CN102502776A - Microwave-hydrothermal Cu1.8S nanowire preparation method - Google Patents

Microwave-hydrothermal Cu1.8S nanowire preparation method Download PDF

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CN102502776A
CN102502776A CN2011103758402A CN201110375840A CN102502776A CN 102502776 A CN102502776 A CN 102502776A CN 2011103758402 A CN2011103758402 A CN 2011103758402A CN 201110375840 A CN201110375840 A CN 201110375840A CN 102502776 A CN102502776 A CN 102502776A
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microwave
reaction
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hydrothermal
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CN102502776B (en
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黄剑锋
齐慧
张培培
曹丽云
吴建鹏
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Qidong Qixiu Vegetable & Fruit professional cooperatives
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Shaanxi University of Science and Technology
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Abstract

A microwave-hydrothermal Cu1.85S nanowire preparation method includes steps of adding soluble copper salt into deionized water to obtain liquor A; adding thiourea into the liquor A to obtain liquor B; adding polyethylene glycol into the liquor B to form precursor liquor C; adding NaOH into the precursor liquor C to adjust the pH (potential of hydrogen) value to range between 4 to 7 to obtain liquor D; pouring the liquor D into a microwave-hydrothermal reaction kettle, sealing the reaction kettle, placing the reaction kettle into a temperature and pressure double-controlled microwave-hydrothermal reaction instrument, selecting a temperature control mode or a pressure control mode to realize reaction, and naturally cooling the temperature and pressure double-controlled microwave-hydrothermal reaction kettle to reach room temperature after the reaction is completed; opening the hydrothermal reaction kettle, collecting a product in a centrifugal manner, washing the product by deionized water and anhydrous ethanol respectively, and drying to obtain a final product of Cu1.8S nanowire. Simple microwave-hydrothermal method preparation process is adopted in the microwave-hydrothermal nanowire preparation method, reaction period is short, energy consumption is low, the reaction is completed in a liquid phase at one step, and post processing is omitted.

Description

A kind of microwave hydrothermal prepares Cu 1.8The method of S nano wire
Technical field
The invention belongs to the preparation method of semiconductor material cupric sulfide, be specifically related to a kind of microwave hydrothermal and prepare Cu 1.8The method of S nano wire.
Background technology
In recent years owing to transient metal sulfide has the very big interest that the potential using value receives researcher at aspects such as semi-conductor, light-emitting device and superconductions.Cupric sulfide is very important p N-type semiconductorN, wherein Cu 2The band-gap energy of S is 1.2eV, Cu 1.8S is 1.5eV, and CuS is 2.0eV, because it has excellent conductivity, electricity, optical property, is widely used in fields such as thermopair, spectral filter, solar cell, transmitter and catalysis.Up to now, the cupric sulfide of successfully synthetic multiple pattern, nanometer plate-like for example, hollow ball-shape, specific morphology such as flower-shaped and tubulose.
The main ultrasonic electrochemical method of method [Yixin Zhao, Hongcheng Pan, the et al.Plasmonic Cu that prepare at present cupric sulfide 2-xS Nanocrystals:Optical and Structural Properties of Copper-Deficient Copper (I) Sulfides [J] .J.AM.CHEM.SOC; 2009; 131:4253-4261], continuous ionic layer absorption [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 SILAR Method [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.], atomic layer deposition method and chemical Vapor deposition process [Liesbeth Reijnen; Ben Meester; Et al.Comparison of CuxS Films Grown by Atomic Layer Deposition andChemical Vapor Deposition [J] .Chem.Mater., 2005,17:2724-2728].Yet these methods need special instrument usually, perhaps need strict experiment condition and long reaction times, and owing in the process of synthetic cupric sulfide, a large amount of H are 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 easy handling, environmental friendliness and method with low cost seem rather important.
Summary of the invention
The objective of the invention is to propose a kind of microwave hydrothermal and prepare Cu 1.8The method of S nano wire.This preparation method reaction time is short, temperature of reaction is low, and environmental friendliness is with low cost, and simple to operate, good reproducibility.
For achieving the above object, the technical scheme that the present invention adopts is:
1) analytically pure soluble copper salt is joined in the deionized water, process Cu 2+Concentration is the clear solution A of 0.01mol/L-2.0mol/L;
2) in A solution, add analytically pure thiocarbamide (SC (NH 2) 2), make Cu in the solution 2+/ SC (NH 2) 2Mol ratio be 1: 1～5 solution B;
3) in B solution, add analytically pure polyoxyethylene glycol (PEG), make that the concentration of PEG is 0.01-0.10g/mL in the solution, form precursor solution C;
4) in the precursor solution C, adding NaOH solution, to regulate pH value be 4～7 must solution D;
5) solution D 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 100-200 ℃, and the hydro-thermal pressure-controlling of voltage-controlled pattern is at 0.1-3Mpa; Reaction 5min-80min, reaction naturally cools to room temperature after finishing;
6) open hydrothermal reaction kettle, product is used deionized water respectively then through centrifugal collection, and absolute ethanol washing obtains final product Cu 40-80 ℃ of drying in vacuum drying oven 1.8The S nano wire.
Described soluble copper salt is cupric nitrate or copper sulfate.
The concentration of described NaOH solution is 1.25mol/L.
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.
Description of drawings
Fig. 1 is the prepared Cu of the embodiment of the invention 1 1.8The X-ray diffraction of S nano wire (XRD) collection of illustrative plates;
Fig. 2 is the Cu of the embodiment of the invention 1 preparation 1.8The SEM photo of S nano wire.
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 joins in the deionized water, processes Cu 2+Concentration is the clear solution A of 0.04mol/L;
2) in A solution, add analytically pure thiocarbamide (SC (NH 2) 2), make Cu in the solution 2+/ SC (NH 2) 2Mol ratio be 1: 2 solution B;
3) in B solution, add analytically pure polyoxyethylene glycol (PEG), make that the concentration of PEG is 0.03g/mL in the solution, form precursor solution C;
4) in the precursor solution C, adding concentration is that to regulate pH value be 4 must solution D for the NaOH solution of 1.25mol/L;
5) solution D 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 180 ℃, reaction 10min, and reaction naturally cools to room temperature after finishing;
6) open hydrothermal reaction kettle, product is used deionized water respectively then through centrifugal collection, and absolute ethanol washing obtains final product Cu 40 ℃ of dryings in vacuum drying oven 1.8The S nano wire.
With Japanese D/max2000PCX-x ray diffractometer x analytic sample of science, the discovery product is Cu with the CuS particle of gained 1.8S (JCPDS 47-1748) sees Fig. 1.This sample is observed with the JSM-6390A type sem that Japanese firm produces, as can be seen from Figure 2 prepared CuS nano wire, diameter is about 300-600nm, and is the winding shape.
Embodiment 2:
1) with analytically pure Salzburg vitriol (CuSO 45H 2O) join in the deionized water, process Cu 2+Concentration is the clear solution A of 0.25mol/L;
2) in A solution, add analytically pure thiocarbamide (SC (NH 2) 2), make Cu in the solution 2+/ SC (NH 2) 2Mol ratio be 1: 3 solution B;
3) in B solution, add analytically pure polyoxyethylene glycol (PEG), make that the concentration of PEG is 0.04g/mL in the solution, form precursor solution C;
4) in the precursor solution C, adding concentration is that to regulate pH value be 5 must solution D for the NaOH solution of 1.25mol/L;
5) solution D 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 150 ℃, reaction 20min, and reaction naturally cools to room temperature after finishing;
6) open hydrothermal reaction kettle, product is used deionized water respectively then through centrifugal collection, and absolute ethanol washing obtains final product Cu 60 ℃ of dryings in vacuum drying oven 1.8The S nano wire.
Embodiment 3:
1) with analytically pure Gerhardite Cu (NO 3) 23H 2O joins in the deionized water, processes Cu 2+Concentration is the clear solution A of 0.01mol/L;
2) in A solution, add analytically pure thiocarbamide (SC (NH 2) 2), make Cu in the solution 2+/ SC (NH 2) 2Mol ratio be 1: 1 solution B;
3) in B solution, add analytically pure polyoxyethylene glycol (PEG), make that the concentration of PEG is 0.01g/mL in the solution, form precursor solution C;
4) in the precursor solution C, adding concentration is that to regulate pH value be 6 must solution D for the NaOH solution of 1.25mol/L;
5) solution D 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 100 ℃, reaction 80min, and reaction naturally cools to room temperature after finishing;
6) open hydrothermal reaction kettle, product is used deionized water respectively then through centrifugal collection, and absolute ethanol washing obtains final product Cu 80 ℃ of dryings in vacuum drying oven 1.8The S nano wire.
Embodiment 4:
1) with analytically pure Salzburg vitriol (CuSO 45H 2O) join in the deionized water, process Cu 2+Concentration is the clear solution A of 0.8mol/L;
2) in A solution, add analytically pure thiocarbamide (SC (NH 2) 2), make Cu in the solution 2+/ SC (NH 2) 2Mol ratio be 1: 5 solution B;
3) in B solution, add analytically pure polyoxyethylene glycol (PEG), make that the concentration of PEG is 0.05g/mL in the solution, form precursor solution C;
4) in the precursor solution C, adding concentration is that to regulate pH value be 7 must solution D for the NaOH solution of 1.25mol/L;
5) solution D 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 200 ℃, reaction 5min, and reaction naturally cools to room temperature after finishing;
6) open hydrothermal reaction kettle, product is used deionized water respectively then through centrifugal collection, and absolute ethanol washing obtains final product Cu 50 ℃ of dryings in vacuum drying oven 1.8The S nano wire.
Embodiment 5:
1) with analytically pure Gerhardite Cu (NO 3) 23H 2O joins in the deionized water, processes Cu 2+Concentration is the clear solution A of 1.2mol/L;
2) in A solution, add analytically pure thiocarbamide (SC (NH 2) 2), make Cu in the solution 2+/ SC (NH 2) 2Mol ratio be 1: 4 solution B;
3) in B solution, add analytically pure polyoxyethylene glycol (PEG), make that the concentration of PEG is 0.08g/mL in the solution, form precursor solution C;
4) in the precursor solution C, adding concentration is that to regulate pH value be 7 must solution D for the NaOH solution of 1.25mol/L;
5) solution D is poured in the microwave hydrothermal reaction kettle, compactedness is 80%, then sealed reactor; Put it in the two control of the temperature and pressure microwave hydrothermal reaction, select voltage-controlled pattern to react, the hydro-thermal pressure-controlling of voltage-controlled pattern is at 0.1Mpa; Reaction 70min, reaction naturally cools to room temperature after finishing;
6) open hydrothermal reaction kettle, product is used deionized water respectively then through centrifugal collection, and absolute ethanol washing obtains final product Cu 70 ℃ of dryings in vacuum drying oven 1.8The S nano wire.
Embodiment 6:
1) with analytically pure Salzburg vitriol (CuSO 45H 2O) join in the deionized water, process Cu 2+Concentration is the clear solution A of 1.6mol/L;
2) in A solution, add analytically pure thiocarbamide (SC (NH 2) 2), make Cu in the solution 2+/ SC (NH 2) 2Mol ratio be 1: 3.5 solution B;
3) in B solution, add analytically pure polyoxyethylene glycol (PEG), make that the concentration of PEG is 0.06g/mL in the solution, form precursor solution C;
4) in the precursor solution C, adding concentration is that to regulate pH value be 5 must solution D for the NaOH solution of 1.25mol/L;
5) solution D is poured in the microwave hydrothermal reaction kettle, compactedness is 70%, then sealed reactor; Put it in the two control of the temperature and pressure microwave hydrothermal reaction, select voltage-controlled pattern to react, the hydro-thermal pressure-controlling of voltage-controlled pattern is at 1.5Mpa; Reaction 50min, reaction naturally cools to room temperature after finishing;
6) open hydrothermal reaction kettle, product is used deionized water respectively then through centrifugal collection, and absolute ethanol washing obtains final product Cu 60 ℃ of dryings in vacuum drying oven 1.8The S nano wire.
Embodiment 7:
1) with analytically pure Gerhardite Cu (NO 3) 23H 2O joins in the deionized water, processes Cu 2+Concentration is the clear solution A of 2.0mol/L;
2) in A solution, add analytically pure thiocarbamide (SC (NH 2) 2), make Cu in the solution 2+/ SC (NH 2) 2Mol ratio be 1: 2.5 solution B;
3) in B solution, add analytically pure polyoxyethylene glycol (PEG), make that the concentration of PEG is 0.1g/mL in the solution, form precursor solution C;
4) in the precursor solution C, adding concentration is that to regulate pH value be 6 must solution D for the NaOH solution of 1.25mol/L;
5) solution D is poured in the microwave hydrothermal reaction kettle, compactedness is 60%, then sealed reactor; Put it in the two control of the temperature and pressure microwave hydrothermal reaction, select voltage-controlled pattern to react, the hydro-thermal pressure-controlling of voltage-controlled pattern is at 3Mpa; Reaction 30min, reaction naturally cools to room temperature after finishing;
6) open hydrothermal reaction kettle, product is used deionized water respectively then through centrifugal collection, and absolute ethanol washing obtains final product Cu 50 ℃ of dryings in vacuum drying oven 1.8The S nano wire.

Claims (3)

1. a microwave hydrothermal prepares Cu 1.8The method of S nano wire is characterized in that:
1) analytically pure soluble copper salt is joined in the deionized water, process Cu 2+Concentration is the clear solution A of 0.01mol/L-2.0mol/L;
2) in A solution, add analytically pure thiocarbamide (SC (NH 2) 2), make Cu in the solution 2+/ SC (NH 2) 2Mol ratio be 1: 1～5 solution B;
3) in B solution, add analytically pure polyoxyethylene glycol (PEG), make that the concentration of PEG is 0.01-0.10g/mL in the solution, form precursor solution C;
4) in the precursor solution C, adding NaOH solution, to regulate pH value be 4～7 must solution D;
5) solution D 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 100-200 ℃, and the hydro-thermal pressure-controlling of voltage-controlled pattern is at 0.1-3Mpa; Reaction 5min-80min, reaction naturally cools to room temperature after finishing;
6) open hydrothermal reaction kettle, product is used deionized water respectively then through centrifugal collection, and absolute ethanol washing obtains final product Cu 40-80 ℃ of drying in vacuum drying oven 1.8The S nano wire.
2. microwave hydrothermal according to claim 1 prepares Cu 1.8The method of S nano wire is characterized in that: described soluble copper salt is cupric nitrate or copper sulfate.
3. microwave hydrothermal according to claim 1 prepares Cu 1.8The method of S nano wire is characterized in that: the concentration of described NaOH solution is 1.25mol/L.
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102775985A (en) * 2012-07-07 2012-11-14 河北联合大学 One method for synthesizing Sr2MgSi2O7nanowire with long afterglow luminescence (Eu2+, dy3+)
CN108315759A (en) * 2018-03-15 2018-07-24 陕西科技大学 A kind of Cu of vanadium modification2S self-supportings electrode material and its synthetic method
CN110156066A (en) * 2019-05-06 2019-08-23 上海应用技术大学 A kind of preparation method of the nano-copper sulfide applied to tumor thermal therapy
CN111137926A (en) * 2020-01-03 2020-05-12 中国科学技术大学 Non-equilibrium state nanowire and preparation method thereof

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CN101798104A (en) * 2010-04-08 2010-08-11 洛阳师范学院 Preparation method for copper sulphide nano particles
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102775985A (en) * 2012-07-07 2012-11-14 河北联合大学 One method for synthesizing Sr2MgSi2O7nanowire with long afterglow luminescence (Eu2+, dy3+)
CN108315759A (en) * 2018-03-15 2018-07-24 陕西科技大学 A kind of Cu of vanadium modification2S self-supportings electrode material and its synthetic method
CN110156066A (en) * 2019-05-06 2019-08-23 上海应用技术大学 A kind of preparation method of the nano-copper sulfide applied to tumor thermal therapy
CN111137926A (en) * 2020-01-03 2020-05-12 中国科学技术大学 Non-equilibrium state nanowire and preparation method thereof

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