CN104162680A - Method for continuously compounding copper nanowires - Google Patents
Method for continuously compounding copper nanowires Download PDFInfo
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- CN104162680A CN104162680A CN201410362522.6A CN201410362522A CN104162680A CN 104162680 A CN104162680 A CN 104162680A CN 201410362522 A CN201410362522 A CN 201410362522A CN 104162680 A CN104162680 A CN 104162680A
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Abstract
The invention relates to a method for continuously compounding copper nanowires. The method comprises the steps that mixed aqueous solution of sodium hydroxide solution, hydrazine hydrate solution, bivalent copper salt and ethidene diamines is continuously fed into a reactor; along with upward floating of reaction liquid in the reactor, restored copper nanowires grow while floating upwards and stay on the reaction liquid at last; products on the upper layer are fished out every 6-12 hours; the fished-out products are washed through deionized water to obtain the copper nanowires with the diameters ranging from 80nm to 120nm and the lengths ranging from 10 microns to 40 microns. The sodium hydroxide in a circulating pool returns to the reactor to be recycled after concentration of the sodium hydroxide is detected, regulated and controlled in an online mode. According to the method, the process and devices are simple, resource waste and environment pollution are avoided by means of cyclic utilization of the sodium hydroxide, and continuous production and large-scale application are achieved. The obtained copper nanowires are uniform in shape and large in length-diameter ratio.
Description
Technical field
The present invention relates to monodimension nanometer material preparing technical field, relate in particular to a kind of continuously synthetic 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, and is considered to the best substitution material of the conductive materials such as ITO, Ag, CNT, GO.
The method of preparing at present Cu nano wire mainly contains template, liquid phase reduction, vacuum vapor deposition etc., and wherein vacuum vapor deposition and solid phase reduction law part are harsh, and cost is higher, is not suitable for large-scale production; Template complex process, remove template trouble, cost is high, established nanostructured is easily destroyed; Liquid phase reduction is the method for current a kind of more flexible, controlled production of copper nano wire, Chang (Langmuir, 2005,21,3746-3748), Rathmell (Adv.Mater.2010,22,3558-3563) and Chinese patent 201110144380.2 etc. all by liquid phase reduction, prepare the copper nano-wire of different draw ratios, and differential responses substrate concentration, charging sequence and reaction mechanism are studied, obtained good result.But because above-mentioned research is all that noncontinuity under low concentration copper source is static synthetic, cause that copper nano-wire output is very low, uniformity and length is difficult to control; Meanwhile, equal disposable a large amount of NaOH of using up in the above-mentioned method of preparing copper nano-wire, does not reuse and will cause certain waste and pollution.
Summary of the invention
The object of the invention is high for cost in current copper nano-wire preparation process, yield poorly, the defect such as poor controllability, noncontinuity, a kind of method of continuously synthetic copper nano-wire is provided, this technique, equipment are simple, by recycling of NaOH, avoid the wasting of resources and environmental pollution, can be continuously produced easily scale application; Gained copper nano-wire diameter is even, and draw ratio is large.
The present invention realizes above-mentioned technical purpose by following technological means.
A method for continuously synthetic copper nano-wire, is characterized in that, concrete steps comprise:
(1) mixed aqueous solution, sodium hydroxide solution and the hydrazine hydrate solution of configuration cupric salt and ethylenediamine; 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) to reactor, add the sodium hydroxide solution in step (1), it is 0.5～1.0 that described sodium hydroxide solution accounts for reactor total measurement (volume), and is heated to 70～100 ℃ by circulator bath pipe; To the first reservoir, add the hydrazine hydrate solution in step (1), the second reservoir adds cupric salt in step (1) and the mixed aqueous solution of ethylenediamine;
(3) utilize the first pump, the second pump respectively the mixed aqueous solution of cupric salt in hydrazine hydrate solution, the second reservoir in the first reservoir and ethylenediamine to be passed in reactor with the phase same rate of 1～5ml/min simultaneously, make its free responding, along with upwards flowing of reactant liquor, floating limit, the copper nano-wire limit growth restoring, finally rests on reactant liquor top;
(4) in step (3), reactant liquor is full of after reactor, by the outlet of reactor top, through filter membrane, is freely expelled in circulatory pool;
(5) by the concentration of sodium hydroxide solution in concentration online monitoring system monitoring circulatory pool, and it is passed into reactor constantly with speed identical in step (3), realizes continuously and producing; When concentration of sodium hydroxide solution is lower than 5mol/L in circulatory pool, fill into sodium hydrate solid, and stirring and dissolving, concentration maintained at 5～15mol/L;
(6) every 6～12h, open seal cover, pull the product that floats over upper strata out, with obtaining copper nano-wire after deionized water washing.
Preferably, cupric salt described in step (1) is a kind of in copper nitrate, copper chloride, copper sulphate or Schweinfurt green.
Preferably, described in step (1), the mol ratio of ethylenediamine and cupric salt is 3:1.
Preferably, described in step (2), sodium hydroxide solution is heated to 80 ℃ by circulator bath pipe.
Preferably, described in step (3), the first pump, the second pump are peristaltic pump.
Preparation method's provided by the invention advantage:
(1) preparation method is simple, controlled, pollution-free, and cost is low, can produce continuously, and output is high;
(2) the copper nano-wire pattern that prepared by the method is even, and draw ratio is large, is having potential using value aspect flexible and transparent conductive material.
(3) can by controlling the reaction time, regulate diameter, the length of copper nano-wire, the diameter that obtains copper nano-wire after washing is 80～120nm, and length is 10～40 μ m.
Accompanying drawing explanation
Fig. 1 is the process flow diagram that synthesizes continuously 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 is seal cover, and 8 is filter membrane, and 9 is water inlet, and 10 is delivery port, 11 is the first pump, and 12 is the second pump, and 13 is the 3rd pump, and 14 is agitator.
The specific embodiment
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 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) to reactor 1, add the sodium hydroxide solution in step (1), its total measurement (volume) that accounts for reactor 1 is 0.5, and is heated to 80 ℃ by circulator bath pipe 10; To the first reservoir 3, add the hydrazine hydrate solution in step (1), the second reservoir 4 adds copper nitrate in step (1) and the mixed aqueous solution of ethylenediamine;
(3) by the mixed aqueous solution of copper nitrate and ethylenediamine in hydrazine hydrate solution, the second reservoir 4 in the first reservoir 3, the speed with 1ml/min passes in reactor 1 simultaneously respectively to utilize the first pump 11, the second pump 12, makes its free responding; Along with upwards flowing of reactant liquor, floating limit, the copper nano-wire limit growth restoring, finally rests on reactant liquor top;
(4) in step (3), reactant liquor is full of after reactor 1, by reactor 1 top outlet, through filter membrane 8, is freely expelled in circulatory pool 5;
(5) utilize the concentration of sodium hydroxide solution in concentration online monitoring system 6 monitoring circulatory pools 5, and by the 3rd pump 13, the speed with 1ml/min is passed in reactor 1 constantly by it, when in circulatory pool 5, concentration of sodium hydroxide solution is lower than 5mol/L, add sodium hydrate solid, make concentration remain on 13.5～15mol/L;
(6) after successive reaction 6h, open seal cover 7, pull the product that floats over upper strata out, with obtaining copper nano-wire after deionized water washing.
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, and as shown in Figure 3, prepared product is even, the continuous copper nano-wire of internal structure.
Fig. 4 is the scanning electron microscope (SEM) photograph of the copper nano-wire of embodiment 1 preparation, as shown in Figure 4, prepared product, its average diameter is 110nm, length is 10～20 μ m.
Embodiment 2
Fig. 1 is 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) to reactor 1, add the sodium hydroxide solution in step (1), its total measurement (volume) that accounts for reactor 1 is 0.8, and is heated to 70 ℃ by circulator bath pipe 2; To the first reservoir 3, add the hydrazine hydrate solution in step (1), the second reservoir 4 adds copper nitrate in step (1) and the mixed aqueous solution of ethylenediamine;
(3) by the mixed aqueous solution of copper nitrate and ethylenediamine in hydrazine hydrate solution, the second reservoir 4 in the first reservoir 3, the speed with 3ml/min passes in reactor 1 simultaneously respectively to utilize the first pump 11, the second pump 12, makes its free responding; Along with upwards flowing of reactant liquor, floating limit, the copper nano-wire limit growth restoring, finally rests on reactant liquor top;
(4) in step (3), reactant liquor is full of after reactor 1, by reactor 1 top outlet, through filter membrane 2, is freely expelled in circulatory pool 5;
(5) utilize the concentration of sodium hydroxide solution in concentration online monitoring system 6 monitoring circulatory pools 5, and by the 3rd pump 13, the speed with 3ml/min is passed in reactor 1 constantly by it, when in circulatory pool 5, concentration of sodium hydroxide solution is lower than 5mol/L, add sodium hydrate solid, make concentration remain on 10.8～12mol/L;
(6) after successive reaction 6h, open seal cover 7, pull the product that floats over upper strata out, with obtaining copper nano-wire after deionized water washing.
Fig. 5 is the scanning electron microscope (SEM) photograph of the copper nano-wire of embodiment 2 preparations, and as shown in Figure 5, prepared product average diameter is 110nm, and length is about 10～28 μ m.
Embodiment 3
Fig. 1 is 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 of sodium hydroxide solution be that the concentration of 8mol/L and hydrazine hydrate solution is 0.1mol/L;
(2) to reactor 1, add the sodium hydroxide solution in step (1), its total measurement (volume) that accounts for reactor 1 is 1.0, and is heated to 100 ℃ by circulator bath pipe 2; To the first reservoir 3, add the hydrazine hydrate solution in step (1), the second reservoir 4 adds copper chloride in step (1) and the mixed aqueous solution of ethylenediamine;
(3) by the mixed aqueous solution of copper chloride and ethylenediamine in hydrazine hydrate solution, the second reservoir 4 in the first reservoir 3, the speed with 3ml/min passes in reactor 1 simultaneously respectively to utilize the first pump 11, the second pump 12, makes its free responding; Along with upwards flowing of reactant liquor, floating limit, the copper nano-wire limit growth restoring, finally rests on reactant liquor top;
(4) in step (3), reactant liquor is full of after reactor 1, by reactor 1 top outlet, through filter membrane 2, is freely expelled in circulatory pool 5;
(5) utilize the concentration of sodium hydroxide solution in concentration online monitoring system 6 monitoring circulatory pools 5, and by the 3rd pump 13, the speed with 3ml/min is passed in reactor 1 constantly by it, when in circulatory pool 5, concentration of sodium hydroxide solution is lower than 5mol/L, add sodium hydrate solid, make concentration remain on 5～6mol/L;
(6) after successive reaction 12h, open seal cover 7, pull the product that floats over upper strata out, with obtaining copper nano-wire after deionized water washing, its average diameter is 100nm, and length is about 10～15 μ m.
Embodiment 4
Fig. 1 is process flow diagram of the present invention, as shown in Figure 1:
(1) mixed aqueous solution of configuration copper sulphate 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 sulphate is 3:1, the concentration of sodium hydroxide solution that be 5mol/L with concentration hydrazine hydrate solution be 0.5mol/L;
(2) to reactor 1, add the sodium hydroxide solution in step (1), its total measurement (volume) that accounts for reactor 1 is 0.5, and is heated to 80 ℃ by circulator bath pipe 2; To the first reservoir 3, add the hydrazine hydrate solution in step (1), the second reservoir 4 adds copper sulphate in step (1) and the mixed aqueous solution of ethylenediamine;
(3) by the mixed aqueous solution of copper sulphate and ethylenediamine in hydrazine hydrate solution, the second reservoir 4 in the first reservoir 3, the speed with 5ml/min passes in reactor 1 simultaneously respectively to utilize the first pump 11, the second pump 12, makes its free responding; Along with upwards flowing of reactant liquor, floating limit, the copper nano-wire limit growth restoring, finally rests on reactant liquor top;
(4) in step (3), reactant liquor is full of after reactor 1, by reactor 1 top outlet, through filter membrane 2, is freely expelled in circulatory pool 5;
(5) utilize the concentration of sodium hydroxide solution in concentration online monitoring system 6 monitoring circulatory pools 5, and by the 3rd pump 13, the speed with 5ml/min is passed in reactor 1 constantly by it, when in circulatory pool 5, concentration of sodium hydroxide solution is lower than 5mol/L, add sodium hydrate solid, make concentration remain on 5mol/L;
(6) after successive reaction 12h, open seal cover 7, pull the product that floats over upper strata out, with obtaining copper nano-wire after deionized water washing, its average diameter is 80nm, and length is about 30～40 μ m.
Described embodiment is preferred embodiment of the present invention; but the present invention is not limited to above-mentioned embodiment; in the situation that not deviating from flesh and blood of the present invention, any apparent improvement, replacement or modification that those skilled in the art can make all belong to protection scope of the present invention.
Claims (5)
1. a method for continuously synthetic copper nano-wire, is characterized in that, concrete steps comprise:
(1) mixed aqueous solution, sodium hydroxide solution and the hydrazine hydrate solution of configuration cupric salt and ethylenediamine; 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) to reactor (1), add the sodium hydroxide solution in step (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 ℃ by circulator bath pipe (2); To the first reservoir (3), add the hydrazine hydrate solution in step (1), the second reservoir (4) adds cupric salt in step (1) and the mixed aqueous solution of ethylenediamine;
(3) by the mixed aqueous solution of cupric salt in hydrazine hydrate solution, the second reservoir (4) in the first reservoir (3) and ethylenediamine, the phase same rate with 1～5ml/min is passed in reactor (1) simultaneously respectively to utilize the first pump (11), the second pump (12), makes its free responding; Along with upwards flowing of reactant liquor, floating limit, the copper nano-wire limit growth restoring, finally rests on reactant liquor top;
(4) in step (3), reactant liquor is full of after reactor (1), by the outlet of reactor (1) top, through filter membrane (8), is freely expelled in circulatory pool (5);
(5) by the concentration of sodium hydroxide solution in concentration online monitoring system (6) monitoring circulatory pool (5), and it is passed in reactor (1) constantly with speed identical in step (3), realizes continuously and producing; When concentration of sodium hydroxide solution is lower than 5mol/L in circulatory pool (5), fill into sodium hydrate solid, and stirring and dissolving, concentration maintained at 5～15mol/L;
(6) every 6～12h, open seal cover (7), pull the product that floats over upper strata out, with obtaining copper nano-wire after deionized water washing.
2. a kind of continuously method of synthetic copper nano-wire according to claim 1, is characterized in that, the described cupric salt of step (1) is a kind of in copper nitrate, copper chloride, copper sulphate or Schweinfurt green.
3. the method for a kind of continuously synthetic copper nano-wire according to claim 1, is characterized in that, the mol ratio of the described ethylenediamine of step (1) and cupric salt is 3:1.
4. the method for a kind of continuously synthetic copper nano-wire according to claim 1, is characterized in that, the described sodium hydroxide solution of step (2) is heated to 80 ℃ by circulator bath pipe (2).
5. the method for a kind of continuously synthetic copper nano-wire according to claim 1, is characterized in that, described the first pump of step (3) (11), the second pump (12) are peristaltic pump.
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| CN106693990A (en) * | 2016-12-31 | 2017-05-24 | 浙江工业大学 | Pt-Cu2O coated Cu nanowire as well as preparation method and application thereof |
| CN108560018A (en) * | 2018-05-07 | 2018-09-21 | 北京化工大学 | A kind of Nanometer Copper electrode material, preparation method and the usage |
| CN109293940A (en) * | 2018-11-22 | 2019-02-01 | 苏州大学 | One-dimensional HKUST-1 nanobelt and preparation method thereof |
| CN110385444A (en) * | 2019-07-31 | 2019-10-29 | 江苏大学 | A kind of method of NANO CRYSTAL COPPER WIRE and wet chemistry method preparation NANO CRYSTAL COPPER WIRE |
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