
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Abstract

The present invention discloses process of preparing nanometer sulfide particle. In the process, metal ion and sulfur-containing compound are reacted inside mixed system comprising alkali metal hydroxide, fatty acid and organic polar solvent to produce nanometer sulfide particle. The prepared monodispresive nanometer sulfide particle may find wide applications in biological marking and analysis, solar cell and other fields. The present invention adopts reaction system comprising water and polar alcohol solvent, rather than great amount of organic solvent, and has less environmental pollution, simple process, high safety, low cost, wide adaptability and wide application foreground.

Description

A kind of method for preparing sulfide nano-particle
Technical field
The present invention relates to a kind of method for preparing sulfide nano-particle.
Background technology
Semi-conductor sulfuration thing nanoparticle has in fields such as biomarker, analysis, solar cells widely to be used, thus the control of sulfide nanocrystalline synthetic be to study one of focus in the world.Extensively adopt the organic liquid phase synthetic method to prepare the metal sulfide semiconductor monodisperse nanoparticle at present in the world, on U.S.'s " inorganic chemistry " magazine, reported to be that liquid-phase system, cadmium metal powder, sulphur powder are the method for raw material synthesizing cadmium sulfide nanometer rod in 1998 with the quadrol as people such as Li Yadongs; People such as Peng XG reported with octadecene non-ligand solvent liquid-phase system in 2002 on " German applied chemistry ", with CdO, sulphur powder be the synthetic CdS of raw material nanocrystalline (Angew.Chem.Int.Ed., 2002,41:2368); People such as T.Hyeon 2003 in " American Chemical Society can will ", have reported the oleylamine system, with metal chloride, sulphur powder be raw material synthetic CdS, ZnS, PbS, MnS nanocrystalline (J.Am.Chem.Soc, 2003,125:11100); L.J.An etc. have reported with the nanocrystalline method of TOPO-oleic acid system synthesizing cadmium sulfide on Germany's " advanced material " magazine; People such as W.S.Chin reported the Hexadecylamine-TOP liquid-phase system in 2004, have been the method for the synthetic silver sulfide monodisperse nanoparticle of presoma with organometallics Ag (SCOPh) on " German applied chemistry ".
In sum, the synthetic method of the at present domestic and international semi-conductor sulfuration thing nanoparticle of reporting is mainly single non-aqueous solvent system, generally all adopts a large amount of organic solvents, has problems such as production cost and environmental pollution.
Summary of the invention
The purpose of this invention is to provide a kind of method for preparing sulfide nano-particle.
The method for preparing sulfide nano-particle provided by the present invention is that metal ion and sulfocompound are reacted in the mixed system of alkali metal hydroxide, lipid acid and organic polar solvent, obtains described sulfide nano-particle.
Wherein, the step of above-mentioned reaction is: earlier alkali metal hydrogen oxygen compound, lipid acid are mixed with organic polar solvent, add metal ion solution and sulfur compound aqueous solution anabolic reaction system then, reaction system 20-300 ℃ of reaction down, is obtained described sulfide nano-particle.
In the reaction process, the volume ratio of lipid acid and organic polar solvent is 1: 0.5-5; The concentration of metal ion in reaction system is 0.01-0.5mol/L, and the concentration of sulfocompound in reaction system is 0.01-0.5mol/L; Alkali metal hydroxide: the mol ratio of metal ion is 1-10: 1.Metal ion is copper, zinc, silver, chromium, manganese or lead ion etc., can be provided by the soluble salt of these metallic elements, as solubility nitrate, vitriol, acetate and hydrochloride etc.Sulfocompound commonly used is sodium sulphite, ammonium sulfide, sulphur hydrogenation ammonium or sulphur urine etc.; Used lipid acid has oleic acid, stearic acid or capric acid etc.; Organic polar solvent can be selected ethanol, acetone, ethylene glycol or glycerol etc.
It is raw material that the present invention adopts inorganic salt, alkali metal hydroxide, sulfocompound, in the mixed system of lipid acid, water, organic polar solvent, react, promptly can obtain the sulfide particles of dispersed nano level, prepared sulfide nano-particle is widely used in fields such as biomarker, analysis and solar cells.The present invention constitutes reaction system with water and alcohols polar solvent, has overcome to adopt cost and the problem of environmental pollution that a large amount of organic solvent brought in the existing method, and the inventive method is easy, safety, cost is low, suitability is wide, is with a wide range of applications.
Description of drawings
Fig. 1 is the prepared silver sulfide X-ray powder diffraction figure of embodiment 1.
Fig. 2 is that embodiment 1 prepared silver sulfide TEM Electronic Speculum detects figure.
Fig. 3 is the prepared zinc sulphide X-ray powder diffraction figure of embodiment 3.
Fig. 4 is that embodiment 3 prepared zinc sulphide TEM Electronic Speculum detect figure.
Fig. 5 is the prepared Cadmium Sulfide X-ray powder diffraction figure of embodiment 5.
Fig. 6 is that embodiment 5 prepared Cadmium Sulfide TEM Electronic Speculum detect figure.
Fig. 7 is the prepared lead sulfide X-ray powder diffraction figure of embodiment 8.
Fig. 8 is that embodiment 8 prepared lead sulfide TEM Electronic Speculum detect figure.
Embodiment
Embodiment 1,
Taking by weighing 0.7gNaOH adds in 10ml oleic acid, the 15ml ethanol mixed solvent, fully behind the about 30mins of reaction, taking by weighing 0.8g analytical pure Silver Nitrate again is dissolved in the 7mL water, take by weighing 0.6g analytical pure sodium sulphite and be dissolved in the 8mL water, silver ions, the sulfonium ion solution of preparing is added in the mixed solvent, stir, place the withstand voltage reactor of stainless steel of 40ml, behind 140 ℃ of reaction 24h, gained precipitates after centrifugation, washing, drying, obtains black powder.Product is accredited as silver sulfide through X-ray powder diffraction as shown in Figure 1; (TEM) carries out morphology analysis to it with transmission electron microscope, and as can be seen from Figure 2 its pattern is the dispersed nano particle, and particle diameter is about 10nm.
Embodiment 2,
Taking by weighing 0.8gKOH adding 20ml is dissolved with in the stearic ethylene glycol solvent of 5g, fully behind the about 30mins of reaction, taking by weighing 0.5g analytical pure Silver Nitrate again is dissolved in the 10mL water, take by weighing 0.4g analytical pure ammonium sulfide and be dissolved in the 10mL water, silver ions, the sulfonium ion solution of preparing is added in the mixed solvent, stir, place the withstand voltage reactor of stainless steel of 40ml, behind 160 ℃ of reaction 24h, gained precipitates after centrifugation, washing, drying, obtains black powder.Product is accredited as silver sulfide through X-ray powder diffraction; (TEM) carries out morphology analysis to it with transmission electron microscope, and observing its pattern is the dispersed nano particle, and particle diameter is about 30nm.
Embodiment 3,
Taking by weighing 0.5gNaOH adds in 5ml oleic acid, the 10ml ethanol mixed solvent, fully behind the about 30mins of reaction, taking by weighing 1g analytical pure zinc chloride again is dissolved in the 10mL water, take by weighing 1g analysis bright sulfur urine and be dissolved in the 15mL water, and zine ion, the sulfonium ion solution that is made into is added in the mixed solvent, stir, place the withstand voltage reactor of stainless steel of 40ml, behind 180 ℃ of reaction 24h, gained precipitates after centrifugation, washing, drying, obtains white powder.Product is accredited as zinc sulphide through X-ray powder diffraction as shown in Figure 3; (TEM) carries out morphology analysis to it with transmission electron microscope, and as can be seen from Figure 4 its pattern is the dispersed nano particle, and particle diameter is between 4-6nm.
Embodiment 4:
Taking by weighing 0.4gKOH adds in the mixed solvent of 10ml oleic acid, 20ml acetone, fully behind the about 30mins of reaction, taking by weighing 0.5g analytical pure zinc chloride again is dissolved in the 5mL water, take by weighing 0.3g analysis bright sulfur hydrogenation ammonium and be dissolved in the 5mL water, and zine ion, the sulfonium ion solution that is made into is added in the mixed solvent, stir, place the withstand voltage reactor of stainless steel of 40ml, behind 160 ℃ of reaction 24h, gained precipitates after centrifugation, washing, drying, obtains white powder.Product is accredited as zinc sulphide through X-ray powder diffraction; (TEM) carries out morphology analysis to it with transmission electron microscope, and observing its pattern is the dispersed nano particle, and particle diameter is between 10-20nm.
Embodiment 5:
Taking by weighing 1gNaOH adds in 10ml oleic acid, the 8ml ethanol mixed solvent, fully behind the about 30mins of reaction, taking by weighing 0.8g analytical pure sulfuric acid chromium again is dissolved in the 10mL water, take by weighing 0.8g analytical pure sodium sulphite and be dissolved in the 10mL water, and chromium ion, the sulfonium ion solution that is made into is added in the mixed solvent, stir, place the withstand voltage reactor of stainless steel of 40ml, behind 180 ℃ of reaction 24h, gained precipitates after centrifugation, washing, drying, obtains yellow powder.Product is accredited as chromic sulfide through X-ray powder diffraction as shown in Figure 5; (TEM) carries out morphology analysis to it with transmission electron microscope, and as can be seen from Figure 6 its pattern is the dispersed nano particle, and particle diameter is between 4-5nm.
Embodiment 6:
Taking by weighing 1gKOH adds in 5ml capric acid, the 20ml ethanol mixed solvent, fully behind the about 30mins of reaction, taking by weighing 1g analytical pure chromium nitrate again is dissolved in the 10mL water, take by weighing 1g analytical pure ammonium sulfide and be dissolved in the 10mL water, and chromium ion, the sulfonium ion solution that is made into is added in the mixed solvent, stir, place the withstand voltage reactor of stainless steel of 40ml, behind 250 ℃ of reaction 24h, gained precipitates after centrifugation, washing, drying, obtains yellow powder.Product is accredited as chromic sulfide through X-ray powder diffraction; (TEM) carries out morphology analysis to it with transmission electron microscope, and observing its pattern is the dispersed nano particle, and particle diameter is between 20-30nm.
Embodiment 7:
Taking by weighing 0.5gNaOH adds in 8ml oleic acid, the 15ml ethanol mixed solvent, fully behind the about 30mins of reaction, taking by weighing 0.5g analytical pure sulfuric acid manganese again is dissolved in the 8mL water, take by weighing 0.5g analytical pure sodium sulphite and be dissolved in the 7mL water, and mn ion, the sulfonium ion solution that is made into is added in the mixed solvent, stir, place the withstand voltage reactor of stainless steel of 40ml, behind 50 ℃ of reaction 24h, gained precipitates after centrifugation, washing, drying, obtains brown ceramic powder.Product is accredited as manganese sulfide through X-ray powder diffraction as shown in Figure 7; (TEM) carries out morphology analysis to it with transmission electron microscope, and as can be seen from Figure 8 its pattern is the dispersed nano particle, and particle diameter is between 5-6nm.
Embodiment 8:
Taking by weighing 0.4gNaOH adds in 10ml oleic acid, the 10ml ethanol mixed solvent, fully behind the about 30mins of reaction, taking by weighing 1g analytical pure lead nitrate again is dissolved in the 10mL water, take by weighing 0.5g analytical pure sodium sulphite and be dissolved in the 10mL water, and lead ion, the sulfonium ion solution that is made into is added in the mixed solvent, stir, place the withstand voltage reactor of stainless steel of 40ml, behind 20 ℃ of reaction 24h, gained precipitates after centrifugation, washing, drying, obtains black powder.Product is accredited as lead sulfide through X-ray powder diffraction as shown in Figure 9; (TEM) carries out morphology analysis to it with transmission electron microscope, and as can be seen from Figure 10 its pattern is the dispersed nano particle, and particle diameter is between 4-5nm.
Embodiment 9:
Taking by weighing 0.4gKOH adds in the mixed solvent of 6ml oleic acid, 18ml glycerol, fully behind the about 30mins of reaction, taking by weighing 0.5g analytical pure neutralized verdigris again is dissolved in the 6mL aqueous solution, take by weighing 1g analytical pure sodium sulphite and be dissolved in the 10mL water, and cupric ion, the sulfonium ion solution that is made into is added in the mixed solvent, stir, place the withstand voltage reactor of stainless steel of 40ml, behind 80 ℃ of reaction 24h, gained precipitates after centrifugation, washing, drying, obtains black powder.Product is accredited as cupric sulfide through X-ray powder diffraction; (TEM) carries out morphology analysis to it with transmission electron microscope, and observing its pattern is the dispersed nano particle, and particle diameter is between 50-60nm.

Claims (7)

1, a kind of method for preparing sulfide nano-particle is that metal ion and sulfocompound are reacted in the mixed system of alkali metal hydroxide, lipid acid and organic polar solvent, obtains described sulfide nano-particle.
2, method according to claim 1, it is characterized in that: the step of described reaction is: earlier alkali metal hydrogen oxygen compound, lipid acid are mixed with organic polar solvent, add metal ion solution and sulfur compound aqueous solution anabolic reaction system then, reaction system 20-300 ℃ of reaction down, is obtained described sulfide nano-particle.
3, method according to claim 2 is characterized in that: the volume ratio of described lipid acid and described organic polar solvent is 1: 0.5-5; The concentration of described metal ion in described reaction system is 0.01-0.5mol/L, and the concentration of described sulfocompound in described reaction system is 0.01-0.5mol/L; Described alkali metal hydroxide: the mol ratio of described metal ion is 1-10: 1.
4, according to claim 1 or 2 or 3 described methods, it is characterized in that: described metal ion is copper, zinc, silver, chromium, manganese or lead ion.
5, according to claim 1 or 2 or 3 described methods, it is characterized in that: described sulfocompound is sodium sulphite, ammonium sulfide, sulphur hydrogenation ammonium or sulphur urine.
6, according to claim 1 or 2 or 3 described methods, it is characterized in that: described lipid acid is oleic acid, stearic acid or capric acid.
7, according to claim 1 or 2 or 3 described methods, it is characterized in that: described organic polar solvent is ethanol, acetone, ethylene glycol or glycerol.
CNB2005101030289A 2005-09-15 2005-09-15 Method for preparing sulfide nanometer particle Expired - Fee Related CN100383048C (en)

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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100497163C (en) * 2007-06-21 2009-06-10 重庆大学 Compound alkali metal hydrate dissolvent synthesis method for metallic sulfide nano crystal material
CN101851010A (en) * 2010-06-08 2010-10-06 南开大学 Synthesizing method for transition metal sulfide
CN101544394B (en) * 2008-03-25 2010-10-13 大同股份有限公司 Porous copper sulfide nano-micron hollow sphere and preparation method thereof
CN102502773A (en) * 2011-11-23 2012-06-20 陕西科技大学 Preparation method of annular self assembled copper sulfide hollow spheres
CN102502774A (en) * 2011-11-23 2012-06-20 陕西科技大学 Method for preparing bar-shaped copper sulfide (CuS) nanocrystallines by microwave solvothermal method
CN102502775A (en) * 2011-11-23 2012-06-20 陕西科技大学 Preparation method of spherical copper sulphide (CuS) particles
CN105776319A (en) * 2016-02-03 2016-07-20 中国科学院新疆理化技术研究所 Preparation method of zinc sulfide granules of hierarchical structure for rapidly detecting explosive atmosphere
CN106848068A (en) * 2017-02-21 2017-06-13 华侨大学 A kind of preparation method of low temperature perovskite solar cell
CN109565073A (en) * 2016-11-28 2019-04-02 株式会社Lg化学 Lithium-sulfur cell positive electrode active materials and its manufacturing method comprising metallic sulfide nano-particle
CN110129109A (en) * 2019-06-17 2019-08-16 中国科学院兰州化学物理研究所 A kind of preparation method and applications of transient metal sulfide nanoparticle

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CN1189399C (en) * 2002-04-23 2005-02-16 中国科学院化学研究所 Process for preparing nano-class Cds semiconductor material
CN1155522C (en) * 2002-11-27 2004-06-30 南开大学 Transition metal sulfied nano-pipe and preparation process and its application
CN1218880C (en) * 2003-01-20 2005-09-14 中国科学院金属研究所 Method for mass producing material in nano structure of fullereneoid of molybdenum disulfide
CN1234612C (en) * 2003-09-02 2006-01-04 浙江大学 Method for preparing nano bars of cadmiun sulfide
CN1261358C (en) * 2004-07-08 2006-06-28 南京大学 PbS nano-ribbon and its producing method

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100497163C (en) * 2007-06-21 2009-06-10 重庆大学 Compound alkali metal hydrate dissolvent synthesis method for metallic sulfide nano crystal material
CN101544394B (en) * 2008-03-25 2010-10-13 大同股份有限公司 Porous copper sulfide nano-micron hollow sphere and preparation method thereof
CN101851010A (en) * 2010-06-08 2010-10-06 南开大学 Synthesizing method for transition metal sulfide
CN102502773A (en) * 2011-11-23 2012-06-20 陕西科技大学 Preparation method of annular self assembled copper sulfide hollow spheres
CN102502774A (en) * 2011-11-23 2012-06-20 陕西科技大学 Method for preparing bar-shaped copper sulfide (CuS) nanocrystallines by microwave solvothermal method
CN102502775A (en) * 2011-11-23 2012-06-20 陕西科技大学 Preparation method of spherical copper sulphide (CuS) particles
CN102502774B (en) * 2011-11-23 2013-08-28 陕西科技大学 Method for preparing bar-shaped copper sulfide (CuS) nanocrystallines by microwave solvothermal method
CN105776319A (en) * 2016-02-03 2016-07-20 中国科学院新疆理化技术研究所 Preparation method of zinc sulfide granules of hierarchical structure for rapidly detecting explosive atmosphere
CN109565073A (en) * 2016-11-28 2019-04-02 株式会社Lg化学 Lithium-sulfur cell positive electrode active materials and its manufacturing method comprising metallic sulfide nano-particle
CN106848068A (en) * 2017-02-21 2017-06-13 华侨大学 A kind of preparation method of low temperature perovskite solar cell
CN110129109A (en) * 2019-06-17 2019-08-16 中国科学院兰州化学物理研究所 A kind of preparation method and applications of transient metal sulfide nanoparticle

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