CN105170994B - A kind of solvent thermal process for preparing copper nano-wire - Google Patents
A kind of solvent thermal process for preparing copper nano-wire Download PDFInfo
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- CN105170994B CN105170994B CN201510594592.9A CN201510594592A CN105170994B CN 105170994 B CN105170994 B CN 105170994B CN 201510594592 A CN201510594592 A CN 201510594592A CN 105170994 B CN105170994 B CN 105170994B
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Abstract
The invention provides a kind of solvent thermal process for preparing copper nano-wire：Four hydration copper formates are mixed with n-octyl amine, is stirred 1~2 hour in 35~45 DEG C, 100~200 revs/min stir under speed, obtains copper formate n-octyl amine complex；Copper formate n-octyl amine complex is mixed with paraffin, oleic acid, oleyl amine, is continuously stirred in 60~80 DEG C, 100~200 revs/min stir under speed 0.5~1.5 hour, obtains reactant mixture；Reactant mixture is added in reaction vessel; under nitrogen protection; reacted 0.25~3 hour in 110~150 DEG C; room temperature is naturally cooled to afterwards; add n-hexane; ultrasonic echography disperses 3~5min, and 3~10min is centrifuged under 10000~15000 revs/min of centrifugation rate, and described copper nano-wire is produced after drying；The inventive method preparation technology environmental protection, equipment requirement is low, and simple to operate, cost is low.
Description
(1) technical field
The present invention relates to a kind of solvent thermal process for preparing copper nano-wire of environmental protection, belong to the preparation of metal nanometer line
Field.
(2) background technology
Metal nanometer line is because with larger draw ratio, larger material specific surface area shows very high catalysis and lived
Property, with very high transmission characteristic, possess higher sensitivity, current-responsive and stability, in fuel cell, bio-sensing
The fields such as device, petrochemical industry have very wide application prospect.Metallic copper has good heat, electrical conductivity, in being metal
Most materials are used as connecting wire, lower-price characteristic big with reserves, copper nano-wire is expected to following micro-
Nanoelectronic Technology field is widely used.Preparation and performance study accordingly, with respect to copper nano-wire are also increasingly by people
Concern.
There are many methods for preparing copper nano-wire at present, wherein more common is template, such as Riveros【Riveros
G, H,Cortes A,et al.Crystallographically-oriented single-crystalline
copper nanowire arrays electrochemically grown into nanoporous anodic alumina
templates[J].Applied Physics A,2005,81(1):17-24.】Woelm Alumina (AAO) is used for template, is passed through
Electrochemical deposition obtains copper nano-wire.Copper nano-wire is prepared with template, the most frequently used material is exactly the cruel film of poly- carbonic acid and porous
Pellumina, but be due to that the pore size of these films in itself is difficult to control to, and go the process of removing template more complicated, yield
It is relatively low, the production of scale is limited to a certain extent.In addition, the compound of reducing agent also native copper is utilized in the solution,
Recycle some conditioning agents to carry out structure directing, finally prepare copper nano-wire, such as Zeng【Yu C,Mei L L,Hua C
Z.Large-Scale Synthesis of High-Quality Ultralong Copper Nanowires[J]
.Langmuir,2005,21(9):3746-8.】Research team first reported by heating NaOH, Cu (NO3)2, EDA (second
Diamines), the mixture of hydrazine hydrate reacts under water bath condition can generate the copper nano-wire of overlength.Solwution method prepares copper nano-wire
Required reaction condition is gentleer, is adapted to industrialization large-scale production, but agents useful for same is unfavorable to environment, and emission is to environment
Pollution is larger.
Dexterously selection melting liquid paraffin is heated solvent to the present invention, thermally decomposes copper complex presoma, prepared by single step
Copper nano-wire.The method of this solvent hot preparation copper nano-wire has not yet seen document so far and patent discloses report.
(3) content of the invention
It is an object of the invention to provide a kind of solvent thermal process for preparing copper nano-wire, this method need not add hydrazine hydrate etc.
Poisonous reducing agent, environmental protection, equipment requirement is low, simple to operate, and cost is low.
To achieve the above object, the present invention is adopted the following technical scheme that：
A kind of solvent thermal process for preparing copper nano-wire, the preparation method is carried out as follows：
(1) by four hydration copper formates mixed with n-octyl amine, 35~45 DEG C, 100~200 revs/min stir under speed stir 1~
2 hours, obtain copper formate-n-octyl amine complex；The ratio between amount of material of the four hydration copper formates and n-octyl amine is 1：1.5~
2.5；
(2) copper formate-n-octyl amine complex obtained by step (1) is mixed with paraffin, oleic acid, oleyl amine, at 60~80 DEG C,
100~200 revs/min stir is continuously stirred 0.5~2 hour under speed, obtains reactant mixture；The copper formate-n-octyl amine coordinates
The mass ratio of thing and oleic acid, oleyl amine, paraffin is 1：0.05~0.15：0.2~0.6：0.5~1.5；
(3) reactant mixture obtained by step (2) is added in reaction vessel, it is under nitrogen protection, anti-in 110~150 DEG C
Answer 0.25~3 hour, naturally cool to room temperature afterwards, add n-hexane, ultrasonic echography disperses 3~5min, 10000~
3~10min is centrifuged under 15000 revs/min of centrifugation rate, described copper nano-wire is produced after drying.
In preparation method step (1) of the present invention, preferably it is described four hydration copper formate and n-octyl amine material amount it
Than for 1：2.
In step (2), the paraffin can be single melting waxes or blended wax.
In step (3), the volumetric usage of the n-hexane is recommended to be calculated as 10~50mL/ with the quality of the reactant mixture
g。
Specifically, recommending preparation method of the present invention to carry out as follows：
(1) by four hydration copper formates mixed with n-octyl amine, 35~45 DEG C, 100~200 revs/min stir under speed stir 1~
2 hours, obtain copper formate-n-octyl amine complex；The ratio between amount of material of the four hydration copper formates and n-octyl amine is 1：2；
(2) copper formate-n-octyl amine complex obtained by step (1) is mixed with paraffin, oleic acid, oleyl amine, (compares stone at 75 DEG C
Wax fusing point is high 15 DEG C, and the paraffin melting point is about 60 DEG C), 100~200 revs/min stir is continuously stirred 1~2 hour under speed, is obtained
Reactant mixture；The mass ratio of the copper formate-n-octyl amine complex and oleic acid, oleyl amine, paraffin is 1：0.05~0.15：
0.2~0.6：0.5~1.5；
(3) reactant mixture obtained by step (2) is added in reaction vessel, it is under nitrogen protection, anti-in 110~150 DEG C
Answer 0.5~2 hour, room temperature is naturally cooled to afterwards, add n-hexane, ultrasonic echography disperses 3~5min, at 12000 revs/min
Centrifugation rate under centrifuge 10min, described copper nano-wire is produced after drying；The volumetric usage of the n-hexane is with the reaction
The quality of mixture is calculated as 10~50mL/g.
Compared with prior art, the beneficial effects are mainly as follows：
(1) the inventive method prepares copper nano-wire, and template and reducing process are replaced with solvent-thermal method, without adding hydrazine hydrate
Etc. poisonous reducing agent, preparation technology environmental protection；
(2) copper nano-wire prepared by the present invention is formed by copper nanocrystallite self assembly, and without template, equipment requirement is low, behaviour
Make simple, cost is low.
(4) illustrate
Fig. 1 is the XRD of obtained copper nano-wire in embodiment 4；
Fig. 2 is the transmission electron microscope photo of obtained copper nano-wire in embodiment 1；
Fig. 3 is the transmission electron microscope photo of obtained copper nano-wire in embodiment 2；
Fig. 4 is the transmission electron microscope photo of obtained copper nano-wire in embodiment 3；
Fig. 5 is the transmission electron microscope photo of obtained copper nano-wire in embodiment 4；
Fig. 6 is the transmission electron microscope photo of obtained copper nano-wire in embodiment 4.
(5) embodiment
With reference to specific embodiment, the present invention is described further, but protection scope of the present invention is not limited in
This.
Embodiment 1
(1) by four hydration copper formates (9.04g, 0.04mol) and n-octyl amine (10.32g, 0.08mol) mixing, 35 DEG C,
Mechanical agitation 1h under conditions of 100 revs/min, obtains copper formate-n-octyl amine complex 19.36g；
(2) oleyl amine (5.35g, 0.02mol) and oleic acid (1.41g, 0.005mol) are added to formic acid obtained by step (1)
In copper-n-octyl amine complex (19.36g, 0.04mol), and paraffin (12g) is added, under 75 DEG C, 100 revs/min of mixing speed
Continuously stir 1 hour, obtain reactant mixture；
(3) reactant mixture 38.12g obtained by step (2) is injected into tri- mouthfuls of distilling flasks of 50ml, in nitrogen protection
Under, in 110 DEG C of heating response 1h, flask to be distilled naturally cools to room temperature, n-hexane is added in the reactive mixture
(480mL), after being disperseed 5 minutes with ultrasonic echography, is centrifuged 10 minutes, after drying i.e. under 12000 turns/min centrifugation rate
Obtain product copper nano-wire 2.56g.
Fig. 2 is the transmission electron microscope photo of copper nano-wire made from the present embodiment, it can be seen that obtained by the present embodiment
Product is copper nano-wire, under conditions of the present embodiment, and nano wire is easily reunited winding, so occur in transmission electron microscope photo
All it is the nanowire cluster wound of reuniting.
Embodiment 2
(1) by four hydration copper formates (4.52g, 0.02mol) and n-octyl amine (5.16g, 0.04mol) mixing, 35 DEG C,
Mechanical agitation 1h under conditions of 140 revs/min, obtains copper formate-n-octyl amine complex 9.68g；
(2) oleyl amine (5.35g, 0.02mol) and oleic acid (1.41g, 0.005mol) are added to formic acid obtained by step (1)
In copper-n-octyl amine complex (9.68g, 0.01mol), and paraffin (12g) is added, under 75 DEG C, 100 revs/min of mixing speed
Continuously stir 1 hour, obtain reactant mixture；
(3) reactant mixture 28.44g obtained by step (2) is injected into tri- mouthfuls of distilling flasks of 50ml, in nitrogen protection
Under, in 150 DEG C of heating response 1h, flask to be distilled naturally cools to room temperature, n-hexane is added in the reactive mixture
(480mL), is disperseed after 5min with ultrasonic echography, and 10min is centrifuged under 12000 turns/min centrifugation rate, is produced after drying
Product copper nano-wire 1.28g.
Fig. 3 is the transmission electron microscope photo of copper nano-wire made from the present embodiment, it can be seen that obtained by the present embodiment
Product is copper nano-wire and copper nano particles, because under this condition, reaction temperature is higher, it is easier to obtain thermodynamically stable
Final product, i.e. near-spherical product, and show that the graininess is due to the reunion of nano wire and is obtained in the nano wire of particle surface
Arrive.
Embodiment 3
(1) by four hydration copper formates (4.52g, 0.02mol) and n-octyl amine (5.16g, 0.04mol) mixing, 35 DEG C,
Mechanical agitation 1h under conditions of 140 revs/min, obtains copper formate-n-octyl amine complex 9.68g；
(2) oleyl amine (5.35g, 0.02mol) and oleic acid (1.41g, 0.005mol) are added to formic acid obtained by step (1)
In copper-n-octyl amine complex (9.68g, 0.01mol), and paraffin (12g) is added, under 75 DEG C, 100 revs/min of mixing speed
Continuously stir 1 hour, obtain reactant mixture；
(3) reactant mixture 28.44g obtained by step (2) is injected into tri- mouthfuls of distilling flasks of 50ml, in nitrogen protection
Under, in 150 DEG C of heating responses 30 minutes, flask to be distilled naturally cooled to room temperature, and n-hexane is added in the reactive mixture
(480mL), is disperseed after 5min with ultrasonic echography, and 10min is centrifuged under 12000 turns/min centrifugation rate, is produced after drying
Product copper nano-wire 1.28g.
Fig. 4 is the transmission electron microscope photo of copper nano-wire made from the present embodiment, it can be seen that obtained by the present embodiment
Product is copper nano-wire, under conditions of the present embodiment, and winding of reuniting occurs in gained nano wire, so going out in transmission electron microscope photo
Existing is all the nanowire cluster wound of reuniting.
Embodiment 4
(1) by four hydration copper formates (4.52g, 0.02mol) and n-octyl amine (5.16g, 0.04mol) mixing, 35 DEG C,
Mechanical agitation 1h under conditions of 140 revs/min, obtains copper formate-n-octyl amine complex 9.68g；
(2) oleyl amine (5.35g, 0.02mol) and oleic acid (1.41g, 0.005mol) are added to formic acid obtained by step (1)
In copper-n-octyl amine complex (9.68g, 0.01mol), and paraffin (12g) is added, under 75 DEG C, 100 revs/min of mixing speed
Continuously stir 1 hour, obtain reactant mixture；
(3) reactant mixture 28.44g obtained by step (2) is injected into tri- mouthfuls of distilling flasks of 50ml, in nitrogen protection
Under, in 130 DEG C of heating response 1h, flask to be distilled naturally cools to room temperature, n-hexane is added in the reactive mixture
(480mL), is disperseed after 5min with ultrasonic echography, and 10min is centrifuged under 12000 turns/min centrifugation rate, is produced after drying
Product copper nano-wire 1.28g.
Fig. 1 is the XRD of copper nano-wire made from the present embodiment, and Fig. 5, Fig. 6 are its transmission electron microscope photos, can be with from Fig. 1
Find out, the position of products therefrom XRD spectral peak has corresponded to the different face of irregular face-centered cubic copper (JCPDF 040836), diffraction
44.88 ° of angle, 52.31 °, 77.37 °, corresponding peak is respectively (111) of irregular face-centered cubic copper, (200), (220) crystal face,
Copper nano-wire prepared by this explanation thermal decomposition method is made up of the elemental copper of irregular face-centred cubic structure；Can from Fig. 5, Fig. 6
Go out, product is copper nano-wire, and nano wire has certain winding, and nano wire is that nanometer little particle is formed by connecting, and illustrates nano wire
It is to be obtained by nanometer little particle self assembly.
The present invention is not limited to embodiment described above, wherein paraffin used can be single fusing point or many
Plant the blended wax that single melting waxes are allocated with arbitrary proportion.
Claims (5)
1. a kind of solvent thermal process for preparing copper nano-wire, it is characterised in that the preparation method is carried out as follows：
(1) four hydration copper formates are mixed with n-octyl amine, stirs 1~2 small in 35~45 DEG C, 100~200 revs/min stir under speed
When, obtain copper formate-n-octyl amine complex；The ratio between amount of material of the four hydration copper formates and n-octyl amine is 1：1.5~
2.5；
(2) copper formate-n-octyl amine complex obtained by step (1) is mixed with paraffin, oleic acid, oleyl amine, at 60~80 DEG C, 100~
200 revs/min stir is continuously stirred 0.5~2 hour under speed, obtains reactant mixture；The copper formate-n-octyl amine complex and oil
Acid, oleyl amine, the mass ratio of paraffin are 1：0.05~0.15：0.2~0.6：0.5~1.5；
(3) reactant mixture obtained by step (2) is added in reaction vessel, under nitrogen protection, in 110~150 DEG C of reactions
0.25~3 hour, naturally cool to room temperature afterwards, add n-hexane, ultrasonic echography disperses 3~5min, 10000~
3~10min is centrifuged under 15000 revs/min of centrifugation rate, described copper nano-wire is produced after drying.
2. the solvent thermal process as claimed in claim 1 for preparing copper nano-wire, it is characterised in that in step (1), four water
It is 1 to close the ratio between amount of material of copper formate and n-octyl amine：2.
3. the solvent thermal process as claimed in claim 1 for preparing copper nano-wire, it is characterised in that in step (2), the paraffin
For single melting waxes or blended wax.
4. the as claimed in claim 1 solvent thermal process for preparing copper nano-wire, it is characterised in that in step (3), it is described just oneself
The volumetric usage of alkane is calculated as 10~50mL/g with the quality of the reactant mixture.
5. the solvent thermal process as claimed in claim 1 for preparing copper nano-wire, it is characterised in that the preparation method is by as follows
Step is carried out：
(1) four hydration copper formates are mixed with n-octyl amine, stirs 1~2 small in 35~45 DEG C, 100~200 revs/min stir under speed
When, obtain copper formate-n-octyl amine complex；The ratio between amount of material of the four hydration copper formates and n-octyl amine is 1：2；
(2) copper formate-n-octyl amine complex obtained by step (1) is mixed with paraffin, oleic acid, oleyl amine, in 75 DEG C, 100~200
Rev/min stir and continuously stirred under speed 1~2 hour, obtain reactant mixture；The copper formate-n-octyl amine complex and oleic acid, oil
Amine, the mass ratio of paraffin are 1：0.05~0.15：0.2~0.6：0.5~1.5；
(3) reactant mixture obtained by step (2) is added in reaction vessel, under nitrogen protection, 0.5 is reacted in 110~150 DEG C
~2 hours, naturally cool to room temperature afterwards, add n-hexane, ultrasonic echography disperses 3~5min, 12000 revs/min from
10min is centrifuged under heart speed, described copper nano-wire is produced after drying；The volumetric usage of the n-hexane is mixed with the reaction
The quality of thing is calculated as 10~50mL/g.
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| CN106221677B (en) * | 2016-08-04 | 2019-09-03 | 浙江工业大学 | A kind of preparation method of cuprous oxide/paraffin photothermal conversion phase-change energy-storage composite material |
| CN108707997A (en) * | 2018-05-29 | 2018-10-26 | 哈尔滨工业大学深圳研究生院 | Redox graphene coats the preparation method of copper nano-wire conducing composite material |
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| CN1283851C (en) * | 2004-07-26 | 2006-11-08 | 中国科学院物理研究所 | Liquid phase method for synthesizing one-dimensional super long Nano line of metal copper |
| US7547347B2 (en) * | 2005-05-13 | 2009-06-16 | University Of Rochester | Synthesis of nano-materials in ionic liquids |
| CN101269843B (en) * | 2008-05-06 | 2010-12-22 | 华东理工大学 | Method for preparing iron oxide nano-wire |
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| CN101602520B (en) * | 2009-07-13 | 2011-08-17 | 浙江大学 | Solvothermal preparation method for one-dimensional tin oxide quantum wire |
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| CN102936357B (en) * | 2012-10-31 | 2014-04-02 | 北京化工大学 | Antistatic agent made from silver nanowire and functional carbon nano tube (CNT) and preparation method |
| CN104668581B (en) * | 2015-03-09 | 2017-03-08 | 浙江工业大学 | A kind of method that solvent-thermal method prepares copper tiny balloon |
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