CN102502775A - Preparation method of spherical copper sulphide (CuS) particles - Google Patents

Preparation method of spherical copper sulphide (CuS) particles Download PDF

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Publication number
CN102502775A
CN102502775A CN2011103758385A CN201110375838A CN102502775A CN 102502775 A CN102502775 A CN 102502775A CN 2011103758385 A CN2011103758385 A CN 2011103758385A CN 201110375838 A CN201110375838 A CN 201110375838A CN 102502775 A CN102502775 A CN 102502775A
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solution
reaction
hydrothermal reaction
deionized water
temperature
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黄剑锋
齐慧
曹丽云
刘佳
吴建鹏
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Shaanxi University of Science and Technology
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Shaanxi University of Science and Technology
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Abstract

The invention relates to a preparation method of spherical (CuS) particles. The preparation method comprises the steps that: copper nitric acid trihydrate is added into a mixed solvent consisting of de-ionized water and ethylene glycol to obtain solution A; thiourea is added into the solution A to obtain solution B; polyvinylpyrrolidone K30 is added into the solution B to form precursor solution C; the precursor solution C is poured into a microwave hydrothermal reaction kettle, then, the reaction kettle is sealed and is put into a temperature and pressure dual-control microwave hydrothermal reaction instrument, a temperature control mode or a pressure control mode is selected for reaction, and the solution is naturally cooled to the room temperature after reaction completion; and the hydrothermal reaction kettle is opened, products are respectively washed by the de-ionized water and absolute ethyl alcohol after centrifugal collection, and final products of spherical CuS particles are obtained after drying. The method has the advantages that a simple microwave hydrothermal method preparation process is adopted, the reaction period is short, the energy consumption is low, the reaction is completed in one step in liquid phases, and the later-period treatment is not needed. The prepared CuS particles have regular sphere shapes and uniform size.

Description

A kind of preparation method of spherical copper sulfide particle
Technical field
The invention belongs to the preparation method of semiconductor material cupric sulfide, be specifically related to a kind of preparation method of spherical copper sulfide particle.
Background technology
In the synthetic field of material, sulfide is because of having the potential using value and receive the extensive interest of researcher and paying close attention at aspects such as semi-conductor, light-emitting device and superconductions.CuS is very important p N-type semiconductorN, and band-gap energy is 1.2eV.Owing to have excellent conductivity, electricity, optical property; Be widely used in fields such as thermopair, optical recording, solar cell, transmitter and catalysis, up to now, successfully synthesize the cupric sulfide of multiple pattern; Nanometer plate-like for example, hollow ball-shape and specific morphology such as flower-shaped.
The method for preparing at present cupric sulfide mainly contains pyrogenic silica [Yu-Biao Chen; Ling Chen; And Li-Ming Wu.Water-Induced Thermolytic Formation of Homogeneous Core-Shell CuS Microspheres and Their Shape Retention on Desulfurization [J] .Crystal Growth&Design, 2008,8:2736-2740], continuous ionic layer absorption method [M.Ali Yildirim; Aytunc Ates; Aykut Astam.Annealing and Light Effect on Structural, Optical and Electrical Properties of CuS, CuZnS and ZnS Thin Films Grown by the SILARMethod [J] .Physica.E; 2009; 41:1365-1372.], hydrothermal method [Ai-Miao Qin, Yue-Ping Fang, et al.Formation of Various Morphologies of Covellite Copper Sulfide Submicron Crystals by a Hydrothermal Method without Surfactant [J] .Crystal Growth&Design; 2005; 5:855-860.] and solvent method [Titipun Thongtem, Chalermchai Pilapong, Somchai Thongtem.Large-Scale Synthesis of CuS Hexaplates in Mixed Solvents Using a Solvothermal Method [J] .Materials Letters; 2010,64:11-14.].Yet these methods need special instrument usually, perhaps need strict experiment condition, long reaction time, and energy consumption is high, and owing in the process of synthetic cupric sulfide, a large amount of H is arranged 2S gas generates, as is reflected in the system of opening wide and carries out, and then can cause certain pollution to environment inevitably.Therefore seek a kind of simply, economical seems rather important with eco-friendly method.
Summary of the invention
The objective of the invention is to propose a kind of method that adopts microwave-hydrothermal method to prepare spherical copper sulfide particle.This method reaction time is short, temperature of reaction is low, and environmental friendliness is with low cost, and simple to operate, and good reproducibility is fit to scale operation.
For achieving the above object, the technical scheme that the present invention adopts is:
1) with analytically pure Gerhardite (Cu (NO 3) 23H 2O) join in the mixed solvent of deionized water and terepthaloyl moietie, process Cu 2+Concentration is the clear solution A of 0.06mol/L-1.2mol/L, and wherein the volume ratio of terepthaloyl moietie and deionized water is 1: 2～5;
2) in solution A, add analytically pure thiocarbamide (SC (NH 2) 2), make Cu in the solution 2+/ SC (NH 2) 2Mol ratio be 1: 0.5～3, the gained solution B;
3) in solution B, add analytically pure Vinylpyrrolidone polymer K30 (PVP), make that the concentration of PVP is 0.002g/mL-0.02g/mL in the solution, form precursor solution C;
4) precursor solution C is poured in the microwave hydrothermal reaction kettle; Compactedness is 50%-80%; Sealed reactor then; Put it in the two control of the temperature and pressure microwave hydrothermal reaction; Select temperature control mode or voltage-controlled pattern to react, the temperature of described temperature control mode is controlled at 150-250 ℃, and the hydro-thermal pressure of voltage-controlled pattern is controlled at 1-2Mpa; Reaction 30min-80min, reaction naturally cools to room temperature after finishing;
5) open hydrothermal reaction kettle, product is used deionized water and absolute ethanol washing respectively then through centrifugal collection, in electric drying oven with forced convection, obtains the spherical copper sulfide particle of final product 40-80 ℃ of drying.
The present invention adopts simple microwave-hydrothermal method preparation technology, and reaction time is short, and energy consumption is low, is reflected in the liquid phase and once accomplishes, and does not need post-processed.The CuS particle that makes has the spherical of rule, and size evenly.
Description of drawings
Fig. 1 is X-ray diffraction (XRD) collection of illustrative plates of the prepared spherical copper sulfide particle of the embodiment of the invention 1;
Fig. 2 is the SEM photo of the spherical copper sulfide particle of the embodiment of the invention 1 preparation.
Embodiment
Below in conjunction with accompanying drawing and embodiment the present invention is done further explain.
Embodiment 1:
1) with analytically pure Gerhardite (Cu (NO 3) 23H 2O) join in the mixed solvent of deionized water and terepthaloyl moietie, process Cu 2+Concentration is the clear solution A of 0.07mol/L, and wherein the volume ratio of terepthaloyl moietie and deionized water is 1: 2.5;
2) in solution A, add analytically pure thiocarbamide (SC (NH 2) 2), make Cu in the solution 2+/ SC (NH 2) 2Mol ratio be 1: 0.8, the gained solution B;
3) in solution B, add analytically pure Vinylpyrrolidone polymer K30 (PVP), make that the concentration of PVP is 0.004g/mL in the solution, form precursor solution C;
4) precursor solution C is poured in the microwave hydrothermal reaction kettle, compactedness is 60%, and sealed reactor puts it in the two control of the temperature and pressure microwave hydrothermal reaction then, selects temperature control mode at 240 ℃, reaction 40min, and reaction naturally cools to room temperature after finishing;
5) open hydrothermal reaction kettle, product is used deionized water and absolute ethanol washing respectively then through centrifugal collection, in electric drying oven with forced convection, obtains the spherical copper sulfide particle of final product 50 ℃ of dryings.
The CuS particle of gained with Japanese D/max2000PCX-x ray diffractometer x analytic sample of science, is found that product is the CuS covellite structure (JCPDS 06-0464) of six side's phases, see Fig. 1.This sample is observed with the JSM-6390A type sem that Japanese firm produces, and (a can find out that made CuS microballoon size is more even in b), and particle diameter is 800-1000nm from Fig. 2.
Embodiment 2:
1) with analytically pure Gerhardite (Cu (NO 3) 23H 2O) join in the mixed solvent of deionized water and terepthaloyl moietie, process Cu 2+Concentration is the clear solution A of 0.06mol/L, and wherein the volume ratio of terepthaloyl moietie and deionized water is 1: 3;
2) in solution A, add analytically pure thiocarbamide (SC (NH 2) 2), make Cu in the solution 2+/ SC (NH 2) 2Mol ratio be 1: 1, the gained solution B;
3) in solution B, add analytically pure Vinylpyrrolidone polymer K30 (PVP), make that the concentration of PVP is 0.008g/mL in the solution, form precursor solution C;
4) precursor solution C is poured in the microwave hydrothermal reaction kettle, compactedness is 70%, and sealed reactor puts it in the two control of the temperature and pressure microwave hydrothermal reaction then, selects temperature control mode at 150 ℃, reaction 80min, and reaction naturally cools to room temperature after finishing;
5) open hydrothermal reaction kettle, product is used deionized water and absolute ethanol washing respectively then through centrifugal collection, in electric drying oven with forced convection, obtains the spherical copper sulfide particle of final product 60 ℃ of dryings.
Embodiment 3:
1) with analytically pure Gerhardite (Cu (NO 3) 23H 2O) join in the mixed solvent of deionized water and terepthaloyl moietie, process Cu 2+Concentration is the clear solution A of 0.12mol/L, and wherein the volume ratio of terepthaloyl moietie and deionized water is 1: 4;
2) in solution A, add analytically pure thiocarbamide (SC (NH 2) 2), make Cu in the solution 2+/ SC (NH 2) 2Mol ratio be 1: 2.5, the gained solution B;
3) in solution B, add analytically pure Vinylpyrrolidone polymer K30 (PVP), make that the concentration of PVP is 0.012g/mL in the solution, form precursor solution C;
4) precursor solution C is poured in the microwave hydrothermal reaction kettle, compactedness is 50%, and sealed reactor puts it in the two control of the temperature and pressure microwave hydrothermal reaction then, selects temperature control mode at 170 ℃, reaction 60min, and reaction naturally cools to room temperature after finishing;
5) open hydrothermal reaction kettle, product is used deionized water and absolute ethanol washing respectively then through centrifugal collection, in electric drying oven with forced convection, obtains the spherical copper sulfide particle of final product 80 ℃ of dryings.
Embodiment 4:
1) with analytically pure Gerhardite (Cu (NO 3) 23H 2O) join in the mixed solvent of deionized water and terepthaloyl moietie, process Cu 2+Concentration is the clear solution A of 1.2mol/L, and wherein the volume ratio of terepthaloyl moietie and deionized water is 1: 4;
2) in solution A, add analytically pure thiocarbamide (SC (NH 2) 2), make Cu in the solution 2+/ SC (NH 2) 2Mol ratio be 1: 2.5, the gained solution B;
3) in solution B, add analytically pure Vinylpyrrolidone polymer K30 (PVP), make that the concentration of PVP is 0.018g/mL in the solution, form precursor solution C;
4) precursor solution C is poured in the microwave hydrothermal reaction kettle, compactedness is 80%, and sealed reactor puts it in the two control of the temperature and pressure microwave hydrothermal reaction then, selects temperature control mode at 250 ℃, reaction 30min, and reaction naturally cools to room temperature after finishing;
5) open hydrothermal reaction kettle, product is used deionized water and absolute ethanol washing respectively then through centrifugal collection, in electric drying oven with forced convection, obtains the spherical copper sulfide particle of final product 40 ℃ of dryings.
Embodiment 5:
1) with analytically pure Gerhardite (Cu (NO 3) 23H 2O) join in the mixed solvent of deionized water and terepthaloyl moietie, process Cu 2+Concentration is the clear solution A of 0.3mol/L, and wherein the volume ratio of terepthaloyl moietie and deionized water is 1: 2;
2) in solution A, add analytically pure thiocarbamide (SC (NH 2) 2), make Cu in the solution 2+/ SC (NH 2) 2Mol ratio be 1: 0.5, the gained solution B;
3) in solution B, add analytically pure Vinylpyrrolidone polymer K30 (PVP), make that the concentration of PVP is 0.002g/mL in the solution, form precursor solution C;
4) precursor solution C is poured in the microwave hydrothermal reaction kettle, compactedness is 55%, and sealed reactor puts it in the two control of the temperature and pressure microwave hydrothermal reaction then, selects voltage-controlled pattern at 1Mpa, reaction 70min, and reaction naturally cools to room temperature after finishing;
5) open hydrothermal reaction kettle, product is used deionized water and absolute ethanol washing respectively then through centrifugal collection, in electric drying oven with forced convection, obtains the spherical copper sulfide particle of final product 70 ℃ of dryings.
Embodiment 6:
1) with analytically pure Gerhardite (Cu (NO 3) 23H 2O) join in the mixed solvent of deionized water and terepthaloyl moietie, process Cu 2+Concentration is the clear solution A of 0.5mol/L, and wherein the volume ratio of terepthaloyl moietie and deionized water is 1: 5;
2) in solution A, add analytically pure thiocarbamide (SC (NH 2) 2), make Cu in the solution 2+/ SC (NH 2) 2Mol ratio be 1: 1.5, the gained solution B;
3) in solution B, add analytically pure Vinylpyrrolidone polymer K30 (PVP), make that the concentration of PVP is 0.02g/mL in the solution, form precursor solution C;
4) precursor solution C is poured in the microwave hydrothermal reaction kettle, compactedness is 65%, and sealed reactor puts it in the two control of the temperature and pressure microwave hydrothermal reaction then, selects voltage-controlled pattern at 1.5Mpa, reaction 50min, and reaction naturally cools to room temperature after finishing;
5) open hydrothermal reaction kettle, product is used deionized water and absolute ethanol washing respectively then through centrifugal collection, in electric drying oven with forced convection, obtains the spherical copper sulfide particle of final product 55 ℃ of dryings.
Embodiment 7:
1) with analytically pure Gerhardite (Cu (NO 3) 23H 2O) join in the mixed solvent of deionized water and terepthaloyl moietie, process Cu 2+Concentration is the clear solution A of 0.8mol/L, and wherein the volume ratio of terepthaloyl moietie and deionized water is 1: 3;
2) in solution A, add analytically pure thiocarbamide (SC (NH 2) 2), make Cu in the solution 2+/ SC (NH 2) 2Mol ratio be 1: 3, the gained solution B;
3) in solution B, add analytically pure Vinylpyrrolidone polymer K30 (PVP), make that the concentration of PVP is 0.015g/mL in the solution, form precursor solution C;
4) precursor solution C is poured in the microwave hydrothermal reaction kettle, compactedness is 75%, and sealed reactor puts it in the two control of the temperature and pressure microwave hydrothermal reaction then, selects voltage-controlled pattern at 2Mpa, reaction 40min, and reaction naturally cools to room temperature after finishing;
5) open hydrothermal reaction kettle, product is used deionized water and absolute ethanol washing respectively then through centrifugal collection, in electric drying oven with forced convection, obtains the spherical copper sulfide particle of final product 75 ℃ of dryings.

Claims (1)

1. the preparation method of a spherical copper sulfide particle is characterized in that:
1) with analytically pure Gerhardite (Cu (NO 3) 23H 2O) join in the mixed solvent of deionized water and terepthaloyl moietie, process Cu 2+Concentration is the clear solution A of 0.06mol/L-1.2mol/L, and wherein the volume ratio of terepthaloyl moietie and deionized water is 1: 2～5;
2) in solution A, add analytically pure thiocarbamide (SC (NH 2) 2), make Cu in the solution 2+/ SC (NH 2) 2Mol ratio be 1: 0.5～3, the gained solution B;
3) in solution B, add analytically pure Vinylpyrrolidone polymer K30 (PVP), make that the concentration of PVP is 0.002g/mL-0.02g/mL in the solution, form precursor solution C;
4) precursor solution C is poured in the microwave hydrothermal reaction kettle; Compactedness is 50%-80%; Sealed reactor then; Put it in the two control of the temperature and pressure microwave hydrothermal reaction; Select temperature control mode or voltage-controlled pattern to react, the temperature of described temperature control mode is controlled at 150-250 ℃, and the hydro-thermal pressure of voltage-controlled pattern is controlled at 1-2Mpa; Reaction 30min-80min, reaction naturally cools to room temperature after finishing;
5) open hydrothermal reaction kettle, product is used deionized water and absolute ethanol washing respectively then through centrifugal collection, in electric drying oven with forced convection, obtains the spherical copper sulfide particle of final product 40-80 ℃ of drying.
CN2011103758385A 2011-11-23 2011-11-23 Preparation method of spherical copper sulphide (CuS) particles Pending CN102502775A (en)

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Cited By (8)

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Publication number Priority date Publication date Assignee Title
CN103638950A (en) * 2013-12-16 2014-03-19 北京科技大学 CuS nanosheet photocatalytic material and preparation method thereof
CN105016374A (en) * 2015-08-14 2015-11-04 天津城建大学 Method for preparing CuS micro-spheres of hierarchic structures
CN105399133A (en) * 2015-12-22 2016-03-16 哈尔滨工业大学 Preparation method of sheet-like flower micro / nano 3D-CuS material
CN106268880A (en) * 2016-08-16 2017-01-04 辽宁石油化工大学 A kind of spherical Bi3o4cl/BiOCl visible light catalyst and preparation method
CN109336163A (en) * 2018-10-22 2019-02-15 温州大学新材料与产业技术研究院 A kind of preparation method of microwave synthesis semiconductor material CuS
CN109942017A (en) * 2019-04-30 2019-06-28 大连理工大学 A kind of sulfide high uniformity microballoon of partial size controllable precise and preparation method thereof
CN111021049A (en) * 2019-11-21 2020-04-17 上海工程技术大学 Preparation method of fluorine-free super-hydrophobic photocatalytic ultraviolet-proof textile
CN111883642A (en) * 2020-08-06 2020-11-03 重庆大学 Cu 2-xS-based thermoelectric material and solvothermal preparation method

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Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103638950A (en) * 2013-12-16 2014-03-19 北京科技大学 CuS nanosheet photocatalytic material and preparation method thereof
CN103638950B (en) * 2013-12-16 2016-01-06 北京科技大学 A kind of CuS nanosheet photocatalytic material and preparation method
CN105016374A (en) * 2015-08-14 2015-11-04 天津城建大学 Method for preparing CuS micro-spheres of hierarchic structures
CN105399133A (en) * 2015-12-22 2016-03-16 哈尔滨工业大学 Preparation method of sheet-like flower micro / nano 3D-CuS material
CN106268880A (en) * 2016-08-16 2017-01-04 辽宁石油化工大学 A kind of spherical Bi3o4cl/BiOCl visible light catalyst and preparation method
CN109336163A (en) * 2018-10-22 2019-02-15 温州大学新材料与产业技术研究院 A kind of preparation method of microwave synthesis semiconductor material CuS
CN109336163B (en) * 2018-10-22 2020-12-29 温州大学新材料与产业技术研究院 Preparation method for microwave synthesis of semiconductor material CuS
CN109942017A (en) * 2019-04-30 2019-06-28 大连理工大学 A kind of sulfide high uniformity microballoon of partial size controllable precise and preparation method thereof
WO2020220708A1 (en) * 2019-04-30 2020-11-05 大连理工大学 Highly uniform sulphide microsphere with precisely controllable particle size and preparation method therefor
CN111021049A (en) * 2019-11-21 2020-04-17 上海工程技术大学 Preparation method of fluorine-free super-hydrophobic photocatalytic ultraviolet-proof textile
CN111883642A (en) * 2020-08-06 2020-11-03 重庆大学 Cu 2-xS-based thermoelectric material and solvothermal preparation method

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Application publication date: 20120620