CN1995475A - Diameter-controllable nm-tube array preparation method - Google Patents
Diameter-controllable nm-tube array preparation method Download PDFInfo
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- CN1995475A CN1995475A CN 200610130329 CN200610130329A CN1995475A CN 1995475 A CN1995475 A CN 1995475A CN 200610130329 CN200610130329 CN 200610130329 CN 200610130329 A CN200610130329 A CN 200610130329A CN 1995475 A CN1995475 A CN 1995475A
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Abstract
The invention discloses a preparing method of metal nanometer line and array with controllable diameter, which comprises the following steps: adopting circulating electrolyser to deposit metal nanometer line array with different diameters in the alumina mould with different apertures; adjusting the diameter of nanometer line between 5nm and 500nm; fitting for synthesizing electrochemical depositing material and nanometer pipe-shaped structure.
Description
[technical field]
The present invention relates to a kind of preparation method of nanostructure, particularly utilize alumina formwork to adopt impulse electrodeposition technology to prepare nano-tube array.
[background technology]
Nanotube is meant the nano material with hollow tubular structures.Since discovery CNT (carbon nano-tube) such as Iijima in 1991, up to the present, scientists has been passed through several different methods, as graphite arc discharge, catalysis thermolysis, laser ablation etc. have synthesized the nano tube structure of the multiple material that comprises carbon nanotube, as sulfide, nitride, oxide compound, the nanotube of metal and organic substance etc.
Because the special construction of nanotube, can provide different contact aspect (as surfaces externally and internally, the edge of pipe, have the tube wall of special construction and hollow structure etc.), on principle, can make its functionalization by different modes, their hollow structure can be used directly as other nano material of template for preparing simultaneously.Therefore the preparation and the performance study of nanotube-shaped material have been the focus of international academic research.
[summary of the invention]
The invention provides a kind of preparation method of nano-tube array of controllable diameter.
The invention discloses a kind of preparation method of nano-tube array of controllable diameter.Select for use sulfuric acid, oxalic acid, phosphoric acid and citric acid as electrolytic solution, adopt the two-step anodization method, under the oxidation voltage condition of 15-300V, aluminium flake can be oxidized to the bilateral alumina formwork in different apertures.Pore size of template can be adjustable in 5nm to 500nm scope.Vacuum evaporation is adopted at the back side of the alumina formwork of bilateral, or magnetron sputtering, or method such as plasma coating covers one deck and is conductive particle that the quantum island the distributes hole wall position attached to the aluminum oxide hole, its thickness is in the 1nm-20nm scope, as negative electrode, with graphite as anode, place solution electrolytic cell assembly capable of circulation, between negative electrode and anode, add all adjustable pulsed voltage of one-period and waveform, adopt the pulse electrodeposition method, galvanic deposit obtains the nano-tube array of different diameter in the alumina formwork in different apertures, and the diameter of nanotube is adjustable in 5nm to 500nm scope.
The above-mentioned pulsed voltage that is added between the two poles of the earth is made of pulsed deposition voltage and pulse delay voltage, wherein: the pulsed deposition time T
OnIn 100 μ s-1s scopes, output pulsed deposition voltage between the two poles of the earth in this section period, pulsed deposition voltage is in 0.1～5V scope; Pulse delay time T
OffIn 100 μ s-1s scopes, output pulse delay voltage between the two poles of the earth in this section period, pulse delay voltage is in-5V～0 scope; Pulse signal frequency f is in the 0.5-5000Hz scope.
Advantage of the present invention:
A kind of preparation method of nano-tube array of different diameter is provided, and this method technology is simple and with low cost, is applicable to that the preparation of its nano tubular structure of material that can adopt electrochemical deposition is synthetic.
[description of drawings]
Fig. 1 is solution electrolytic cell assembly figure capable of circulation;
Fig. 2 is the pulse electrodeposition schematic diagram;
Stereoscan photograph before Fig. 3 alumina formwork gold evaporation particle;
Stereoscan photograph behind Fig. 4 alumina formwork gold evaporation particle;
Fig. 5 Zn nano-tube array stereoscan photograph;
Fig. 6 Zn nano-tube array transmission electron microscope photo.
[embodiment]
Adopt the two-step anodization method in 0.3M/L oxalic acid electrolytic solution, to add 60V voltage and can make the alumina formwork that the aperture is 80nm, as shown in Figure 3.One side of this bilateral alumina formwork is plated one deck with the method for evaporation be the hole wall position of the gold grain of quantum island distribution attached to the aluminum oxide hole, thickness is approximately 10nm, as shown in Figure 4, and as the negative electrode in the deposition process; With graphite flake as anode, place solution electric deposition device capable of circulation, (1 electrolyzer, 2 liquid outlets, 3 conduits, 4 recycle pumps, 5 turbo flow meters, 6 fluid inlets among the figure) as shown in Figure 1, the two poles of the earth link to each other with a producer that can produce pulse electrical signal respectively, with the electrical signal between oscilloscope monitoring the two poles of the earth.The composition of electrodeposit liquid is: 40g/L ZnSO
4, 15g/L ZnCl
2With 15g/L H
3BO
4, the pH value of solution is 3.5-4.5, working temperature is a room temperature.Output electrical signal synoptic diagram between the two poles of the earth as shown in Figure 2.Pulse signal voltage is 4.0-4.5V, frequency f=2.5Hz.In each cycle, burst length T
OnBe 200ms, time of lag T
OffBe 200ms.At T
OnIn time period, export high level between the two poles of the earth, at negative electrode/deposit fluid Zn at the interface
2+Be reduced into the Zn atom, at T
OffIn time period, be zero output between the two poles of the earth, obtain the Zn nano-tube array of in the alumina formwork hole, growing like this.The Zn nano-tube array is carried out morphology observation and structural characterization, see Fig. 5 and Fig. 6, employed testing tool is respectively FEI Sirion 200 type field emission scanning electron microscopes and JEOL 2010 type transmission electron microscopes.
Adopt the two-step anodization method in the 0.1M/L phosphoric acid electrolyte, to add 170V voltage and can make the alumina formwork that the aperture is 225nm.One side of this bilateral alumina formwork is plated one deck with the method for evaporation be the hole wall position of the silver-colored particle of quantum island distribution attached to the aluminum oxide hole, thickness is approximately 15nm, as the negative electrode in the deposition process; As anode, place solution electric deposition device capable of circulation with graphite flake, shown in figure one, the two poles of the earth link to each other with a producer that can produce pulse electrical signal respectively, with the electrical signal between oscilloscope monitoring the two poles of the earth.The composition of electrodeposit liquid is: 20g/LBiCl
3, the 80g/L glycerol, 55g/L tartrate and 0.4M/LHl, the pH value of solution is 2.5-3.0, working temperature is a room temperature.Output electrical signal synoptic diagram between the two poles of the earth as shown in Figure 2.Pulse signal voltage is 3.0-3.5V, frequency f=200Hz.In each cycle, burst length T
OnBe 1ms, time of lag T
OffBe 4ms.At T
OnIn time period, export high level between the two poles of the earth, at negative electrode/deposit fluid Bi at the interface
3+Be reduced into the Bi atom, at T
OffIn time period, be zero output between the two poles of the earth, obtain the Bi nano-tube array of in the alumina formwork hole, growing like this.
Adopt the two-step anodization method in 0.2M/L citric acid electrolytic solution, to add 200V voltage and can make the alumina formwork that the aperture is 500nm.One side of this bilateral alumina formwork is plated one deck with the method for evaporation be the hole wall position of the gold grain of quantum island distribution attached to the aluminum oxide hole, thickness is approximately 20nm, as the negative electrode in the deposition process; As anode, place solution electric deposition device capable of circulation with graphite flake, shown in figure one, the two poles of the earth link to each other with a producer that can produce pulse electrical signal respectively, with the electrical signal between oscilloscope monitoring the two poles of the earth.The composition of electrodeposit liquid is: 35g/L SbCl
3, 25g/L S powder and 15g/LH
3BO
4, the pH value of solution is a room temperature for the 3.0-3.5 working temperature.Output electrical signal synoptic diagram between the two poles of the earth as shown in Figure 2.Pulse signal voltage is 2.0-2.5V, frequency f=20Hz.In each cycle, burst length T
OnBe 30ms, time of lag T
OffBe 20ms.At T
OnIn time period, export high level between the two poles of the earth, at Sb during this period of time
2S
3In cathodic deposition.At T
OffIn time period, between the two poles of the earth zero output,, obtain the Sb that in the alumina formwork hole, grows like this
2S
3Nano-tube array.
Claims (5)
1, a kind of preparation method of nano-tube array of controllable diameter, it is characterized in that: the one side plating one deck at alumina formwork is the conductive particle that the quantum island distributes, be placed on then in a kind of solution electrolytic cell assembly capable of circulation, adopt the pulse electrodeposition method, galvanic deposit nano-tube array in alumina formwork, by adjusting the aperture size on the alumina formwork, the diameter that makes nanotube is in 5nm to 500nm scope.
2, according to the preparation method of the nano-tube array of the described a kind of controllable diameter of claim 1, it is characterized in that the conductive particle that the aluminum oxide bilateral template back side is covered is the hole wall position of quantum island attached to the aluminum oxide hole, conductive particle is gold or silver or copper; Adopt vacuum evaporation or magnetron sputtering or plasma film coating method to obtain, its thickness is at 1nm---in the 20nm scope.
3, according to the preparation method of the nano-tube array of the described a kind of controllable diameter of claim 1, it is characterized in that described solution electrolytic cell assembly capable of circulation mainly is made of electrolyzer, recycle pump, turbo flow meter and the conduit that is used to be communicated with, the container side upper and lower is respectively equipped with fluid inlet and liquid outlet, the two links to each other with turbo flow meter with recycle pump successively by conduit, and this device is mainly used in the preparation process of low dimension nano material.
4, according to the preparation method of the nano-tube array of the described a kind of controllable diameter of claim 1, it is characterized in that adopting the pulse electrodeposition legal system to be equipped with nano-tube array, its step comprises: the back side of the alumina formwork of bilateral is covered one deck conductive particle as negative electrode, with graphite as anode, place the round-robin electrodeposit liquid, between negative electrode and anode, add all adjustable pulsed voltage of one-period and waveform, obtain nano-tube array in cathodic deposition; The pulsed voltage that is added between the two poles of the earth is made of pulsed deposition voltage and pulse delay voltage, wherein: the pulsed deposition time T
OnIn 100 μ s-1s scopes, output pulsed deposition voltage between the two poles of the earth in this section period, pulsed deposition voltage is in 0.1～5V scope; Pulse delay time T
OffIn 100 μ s-1s scopes, output pulse delay voltage between the two poles of the earth in this section period, pulse delay voltage is in-5V～0 scope; Pulse signal frequency f is in the 0.5-5000Hz scope.
5,, it is characterized in that this kind method is applicable to that the preparation of its nano tubular structure of material that can adopt electrochemical deposition is synthetic according to the preparation method of the nano-tube array of the described a kind of controllable diameter of claim 1.
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| CN 200610130329 CN1995475A (en) | 2006-12-18 | 2006-12-18 | Diameter-controllable nm-tube array preparation method |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108277462A (en) * | 2017-12-27 | 2018-07-13 | 浙江交通科技股份有限公司 | A kind of method that pulse electrodeposition prepares magnetic metal nanotube |
| CN108360026A (en) * | 2017-12-29 | 2018-08-03 | 郑州轻工业学院 | A kind of method that direct electro-deposition prepares metal nano-tube array |
-
2006
- 2006-12-18 CN CN 200610130329 patent/CN1995475A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108277462A (en) * | 2017-12-27 | 2018-07-13 | 浙江交通科技股份有限公司 | A kind of method that pulse electrodeposition prepares magnetic metal nanotube |
| CN108360026A (en) * | 2017-12-29 | 2018-08-03 | 郑州轻工业学院 | A kind of method that direct electro-deposition prepares metal nano-tube array |
| CN108360026B (en) * | 2017-12-29 | 2019-11-29 | 郑州轻工业学院 | A kind of method that direct electro-deposition prepares metal nano-tube array |
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