CN103084581B - Preparation method for copper nanowire - Google Patents
Preparation method for copper nanowire Download PDFInfo
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Abstract
The invention belongs to the technical field of novel function nanometer material preparation, and discloses a preparation method for a copper nanowire. Reducing agent is added to copper source on the premise that morphology control agent and chemical potential control agent are exist in water solution, and the copper nanowire are obtained after separation and under the condition that reaction is carried out for at least one hour in temperature of 25 DEG C to 100 DEG C, wherein the copper source is one or combination of copper hydroxide and copper oxide, the morphology control agent is one kind or combination of more than two kinds of polyethylene polyamine, the chemical potential control agent is one or combination of sodium hydroxide and potassium hydroxide, and the reducing agent is one or combination of hydrazine hydrate and hydroxylamine. The preparation method for the copper nanowire has the advantages of being simple in technology and device, cheap and easy-getting in raw materials, low in cost, high in productivity, suitable for large-scale industrial production, and the like. Prepared copper nanometers are uniform in diameter, diameters and lengths of the copper nanometers can be controlled through changing concentration of the morphology control agent and concentration and reaction temperature of the copper resource.
Description
Technical field
The invention belongs to technical field of novel function nanometer material preparation, particularly a kind of preparation method of copper nano-wire.
Background technology
Copper nano-wire has been widely used at field tools such as electronic material, conductive material, catalysis, polymer-based self-lubricating materials.Document shows, copper nano-wire can substitute expensive silver and rare metal indium as flexible and transparent conductive electrode material, in the field such as solar cell, display of a new generation, there is huge application potential (Aaron R. Rathmell et al, Adv. Mater. 2010,22,3558 – 3563).Copper nano-wire can the prerequisite of practical application be the successful exploitation of its scale technology of preparing.The preparation of copper nano-wire adopts template method usually; such as; Neumann; the people such as Rd adopt anode oxidation alumina to be Template preparation copper nano-wire, not only relate to and use expensive masterplate, and the process of removing masterplate is also very complicated; productive rate is very low; requirement (Adv. Mater. 2001,13,62 65) prepared by scale cannot be reached.The people such as Yunfeng Lu adopt octadecylamine to be Spawn preparation copper nano-wire as masterplate, platinum nanoparticle, owing to needing to consume platinum nanoparticle that is expensive and that prepare not easily, therefore industrialized preparation (J. Am. Chem. Soc. 2012,134,14,283 14286) is not suitable for yet.The people such as Hua Chun Zeng adopt ethylenediamine to be pattern controlling agent at ambient pressure, and copper nitrate is copper source, has prepared copper nano-wire (Langmuir 2005,21,3746-3748) in high-concentration sodium hydroxide solution.Inventor cooperates to have further developed this preparation method with people such as Hua Chun Zeng, makes it not only to may be used for preparing copper nano-wire, can also prepare the hud typed composite nano-line of [email protected] because used high-concentration alkali liquor is difficult to recycle and reuse, make preparation cost very high (Chem Mate, 2010,22 (4), 1282-1284).
Summary of the invention
Preparation method that the object of the present invention is to provide a kind of cheapness, that be applicable to copper nano-wire prepared by scale, obtained copper nano-wire diameter and adjustable length, purity is high.
The technical solution used in the present invention is as follows:
A kind of preparation method of copper nano-wire: in aqueous, copper source, under the existence of pattern controlling agent and chemical potential adjusting control agent, adds reducing agent, reacts at least 1h, namely obtain copper nano-wire after separation under the condition of 25-100 DEG C; Wherein, described copper source is one or both the combination in Kocide SD, cupric oxide, described pattern controlling agent is one or more the combination in polyethylene polyamine, described chemical potential adjusting control agent is one or both the combination in NaOH, potassium hydroxide, and described reducing agent is one or both the combination in hydrazine hydrate, azanol.
Described polyethylene polyamine is diethylenetriamine, triethylene tetramine or TEPA.
Copper source and reducing agent consumption meet nonstoichiometric molar ratio, and copper source concentration controls at 0.01-0.5mol/L, and pattern controlling agent concentration controls at 0.02-2mol/L, and chemical potential adjusting control agent concentration controls at 2-15mol/L.Based on copper source, the consumption of reducing agent substantially by metering than feeding intake, chemical potential adjusting control agent is used to regulation and control reaction speed and the reaction mechanism mechanism of reaction, pattern controlling agent has impact to the reaction mechanism mechanism of reaction equally, there is specific scope, otherwise prepare not nanowire, the powder of copper can only be obtained.
The present invention with Kocide SD or cupric oxide for copper source, with hydrazine hydrate or azanol for reducing agent under suitable condition by the copper reduction of oxidation state for metallic copper, the pattern of the copper obtained by control and particle diameter, obtain copper nano-wire.When reducing agent is respectively hydrazine hydrate, azanol, involved chemical equation following (I) and (II):
The inventive method for copper source, with hydrazine hydrate or azanol for reducing agent, does not introduce the anion of any needs removing with Kocide SD or cupric oxide in reaction system, byproduct of reaction is only water and nitrogen, can remove easily, so reaction mother liquor can Reusability, significantly reduce preparation cost.Be different from existing copper nitrate, copper sulphate and the copper acetate of adopting is the masterplate synthetic method in copper source more, provides a kind of new approaches preparing Nanometer Copper.Pattern controlling agent of the present invention is polyethylene polyamine, and its boiling point is very high is not easy volatilization, is different from the ethylenediamine (highly volatile) that existing method adopts.
This preparation method has technique, equipment is simple, cheaper starting materials is easy to get, cost is low, and productive rate high, is applicable to large-scale industrial production.Prepared copper nano-wire diameter is homogeneous, and can regulate and control diameter and the length of copper nano-wire by changing the concentration of pattern controlling agent, the concentration in copper source and reaction temperature, generally lower concentration is conducive to forming thinner copper nano-wire.
Accompanying drawing explanation
Fig. 1 is the XRD figure of the copper nano-wire that embodiment 1 obtains.
Fig. 2 is the transmission electron microscope figure of the copper nano-wire that embodiment 1 obtains.
Fig. 3 is the scanning electron microscope diagram of the copper nano-wire that embodiment 1 obtains.
Detailed description of the invention
With specific embodiment, technical scheme of the present invention is described below, but protection scope of the present invention is not limited thereto:
Embodiment 1
In 500mL flask, add the NaOH solution that 300ml concentration is 7M, under then slowly stirring, add 3g triethylene tetramine, 1.5g Cu (OH)
2with 1.5ml 80%(mass fraction, lower same) hydrazine hydrate aqueous solution, isothermal reaction 1 hour in 80 DEG C of water-baths.Solution becomes brownish red from blueness gradually, and has a large amount of solid flotation on liquid level, is taken out by flask from water-bath, be cooled to room temperature, filter and obtain brown-red solid, and wash 3 times with 5% hydrazine hydrate aqueous solution, then vacuum drying at 60 DEG C, obtains copper nano-wire product.
The XRD figure of copper nano-wire is shown in Fig. 1, and as seen from the figure, XRD result shows that prepared product is the metallic copper of pure face-centred cubic structure, does not occur the diffraction maximum of Kocide SD, cuprous oxide or cupric oxide, illustrates that product purity prepared by this method is very high.
The transmission electron microscope figure of copper nano-wire is shown in Fig. 2, and as seen from the figure, prepared NANO CRYSTAL COPPER WIRE uniform diameter, between 50-100nm, does not occur the product of nanoparticle or other pattern, shows that product prepared by the inventive method is copper nano-wire.
The scanning electron microscope diagram of copper nano-wire is shown in Fig. 3; as seen from the figure; prepared NANO CRYSTAL COPPER WIRE length is between 5-20um; diameter 50-100nm; there is not the product of nanoparticle or other pattern; consistent with the result of transmission electron microscope, show that product prepared by the inventive method is copper nano-wire.
Embodiment 2
In 500mL flask, add the NaOH solution that 300ml concentration is 7M, under then slowly stirring, add 1g triethylene tetramine, 1.5g Cu (OH)
2with 1.5ml 80% hydrazine hydrate aqueous solution, isothermal reaction 1 hour in 80 DEG C of water-baths.Solution becomes brownish red from blueness gradually, and has a large amount of solid flotation on liquid level, is taken out by flask from water-bath, be cooled to room temperature, filter and obtain brown-red solid, and wash 3 times with 5% hydrazine hydrate aqueous solution, then vacuum drying at 60 DEG C, obtains copper nano-wire product.Prepared NANO CRYSTAL COPPER WIRE length between 5-20um, between diameter 50-100nm.
Embodiment 3
In 500mL flask, add the NaOH solution that 300ml concentration is 7M, under then slowly stirring, add 9g triethylene tetramine, 1.5g Cu (OH)
2with 1.5ml 80% hydrazine hydrate aqueous solution, isothermal reaction 1 hour in 80 DEG C of water-baths.Solution becomes brownish red from blueness gradually, and has a large amount of solid flotation on liquid level, is taken out by flask from water-bath, be cooled to room temperature, filter and obtain brown-red solid, and wash 3 times with 5% hydrazine hydrate aqueous solution, then vacuum drying at 60 DEG C, obtains copper nano-wire product.Prepared NANO CRYSTAL COPPER WIRE length between 5-20um, between diameter 50-100nm.
Embodiment 4
In 500mL flask, add the NaOH solution that 300ml concentration is 7M, under then slowly stirring, add 30g triethylene tetramine, 15g Cu (OH)
2with 15ml 80% hydrazine hydrate aqueous solution, isothermal reaction 2 hours in 80 DEG C of water-baths.Solution becomes brownish red from blueness gradually, and has a large amount of solid flotation on liquid level, is taken out by flask from water-bath, be cooled to room temperature, filter and obtain brown-red solid, and wash 3 times with 5% hydrazine hydrate aqueous solution, then vacuum drying at 60 DEG C, obtains copper nano-wire product.Prepared NANO CRYSTAL COPPER WIRE length between 3-10um, between diameter 100-300nm.
Embodiment 5
In 500mL flask, add the NaOH solution that 300ml concentration is 7M, under then slowly stirring, add 3g diethylenetriamine, 1.5g Cu (OH)
2with 1.5ml 80% hydrazine hydrate aqueous solution, isothermal reaction 1 hour in 80 DEG C of water-baths.Solution becomes brownish red from blueness gradually, and has a large amount of solid flotation on liquid level, is taken out by flask from water-bath, be cooled to room temperature, filter and obtain brown-red solid, and wash 3 times with 5% hydrazine hydrate aqueous solution, then vacuum drying at 60 DEG C, obtains copper nano-wire product.Prepared NANO CRYSTAL COPPER WIRE length between 5-20um, between diameter 50-100nm.
Embodiment 6
In 500mL flask, add the NaOH solution that 300ml concentration is 7M, under then slowly stirring, add 1g diethylenetriamine, 1.5g Cu (OH)
2with 1.5ml 80% hydrazine hydrate aqueous solution, isothermal reaction 1 hour in 80 DEG C of water-baths.Solution becomes brownish red from blueness gradually, and has a large amount of solid flotation on liquid level, is taken out by flask from water-bath, be cooled to room temperature, filter and obtain brown-red solid, and wash 3 times with 5% hydrazine hydrate aqueous solution, then vacuum drying at 60 DEG C, obtains copper nano-wire product.Prepared NANO CRYSTAL COPPER WIRE length between 5-20um, between diameter 50-100nm.
Embodiment 7
In 500mL flask, add the NaOH solution that 300ml concentration is 7M, under then slowly stirring, add 9g diethylenetriamine, 1.5g Cu (OH)
2with 1.5ml 80% hydrazine hydrate aqueous solution, isothermal reaction 1 hour in 80 DEG C of water-baths.Solution becomes brownish red from blueness gradually, and has a large amount of solid flotation on liquid level, is taken out by flask from water-bath, be cooled to room temperature, filter and obtain brown-red solid, and wash 3 times with 5% hydrazine hydrate aqueous solution, then vacuum drying at 60 DEG C, obtains copper nano-wire product.Prepared NANO CRYSTAL COPPER WIRE length between 5-20um, between diameter 50-100nm.
Embodiment 8
In 500mL flask, add the NaOH solution that 300ml concentration is 7M, under then slowly stirring, add 30g diethylenetriamine, 15g Cu (OH)
2with 15ml 80% hydrazine hydrate aqueous solution, isothermal reaction 2 hours in 80 DEG C of water-baths.Solution becomes brownish red from blueness gradually, and has a large amount of solid flotation on liquid level, is taken out by flask from water-bath, be cooled to room temperature, filter and obtain brown-red solid, and wash 3 times with 5% hydrazine hydrate aqueous solution, then vacuum drying at 60 DEG C, obtains copper nano-wire product.Prepared NANO CRYSTAL COPPER WIRE length between 3-10um, between diameter 100-300nm.
Embodiment 9
In 500mL flask, add the NaOH solution that 300ml concentration is 7M, under then slowly stirring, add 3g TEPA, 1.5g Cu (OH)
2with 1.5ml 80% hydrazine hydrate aqueous solution, isothermal reaction 1 hour in 80 DEG C of water-baths.Solution becomes brownish red from blueness gradually, and has a large amount of solid flotation on liquid level, is taken out by flask from water-bath, be cooled to room temperature, filter and obtain brown-red solid, and wash 3 times with 5% hydrazine hydrate aqueous solution, then vacuum drying at 60 DEG C, obtains copper nano-wire product.Prepared NANO CRYSTAL COPPER WIRE length between 5-20um, between diameter 50-100nm.
Embodiment 10
In 500mL flask, add the NaOH solution that 300ml concentration is 7M, under then slowly stirring, add 1g TEPA, 1.5g Cu (OH)
2with 1.5ml 80% hydrazine hydrate aqueous solution, isothermal reaction 1 hour in 80 DEG C of water-baths.Solution becomes brownish red from blueness gradually, and has a large amount of solid flotation on liquid level, is taken out by flask from water-bath, be cooled to room temperature, filter and obtain brown-red solid, and wash 3 times with 5% hydrazine hydrate aqueous solution, then vacuum drying at 60 DEG C, obtains copper nano-wire product.Prepared NANO CRYSTAL COPPER WIRE length between 5-20um, between diameter 50-100nm.
Embodiment 11
In 500mL flask, add the NaOH solution that 300ml concentration is 7M, under then slowly stirring, add 9g TEPA, 1.5g Cu (OH)
2with 1.5ml 80% hydrazine hydrate aqueous solution, isothermal reaction 1 hour in 80 DEG C of water-baths.Solution becomes brownish red from blueness gradually, and has a large amount of solid flotation on liquid level, is taken out by flask from water-bath, be cooled to room temperature, filter and obtain brown-red solid, and wash 3 times with 5% hydrazine hydrate aqueous solution, then vacuum drying at 60 DEG C, obtains copper nano-wire product.Prepared NANO CRYSTAL COPPER WIRE length between 5-20um, between diameter 50-100nm.
Embodiment 12
In 500mL flask, add the NaOH solution that 300ml concentration is 7M, under then slowly stirring, add 30g TEPA, 15g Cu (OH)
2with 15ml 80% hydrazine hydrate aqueous solution, isothermal reaction 2 hours in 80 DEG C of water-baths.Solution becomes brownish red from blueness gradually, and has a large amount of solid flotation on liquid level, is taken out by flask from water-bath, be cooled to room temperature, filter and obtain brown-red solid, and wash 3 times with 5% hydrazine hydrate aqueous solution, then vacuum drying at 60 DEG C, obtains copper nano-wire product.Prepared NANO CRYSTAL COPPER WIRE length between 3-10um, between diameter 100-300nm.
Embodiment 13
In 500mL flask, add the NaOH solution that 300ml concentration is 7M, under then slowly stirring, add 3g triethylene tetramine, 1.2g CuO and 1.5ml 80% hydrazine hydrate aqueous solution, isothermal reaction 4 hours in 80 DEG C of water-baths.Solution gradually becomes brownish red, and has a large amount of solid flotation on liquid level, is taken out by flask, be cooled to room temperature from water-bath, filters and obtains brown-red solid, and wash 3 times with 5% hydrazine hydrate aqueous solution, and then vacuum drying at 60 DEG C, obtains copper nano-wire product.Prepared NANO CRYSTAL COPPER WIRE length between 1-10um, between diameter 50-200nm.
Embodiment 14
In 500mL flask, add the NaOH solution that 300ml concentration is 7M, under then slowly stirring, add 3g diethylenetriamine, 1.2g CuO and 1.5ml 80% hydrazine hydrate aqueous solution, isothermal reaction 4 hours in 80 DEG C of water-baths.Solution gradually becomes brownish red, and has a large amount of solid flotation on liquid level, is taken out by flask, be cooled to room temperature from water-bath, filters and obtains brown-red solid, and wash 3 times with 5% hydrazine hydrate aqueous solution, and then vacuum drying at 60 DEG C, obtains copper nano-wire product.Prepared NANO CRYSTAL COPPER WIRE length between 1-10um, between diameter 50-200nm.
Embodiment 15
In 500mL flask, add the NaOH solution that 300ml concentration is 7M, under then slowly stirring, add 3g TEPA, 1.2g CuO and 1.5ml 80% hydrazine hydrate aqueous solution, isothermal reaction 4 hours in 80 DEG C of water-baths.Solution gradually becomes brownish red, and has a large amount of solid flotation on liquid level, is taken out by flask, be cooled to room temperature from water-bath, filters and obtains brown-red solid, and wash 3 times with 5% hydrazine hydrate aqueous solution, and then vacuum drying at 60 DEG C, obtains copper nano-wire product.Prepared NANO CRYSTAL COPPER WIRE length between 1-10um, between diameter 50-200nm.
Embodiment 16
In 500mL flask, add NaOH solution that 150ml concentration is 7M and 150ml concentration is the KOH solution of 7M, under then slowly stirring, add 1g triethylene tetramine, 1.5g Cu (OH)
2with 1.5ml 80% hydrazine hydrate aqueous solution, isothermal reaction 1 hour in 80 DEG C of water-baths.Solution becomes brownish red from blueness gradually, and has a large amount of solid flotation on liquid level, is taken out by flask from water-bath, be cooled to room temperature, filter and obtain brown-red solid, and wash 3 times with 5% hydrazine hydrate aqueous solution, then vacuum drying at 60 DEG C, obtains copper nano-wire product.Prepared NANO CRYSTAL COPPER WIRE length between 5-20um, between diameter 50-100nm.
Embodiment 17
In 500mL flask, add the NaOH solution that 300ml concentration is 7M, under then slowly stirring, add 1g triethylene tetramine, 1.5g Cu (OH)
2with 1.5ml 80% hydrazine hydrate aqueous solution, isothermal reaction 4 hours in 40 DEG C of water-baths.Solution becomes brownish red from blueness gradually, and has a large amount of solid flotation on liquid level, is taken out by flask from water-bath, be cooled to room temperature, filter and obtain brown-red solid, and wash 3 times with 5% hydrazine hydrate aqueous solution, then vacuum drying at 60 DEG C, obtains copper nano-wire product.Prepared NANO CRYSTAL COPPER WIRE length between 5-20um, between diameter 50-150nm.
Embodiment 18
In 500mL flask, add the NaOH solution that 300ml concentration is 7M, under then slowly stirring, add 10g TEPA, 10g diethylenetriamine, 10g triethylene tetramine, 15g Cu (OH)
2with 15ml 80% hydrazine hydrate aqueous solution, isothermal reaction 2 hours in 80 DEG C of water-baths.Solution becomes brownish red from blueness gradually, and has a large amount of solid flotation on liquid level, is taken out by flask from water-bath, be cooled to room temperature, filter and obtain brown-red solid, and wash 3 times with 5% hydrazine hydrate aqueous solution, then vacuum drying at 60 DEG C, obtains copper nano-wire product.Prepared NANO CRYSTAL COPPER WIRE length between 3-10um, between diameter 100-500nm.
Embodiment 19
In 500mL flask, add the KOH solution that 300ml concentration is 7M, under then slowly stirring, add 30g TEPA, 15g Cu (OH)
2with 15ml 80% hydrazine hydrate aqueous solution, isothermal reaction 2 hours in 80 DEG C of water-baths.Solution becomes brownish red from blueness gradually, and has a large amount of solid flotation on liquid level, is taken out by flask from water-bath, be cooled to room temperature, filter and obtain brown-red solid, and wash 3 times with 5% hydrazine hydrate aqueous solution, then vacuum drying at 60 DEG C, obtains copper nano-wire product.Prepared NANO CRYSTAL COPPER WIRE length between 3-10um, between diameter 100-500nm.
Embodiment 20
In 500mL flask, add the NaOH solution that 300ml concentration is 7M, under then slowly stirring, add 30g TEPA, 15g Cu (OH)
2with 60ml 50%(mass fraction, lower same) aqueous hydroxylamine solution, isothermal reaction 4 hours in 80 DEG C of water-baths.Solution becomes brownish red from blueness gradually, and has a large amount of solid flotation on liquid level, is taken out by flask from water-bath, be cooled to room temperature, filter and obtain brown-red solid, and wash 3 times with 5% hydrazine hydrate aqueous solution, then vacuum drying at 60 DEG C, obtains copper nano-wire product.Prepared NANO CRYSTAL COPPER WIRE length between 3-15um, between diameter 100-500nm.
Embodiment 21
In 500mL flask, add the NaOH solution that 300ml concentration is 7M, under then slowly stirring, add 30g TEPA, 15g Cu (OH)
2with 10ml 80% hydrazine hydrate aqueous solution and 20ml 50% aqueous hydroxylamine solution, isothermal reaction 3 hours in 80 DEG C of water-baths.Solution becomes brownish red from blueness gradually, and has a large amount of solid flotation on liquid level, is taken out by flask from water-bath, be cooled to room temperature, filter and obtain brown-red solid, and wash 3 times with 5% hydrazine hydrate aqueous solution, then vacuum drying at 60 DEG C, obtains copper nano-wire product.Prepared NANO CRYSTAL COPPER WIRE length between 1-10um, between diameter 100-300nm.
Embodiment 22
In 500mL flask, add the NaOH solution that 300ml concentration is 2M, under then slowly stirring, add 3g triethylene tetramine, 1.5g Cu (OH)
2with 1.5ml 80% hydrazine hydrate aqueous solution, isothermal reaction 6 hours in 80 DEG C of water-baths.Solution becomes brownish red from blueness gradually, and has a large amount of solid flotation on liquid level, is taken out by flask from water-bath, be cooled to room temperature, filter and obtain brown-red solid, and wash 3 times with 5% hydrazine hydrate aqueous solution, then vacuum drying at 60 DEG C, obtains copper nano-wire product.
Embodiment 23
In 500mL flask, add the NaOH solution that 300ml concentration is 4M, under then slowly stirring, add 3g triethylene tetramine, 1.5g Cu (OH)
2with 1.5ml 80% hydrazine hydrate aqueous solution, isothermal reaction 4 hours in 80 DEG C of water-baths.Solution becomes brownish red from blueness gradually, and has a large amount of solid flotation on liquid level, is taken out by flask from water-bath, be cooled to room temperature, filter and obtain brown-red solid, and wash 3 times with 5% hydrazine hydrate aqueous solution, then vacuum drying at 60 DEG C, obtains copper nano-wire product.
Embodiment 24
In 500mL flask, add the NaOH solution that 300ml concentration is 10M, under then slowly stirring, add 3g triethylene tetramine, 1.5g Cu (OH)
2with 1.5ml 80% hydrazine hydrate aqueous solution, isothermal reaction 1 hour in 80 DEG C of water-baths.Solution becomes brownish red from blueness gradually, and has a large amount of solid flotation on liquid level, is taken out by flask from water-bath, be cooled to room temperature, filter and obtain brown-red solid, and wash 3 times with 5% hydrazine hydrate aqueous solution, then vacuum drying at 60 DEG C, obtains copper nano-wire product.
Embodiment 25
In 500mL flask, add the NaOH solution that 300ml concentration is 15M, under then slowly stirring, add 3g triethylene tetramine, 1.5g Cu (OH)
2with 1.5ml 80% hydrazine hydrate aqueous solution, isothermal reaction 1 hour in 80 DEG C of water-baths.Solution becomes brownish red from blueness gradually, and has a large amount of solid flotation on liquid level, is taken out by flask from water-bath, be cooled to room temperature, filter and obtain brown-red solid, and wash 3 times with 5% hydrazine hydrate aqueous solution, then vacuum drying at 60 DEG C, obtains copper nano-wire product.
Embodiment 26
In 500mL flask, add the NaOH solution that 300ml concentration is 2M, under then slowly stirring, add 3g triethylene tetramine, 1.5g Cu (OH)
2with 1.5ml 80% hydrazine hydrate aqueous solution, isothermal reaction 4 hours in 100 DEG C of water-baths.Solution becomes brownish red from blueness gradually, and has a large amount of solid flotation on liquid level, is taken out by flask from water-bath, be cooled to room temperature, filter and obtain brown-red solid, and wash 3 times with 5% hydrazine hydrate aqueous solution, then vacuum drying at 60 DEG C, obtains copper nano-wire product.
Embodiment 27
In 500mL flask, add the NaOH solution that 300ml concentration is 7M, under then slowly stirring, add 3g triethylene tetramine, 1.5g Cu (OH)
2with 1.5ml 80% hydrazine hydrate aqueous solution, isothermal reaction 6 hours in 25 DEG C of water-baths.Solution becomes brownish red from blueness gradually, and has a large amount of solid flotation on liquid level, is taken out by flask from water-bath, be cooled to room temperature, filter and obtain brown-red solid, and wash 3 times with 5% hydrazine hydrate aqueous solution, then vacuum drying at 60 DEG C, obtains copper nano-wire product.
Embodiment 28
In 500mL flask, add the NaOH solution that 300ml concentration is 7M, under then slowly stirring, add 3g triethylene tetramine, 1.5g Cu (OH)
2with 1.5ml 80% hydrazine hydrate aqueous solution, isothermal reaction 3 hours in 60 DEG C of water-baths.Solution becomes brownish red from blueness gradually, and has a large amount of solid flotation on liquid level, is taken out by flask from water-bath, be cooled to room temperature, filter and obtain brown-red solid, and wash 3 times with 5% hydrazine hydrate aqueous solution, then vacuum drying at 60 DEG C, obtains copper nano-wire product.
Claims (2)
1. a preparation method for copper nano-wire, is characterized in that: in aqueous, and copper source, under the existence of pattern controlling agent and chemical potential adjusting control agent, adds reducing agent, reacts at least 1h, namely obtain copper nano-wire after separation under the condition of 25-100 DEG C; Wherein, described copper source is one or both the combination in Kocide SD, cupric oxide, described pattern controlling agent is one or more the combination in polyethylene polyamine, described chemical potential adjusting control agent is one or both the combination in NaOH, potassium hydroxide, and described reducing agent is one or both the combination in hydrazine hydrate, azanol; Copper source and reducing agent consumption meet nonstoichiometric molar ratio, and copper source concentration controls at 0.01-0.5mol/L, and pattern controlling agent concentration controls at 0.02-2mol/L, and chemical potential adjusting control agent concentration controls at 2-15mol/L.
2. preparation method as claimed in claim 1, is characterized in that: described polyethylene polyamine is diethylenetriamine, triethylene tetramine or TEPA.
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