CN104985174B - Method that is a kind of quick and being prepared on a large scale electrum nanotube - Google Patents
Method that is a kind of quick and being prepared on a large scale electrum nanotube Download PDFInfo
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- CN104985174B CN104985174B CN201510276269.7A CN201510276269A CN104985174B CN 104985174 B CN104985174 B CN 104985174B CN 201510276269 A CN201510276269 A CN 201510276269A CN 104985174 B CN104985174 B CN 104985174B
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Abstract
The invention provides method that is a kind of quick and being prepared on a large scale electrum nanotube, comprise the following steps：The preparation of nano silver wire：Solid sodium chloride and polyvinylpyrrolidone are dissolved in ethylene glycol solution, are stirred continuously and are heated to 170 175 DEG C, react 10 15min；Then to silver nitrate ethylene glycol solution is added dropwise in mixed liquor, continue to heat 30min at 170 175 DEG C after completion of dropping, nano silver wire solution is obtained by being cooled to room temperature；The preparation of electrum nanotube：During above-mentioned nano silver wire solution and deionized water added into container together, taken out after boiling is heated in microwave reactor, immediately to adding chlorauric acid solution in reaction solution, rock to uniform, it is placed again into reacting 1 2min in microwave reactor, take out, be cooled to room temperature, electrum nanotube is obtained final product after centrifugation.The method of the invention has the advantages that easy to operate, the quick, reaction time is short, the consumption energy is few, yield is high and reproducible, the alloy nanotube good dispersion prepared by the present invention, function admirable.
Description
Technical field
The invention belongs to technical field of material, more particularly to one kind is quick and is prepared on a large scale electrum nanotube
Method.
Background technology
Since gold nanotubes in 2000 by Tokyo polytechnical university computer MSR Information system synthesize since, metal nano-tube due to
Except the general aspects with nano material, such as quantum size effect, small-size effect, surface and interfacial effect and macroscopic quantum
Outside tunnel-effect etc., also with special tubular structure and direct electron transfer ability.These properties make it in optics, electricity
The aspects such as, electromagnetism, superconduction and catalysis activity high show special performance, are constantly subjected to extensive concern,
As frontier nature problem now.But, due to gold nanotubes size is excessively small and also be difficult prepare so that hinder its
The application of every field.
In early days, laboratory prepares the method for metal nano-tube chemical deposition and electrochemical deposition method.Chemical deposition
Although metal nano-tube can be prepared well, step is various, more takes.The General Principle of preparation is first by template
Functionalization, recycles redox reaction metallic atom deposited on tube wall, grown, with the extension of sedimentation time, its shape
Looks can realize hollow pipe to the change of solid tubes, and the deposition short period just can obtain tubular structure.And electrochemical deposition method is most
Pipe step is simple, time saving, but more harsh in design, is difficult to realize.
Certainly, current laboratory prepares metal nano-tube by the method for heating response nano silver wire, but uses
Heating means the stable reaction is successfully carried out, because the heat time is long, always cause nano silver wire to be reunited, so that nothing
Method obtains metal nano-tube；Additionally, this method repetitive rate is low, because to avoid reuniting and preparing nanometer with being unable to large-scale
Pipe.
The content of the invention
For Shortcomings in the prior art, the invention provides a kind of quick and be prepared on a large scale electrum nanotube
Method, by using heating using microwave, the displacement step such as nano silver wire greatly shorten the reaction time, it is to avoid because nano wire
Reunion the problems such as cannot synthesize electrum nanotube or relatively low repetitive rate, can quickly and largely prepare excellent gold
Silver nanotube.
The present invention is to realize above-mentioned technical purpose by following technological means.
One kind is quick and is prepared on a large scale electrum nanotube, and the pipe thickness of the electrum nanotube is 4nm,
Outside dimension is 80nm-250nm, and the content ratio of gold and silver is 1:1-4.
Method that is a kind of quick and being prepared on a large scale electrum nanotube, comprises the following steps：
(1) preparation of nano silver wire：Solid sodium chloride and polyvinylpyrrolidone PVP are dissolved in ethylene glycol solution,
It is stirred continuously and is heated to 170-175 DEG C, reaction 10-15min obtains mixed liquor；To dropwise addition silver nitrate ethylene glycol solution in mixed liquor,
Continue to heat 30min at 170-175 DEG C after completion of dropping, be cooled to room temperature, you can obtain nano silver wire solution；
(2) preparation of electrum nanotube：Nano silver wire solution and deionized water described in step (1) are added together
In container, taken out after boiling is heated in microwave reactor, chlorauric acid solution is added thereto to immediately, rocked to uniform, then
Secondary being put into microwave reactor reacts 1-2min, takes out, and is cooled to room temperature, and electrum nanotube is obtained final product after centrifugation.
Preferably, the solid-to-liquid ratio of sodium chloride, polyvinylpyrrolidone PVP and ethylene glycol solution is described in step (1)
0.007-1mg：198mg：10ml.
Preferably, the concentration of silver nitrate ethylene glycol solution described in step (1) is 0.12mol/L, the silver nitrate second two
The volume ratio of alcoholic solution and ethylene glycol solution is 1:2.
Preferably, the rate of addition of silver nitrate ethylene glycol solution described in step (1) is 4-6ml/h.
Preferably, the concentration of nano silver wire solution described in step (2) is 2mmol/L, the nano silver wire solution and is gone
The volume ratio of ionized water is 0.025-5:1.
Preferably, the concentration of chlorauric acid solution described in step (2) is 1mmol/L, the chlorauric acid solution and silver nanoparticle
The volume ratio of line solution is 1:0.75-2.
Beneficial effects of the present invention：
Method that is of the present invention quick and being prepared on a large scale electrum nanotube, by the silver nanoparticle that will be prepared
Line and the chlorauric acid solution heating response in microwave reactor, can quickly obtain electrum nanotube；When nano silver wire is molten
When the concentration of liquid and chlorauric acid solution expands several ten times larger simultaneously, the alloy nanotube of large batch of function admirable is can obtain.Pass through
The ratio of control nano silver wire and gold chloride, is capable of achieving the controllable adjustment to the gold and silver ratio of nanotube.Prepared by the present invention
Alloy nanotube good dispersion, function admirable.The method of the invention have easy to operate, the quick, reaction time it is short, consumption energy
Source is few, yield is high and it is reproducible the advantages of.
Brief description of the drawings
Fig. 1 is the scanning electron microscope (SEM) photograph of the gained electrum nanotube of the embodiment of the present invention 1.
Fig. 2 is the transmission electron microscope picture of the gained electrum nanotube of the embodiment of the present invention 1.
Fig. 3 is the elementary analysis spectrogram of the gained electrum nanotube of the embodiment of the present invention 1.
Fig. 4 is the transmission electron microscope picture of the gained electrum nanotube of the embodiment of the present invention 2.
Fig. 5 is the elementary analysis spectrogram of the gained electrum nanotube of the embodiment of the present invention 2.
Fig. 6 is the transmission electron microscope picture of the gained electrum nanotube of the embodiment of the present invention 3.
Fig. 7 is the elementary analysis spectrogram of the gained electrum nanotube of the embodiment of the present invention 3.
Fig. 8 is the transmission electron microscope picture of the gained electrum nanotube of the embodiment of the present invention 4.
Specific embodiment
Below in conjunction with the accompanying drawings and specific embodiment the present invention is further illustrated, but protection scope of the present invention is simultaneously
Not limited to this.
Embodiment 1
The preparation of nano silver wire：0.007mg solid sodium chlorides and 198mg polyvinylpyrrolidones PVP are dissolved in 10ml
In ethylene glycol solution, 170-175 DEG C is heated under magnetic stirring, after reaction 10min, be added dropwise thereto with the speed of 4ml/h
The concentration of 5ml is the silver nitrate ethylene glycol solution of 0.12mol/L, after after solution completion of dropping, is continually maintained in 170-175 DEG C of temperature
After the lower heating 30min of degree, nano silver wire solution is obtained by being cooled to room temperature.
The preparation of electrum nanotube：Compound concentration is the nano silver wire solution of 2mmol/L, takes the silver nanoparticle of 0.75ml
The deionized water of line solution and 50ml is added in container together, container is positioned in microwave reactor and is heated to boiling, is taken out
The chlorauric acid solution 1ml for adding configured good concentration to be 1mmol/L immediately afterwards, rocks to uniform, and container is placed into micro- again
1-2min is reacted in ripple reactor, finally take out be cooled to room temperature, after being centrifuged can obtain the electrum nanotube,
Its yield is up to 90%.
The cross section being broken from Fig. 1 can be seen that nano wire and has been prepared to electrum nanotube, it was demonstrated that this
The feasibility of experimental technique.
Figure it is seen that the electrum nanotube good dispersion, pipe thickness are uniform, closed by weighing
Gold nanotubes 0.4mg, pipe thickness is 4nm, and external diameter is 80nm.
Following atomic percent can be obtained from Fig. 3：
| Element | Atomic percent |
| C K | 19.86 |
| Cu K | 54.46 |
| Ag L | 15.73 |
| Au L | 9.95 |
| Total amount | 100 |
The content ratio for therefore deducing that gold and silver in electrum nanotube is 1:1.5.
Embodiment 2
The preparation of nano silver wire：1mg solid sodium chlorides and 198mg polyvinylpyrrolidones PVP are dissolved in 10ml second two
In alcoholic solution, 170-175 DEG C is heated under magnetic stirring, after reaction 10min, be added dropwise 5ml's thereto with the speed of 5ml/h
Concentration is the silver nitrate ethylene glycol solution of 0.12mol/L, after after solution completion of dropping, is continually maintained at a temperature of 170-175 DEG C
After heating 30min, nano silver wire solution is obtained by being cooled to room temperature.
The preparation of electrum nanotube：Compound concentration is the nano silver wire solution of 2mmol/L, takes the silver nanoparticle of 1.25ml
The deionized water of line solution and 50ml is added in container together, container is positioned in microwave reactor and is heated to boiling, is taken out
The chlorauric acid solution 1ml for adding configured good concentration to be 1mmol/L immediately afterwards, rocks to uniform, and container is placed into micro- again
1-2min is reacted in ripple reactor, finally take out be cooled to room temperature, after being centrifuged can obtain the electrum nanotube,
Its yield is up to 91%.
As seen from Figure 4, the electrum nanotube good dispersion, pipe thickness uniformly, by weighing are closed
Gold nanotubes 0.5mg, pipe thickness is 4nm, and external diameter is 80nm.
From Fig. 5 following atomic percent is obtained in the elementary analysis spectrogram of alloy nanotube：
| Element | Atomic percent |
| C K | 23.17 |
| Cu K | 47.01 |
| Ag L | 21.25 |
| Au L | 8.57 |
| Total amount | 100 |
The content ratio for therefore deducing that gold and silver is 1:2.5.
Embodiment 3
The preparation of nano silver wire：0.007mg solid sodium chlorides and 198mg polyvinylpyrrolidones PVP are dissolved in 10ml
In ethylene glycol solution, 170-175 DEG C is heated under magnetic stirring, after reaction 10min, be added dropwise thereto with the speed of 5ml/h
The concentration of 5ml is the silver nitrate ethylene glycol solution of 0.12mol/L, after after solution completion of dropping, is continually maintained in 170-175 DEG C of temperature
After the lower heating 30min of degree, nano silver wire solution is obtained by being cooled to room temperature.
The preparation of electrum nanotube：Compound concentration is the nano silver wire solution of 2mmol/L, takes the nano silver wire of 2ml
The deionized water of solution and 50ml is added in container together, container is positioned in microwave reactor and is heated to boiling, after taking-up
The chlorauric acid solution 1ml for adding configured good concentration to be 1mmol/L immediately, rocks to uniform, and container is placed into microwave again
1-2min is reacted in reactor, finally take out be cooled to room temperature, after being centrifuged can obtain the electrum nanotube, its
Yield is up to 90%.
As seen from Figure 6, the electrum nanotube good dispersion, pipe thickness is uniform, is closed by weighing
Gold nanotubes 0.6mg, pipe thickness is 4nm, and external diameter is 80nm.
From Fig. 7 following atomic percent is obtained in the elementary analysis spectrogram of alloy nanotube：
| Element | Atomic percent |
| C K | 17.19 |
| Cu K | 47.75 |
| Ag L | 28.48 |
| Au L | 6.57 |
| Total amount | 100 |
Thus, it is possible to the content ratio for drawing gold and silver is 1:4.0.
Embodiment 4
The preparation of nano silver wire：0.007mg solid sodium chlorides and 198mg polyvinylpyrrolidones PVP are dissolved in 10ml
In ethylene glycol solution, 170-175 DEG C DEG C is heated under magnetic stirring, after reaction 10min, dripped thereto with the speed of 5ml/h
Plus the concentration of 5ml is the silver nitrate ethylene glycol solution of 0.12mol/L, after after solution completion of dropping, is continually maintained in 170-175 DEG C
After heating 30min at a temperature of DEG C, nano silver wire solution is obtained by being cooled to room temperature.
The preparation of electrum nanotube：Compound concentration is the nano silver wire solution of 2mmol/L, takes the silver nanoparticle of 250ml
The deionized water of line solution and 50ml is added in container together, container is positioned in microwave reactor and is heated to boiling, is taken out
The chlorauric acid solution 200ml for adding configured good concentration to be 1mmol/L immediately afterwards, rocks to uniform, again places container
1-2min is reacted in microwave reactor, is finally taken out and is cooled to room temperature, after being centrifuged can the electrum nanometer
Pipe, its yield is up to 90%.
As seen from Figure 8, the electrum nanotube good dispersion, pipe thickness is uniform, is closed by weighing
Gold nanotubes 0.1g, pipe thickness is 4nm, and external diameter is 80nm, and the content ratio of gold and silver is 1:2.5.
The customary preparation methods of electrum nanotube：Compound concentration is the nano silver wire solution of 2mmol/L, takes 1.25ml
Nano silver wire solution and the deionized water of 50ml add container together, container be positioned on oil bath pan be heated to boiling,
The chlorauric acid solution 1ml for adding configured good concentration to be 1mmol/L after taking-up immediately, can have found that nano silver wire occurs after rocking
Reunite, generate black precipitate, solution colour is changed into transparent, and experiment success rate is low, generation alloy nanotube yield is very low.
Preferred embodiment but the present invention is not limited to above-mentioned implementation method to the embodiment for of the invention, not
In the case of substance of the invention, any conspicuously improved, replacement that those skilled in the art can make
Or modification belongs to protection scope of the present invention.
Claims (6)
1. method that is a kind of quick and being prepared on a large scale electrum nanotube, it is characterised in that comprise the following steps：
(1) preparation of nano silver wire：Solid sodium chloride and polyvinylpyrrolidone PVP are dissolved in ethylene glycol solution, constantly
170-175 DEG C is heated with stirring to, reaction 10-15min obtains mixed liquor；To silver nitrate ethylene glycol solution is added dropwise in mixed liquor, it is added dropwise
Continue to heat 30min at 170-175 DEG C after finishing, be cooled to room temperature, you can obtain nano silver wire solution；
(2) preparation of electrum nanotube：Nano silver wire solution and deionized water described in step (1) are added into container together
In, taken out after boiling is heated in microwave reactor, chlorauric acid solution is added thereto to immediately, rock to uniform, put again
Enter and react 1-2min in microwave reactor, take out, be cooled to room temperature, electrum nanotube is obtained final product after centrifugation；
The pipe thickness of prepared electrum nanotube is 4nm, and outside dimension is 80nm-250nm, the content ratio of gold and silver
It is 1:1-4.
2. method that is according to claim 1 a kind of quick and being prepared on a large scale electrum nanotube, it is characterised in that
The solid-to-liquid ratio of sodium chloride, polyvinylpyrrolidone PVP and ethylene glycol solution described in step (1) is 0.007-1mg：198mg：
10ml。
3. method that is according to claim 1 a kind of quick and being prepared on a large scale electrum nanotube, it is characterised in that
The concentration of silver nitrate ethylene glycol solution described in step (1) is 0.12mol/L, and the silver nitrate ethylene glycol solution and ethylene glycol are molten
The volume ratio of liquid is 1:2.
4. method that is according to claim 1 a kind of quick and being prepared on a large scale electrum nanotube, it is characterised in that
The rate of addition of silver nitrate ethylene glycol solution described in step (1) is 4-6ml/h.
5. method that is according to claim 1 a kind of quick and being prepared on a large scale electrum nanotube, it is characterised in that
The concentration of nano silver wire solution described in step (2) is 2mmol/L, and the volume ratio of the nano silver wire solution and deionized water is
0.025-5:1。
6. method that is according to claim 1 a kind of quick and being prepared on a large scale electrum nanotube, it is characterised in that
The concentration of chlorauric acid solution described in step (2) is 1mmol/L, and the volume ratio of the chlorauric acid solution and nano silver wire solution is
1:0.75-2。
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| CN105810833B (en) * | 2016-03-24 | 2018-08-17 | 山西阳泰龙焱能源科技有限公司 | The preparation method of electrode before a kind of organic thin film solar cell |
| CN106001552A (en) * | 2016-07-07 | 2016-10-12 | 中国科学院合肥物质科学研究院 | Preparation method of silver @ metallic oxide composite nanometer line |
| CN106975756B (en) * | 2017-04-07 | 2019-02-15 | 厦门大学 | A kind of preparation method of rhodium tellurium alloy hollow nanotube |
| CN108067268A (en) * | 2017-12-27 | 2018-05-25 | 福州大学 | A kind of preparation and its application of 1-dimention nano tubulose Ag/AgCl/AgBr composite heterogenous junction visible light catalysts |
| CN108213460B (en) * | 2018-03-16 | 2021-05-28 | 西北大学 | Microwave preparation method of monodisperse gold-silver alloy nanoparticles |
| CN108927531A (en) * | 2018-08-22 | 2018-12-04 | 华南理工大学 | A kind of silver nanowires and its preparation method and application based on more nucleation controlling agents |
| CN110653380B (en) * | 2019-10-31 | 2022-08-19 | 合肥工业大学 | Method for rapidly preparing gold nanoparticles in alcohol phase at normal temperature |
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| CN101934378A (en) * | 2010-09-10 | 2011-01-05 | 浙江大学 | High-concentration fast preparation method for silver nanowires |
| CN101934377A (en) * | 2010-09-14 | 2011-01-05 | 浙江大学 | Quick and efficient synthesis method for silver nanowires |
| CN103084584A (en) * | 2013-01-29 | 2013-05-08 | 中国科学院理化技术研究所 | Method of preparing silver nanowire by utilization of hydrothermal method |
| CN103990793B (en) * | 2014-05-09 | 2017-03-29 | 北京华纳高科科技有限公司 | Hollow real wall gold/gold silver nanotube of a kind of high length-diameter ratio and preparation method thereof |
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