CN100344531C - Process of preparing monodisperse nanometer semiconductor selenide particle - Google Patents
Process of preparing monodisperse nanometer semiconductor selenide particle Download PDFInfo
- Publication number
- CN100344531C CN100344531C CNB2005101092158A CN200510109215A CN100344531C CN 100344531 C CN100344531 C CN 100344531C CN B2005101092158 A CNB2005101092158 A CN B2005101092158A CN 200510109215 A CN200510109215 A CN 200510109215A CN 100344531 C CN100344531 C CN 100344531C
- Authority
- CN
- China
- Prior art keywords
- selenium
- selenide
- polar solvent
- organic polar
- metal ion
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Images
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
- Photovoltaic Devices (AREA)
Abstract
The present invention discloses a method for preparing the nanometer particles of semiconductor selenide, which comprises the following steps: making a metallic ion solution and a selenium source react in a mixed system of alkali metal hydroxide, fatty acid and an organic polar solvent to obtain the nanometer particles of monodisperse semiconductor selenide. The selenium source is a system composed of a compound containing selenium and a reducing agent, or is metal selenium powder. The present invention forms a mixed solvent system by the fatty acid and the organic polar solvent. Soluble metal salt, the selenium source and the alkali metal hydroxide are used as raw materials for preparing the nanometer particles of the monodisperse semiconductor selenide. The method of the present invention has the advantages of convenience, safety, low cost and wide applicability; simultaneously, the present invention is suitable for synthesizing various kinds of nanometer particles of semiconductor selenide; the present invention overcomes the problems of high cost and environmental pollution because large numbers of organic solvents are used in the existing synthetic route; the nanometer particles of the semiconductor selenide can be widely applied to the fields of biological tag, analysis, solar batteries, etc.
Description
Technical field
The present invention relates to preparation of nanomaterials, particularly relate to a kind of method for preparing nanometer semiconductor selenide particle.
Background technology
Nanometer semiconductor selenide particle has in fields such as biomarker, analysis, solar cells widely to be used.Developed at present the method for multiple synthetic selenide nanometer particle, on " nature " magazine, reported to be stablizer and style control agent in 2000, be raw material as people such as Peng XG with organic cadmium of metal and selenium powder with TOPO-HPA, the method of synthesizing cadmium selenide nano-crystal (2000,404 volume 59-61 pages or leaves); Subsequently calendar year 2001 in " American Chemical Society can will ", have reported again with TOPO-HPA be stablizer, Cadmium oxide be the raw material synthesizing cadmium selenide nano-crystal method (J.Am.Chem.Soc., 2001,123:183); People such as Li Yadong have reported on U.S.'s " inorganic chemistry " magazine with the reaction at aqueous phase direct reaction synthesizing CdSe and zinc selenide of cadmium metal powder, zinc powder and selenium powder calendar year 2001, but this method is difficult to realize the control (calendar year 2001,40 volume 3840-3841 pages or leaves) to the product size.
In sum, at present the synthetic method of the domestic and international nanometer semiconductor selenide particle of reporting has generally all used a large amount of organic solvents to be liquid-phase system, still lacks at present based on the water liquid-phase system, applicable to the report of multiple semiconductor selenide monodisperse nanoparticle synthetic method.
Summary of the invention
The purpose of this invention is to provide a kind of method for preparing monodisperse nanometer semiconductor selenide particle.
The method for preparing monodisperse nanometer semiconductor selenide particle provided by the present invention, be that metal ion solution and selenium source are reacted in the mixed system of alkali metal hydroxide, lipid acid and organic polar solvent, obtain described monodisperse nanometer semiconductor selenide particle; Described selenium source is the system that selenium-containing compound and reductive agent are formed, and perhaps is the metal selenium powder.
The step of above-mentioned reaction is: earlier solid alkali metal oxyhydroxide is joined in the mixed solvent of lipid acid and organic polar solvent, add metal ion solution and selenium source after the mixing again, 20-300 ℃ of reaction down, obtain described monodisperse nano metal oxide particle then.
Wherein, selenium-containing compound commonly used is a Sodium Selenite in the selenium source of above-mentioned selenium-containing compound and reductive agent composition, and reductive agent is a hydrazine hydrate, and the mol ratio of reductive agent and described selenium-containing compound is 5-10: 1.
In the reaction system, the volume ratio of lipid acid and organic polar solvent is 1: 0.5-10; The concentration of metal ion solution is 0.01-0.5mol/L, and the mol ratio of selenium element and metal ion is 0.1-6 in the selenium source: 1; The mol ratio of alkali metal hydroxide and described metal ion is 1-10: 1.
Metal ion is zinc, silver, cadmium, manganese or lead ion etc., can its soluble salt, and waiting as nitrate, vitriol, acetate or hydrochloride provides; Lipid acid is oleic acid, stearic acid or capric acid etc.; Organic polar solvent is ethanol, acetone, ethylene glycol, quadrol or glycerol etc.
The present invention constitutes mixed solvent system with lipid acid and polar solvent, is raw material with soluble metallic salt, selenium source and alkali metal hydroxide, prepares monodisperse nanometer semiconductor selenide particle.The inventive method is easy, safety, cost is low, suitability is wide, be applicable to the synthetic of multiple nanometer semiconductor selenide particle simultaneously, overcome and adopted cost and the problem of environmental pollution that a large amount of organic solvent brought in the existing synthetic route, the nanometer semiconductor selenide particle that is obtained can be widely used in fields such as biomarker, analysis, solar cell.
Description of drawings
Fig. 1 is the prepared zinc selenide X-ray powder diffraction figure of embodiment 2.
Fig. 2 is that embodiment 2 prepared zinc selenide TEM Electronic Speculum detect figure.
Fig. 3 is the prepared cadmium selenide X-ray powder diffraction figure of embodiment 4.
Fig. 4 is that embodiment 4 prepared cadmium selenide TEM Electronic Speculum detect figure.
Fig. 5 is the prepared lead selenide X-ray powder diffraction figure of embodiment 8.
Fig. 6 is that embodiment 8 prepared lead selenide TEM Electronic Speculum detect figure.
Fig. 7 is that embodiment 9 prepared lead selenide TEM Electronic Speculum detect figure.
Embodiment
Embodiment 1,
Taking by weighing 0.7gNaOH adds in the mixed solvent of 10ml oleic acid, 15ml ethylene glycol, fully behind the about 30mins of reaction, taking by weighing 0.8g analytical pure Silver Nitrate again is dissolved in the 20mL water, take by weighing 0.4g analytical pure selenium powder, silver ion solution and the selenium powder that is made into 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 selenide 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 20nm.
Embodiment 2:
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 20mL water, take by weighing 0.8g analytical pure selenium powder, and with in the zine ion solution and selenium powder adding mixed solvent that are made into, stir, place the withstand voltage reactor of stainless steel of 40ml, behind 180 ℃ of reaction 24h, gained precipitates through centrifugation, 1molL
-1After NaOH solution washing, deionized water wash, the drying, obtain yellow powder.Product is accredited as zinc selenide 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 between 15-20nm.
Embodiment 3:
Taking by weighing 0.4gKOH adds in the mixed solvent of 10ml oleic acid, 10ml acetone, fully behind the about 30mins of reaction, taking by weighing 0.5g analytical pure zinc chloride again is dissolved in the 5mL water, taking by weighing 0.3g analytical pure Sodium Selenite is dissolved in the 5mL water, zine ion, plasma selenium solution and the 10ml analytical pure hydrazine hydrate (volumetric concentration 80%) that is made into added in the mixed solvent, stir, place the withstand voltage reactor of stainless steel of 40ml, behind 160 ℃ of reaction 24h, the gained precipitation obtains yellow powder after centrifugation, washing, drying.Product is accredited as zinc selenide 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 4:
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 cadmium again heats in 20mL water and makes its dissolving, and with in the cadmium-ion solution and 1.0g analytical pure selenium powder adding mixed solvent that are made into, stir, place the withstand voltage reactor of stainless steel of 40ml, behind 180 ℃ of reaction 24h, gained precipitates through centrifugation, 1molL
-1After NaOH solution washing, deionized water wash, the drying, obtain black powder.Product is accredited as cadmium selenide 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 ~ 5nm.
Embodiment 5:
Taking by weighing 1gKOH adds in the mixed solvent of 5ml capric acid, 5ml glycerol, fully behind the about 30mins of reaction, taking by weighing 1g analytical pure cadmium nitrate again is dissolved in the 10mL water, taking by weighing 1g analytical pure Sodium Selenite is dissolved in the 10mL water, cadmium ion, plasma selenium solution and the 10mL analytical pure hydrazine hydrate (volumetric concentration 80%) that is made into added in the mixed solvent, stir, place the withstand voltage reactor of stainless steel of 40ml, behind 250 ℃ of reaction 24h, the gained precipitation obtains black powder after centrifugation, washing, drying.Product is accredited as cadmium selenide 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 6:
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 17mL water, the mn ion solution and the 0.5g analytical pure selenium powder that are made into are added in the mixed solvent, stir, place the withstand voltage reactor of stainless steel of 40ml, behind 50 ℃ of reaction 24h, gained precipitates through centrifugation, 1molL
-1After NaOH solution washing, deionized water wash, the drying, obtain black powder.Product is accredited as manganese selenide 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 5-6nm.
Embodiment 7:
Take by weighing in 0.5gNaOH, the 3g analytical pure stearic acid adding 20ml ethanol, fully behind the about 30mins of reaction, taking by weighing 0.5g analytical pure sulfuric acid manganese again is dissolved in the 6mL water, taking by weighing 0.3g analytical pure Sodium Selenite is dissolved in the 4mL water, mn ion, selenium solution and the 10mL analytical pure hydrazine hydrate (volumetric concentration 80%) that is made into added in the mixed solvent, stir, place the withstand voltage reactor of stainless steel of 40ml, behind 70 ℃ of reaction 24h, the gained precipitation obtains black powder after centrifugation, washing, drying.Product is accredited as manganese selenide through X-ray powder diffraction; (TEM) carries out morphology analysis to it with transmission electron microscope, and can observe its pattern is the dispersed nano particle, and particle diameter is between 40-50nm.
Embodiment 8:
Taking by weighing 0.4gNaOH adds in the mixed solvent of 10ml oleic acid, 10ml quadrol, fully behind the about 30mins of reaction, taking by weighing 1g analytical pure lead nitrate again is dissolved in the 5mL water, taking by weighing 0.5g analytical pure Sodium Selenite is dissolved in the 5mL water, lead ion, plasma selenium solution and the 8mL analytical pure hydrazine hydrate (volumetric concentration 80%) that is made into added in the mixed solvent, stir, place the withstand voltage reactor of stainless steel of 40ml, behind 20 ℃ of reaction 24h, the gained precipitation obtains black powder after centrifugation, washing, drying.Product is accredited as lead selenide 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 4-5nm.
Embodiment 9:
Taking by weighing 1gNaOH adds in the mixed solvent of 10ml oleic acid, 10ml quadrol, fully behind the about 30mins of reaction, taking by weighing 1g analytical pure lead nitrate again is dissolved in the 5mL water, taking by weighing 0.5g analytical pure Sodium Selenite is dissolved in the 5mL water, lead ion, plasma selenium solution and the 8mL analytical pure hydrazine hydrate (volumetric concentration 80%) that is made into added in the mixed solvent, stir, place the withstand voltage reactor of stainless steel of 40ml, behind 20 ℃ of reaction 24h, the gained precipitation obtains black powder after centrifugation, washing, drying.Product is accredited as lead selenide 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 7-8nm.
Claims (4)
1, a kind of method for preparing monodisperse nanometer semiconductor selenide particle, be with metal ion solution and selenium source in the mixed system of alkali metal hydroxide, lipid acid and organic polar solvent, under 20-300 ℃ condition, react, obtain described monodisperse nanometer semiconductor selenide particle; Described selenium source is that mol ratio is 1: the system that the selenium-containing compound Sodium Selenite of 5-10 and reductive agent hydrazine hydrate are formed perhaps is the metal selenium powder; Described metal ion is zinc, silver, cadmium, manganese or lead ion; Described lipid acid is oleic acid, stearic acid or capric acid; The volume ratio of described lipid acid and organic polar solvent is 1: 0.5-10; The mol ratio of selenium element and metal ion is 0.1-6 in the described selenium source: 1; The mol ratio of described alkali metal hydroxide and described metal ion is 1-10: 1.
2, method according to claim 1, it is characterized in that: the step of described reaction is: earlier solid alkali metal oxyhydroxide is joined in the mixed solvent of lipid acid and organic polar solvent, add metal ion solution and selenium source after the mixing again, obtain described monodisperse nano metal oxide particle.
3, method according to claim 1 and 2 is characterized in that: the concentration of described metal ion solution is 0.01-0.5mol/L.
4, method according to claim 1 and 2 is characterized in that: described organic polar solvent is ethanol, acetone, ethylene glycol, quadrol or glycerol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005101092158A CN100344531C (en) | 2005-10-19 | 2005-10-19 | Process of preparing monodisperse nanometer semiconductor selenide particle |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005101092158A CN100344531C (en) | 2005-10-19 | 2005-10-19 | Process of preparing monodisperse nanometer semiconductor selenide particle |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1772599A CN1772599A (en) | 2006-05-17 |
| CN100344531C true CN100344531C (en) | 2007-10-24 |
Family
ID=36759768
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005101092158A Expired - Fee Related CN100344531C (en) | 2005-10-19 | 2005-10-19 | Process of preparing monodisperse nanometer semiconductor selenide particle |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100344531C (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102086043A (en) * | 2009-12-08 | 2011-06-08 | 中国科学院福建物质结构研究所 | Preparation method for metal chalcogenide crystalline microporous material |
| CN105036092B (en) * | 2015-08-07 | 2017-05-24 | 中南大学 | Preparation method of spherical silver selenide particles |
| CN109036863B (en) * | 2018-07-23 | 2020-09-15 | 浙江大学 | Selenide @ carbon-based fiber supercapacitor electrode material and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1384047A (en) * | 2002-06-07 | 2002-12-11 | 清华大学 | Synthesis of several metal selenides and tellurides as semiconductor material |
| CN1424248A (en) * | 2003-01-10 | 2003-06-18 | 清华大学 | Synthesis of nano hollow balls of zinc selenide |
| CN1526637A (en) * | 2003-09-25 | 2004-09-08 | 浙江大学 | Prepn of Bi2Te3-base compound nanotube |
| EP1491502A2 (en) * | 2003-05-30 | 2004-12-29 | Hitachi Software Engineering Co., Ltd. | A method for producing nanoparticles through size-selective photoetching |
| CN1571190A (en) * | 2004-05-13 | 2005-01-26 | 浙江大学 | Method for preparing transition metal distibide |
| CN1631793A (en) * | 2004-11-05 | 2005-06-29 | 中国科学院长春应用化学研究所 | Synthesis method for cadmium selenide and cadmium telluride quantum dot |
-
2005
- 2005-10-19 CN CNB2005101092158A patent/CN100344531C/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1384047A (en) * | 2002-06-07 | 2002-12-11 | 清华大学 | Synthesis of several metal selenides and tellurides as semiconductor material |
| CN1424248A (en) * | 2003-01-10 | 2003-06-18 | 清华大学 | Synthesis of nano hollow balls of zinc selenide |
| EP1491502A2 (en) * | 2003-05-30 | 2004-12-29 | Hitachi Software Engineering Co., Ltd. | A method for producing nanoparticles through size-selective photoetching |
| CN1526637A (en) * | 2003-09-25 | 2004-09-08 | 浙江大学 | Prepn of Bi2Te3-base compound nanotube |
| CN1571190A (en) * | 2004-05-13 | 2005-01-26 | 浙江大学 | Method for preparing transition metal distibide |
| CN1631793A (en) * | 2004-11-05 | 2005-06-29 | 中国科学院长春应用化学研究所 | Synthesis method for cadmium selenide and cadmium telluride quantum dot |
Non-Patent Citations (1)
| Title |
|---|
| 室温合成硒化银纳米粒子及其X射线光电子能谱表征 夏传俊、杨耿，安徽大学学报(自然科学版)，第28卷第2期 2004 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1772599A (en) | 2006-05-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100383048C (en) | Method for preparing sulfide nanometer particle | |
| Ha et al. | Hydrothermal synthesis and characterization of self-assembled h-WO3 nanowires/nanorods using EDTA salts | |
| Li et al. | Preparation and characterization of nano-structured lead oxide from spent lead acid battery paste | |
| Lu et al. | Flexible SnS nanobelts: Facile synthesis, formation mechanism and application in Li-ion batteries | |
| Cheng et al. | Near surface nucleation and particle mediated growth of colloidal Au nanocrystals | |
| CN1923702A (en) | Preparation method of monodisperse spherical zine sulfide nano particles | |
| CN100344531C (en) | Process of preparing monodisperse nanometer semiconductor selenide particle | |
| JP2006089786A (en) | Method for producing metallic nano-particle dispersed in polar solvent | |
| Zeng et al. | Synthesis of sea-urchin shaped γ-MnO 2 nanostructures and their application in lithium batteries | |
| US10464136B2 (en) | Preparation method of copper nano-structures | |
| EP2233434A1 (en) | Process for producing electroconductive inorganic oxide particles and electroconductive inorganic oxide particles produced by the process | |
| CN100357184C (en) | Prepn process of monodisperse nanometer metal oxide particle | |
| CN101774628B (en) | Preparation method of water-soluble metal sulfide semiconductor nanoparticle | |
| CN1757470A (en) | Method for preparing single dispersion metal nanometer particles | |
| Zhou et al. | Large-area synthesis of high-quality β-MnO2 nanowires and the mechanism of formation through a facile mineralization process | |
| EP4375648A1 (en) | Hydrogen leakage detecting material, and preparation method therefor and use thereof | |
| Fan et al. | The built-in electric field and spin-pinning effect in BiVO4/Fe0. 4Co0. 6Se2/Co (Fe) OxHy for enhanced photoelectrochemical water oxidation | |
| Posudievsky et al. | 12-Phosphormolibdic acid doped polyaniline–V2O5 composite | |
| Li et al. | Chelating ligand-mediated hydrothermal synthesis of samarium orthovanadate with decavanadate as vanadium source | |
| Soulmi et al. | Structural and Morphological Description of Sn/SnO x Core–Shell Nanoparticles Synthesized and Isolated from Ionic Liquid | |
| Fang et al. | Fabrication of hierarchical CdS microspheres assembled by nanowires: solid state electro-chemiluminescence in H 2 O 2 solution | |
| CN1321897C (en) | Method for preparing monodisperse rare-earth fluoride nano particles | |
| Wang et al. | Facile synthesis of gadolinium vanadate nanowires for sensitive detection of cobalt ions | |
| CN1775691A (en) | Method for preparing rare-earth fluoride hollour nano particle by microwave synthesis | |
| Zhao et al. | In situ construction of Z-type defective Al2O3/BiPO4 for efficient photocatalytic degradation of organic dyes |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20071024 Termination date: 20091119 |