CN104162680B - A kind of method of continuous synthesis copper nano-wire - Google Patents
A kind of method of continuous synthesis copper nano-wire Download PDFInfo
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- CN104162680B CN104162680B CN201410362522.6A CN201410362522A CN104162680B CN 104162680 B CN104162680 B CN 104162680B CN 201410362522 A CN201410362522 A CN 201410362522A CN 104162680 B CN104162680 B CN 104162680B
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Abstract
A kind of method that the present invention relates to continuous synthesis copper nano-wire.The mixed aqueous solution of sodium hydroxide solution, hydrazine hydrate solution, cupric salt and ethylenediamine is passed in reactor continuously, along with in reactor, reactant liquor flows up, floating limit, the copper nano-wire limit growth restored, finally rest on reactant liquor top, pull the product floating over upper strata out every 6～12h, with after deionized water wash diameter be 80～120nm, length is 10～40 μm of copper nano-wires.Sodium hydroxide in circulatory pool regulates and controls to be back in reactor after its concentration through on-line checking and recycles.Present invention process, equipment are simple, and recycling by sodium hydroxide, it is to avoid the wasting of resources and environmental pollution can be continuously produced, and easy scale is applied；Gained copper nano-wire pattern is uniform, and draw ratio is big.
Description
Technical field
The present invention relates to monodimension nanometer material preparing technical field, particularly relate to a kind of continuous synthesis copper nano-wire method.
Background technology
Copper nano-wire is because its electrical conductivity is high, low cost and other advantages, and the application in high transmission rate, low-resistance flexible transparent conducting film receives much concern, it is believed that be the best substitution material of the conductive materials such as ITO, Ag, CNT, GO.
The method preparing Cu nano wire at present mainly has template, liquid phase reduction, vacuum vapor deposition etc., and wherein vacuum vapor deposition and solid phase reduction law part are harsh, relatively costly, are not suitable for large-scale production；Template complex process, to remove template trouble, cost high, and established nanostructured is easily destroyed；Liquid phase reduction is the method for a kind of production copper nano-wire more flexible, controlled at present, Chang (Langmuir, 2005,21,3746-3748), Rathmell (Adv.Mater.2010,22,3558-3563) and Chinese patent 201110144380.2 etc. prepare the copper nano-wire of different draw ratio each through liquid phase reduction, and differential responses substrate concentration, charging sequence and reaction mechanism have been studied, yield good result.But owing to the studies above is all the noncontinuity static monitor under low concentration copper source, cause that copper nano-wire yield is very low, uniformity and length are difficult to control to；Meanwhile, in the above-mentioned method preparing copper nano-wire, all disposable substantial amounts of sodium hydroxide of using up, does not reuse and will result in certain waste and pollution.
Summary of the invention
It is an object of the invention to high for cost in current copper nano-wire preparation process, yield poorly, the defect such as poor controllability, noncontinuity; a kind of method that continuous synthesis copper nano-wire is provided; this technique, equipment are simple; recycling by sodium hydroxide; avoid the wasting of resources and environmental pollution; can be continuously produced, easy scale is applied；Gained copper nano-wire uniform diameter, draw ratio is big.
The present invention realizes above-mentioned technical purpose by techniques below means.
A kind of method of continuous synthesis copper nano-wire, it is characterised in that concrete steps include:
(1) configuration cupric salt and the mixed aqueous solution of ethylenediamine, sodium hydroxide solution and hydrazine hydrate solution；Described cupric salt concentration is 0.05～0.2mol/L, and the mol ratio of described ethylenediamine and cupric salt is 2～4:1；Described concentration of sodium hydroxide solution is 5～15mol/L；Described hydrazine hydrate solution concentration is 0.1～0.6mol/L；
(2) adding the sodium hydroxide solution in step (1) to reactor, it is 0.5～1.0 that described sodium hydroxide solution accounts for reactor total measurement (volume), and is heated to 70～100 DEG C by circulator bath pipe；Adding the hydrazine hydrate solution in step (1) to the first reservoir, the second reservoir adds the mixed aqueous solution of the cupric salt in step (1) and ethylenediamine；
(3) utilize the first pump, the second pump to be passed in reactor with the phase same rate of 1～5ml/min by the mixed aqueous solution of cupric salt in hydrazine hydrate solution, the second reservoir in the first reservoir with ethylenediamine respectively simultaneously, make its free responding, along with flowing up of reactant liquor, floating limit, the copper nano-wire limit growth restored, finally rests on reactant liquor top；
(4) after in step (3), reactant liquor is full of reactor, reactor upper outlet freely it is expelled in circulatory pool through filter membrane；
(5) monitor the concentration of sodium hydroxide solution in circulatory pool by concentration online monitoring system, and it is passed into reactor constantly with speed identical in step (3), it is achieved produce continuously；When concentration of sodium hydroxide solution is lower than 5mol/L in circulatory pool, fill into sodium hydrate solid stirring and dissolving, maintain concentration at 5～15mol/L；
(6) every 6～12h, open sealing lid, pull the product floating over upper strata out, with namely obtaining copper nano-wire after deionized water wash.
Preferably, cupric salt described in step (1) is the one in copper nitrate, copper chloride, copper sulfate or Schweinfurt green.
Preferably, ethylenediamine described in step (1) is 3:1 with the mol ratio of cupric salt.
Preferably, sodium hydroxide solution described in step (2) is heated to 80 DEG C by circulator bath pipe.
Preferably, described in step (3), the first pump, the second pump are peristaltic pump.
The advantage of preparation method provided by the invention:
(1) preparation method is simple, controlled, pollution-free, and cost is low, can produce continuously, and yield is high；
(2) the copper nano-wire pattern that prepared by the method is uniform, and draw ratio is big, has potential using value in flexible and transparent conductive material.
(3) can passing through to control response time the adjustment diameter of copper nano-wire, length, the diameter obtaining copper nano-wire after washing is 80～120nm, and length is 10～40 μm.
Accompanying drawing explanation
Fig. 1 is the process flow diagram of continuous synthesis copper nano-wire.
Fig. 2 is the X-ray diffractogram of copper nano-wire in embodiment 1.
Fig. 3 is the transmission electron microscope picture of copper nano-wire in embodiment 1.
Fig. 4 is the scanning electron microscope (SEM) photograph of copper nano-wire in embodiment 1.
Fig. 5 is the scanning electron microscope (SEM) photograph of copper nano-wire in embodiment 2.
In figure, 1 is reactor, and 2 is circulator bath pipe, and 3 is the first fluid reservoir, and 4 is the second fluid reservoir, and 5 is circulatory pool, 6 is concentration online monitoring system, and 7 for sealing lid, and 8 is filter membrane, and 9 is water inlet, and 10 is outlet, 11 is the first pump, and 12 is the second pump, and 13 is the 3rd pump, and 14 is agitator.
Detailed description of the invention
Below in conjunction with accompanying drawing and specific embodiment, the present invention is further illustrated, but protection scope of the present invention is not limited to this.
Embodiment 1
Fig. 1 is the process flow diagram of the present invention, as shown in Figure 1:
(1) mixed aqueous solution of configuration copper nitrate and ethylenediamine, sodium hydroxide solution and hydrazine hydrate solution；Wherein copper nitrate concentration is 0.1mol/L, and the mol ratio of ethylenediamine and copper nitrate is 2:1, and the concentration of sodium hydroxide solution is 15mol/L, and the concentration of hydrazine hydrate solution is 0.2mol/L；
(2) adding the sodium hydroxide solution in step (1) to reactor 1, its total measurement (volume) accounting for reactor 1 is 0.5, and is heated to 80 DEG C by circulator bath pipe 10；Adding the hydrazine hydrate solution in step (1) to the first reservoir 3, the second reservoir 4 adds the mixed aqueous solution of the copper nitrate in step (1) and ethylenediamine；
(3) utilize first pump the 11, second pump 12 to pass in reactor 1 by the mixed aqueous solution of copper nitrate in hydrazine hydrate solution, the second reservoir 4 in the first reservoir 3 Yu ethylenediamine with the speed of 1ml/min respectively so that it is free responding simultaneously；Along with flowing up of reactant liquor, the floating limit, copper nano-wire limit restored grows, and finally rests on reactant liquor top；
(4) after in step (3), reactant liquor is full of reactor 1, reactor 1 upper outlet freely it is expelled in circulatory pool 5 through filter membrane 8；
(5) concentration online monitoring system 6 is utilized to monitor the concentration of sodium hydroxide solution in circulatory pool 5, and passed through the 3rd pump 13 and be passed in reactor 1 constantly with the speed of 1ml/min, when in circulatory pool 5, concentration of sodium hydroxide solution is lower than 5mol/L, add sodium hydrate solid, make concentration be maintained at 13.5～15mol/L；
(6), after successive reaction 6h, open sealing lid 7, pull the product floating over upper strata out, with namely obtaining copper nano-wire after deionized water wash.
Fig. 2 is the X-ray diffractogram of the copper nano-wire of embodiment 1 preparation, and as shown in Figure 2, prepared product is pure face-centred cubic structure copper nano-wire.
Fig. 3 is the transmission electron microscope picture of the copper nano-wire of embodiment 1 preparation, from the figure 3, it may be seen that prepared product is consistent internal structure, continuous print copper nano-wire.
Fig. 4 is the scanning electron microscope (SEM) photograph of the copper nano-wire of embodiment 1 preparation, and as shown in Figure 4, prepared product, its average diameter is 110nm, and length is 10～20 μm.
Embodiment 2
Fig. 1 is the process flow diagram of the present invention, as shown in Figure 1:
(1) mixed aqueous solution of configuration copper nitrate and ethylenediamine, sodium hydroxide solution and hydrazine hydrate solution；Wherein copper nitrate concentration is 0.1mol/L, and the mol ratio of ethylenediamine and copper nitrate is 2:1, and the concentration of sodium hydroxide solution is 12mol/L, and the concentration of hydrazine hydrate solution is 0.2mol/L；
(2) adding the sodium hydroxide solution in step (1) to reactor 1, its total measurement (volume) accounting for reactor 1 is 0.8, and is heated to 70 DEG C by circulator bath pipe 2；Adding the hydrazine hydrate solution in step (1) to the first reservoir 3, the second reservoir 4 adds the mixed aqueous solution of the copper nitrate in step (1) and ethylenediamine；
(3) utilize first pump the 11, second pump 12 to pass in reactor 1 by the mixed aqueous solution of copper nitrate in hydrazine hydrate solution, the second reservoir 4 in the first reservoir 3 Yu ethylenediamine with the speed of 3ml/min respectively so that it is free responding simultaneously；Along with flowing up of reactant liquor, the floating limit, copper nano-wire limit restored grows, and finally rests on reactant liquor top；
(4) after in step (3), reactant liquor is full of reactor 1, reactor 1 upper outlet freely it is expelled in circulatory pool 5 through filter membrane 2；
(5) concentration online monitoring system 6 is utilized to monitor the concentration of sodium hydroxide solution in circulatory pool 5, and passed through the 3rd pump 13 and be passed in reactor 1 constantly with the speed of 3ml/min, when in circulatory pool 5, concentration of sodium hydroxide solution is lower than 5mol/L, add sodium hydrate solid, make concentration be maintained at 10.8～12mol/L；
(6), after successive reaction 6h, open sealing lid 7, pull the product floating over upper strata out, with namely obtaining copper nano-wire after deionized water wash.
Fig. 5 is the scanning electron microscope (SEM) photograph of the copper nano-wire of embodiment 2 preparation, and as shown in Figure 5, prepared product average diameter is 110nm, and length is about 10～28 μm.
Embodiment 3
Fig. 1 is the process flow diagram of the present invention, as shown in Figure 1:
(1) mixed aqueous solution of configuration copper chloride and ethylenediamine, sodium hydroxide solution and hydrazine hydrate solution, wherein copper chloride concentration is 0.05mol/L, and the mol ratio of ethylenediamine and copper chloride is 2:1, the concentration that concentration is 8mol/L and hydrazine hydrate solution of sodium hydroxide solution be 0.1mol/L；
(2) adding the sodium hydroxide solution in step (1) to reactor 1, its total measurement (volume) accounting for reactor 1 is 1.0, and is heated to 100 DEG C by circulator bath pipe 2；Adding the hydrazine hydrate solution in step (1) to the first reservoir 3, the second reservoir 4 adds the mixed aqueous solution of the copper chloride in step (1) and ethylenediamine；
(3) utilize first pump the 11, second pump 12 to pass in reactor 1 by the mixed aqueous solution of copper chloride in hydrazine hydrate solution, the second reservoir 4 in the first reservoir 3 Yu ethylenediamine with the speed of 3ml/min respectively so that it is free responding simultaneously；Along with flowing up of reactant liquor, the floating limit, copper nano-wire limit restored grows, and finally rests on reactant liquor top；
(4) after in step (3), reactant liquor is full of reactor 1, reactor 1 upper outlet freely it is expelled in circulatory pool 5 through filter membrane 2；
(5) concentration online monitoring system 6 is utilized to monitor the concentration of sodium hydroxide solution in circulatory pool 5, and passed through the 3rd pump 13 and be passed in reactor 1 constantly with the speed of 3ml/min, when in circulatory pool 5, concentration of sodium hydroxide solution is lower than 5mol/L, add sodium hydrate solid, make concentration be maintained at 5～6mol/L；
(6) after successive reaction 12h, opening sealing lid 7, pull the product floating over upper strata out, with namely obtaining copper nano-wire after deionized water wash, its average diameter is 100nm, and length is about 10～15 μm.
Embodiment 4
Fig. 1 is the process flow diagram of the present invention, as shown in Figure 1:
(1) mixed aqueous solution of configuration copper sulfate and ethylenediamine, sodium hydroxide solution and hydrazine hydrate solution, wherein concentration of copper sulfate is 0.2mol/L, and the mol ratio of ethylenediamine and copper sulfate is 3:1, and the concentration with hydrazine hydrate solution that the concentration of sodium hydroxide solution is 5mol/L is 0.5mol/L；
(2) adding the sodium hydroxide solution in step (1) to reactor 1, its total measurement (volume) accounting for reactor 1 is 0.5, and is heated to 80 DEG C by circulator bath pipe 2；Adding the hydrazine hydrate solution in step (1) to the first reservoir 3, the second reservoir 4 adds the mixed aqueous solution of the copper sulfate in step (1) and ethylenediamine；
(3) utilize first pump the 11, second pump 12 to pass in reactor 1 by the mixed aqueous solution of copper sulfate in hydrazine hydrate solution, the second reservoir 4 in the first reservoir 3 Yu ethylenediamine with the speed of 5ml/min respectively so that it is free responding simultaneously；Along with flowing up of reactant liquor, the floating limit, copper nano-wire limit restored grows, and finally rests on reactant liquor top；
(4) after in step (3), reactant liquor is full of reactor 1, reactor 1 upper outlet freely it is expelled in circulatory pool 5 through filter membrane 2；
(5) concentration online monitoring system 6 is utilized to monitor the concentration of sodium hydroxide solution in circulatory pool 5, and passed through the 3rd pump 13 and be passed in reactor 1 constantly with the speed of 5ml/min, when in circulatory pool 5, concentration of sodium hydroxide solution is lower than 5mol/L, add sodium hydrate solid, make concentration be maintained at 5mol/L；
(6) after successive reaction 12h, opening sealing lid 7, pull the product floating over upper strata out, with namely obtaining copper nano-wire after deionized water wash, its average diameter is 80nm, and length is about 30～40 μm.
Described embodiment be the present invention preferred embodiment; but the present invention is not limited to above-mentioned embodiment; when without departing substantially from the flesh and blood of the present invention, those skilled in the art can make any conspicuously improved, replace or modification belongs to protection scope of the present invention.
Claims (5)
1. the method for a continuous synthesis copper nano-wire, it is characterised in that concrete steps include:
(1) configuration cupric salt and the mixed aqueous solution of ethylenediamine, sodium hydroxide solution and hydrazine hydrate solution；Described cupric salt concentration is 0.05～0.2mol/L, and the mol ratio of described ethylenediamine and cupric salt is 2～4:1；Described concentration of sodium hydroxide solution is 5～15mol/L；Described hydrazine hydrate solution concentration is 0.1～0.6mol/L；
(2) sodium hydroxide solution in step (1) is added to reactor (1), it is 0.5～1.0 that described sodium hydroxide solution accounts for reactor (1) total measurement (volume), and is heated to 70～100 DEG C by circulator bath pipe (2)；Adding the hydrazine hydrate solution in step (1) to the first reservoir (3), the second reservoir (4) adds the mixed aqueous solution of the cupric salt in step (1) and ethylenediamine；
(3) utilize the first pump (11), the second pump (12) to be passed in reactor (1) by the mixed aqueous solution of cupric salt in hydrazine hydrate solution, the second reservoir (4) in the first reservoir (3) with ethylenediamine with the phase same rate of 1～5ml/min respectively so that it is free responding simultaneously；Along with flowing up of reactant liquor, the floating limit, copper nano-wire limit restored grows, and finally rests on reactant liquor top；
(4) after in step (3), reactant liquor is full of reactor (1), reactor (1) upper outlet freely it is expelled in circulatory pool (5) through filter membrane (8)；
(5) concentration of sodium hydroxide solution in circulatory pool (5) is monitored by concentration online monitoring system (6), and it is passed in reactor (1) constantly with speed identical in step (3), it is achieved produce continuously；When concentration of sodium hydroxide solution is lower than 5mol/L in circulatory pool (5), fill into sodium hydrate solid stirring and dissolving, maintain concentration at 5～15mol/L；
(6) every 6～12h, open sealing lid (7), pull the product floating over upper strata out, with namely obtaining copper nano-wire after deionized water wash.
2. the method for a kind of continuous synthesis copper nano-wire according to claim 1, it is characterised in that step (1) described cupric salt is the one in copper nitrate, copper chloride, copper sulfate or Schweinfurt green.
3. the method for a kind of continuous synthesis copper nano-wire according to claim 1, it is characterised in that the mol ratio of step (1) described ethylenediamine and cupric salt is 3:1.
4. the method for a kind of continuous synthesis copper nano-wire according to claim 1, it is characterised in that step (2) described sodium hydroxide solution is heated to 80 DEG C by circulator bath pipe (2).
5. the method for a kind of continuous synthesis copper nano-wire according to claim 1, it is characterised in that described first pump (11) of step (3), the second pump (12) are peristaltic pump.
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| CN106693990B (en) * | 2016-12-31 | 2019-09-03 | 浙江工业大学 | Pt-Cu2O wraps up Cu nano wire and the preparation method and application thereof |
| CN108560018B (en) * | 2018-05-07 | 2020-04-28 | 北京化工大学 | Nano-copper electrode material, preparation method and application thereof |
| CN109293940B (en) * | 2018-11-22 | 2020-10-16 | 苏州大学 | One-dimensional HKUST-1 nanobelt and preparation method thereof |
| CN110385444B (en) * | 2019-07-31 | 2022-06-21 | 江苏大学 | Nano copper wire and method for preparing nano copper wire by wet chemical method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1727523A (en) * | 2004-07-26 | 2006-02-01 | 中国科学院物理研究所 | The method of liquid phase synthesizing one-dimensional super long Nano line of metal copper |
| CN102251278A (en) * | 2011-05-31 | 2011-11-23 | 常州大学 | Controllable preparation method of monocrystal copper nanowires |
| CN102601382A (en) * | 2012-03-27 | 2012-07-25 | 苏州冷石纳米材料科技有限公司 | Method for massively preparing overlength copper nanowires |
| CN103370455A (en) * | 2011-02-15 | 2013-10-23 | 卡尔斯特里姆保健公司 | Nanowire preparation methods, compositions, and articles |
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| CN1727523A (en) * | 2004-07-26 | 2006-02-01 | 中国科学院物理研究所 | The method of liquid phase synthesizing one-dimensional super long Nano line of metal copper |
| CN103370455A (en) * | 2011-02-15 | 2013-10-23 | 卡尔斯特里姆保健公司 | Nanowire preparation methods, compositions, and articles |
| CN102251278A (en) * | 2011-05-31 | 2011-11-23 | 常州大学 | Controllable preparation method of monocrystal copper nanowires |
| CN102601382A (en) * | 2012-03-27 | 2012-07-25 | 苏州冷石纳米材料科技有限公司 | Method for massively preparing overlength copper nanowires |
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