CN103084581A - Preparation method for copper nanowire - Google Patents
Preparation method for copper nanowire Download PDFInfo
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- CN103084581A CN103084581A CN2013100059551A CN201310005955A CN103084581A CN 103084581 A CN103084581 A CN 103084581A CN 2013100059551 A CN2013100059551 A CN 2013100059551A CN 201310005955 A CN201310005955 A CN 201310005955A CN 103084581 A CN103084581 A CN 103084581A
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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 new function nano material preparing technical field, particularly a kind of preparation method of copper nano-wire.
Background technology
Copper nano-wire has purposes widely in fields 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 the flexible and transparent conductive electrode material, has huge application potential (Aaron R. Rathmell et al in fields such as the solar cell of a new generation, displays, Adv. Mater. 2010,22,3558 – 3563).Copper nano-wire can practical application prerequisite be the develop of its scale technology of preparing.Template method is adopted in the preparation of copper nano-wire usually; for example; Neumann; it is that template has prepared copper nano-wire that the people such as Rd adopt anode oxidation alumina, not only relate to use expensive masterplate, and it is also very complicated to remove the process of masterplate; productive rate is very low; can't reach the requirement (Adv. Mater. 2001,13,62 65) of scale preparation.It is that seed has prepared copper nano-wire as masterplate, platinum nanoparticle that the people such as Yunfeng Lu adopt octadecylamine, because needs consume platinum nanoparticle expensive and that preparation is difficult for, therefore be not suitable for industrialized preparation (J. Am. Chem. Soc. 2012,134,14,283 14286) yet.The people such as Hua Chun Zeng adopt ethylenediamine under normal pressure be the pattern controlling agent, and copper nitrate is the copper source, and (Langmuir 2005,21,3746-3748) to have prepared copper nano-wire in high-concentration sodium hydroxide solution.Inventor and the people such as Hua Chun Zeng cooperate to have further developed this preparation method, make it not only can for the preparation of copper nano-wire, can also prepare the hud typed composite nano-line of [email protected] because high-concentration alkali liquor used is difficult to recycle and reuse, make preparation cost very high (Chem Mate, 2010,22 (4), 1282-1284).
Summary of the invention
The object of the present invention is to provide preparation method a kind of cheapness, that be fit to the copper nano-wire of scale preparation, the copper nano-wire diameter and the length that make are adjustable, and purity is high.
The technical solution used in the present invention is as follows:
A kind of preparation method of copper nano-wire: in the aqueous solution, the copper source adds reducing agent under the existence of pattern controlling agent and chemical potential adjusting control agent, react 1h at least under the condition of 25-100 ℃, namely obtains copper nano-wire after separation; 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 the stoichiometry mol ratio, and copper source concentration is controlled at 0.01-0.5mol/L, and pattern controlling agent concentration is controlled at 0.02-2mol/L, and chemical potential adjusting control agent concentration is controlled at 2-15mol/L.Take in the copper source as the basis, the consumption of reducing agent substantially by metering than feeding intake, the chemical potential adjusting control agent is used for reaction speed and the reaction mechanism mechanism of reaction, the pattern controlling agent is influential to the reaction mechanism mechanism of reaction equally, specific scope is arranged, otherwise can not prepare nano wire, can only obtain the powder of copper.
The present invention is take Kocide SD or cupric oxide as the copper source, take hydrazine hydrate or azanol as reducing agent under suitable condition with the copper reduction of oxidation state as metallic copper, control pattern and the particle diameter of prepared copper, namely get copper nano-wire.When reducing agent is respectively hydrazine hydrate, azanol, related chemical equation following (I) and (II):
The inventive method is take Kocide SD or cupric oxide as the copper source, take hydrazine hydrate or azanol as reducing agent, do not introduce the anion that any needs are removed in reaction system, byproduct of reaction is only water and nitrogen, can remove easily, so but the reaction mother liquor Reusability has greatly reduced preparation cost.Being different from existing many employing copper nitrates, copper sulphate and copper acetate is the masterplate synthetic method in copper source, and a kind of new approaches of preparation Nanometer Copper are provided.Pattern controlling agent of the present invention is polyethylene polyamine, and very high being not easy of its boiling point volatilized, and is different from the ethylenediamine (highly volatile) that existing method adopts.
This preparation method has technique, equipment is simple, raw material is cheap and easy to get, cost is low, and the productive rate high is fit to large-scale industrial production.Prepared copper nano-wire diameter homogeneous, diameter and length that the concentration in concentration that can be by changing the pattern controlling agent, copper source and reaction temperature regulate and control copper nano-wire, general lower concentration is conducive to form thinner copper nano-wire.
Description of drawings
Fig. 1 is the XRD figure of the copper nano-wire that makes of embodiment 1.
Fig. 2 is the transmission electron microscope figure of the copper nano-wire that makes of embodiment 1.
Fig. 3 is the scanning electron microscope diagram of the copper nano-wire that makes of embodiment 1.
The specific embodiment
Below with specific embodiment, technical scheme of the present invention is described, but protection scope of the present invention is not limited to this:
Embodiment 1
Adding 300ml concentration in the 500mL flask is the NaOH solution of 7M, adds 3g triethylene tetramine, 1.5g Cu (OH) under then slowly stirring
2With 1.5ml 80%(mass fraction, lower same) hydrazine hydrate aqueous solution, isothermal reaction is 1 hour in 80 ℃ of water-baths.Solution becomes brownish red by blueness gradually, and has a large amount of solids to swim on liquid level, and flask is taken out from water-bath, be cooled to room temperature, filter and obtain the brownish red solid, and wash 3 times with 5% hydrazine hydrate aqueous solution, then 60 ℃ of lower vacuum drying, namely get the copper nano-wire product.
The XRD figure of copper nano-wire sees Fig. 1, and as seen from the figure, the XRD result shows that prepared product is the metallic copper of pure face-centred cubic structure, the diffraction maximum of Kocide SD, cuprous oxide or cupric oxide do not occur, illustrates that the product purity of this method preparation is very high.
The transmission electron microscope figure of copper nano-wire sees Fig. 2, and as seen from the figure, prepared NANO CRYSTAL COPPER WIRE diameter is even, between 50-100nm, nanoparticle or the product of other pattern do not occur, shows that the product of the inventive method preparation is copper nano-wire.
The scanning electron microscope diagram of copper nano-wire is seen Fig. 3; as seen from the figure; prepared NANO CRYSTAL COPPER WIRE length is between 5-20um; diameter 50-100nm; nanoparticle or the product of other pattern do not appear; consistent with the result of transmission electron microscope, show that the product of the inventive method preparation is copper nano-wire.
Embodiment 2
Adding 300ml concentration in the 500mL flask is the NaOH solution of 7M, adds 1g triethylene tetramine, 1.5g Cu (OH) under then slowly stirring
2With 1.5ml 80% hydrazine hydrate aqueous solution, isothermal reaction is 1 hour in 80 ℃ of water-baths.Solution becomes brownish red by blueness gradually, and has a large amount of solids to swim on liquid level, and flask is taken out from water-bath, be cooled to room temperature, filter and obtain the brownish red solid, and wash 3 times with 5% hydrazine hydrate aqueous solution, then 60 ℃ of lower vacuum drying, namely get the copper nano-wire product.Prepared NANO CRYSTAL COPPER WIRE length is between 5-20um, between diameter 50-100nm.
Embodiment 3
Adding 300ml concentration in the 500mL flask is the NaOH solution of 7M, adds 9g triethylene tetramine, 1.5g Cu (OH) under then slowly stirring
2With 1.5ml 80% hydrazine hydrate aqueous solution, isothermal reaction is 1 hour in 80 ℃ of water-baths.Solution becomes brownish red by blueness gradually, and has a large amount of solids to swim on liquid level, and flask is taken out from water-bath, be cooled to room temperature, filter and obtain the brownish red solid, and wash 3 times with 5% hydrazine hydrate aqueous solution, then 60 ℃ of lower vacuum drying, namely get the copper nano-wire product.Prepared NANO CRYSTAL COPPER WIRE length is between 5-20um, between diameter 50-100nm.
Embodiment 4
Adding 300ml concentration in the 500mL flask is the NaOH solution of 7M, adds 30g triethylene tetramine, 15g Cu (OH) under then slowly stirring
2With 15ml 80% hydrazine hydrate aqueous solution, isothermal reaction is 2 hours in 80 ℃ of water-baths.Solution becomes brownish red by blueness gradually, and has a large amount of solids to swim on liquid level, and flask is taken out from water-bath, be cooled to room temperature, filter and obtain the brownish red solid, and wash 3 times with 5% hydrazine hydrate aqueous solution, then 60 ℃ of lower vacuum drying, namely get the copper nano-wire product.Prepared NANO CRYSTAL COPPER WIRE length is between 3-10um, between diameter 100-300nm.
Embodiment 5
Adding 300ml concentration in the 500mL flask is the NaOH solution of 7M, adds 3g diethylenetriamine, 1.5g Cu (OH) under then slowly stirring
2With 1.5ml 80% hydrazine hydrate aqueous solution, isothermal reaction is 1 hour in 80 ℃ of water-baths.Solution becomes brownish red by blueness gradually, and has a large amount of solids to swim on liquid level, and flask is taken out from water-bath, be cooled to room temperature, filter and obtain the brownish red solid, and wash 3 times with 5% hydrazine hydrate aqueous solution, then 60 ℃ of lower vacuum drying, namely get the copper nano-wire product.Prepared NANO CRYSTAL COPPER WIRE length is between 5-20um, between diameter 50-100nm.
Embodiment 6
Adding 300ml concentration in the 500mL flask is the NaOH solution of 7M, adds 1g diethylenetriamine, 1.5g Cu (OH) under then slowly stirring
2With 1.5ml 80% hydrazine hydrate aqueous solution, isothermal reaction is 1 hour in 80 ℃ of water-baths.Solution becomes brownish red by blueness gradually, and has a large amount of solids to swim on liquid level, and flask is taken out from water-bath, be cooled to room temperature, filter and obtain the brownish red solid, and wash 3 times with 5% hydrazine hydrate aqueous solution, then 60 ℃ of lower vacuum drying, namely get the copper nano-wire product.Prepared NANO CRYSTAL COPPER WIRE length is between 5-20um, between diameter 50-100nm.
Embodiment 7
Adding 300ml concentration in the 500mL flask is the NaOH solution of 7M, adds 9g diethylenetriamine, 1.5g Cu (OH) under then slowly stirring
2With 1.5ml 80% hydrazine hydrate aqueous solution, isothermal reaction is 1 hour in 80 ℃ of water-baths.Solution becomes brownish red by blueness gradually, and has a large amount of solids to swim on liquid level, and flask is taken out from water-bath, be cooled to room temperature, filter and obtain the brownish red solid, and wash 3 times with 5% hydrazine hydrate aqueous solution, then 60 ℃ of lower vacuum drying, namely get the copper nano-wire product.Prepared NANO CRYSTAL COPPER WIRE length is between 5-20um, between diameter 50-100nm.
Embodiment 8
Adding 300ml concentration in the 500mL flask is the NaOH solution of 7M, adds 30g diethylenetriamine, 15g Cu (OH) under then slowly stirring
2With 15ml 80% hydrazine hydrate aqueous solution, isothermal reaction is 2 hours in 80 ℃ of water-baths.Solution becomes brownish red by blueness gradually, and has a large amount of solids to swim on liquid level, and flask is taken out from water-bath, be cooled to room temperature, filter and obtain the brownish red solid, and wash 3 times with 5% hydrazine hydrate aqueous solution, then 60 ℃ of lower vacuum drying, namely get the copper nano-wire product.Prepared NANO CRYSTAL COPPER WIRE length is between 3-10um, between diameter 100-300nm.
Embodiment 9
Adding 300ml concentration in the 500mL flask is the NaOH solution of 7M, adds 3g TEPA, 1.5g Cu (OH) under then slowly stirring
2With 1.5ml 80% hydrazine hydrate aqueous solution, isothermal reaction is 1 hour in 80 ℃ of water-baths.Solution becomes brownish red by blueness gradually, and has a large amount of solids to swim on liquid level, and flask is taken out from water-bath, be cooled to room temperature, filter and obtain the brownish red solid, and wash 3 times with 5% hydrazine hydrate aqueous solution, then 60 ℃ of lower vacuum drying, namely get the copper nano-wire product.Prepared NANO CRYSTAL COPPER WIRE length is between 5-20um, between diameter 50-100nm.
Embodiment 10
Adding 300ml concentration in the 500mL flask is the NaOH solution of 7M, adds 1g TEPA, 1.5g Cu (OH) under then slowly stirring
2With 1.5ml 80% hydrazine hydrate aqueous solution, isothermal reaction is 1 hour in 80 ℃ of water-baths.Solution becomes brownish red by blueness gradually, and has a large amount of solids to swim on liquid level, and flask is taken out from water-bath, be cooled to room temperature, filter and obtain the brownish red solid, and wash 3 times with 5% hydrazine hydrate aqueous solution, then 60 ℃ of lower vacuum drying, namely get the copper nano-wire product.Prepared NANO CRYSTAL COPPER WIRE length is between 5-20um, between diameter 50-100nm.
Embodiment 11
Adding 300ml concentration in the 500mL flask is the NaOH solution of 7M, adds 9g TEPA, 1.5g Cu (OH) under then slowly stirring
2With 1.5ml 80% hydrazine hydrate aqueous solution, isothermal reaction is 1 hour in 80 ℃ of water-baths.Solution becomes brownish red by blueness gradually, and has a large amount of solids to swim on liquid level, and flask is taken out from water-bath, be cooled to room temperature, filter and obtain the brownish red solid, and wash 3 times with 5% hydrazine hydrate aqueous solution, then 60 ℃ of lower vacuum drying, namely get the copper nano-wire product.Prepared NANO CRYSTAL COPPER WIRE length is between 5-20um, between diameter 50-100nm.
Embodiment 12
Adding 300ml concentration in the 500mL flask is the NaOH solution of 7M, adds 30g TEPA, 15g Cu (OH) under then slowly stirring
2With 15ml 80% hydrazine hydrate aqueous solution, isothermal reaction is 2 hours in 80 ℃ of water-baths.Solution becomes brownish red by blueness gradually, and has a large amount of solids to swim on liquid level, and flask is taken out from water-bath, be cooled to room temperature, filter and obtain the brownish red solid, and wash 3 times with 5% hydrazine hydrate aqueous solution, then 60 ℃ of lower vacuum drying, namely get the copper nano-wire product.Prepared NANO CRYSTAL COPPER WIRE length is between 3-10um, between diameter 100-300nm.
Embodiment 13
Adding 300ml concentration in the 500mL flask is the NaOH solution of 7M, adds 3g triethylene tetramine, 1.2g CuO and 1.5ml 80% hydrazine hydrate aqueous solution under then slowly stirring, and isothermal reaction is 4 hours in 80 ℃ of water-baths.Solution gradually becomes brownish red, and has a large amount of solids to swim on liquid level, and flask is taken out from water-bath, is cooled to room temperature, filters to obtain the brownish red solid, and washs 3 times with 5% hydrazine hydrate aqueous solution, and then 60 ℃ of lower vacuum drying, namely get the copper nano-wire product.Prepared NANO CRYSTAL COPPER WIRE length is between 1-10um, between diameter 50-200nm.
Embodiment 14
Adding 300ml concentration in the 500mL flask is the NaOH solution of 7M, adds 3g diethylenetriamine, 1.2g CuO and 1.5ml 80% hydrazine hydrate aqueous solution under then slowly stirring, and isothermal reaction is 4 hours in 80 ℃ of water-baths.Solution gradually becomes brownish red, and has a large amount of solids to swim on liquid level, and flask is taken out from water-bath, is cooled to room temperature, filters to obtain the brownish red solid, and washs 3 times with 5% hydrazine hydrate aqueous solution, and then 60 ℃ of lower vacuum drying, namely get the copper nano-wire product.Prepared NANO CRYSTAL COPPER WIRE length is between 1-10um, between diameter 50-200nm.
Embodiment 15
Adding 300ml concentration in the 500mL flask is the NaOH solution of 7M, adds 3g TEPA, 1.2g CuO and 1.5ml 80% hydrazine hydrate aqueous solution under then slowly stirring, and isothermal reaction is 4 hours in 80 ℃ of water-baths.Solution gradually becomes brownish red, and has a large amount of solids to swim on liquid level, and flask is taken out from water-bath, is cooled to room temperature, filters to obtain the brownish red solid, and washs 3 times with 5% hydrazine hydrate aqueous solution, and then 60 ℃ of lower vacuum drying, namely get the copper nano-wire product.Prepared NANO CRYSTAL COPPER WIRE length is between 1-10um, between diameter 50-200nm.
Embodiment 16
Adding 150ml concentration in the 500mL flask is the NaOH solution of 7M and the KOH solution that 150ml concentration is 7M, adds 1g triethylene tetramine, 1.5g Cu (OH) under then slowly stirring
2With 1.5ml 80% hydrazine hydrate aqueous solution, isothermal reaction is 1 hour in 80 ℃ of water-baths.Solution becomes brownish red by blueness gradually, and has a large amount of solids to swim on liquid level, and flask is taken out from water-bath, be cooled to room temperature, filter and obtain the brownish red solid, and wash 3 times with 5% hydrazine hydrate aqueous solution, then 60 ℃ of lower vacuum drying, namely get the copper nano-wire product.Prepared NANO CRYSTAL COPPER WIRE length is between 5-20um, between diameter 50-100nm.
Embodiment 17
Adding 300ml concentration in the 500mL flask is the NaOH solution of 7M, adds 1g triethylene tetramine, 1.5g Cu (OH) under then slowly stirring
2With 1.5ml 80% hydrazine hydrate aqueous solution, isothermal reaction is 4 hours in 40 ℃ of water-baths.Solution becomes brownish red by blueness gradually, and has a large amount of solids to swim on liquid level, and flask is taken out from water-bath, be cooled to room temperature, filter and obtain the brownish red solid, and wash 3 times with 5% hydrazine hydrate aqueous solution, then 60 ℃ of lower vacuum drying, namely get the copper nano-wire product.Prepared NANO CRYSTAL COPPER WIRE length is between 5-20um, between diameter 50-150nm.
Embodiment 18
Adding 300ml concentration in the 500mL flask is the NaOH solution of 7M, adds 10g TEPA, 10g diethylenetriamine, 10g triethylene tetramine, 15g Cu (OH) under then slowly stirring
2With 15ml 80% hydrazine hydrate aqueous solution, isothermal reaction is 2 hours in 80 ℃ of water-baths.Solution becomes brownish red by blueness gradually, and has a large amount of solids to swim on liquid level, and flask is taken out from water-bath, be cooled to room temperature, filter and obtain the brownish red solid, and wash 3 times with 5% hydrazine hydrate aqueous solution, then 60 ℃ of lower vacuum drying, namely get the copper nano-wire product.Prepared NANO CRYSTAL COPPER WIRE length is between 3-10um, between diameter 100-500nm.
Embodiment 19
Adding 300ml concentration in the 500mL flask is the KOH solution of 7M, adds 30g TEPA, 15g Cu (OH) under then slowly stirring
2With 15ml 80% hydrazine hydrate aqueous solution, isothermal reaction is 2 hours in 80 ℃ of water-baths.Solution becomes brownish red by blueness gradually, and has a large amount of solids to swim on liquid level, and flask is taken out from water-bath, be cooled to room temperature, filter and obtain the brownish red solid, and wash 3 times with 5% hydrazine hydrate aqueous solution, then 60 ℃ of lower vacuum drying, namely get the copper nano-wire product.Prepared NANO CRYSTAL COPPER WIRE length is between 3-10um, between diameter 100-500nm.
Embodiment 20
Adding 300ml concentration in the 500mL flask is the NaOH solution of 7M, adds 30g TEPA, 15g Cu (OH) under then slowly stirring
2With 60ml 50%(mass fraction, lower same) aqueous hydroxylamine solution, isothermal reaction is 4 hours in 80 ℃ of water-baths.Solution becomes brownish red by blueness gradually, and has a large amount of solids to swim on liquid level, and flask is taken out from water-bath, be cooled to room temperature, filter and obtain the brownish red solid, and wash 3 times with 5% hydrazine hydrate aqueous solution, then 60 ℃ of lower vacuum drying, namely get the copper nano-wire product.Prepared NANO CRYSTAL COPPER WIRE length is between 3-15um, between diameter 100-500nm.
Embodiment 21
Adding 300ml concentration in the 500mL flask is the NaOH solution of 7M, adds 30g TEPA, 15g Cu (OH) under then slowly stirring
2With 10ml 80% hydrazine hydrate aqueous solution and 20ml 50% aqueous hydroxylamine solution, isothermal reaction is 3 hours in 80 ℃ of water-baths.Solution becomes brownish red by blueness gradually, and has a large amount of solids to swim on liquid level, and flask is taken out from water-bath, be cooled to room temperature, filter and obtain the brownish red solid, and wash 3 times with 5% hydrazine hydrate aqueous solution, then 60 ℃ of lower vacuum drying, namely get the copper nano-wire product.Prepared NANO CRYSTAL COPPER WIRE length is between 1-10um, between diameter 100-300nm.
Embodiment 22
Adding 300ml concentration in the 500mL flask is the NaOH solution of 2M, adds 3g triethylene tetramine, 1.5g Cu (OH) under then slowly stirring
2With 1.5ml 80% hydrazine hydrate aqueous solution, isothermal reaction is 6 hours in 80 ℃ of water-baths.Solution becomes brownish red by blueness gradually, and has a large amount of solids to swim on liquid level, and flask is taken out from water-bath, be cooled to room temperature, filter and obtain the brownish red solid, and wash 3 times with 5% hydrazine hydrate aqueous solution, then 60 ℃ of lower vacuum drying, namely get the copper nano-wire product.
Embodiment 23
Adding 300ml concentration in the 500mL flask is the NaOH solution of 4M, adds 3g triethylene tetramine, 1.5g Cu (OH) under then slowly stirring
2With 1.5ml 80% hydrazine hydrate aqueous solution, isothermal reaction is 4 hours in 80 ℃ of water-baths.Solution becomes brownish red by blueness gradually, and has a large amount of solids to swim on liquid level, and flask is taken out from water-bath, be cooled to room temperature, filter and obtain the brownish red solid, and wash 3 times with 5% hydrazine hydrate aqueous solution, then 60 ℃ of lower vacuum drying, namely get the copper nano-wire product.
Embodiment 24
Adding 300ml concentration in the 500mL flask is the NaOH solution of 10M, adds 3g triethylene tetramine, 1.5g Cu (OH) under then slowly stirring
2With 1.5ml 80% hydrazine hydrate aqueous solution, isothermal reaction is 1 hour in 80 ℃ of water-baths.Solution becomes brownish red by blueness gradually, and has a large amount of solids to swim on liquid level, and flask is taken out from water-bath, be cooled to room temperature, filter and obtain the brownish red solid, and wash 3 times with 5% hydrazine hydrate aqueous solution, then 60 ℃ of lower vacuum drying, namely get the copper nano-wire product.
Embodiment 25
Adding 300ml concentration in the 500mL flask is the NaOH solution of 15M, adds 3g triethylene tetramine, 1.5g Cu (OH) under then slowly stirring
2With 1.5ml 80% hydrazine hydrate aqueous solution, isothermal reaction is 1 hour in 80 ℃ of water-baths.Solution becomes brownish red by blueness gradually, and has a large amount of solids to swim on liquid level, and flask is taken out from water-bath, be cooled to room temperature, filter and obtain the brownish red solid, and wash 3 times with 5% hydrazine hydrate aqueous solution, then 60 ℃ of lower vacuum drying, namely get the copper nano-wire product.
Embodiment 26
Adding 300ml concentration in the 500mL flask is the NaOH solution of 2M, adds 3g triethylene tetramine, 1.5g Cu (OH) under then slowly stirring
2With 1.5ml 80% hydrazine hydrate aqueous solution, isothermal reaction is 4 hours in 100 ℃ of water-baths.Solution becomes brownish red by blueness gradually, and has a large amount of solids to swim on liquid level, and flask is taken out from water-bath, be cooled to room temperature, filter and obtain the brownish red solid, and wash 3 times with 5% hydrazine hydrate aqueous solution, then 60 ℃ of lower vacuum drying, namely get the copper nano-wire product.
Embodiment 27
Adding 300ml concentration in the 500mL flask is the NaOH solution of 7M, adds 3g triethylene tetramine, 1.5g Cu (OH) under then slowly stirring
2With 1.5ml 80% hydrazine hydrate aqueous solution, isothermal reaction is 6 hours in 25 ℃ of water-baths.Solution becomes brownish red by blueness gradually, and has a large amount of solids to swim on liquid level, and flask is taken out from water-bath, be cooled to room temperature, filter and obtain the brownish red solid, and wash 3 times with 5% hydrazine hydrate aqueous solution, then 60 ℃ of lower vacuum drying, namely get the copper nano-wire product.
Embodiment 28
Adding 300ml concentration in the 500mL flask is the NaOH solution of 7M, adds 3g triethylene tetramine, 1.5g Cu (OH) under then slowly stirring
2With 1.5ml 80% hydrazine hydrate aqueous solution, isothermal reaction is 3 hours in 60 ℃ of water-baths.Solution becomes brownish red by blueness gradually, and has a large amount of solids to swim on liquid level, and flask is taken out from water-bath, be cooled to room temperature, filter and obtain the brownish red solid, and wash 3 times with 5% hydrazine hydrate aqueous solution, then 60 ℃ of lower vacuum drying, namely get the copper nano-wire product.
Claims (3)
1. the preparation method of a copper nano-wire is characterized in that: in the aqueous solution, the copper source adds reducing agent under the existence of pattern controlling agent and chemical potential adjusting control agent, react 1h at least under the condition of 25-100 ℃, namely obtains copper nano-wire after separation; 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.
2. preparation method as claimed in claim 1, it is characterized in that: described polyethylene polyamine is diethylenetriamine, triethylene tetramine or TEPA.
3. preparation method as claimed in claim 1 or 2, it is characterized in that: copper source and reducing agent consumption meet the stoichiometry mol ratio, and copper source concentration is controlled at 0.01-0.5mol/L, and pattern controlling agent concentration is controlled at 0.02-2mol/L, and chemical potential adjusting control agent concentration is controlled at 2-15mol/L.
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| CN111318719B (en) * | 2020-03-03 | 2023-04-18 | 河南大学 | Antioxidant copper nanowire, preparation method thereof and application of antioxidant copper nanowire in preparation of PEEK composite material |
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