CN102502776B - Method for preparing Cu1.8S nanowire by microwave-hydrothermal method - Google Patents
Method for preparing Cu1.8S nanowire by microwave-hydrothermal method Download PDFInfo
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- CN102502776B CN102502776B CN 201110375840 CN201110375840A CN102502776B CN 102502776 B CN102502776 B CN 102502776B CN 201110375840 CN201110375840 CN 201110375840 CN 201110375840 A CN201110375840 A CN 201110375840A CN 102502776 B CN102502776 B CN 102502776B
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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
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 because transient metal sulfide has at aspects such as semi-conductor, light-emitting device and superconductions the very big interest that potential using value is subject to researcher.Cupric sulfide is very important p-type semi-conductor, 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 the fields such as thermopair, spectral filter, solar cell, sensor and catalysis.Up to now, the successful cupric sulfide of synthetic different morphologies, nanometer plate-like for example, hollow ball-shape, the 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, or need strict experiment condition and long reaction times, and owing in the process at synthetic cupric sulfide, a large amount of H being arranged
2s gas generates, and as reaction, in the system of opening wide, carries out, and inevitably can cause certain pollution to environment.Therefore find 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, reproducible.
For achieving the above object, the technical solution used in the present invention is:
1) analytically pure soluble copper salt is joined in deionized water, make Cu
2+the clear solution A that concentration is 0.01mol/L-2.0mol/L;
2) add analytically pure thiocarbamide (SC (NH in A solution
2)
2), make Cu in solution
2+/ SC (NH
2)
2mol ratio be 1: 1～5 solution B;
3) add analytically pure polyoxyethylene glycol (PEG) in B solution, the concentration that makes PEG in solution is 0.01-0.10g/mL, forms precursor solution C;
4) to adding in the precursor solution C NaOH solution to regulate pH value, be 4～7 must solution D;
5) solution D is poured in microwave hydrothermal reaction kettle, compactedness is 50%-80%, then sealed reactor, put it in the warm-pressing double-control microwave hydrothermal reaction, select temperature control mode or voltage-controlled pattern to be reacted, the temperature of described temperature control mode is controlled at 100-200 ℃, and the Hydro-thermal pressure of voltage-controlled pattern is controlled at 0.1-3Mpa, reaction 5min-80min, reaction naturally cools to room temperature after finishing;
6) open hydrothermal reaction kettle, product, through centrifugal collection, is then used respectively deionized water, 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, and reaction once completes in liquid phase, does not need post-processed.
The accompanying drawing explanation
Fig. 1 is the prepared Cu of the embodiment of the present 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 present invention 1 preparation
1.8the SEM photo of S nano wire.
Embodiment
Below in conjunction with drawings and Examples, the present invention is described in further detail.
Embodiment 1:
1) by analytically pure Gerhardite Cu (NO
3)
23H
2o joins in deionized water, makes Cu
2+the clear solution A that concentration is 0.04mol/L;
2) add analytically pure thiocarbamide (SC (NH in A solution
2)
2), make Cu in solution
2+/ SC (NH
2)
2mol ratio be 1: 2 solution B;
3) add analytically pure polyoxyethylene glycol (PEG) in B solution, the concentration that makes PEG in solution is 0.03g/mL, forms precursor solution C;
4) to adding in the precursor solution C NaOH solution that concentration is 1.25mol/L to regulate pH value, be 4 must solution D;
5) solution D is poured in microwave hydrothermal reaction kettle, compactedness is 50%, and then sealed reactor, put it in the warm-pressing double-control microwave hydrothermal reaction, selects temperature control mode at 180 ℃, reaction 10min, and reaction naturally cools to room temperature after finishing;
6) open hydrothermal reaction kettle, product, through centrifugal collection, is then used respectively deionized water, and absolute ethanol washing obtains final product Cu 40 ℃ of dryings in vacuum drying oven
1.8the S nano wire.
By Rigaku D/max2000PCX-x ray diffractometer x analytic sample for the CuS particle of gained, the discovery product is Cu
1.8s (JCPDS 47-1748), be shown in Fig. 1.The JSM-6390A type scanning electronic microscope that this sample is produced with Japanese firm is observed, as can be seen from Figure 2 prepared CuS nano wire, and diameter is about 300-600nm, and is the winding shape.
Embodiment 2:
1) by analytically pure Salzburg vitriol (CuSO
45H
2o) join in deionized water, make Cu
2+the clear solution A that concentration is 0.25mol/L;
2) add analytically pure thiocarbamide (SC (NH in A solution
2)
2), make Cu in solution
2+/ SC (NH
2)
2mol ratio be 1: 3 solution B;
3) add analytically pure polyoxyethylene glycol (PEG) in B solution, the concentration that makes PEG in solution is 0.04g/mL, forms precursor solution C;
4) to adding in the precursor solution C NaOH solution that concentration is 1.25mol/L to regulate pH value, be 5 must solution D;
5) solution D is poured in microwave hydrothermal reaction kettle, compactedness is 60%, and then sealed reactor, put it in the warm-pressing double-control microwave hydrothermal reaction, selects temperature control mode at 150 ℃, reaction 20min, and reaction naturally cools to room temperature after finishing;
6) open hydrothermal reaction kettle, product, through centrifugal collection, is then used respectively deionized water, and absolute ethanol washing obtains final product Cu 60 ℃ of dryings in vacuum drying oven
1.8the S nano wire.
Embodiment 3:
1) by analytically pure Gerhardite Cu (NO
3)
23H
2o joins in deionized water, makes Cu
2+the clear solution A that concentration is 0.01mol/L;
2) add analytically pure thiocarbamide (SC (NH in A solution
2)
2), make Cu in solution
2+/ SC (NH
2)
2mol ratio be 1: 1 solution B;
3) add analytically pure polyoxyethylene glycol (PEG) in B solution, the concentration that makes PEG in solution is 0.01g/mL, forms precursor solution C;
4) to adding in the precursor solution C NaOH solution that concentration is 1.25mol/L to regulate pH value, be 6 must solution D;
5) solution D is poured in microwave hydrothermal reaction kettle, compactedness is 70%, and then sealed reactor, put it in the warm-pressing double-control microwave hydrothermal reaction, selects temperature control mode at 100 ℃, reaction 80min, and reaction naturally cools to room temperature after finishing;
6) open hydrothermal reaction kettle, product, through centrifugal collection, is then used respectively deionized water, and absolute ethanol washing obtains final product Cu 80 ℃ of dryings in vacuum drying oven
1.8the S nano wire.
Embodiment 4:
1) by analytically pure Salzburg vitriol (CuSO
45H
2o) join in deionized water, make Cu
2+the clear solution A that concentration is 0.8mol/L;
2) add analytically pure thiocarbamide (SC (NH in A solution
2)
2), make Cu in solution
2+/ SC (NH
2)
2mol ratio be 1: 5 solution B;
3) add analytically pure polyoxyethylene glycol (PEG) in B solution, the concentration that makes PEG in solution is 0.05g/mL, forms precursor solution C;
4) to adding in the precursor solution C NaOH solution that concentration is 1.25mol/L to regulate pH value, be 7 must solution D;
5) solution D is poured in microwave hydrothermal reaction kettle, compactedness is 80%, and then sealed reactor, put it in the warm-pressing double-control microwave hydrothermal reaction, selects temperature control mode at 200 ℃, reaction 5min, and reaction naturally cools to room temperature after finishing;
6) open hydrothermal reaction kettle, product, through centrifugal collection, is then used respectively deionized water, and absolute ethanol washing obtains final product Cu 50 ℃ of dryings in vacuum drying oven
1.8the S nano wire.
Embodiment 5:
1) by analytically pure Gerhardite Cu (NO
3)
23H
2o joins in deionized water, makes Cu
2+the clear solution A that concentration is 1.2mol/L;
2) add analytically pure thiocarbamide (SC (NH in A solution
2)
2), make Cu in solution
2+/ SC (NH
2)
2mol ratio be 1: 4 solution B;
3) add analytically pure polyoxyethylene glycol (PEG) in B solution, the concentration that makes PEG in solution is 0.08g/mL, forms precursor solution C;
4) to adding in the precursor solution C NaOH solution that concentration is 1.25mol/L to regulate pH value, be 7 must solution D;
5) solution D is poured in microwave hydrothermal reaction kettle, compactedness is 80%, then sealed reactor, put it in the warm-pressing double-control microwave hydrothermal reaction, select voltage-controlled pattern to be reacted, the Hydro-thermal pressure of voltage-controlled pattern is controlled at 0.1Mpa, reaction 70min, and reaction naturally cools to room temperature after finishing;
6) open hydrothermal reaction kettle, product, through centrifugal collection, is then used respectively deionized water, and absolute ethanol washing obtains final product Cu 70 ℃ of dryings in vacuum drying oven
1.8the S nano wire.
Embodiment 6:
1) by analytically pure Salzburg vitriol (CuSO
45H
2o) join in deionized water, make Cu
2+the clear solution A that concentration is 1.6mol/L;
2) add analytically pure thiocarbamide (SC (NH in A solution
2)
2), make Cu in solution
2+/ SC (NH
2)
2mol ratio be 1: 3.5 solution B;
3) add analytically pure polyoxyethylene glycol (PEG) in B solution, the concentration that makes PEG in solution is 0.06g/mL, forms precursor solution C;
4) to adding in the precursor solution C NaOH solution that concentration is 1.25mol/L to regulate pH value, be 5 must solution D;
5) solution D is poured in microwave hydrothermal reaction kettle, compactedness is 70%, then sealed reactor, put it in the warm-pressing double-control microwave hydrothermal reaction, select voltage-controlled pattern to be reacted, the Hydro-thermal pressure of voltage-controlled pattern is controlled at 1.5Mpa, reaction 50min, and reaction naturally cools to room temperature after finishing;
6) open hydrothermal reaction kettle, product, through centrifugal collection, is then used respectively deionized water, and absolute ethanol washing obtains final product Cu 60 ℃ of dryings in vacuum drying oven
1.8the S nano wire.
Embodiment 7:
1) by analytically pure Gerhardite Cu (NO
3)
23H
2o joins in deionized water, makes Cu
2+the clear solution A that concentration is 2.0mol/L;
2) add analytically pure thiocarbamide (SC (NH in A solution
2)
2), make Cu in solution
2+/ SC (NH
2)
2mol ratio be 1: 2.5 solution B;
3) add analytically pure polyoxyethylene glycol (PEG) in B solution, the concentration that makes PEG in solution is 0.1g/mL, forms precursor solution C;
4) to adding in the precursor solution C NaOH solution that concentration is 1.25mol/L to regulate pH value, be 6 must solution D;
5) solution D is poured in microwave hydrothermal reaction kettle, compactedness is 60%, then sealed reactor, put it in the warm-pressing double-control microwave hydrothermal reaction, select voltage-controlled pattern to be reacted, the Hydro-thermal pressure of voltage-controlled pattern is controlled at 3Mpa, reaction 30min, reaction naturally cools to room temperature after finishing;
6) open hydrothermal reaction kettle, product, through centrifugal collection, is then used respectively deionized water, 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 deionized water, make Cu
2+the clear solution A that concentration is 0.01mol/L-2.0mol/L;
2) add analytically pure thiocarbamide (SC (NH in A solution
2)
2), make Cu in solution
2+/ SC (NH
2)
2mol ratio be 1: 1～5 solution B;
3) add analytically pure polyoxyethylene glycol (PEG) in B solution, the concentration that makes PEG in solution is 0.01-0.10g/mL, forms precursor solution C;
4) to adding in the precursor solution C NaOH solution to regulate pH value, be 4～7 must solution D;
5) solution D is poured in microwave hydrothermal reaction kettle, compactedness is 50%-80%, then sealed reactor, put it in the warm-pressing double-control microwave hydrothermal reaction, select temperature control mode or voltage-controlled pattern to be reacted, the temperature of described temperature control mode is controlled at 100-200 ℃, and the Hydro-thermal pressure of voltage-controlled pattern is controlled at 0.1-3MPa, reaction 5min-80min, reaction naturally cools to room temperature after finishing;
6) open hydrothermal reaction kettle, product, through centrifugal collection, is then used respectively deionized water, 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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| CN108315759B (en) * | 2018-03-15 | 2019-07-12 | 陕西科技大学 | A kind of Cu of vanadium modification2S self-supporting 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 |
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