CN1769519A - Metal nanometertube preparation method - Google Patents
Metal nanometertube preparation method Download PDFInfo
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- CN1769519A CN1769519A CN 200410088726 CN200410088726A CN1769519A CN 1769519 A CN1769519 A CN 1769519A CN 200410088726 CN200410088726 CN 200410088726 CN 200410088726 A CN200410088726 A CN 200410088726A CN 1769519 A CN1769519 A CN 1769519A
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Abstract
This invention relates to the metal nanometer tube making method, which includes the following steps: fistly making the metal colloid water-solubility solution, then extracting the metal from the water-solubility solution by the organic substance that has the coordination action with the metal, and distributing it in the organic solvent to get the metal colloid solution. The metal will deposit on the substrate when various substrates dips in this solution. If the substrate is the moulding board with the nanometer opening, then the metal will deposit on the inwall of the opening to form the matel nanometer tube. Controlling the dipping time and dipping number can get the nanometer tubes with different thickness. Using the moulding boards with different internal diameter nanometer opening can get the namometer tubes with different diametics. And using this invention can not only obtain the metal namometer tube whose structure and dimension can be controlled, and can obtain the metal nanometer tube array whose height is ordered.
Description
Technical field
The present invention relates to the preparation method of metal nano-tube, particularly relate to the preparation method of the metal nano-tube of high-sequential, controllable diameter.
Background technology
Since Iijima discovery carbon nanotube in 1991, various nanotubes caused people's extensive concern.Metal nano-tube, inorganic oxide and sulfide nano-tube, polymer nanotube etc. have been made in recent years, they have shown great application prospect at aspects such as optical physics, photochemistry, magnetics, mechanics, electronics, sensings, and have profound significance for the fundamental research of scientific domain.
In present prior art, the method for preparing nanotube is a lot.The physics method is arranged, mainly comprise laser ablation method, using vaporization condensation process, arc discharge method etc.; Chemical method mainly comprises chemical Vapor deposition process, solution reaction method, template and synthetic method etc.; Compare with the physics method, chemical method synthetic equipment is simple, cost is low and can control the size and the shape of nanotube, and obtains the nano-tube array of high-sequential.Thereby the physics method seldom is applied in the preparation of other material except demonstrating in the preparation of a few materials certain advantage at present.At present in the chemical synthesis that adopts, the template synthesis method is the important method of the development in recent years nano structural material assembling of getting up.Its advantage is: (1) preparation technology is simple, pore size is evenly adjustable, cheap; (2) high temperature resistant, the insulation, transparent of some template itself in visible and most of infrared light district; (3) be applicable to the assembling of multiple materials such as metal, alloy, nonmetal, conductor oxidate and sulfide, conducting polymer, high molecular polymer; (4) be fit to preparation diameter of nano particles single array system of disperseing of the same size, remove template and obtain nanoparticle, line, rod and pipe nano structured unit, duplicate templates such as metal and high molecular polymer; (5) adopt layer assembly, can prepare co-axial nano sleeve pipe (or cable) and sandwich style nano structural material; (6) performance that the composition that can be by changing assembled material in the template and the shape of nano particle are regulated nano structural material.Utilize template at present, people have not only prepared the material and the nanostructure primitive thereof of multiple ordered nano array, and studied their nano-meter characteristics such as light, magnetic, electricity, catalysis, also explored their application prospects simultaneously at aspects such as the electrode materials of optical material, vertical magnetism record material, lithium cell and photocatalysts.
The method for preparing at present nanotube in template mainly contains electrochemical deposition, chemical vapour deposition, sol-gel method, vacuum filtration, high temperature pyrolysated method
Summary of the invention
The object of the present invention is to provide a kind of very simple in foraminous die plate the preparation method of the metal nano-tube of controlled, controllable structure, the high-sequential of preparation size.
For achieving the above object, the present invention mainly realizes the preparation of metal nano-tube and array thereof according to the following step:
At first metallic compound is dissolved in the ethylene glycol solution, adds the ethylene glycol solution reaction of sodium hydroxide again, keeping the pH value is 7-11.5.Under nitrogen protection, be heated to 150-180 ℃, constant temperature back flow reaction 1-3 hour.Nitrogen shields to reaction system on the one hand, takes away water and organic by-products by reaction system on the other hand.Cool to room temperature promptly makes the water-soluble glue liquid solution of metal.
To there be the organism of coordination to be dissolved in the organic solvents such as toluene, chloroform with metal.The water-soluble glue liquid solution of getting a certain amount of metal that makes mixes mutually with organic solution, the mol ratio of organism and metal is 0.5-1: 1, the adding deionized water extracts after stirring 15-60min, solution is divided into two-phase, one deck is water white water, and another layer is the organic phase that contains the dark color of metal nanoparticle.After extracting three times that organic phase is centrifugal, get organic phase and carry out the vacuum outgas processing.With the solution liquid nitrogen freezing, the gas in the extraction system allows solution thaw naturally then earlier, and feeds high pure nitrogen.Triplicate is got supernatant liquid, obtains the metal-sol that organism is modified.
Substrate is soaked in the solution that obtains, covers bottle cap and leave standstill.The metallic particles that organism is modified can deposit in the substrate in spontaneous absorption.If adopting foraminous die plate is substrate, then the metal of organism modification can deposit on the cell walls, thereby forms metal nano-tube.
The present invention has following characteristics:
1, the organism of utilization of the present invention and metal-complexing loses and the metal-complexing ability after oxidized, the characteristics that cause metal deposition, at room temperature or a little more than making metal deposition under the room temperature in the nano-form duct, have simple economy, easy to operate, instrument, advantage that adjustable scope is big especially.
2, by changing soak time, soaking the thickness that number of times can be regulated metal nano-tube.And the diameter of metal nano-tube is by the aperture decision of template.Therefore utilize the present invention can directly control the internal diameter and the external diameter of the metal nano-tube that makes.
3, adopt the foraminous die plate of duct ordered arrangement, aperture uniformity, can prepare high-sequential, the uniform nano-tube array of diameter, lay the foundation for making up nano-device.
Description of drawings
Fig. 1 is the schema of metal nano-tube preparation;
Fig. 2 is the stereoscan photograph of the porous anodic alumina template of embodiment of the invention employing;
Fig. 3 is the stereoscan photograph of the Pt nanotube side-view of embodiment of the invention preparation;
Fig. 4 is the stereoscan photograph of the Pt nanotube vertical view of embodiment of the invention preparation;
Fig. 5 is the transmission electron microscope photo of the Pt nanotube of embodiment of the invention preparation.
Embodiment
Make the water-sol of metal earlier with metallic compound, the toluene solution of using triphenylphosphine again with metal extraction in toluene solution, triphenylphosphine and metal-complexing are because but triphenylphosphine is soluble in organic solvent such as toluene is water insoluble, so metal can be transferred to organic phase from water.Then template is soaked in the toluene solution of the metal that triphenylphosphine modifies, as shown in Figure 1, the colloidal metal solution that triphenylphosphine is modified enters among the duct of template, lose coordination with metal because triphenylphosphine is oxidized, metallic particles deposits on the inwall of duct, along with sedimentary particle increases, form thin film gradually and cover on the whole inwall, the tube wall of the metal nano-tube that just obtains.Template is taken out from solution, use the acetone supersound washing, drying.Promptly obtain being arranged in the metal nano-tube in template duct.Can select whether to remove template as required.
Embodiment 1:
In the 250ml two-mouth bottle, add 20ml H
2PtCl6H
2The ethylene glycol solution of O, the ethylene glycol solution with 20ml NaOH under the induction stirring is added drop-wise in the ethylene glycol solution of Platinic chloride, pH is remained in the 7-11.5 scope get final product, and obtains yellow transparent platinic hydroxide colloidal solution.Under induction stirring, heated this system 3 hours down, and in heat-processed, make N in 180 ℃
2Air communication is crossed reaction system (N
2Flow do not have specific requirement) take away water and organic by-products, make red-brown platinum colloid (3.7mg Pt/ml) solution.This colloid is highly stable, and long-time placement is not observed precipitation and generated.
Get platinum colloidal solution and the 40ml ethanol that 10ml makes and under agitation join simultaneously in the toluene solution of 50ml triphenylphosphine, the mol ratio of triphen methylphosphine and platinum is 0.5, and mixed system is the platinum colloidal solution that homogeneous red-brown triphenylphosphine is modified.After stirring 15min, the 100ml deionized water is joined in the above-mentioned colloidal solution, make the system phase-splitting.The triphenyl platinum of modifying of seeing is arranged in the henna toluene oil phase in upper strata, and lower floor is colourless water.Behind the separatory with oil phase with deionized water washed twice again, obtain the toluene colloidal solution of the platinum that the transparent triphenylphosphine of red-brown modifies.
The toluene colloidal solution of the platinum that prepared triphenylphosphine is modified carries out vacuum outgas to be handled: earlier with the solution liquid nitrogen freezing, the gas in the extraction system allows it thaw naturally then, and the feeding high pure nitrogen.With solution centrifugal, then the upper strata stillness of night is poured in the previously prepd weighing bottle behind the triplicate.
Alumina formwork is soaked in the solution that obtains, covers bottle cap and left standstill 24 hours.The triphenyl spontaneous absorption of platinum grain of modifying of seeing deposits in the duct of alumina formwork, forms the platinum nanotube.Template is taken out from solution, be dipped in supersound washing in the acetone soln, seasoning then promptly gets metal nano-tube of the present invention.
The metal nano-tube that makes is heated to 400 ℃ in retort furnace, constant temperature stops heating after two hours, and cool to room temperature is sloughed template.
Referring to Fig. 2, select for use for the aperture is 200nm, pore distribution is sexangle, the porous alumina formwork of the about 60m of thickness.
Referring to Fig. 3, from then on side-view is substrate with template shown in Figure 2, the orderly platinum nanotube for being arranged in parallel that obtains.The about 200nm of external diameter of pipe matches with the aperture of used alumina formwork.
Referring to Fig. 4, from then on vertical view can be seen the opening of the platinum nanotube that makes, and horizontal a large amount of ordered arrangement.
Referring to Fig. 5, from then on the tube wall of the platinum nanotube that makes as can be seen of electromicroscopic photograph is piled up by platinum grain and is formed.
Claims (8)
1, a kind of preparation method of metal nano-tube, key step is:
A) metallic compound is dissolved in the ethylene glycol solution, the ethylene glycol solution that adds sodium hydroxide again mixes, and keeping the pH value is 7-11.5; Mixing solutions is warmed up to 150-180 ℃, constant temperature back flow reaction 1-3 hour, this is reflected under the nitrogen atmosphere protection and carries out, and cool to room temperature promptly makes the water-soluble glue liquid solution of metal;
Described metallic compound comprises the compound of platinum, rhodium, ruthenium, palladium, and transistion metal compound;
B) will there be the organism of coordination to be dissolved in toluene or the chloroform organic solvent with metal, the preparation organic solution;
Described organism is meant and can carries out ligand complex with metal, metal transferred to the organism of organic phase from water;
C) the water-soluble glue liquid solution of the metal that step a is made mixes with the organic solution that step b makes, and the mol ratio of organism and metal is 0.5-1: 1; Change in the separating funnel after stirring 15-60min, add deionized water and extract solution layering, aqueous phase discarded; The organic phase vacuum outgas is handled, and its process is: the organic phase liquid nitrogen freezing, and extraction system gas wherein allows it thaw naturally then, and feeds pure nitrogen gas, gets supernatant liquid, obtains the metal-sol that organism is modified;
D) under the room temperature to 40 ℃, substrate is immersed in the metal-sol that the organism that makes modifies, take out after 15-24 hour dry, target product; Described substrate is various metal oxides, nonmetal, inorganic and organic nano foraminous die plate.
2. preparation method according to claim 1 is characterized in that, the organism among the step b comprises: triphenylphosphine or amide compound.
3. preparation method according to claim 1 is characterized in that, the organic phase among the step c is used the deionized water extracted several times again after extraction.
4. preparation method according to claim 1 is characterized in that, the organic phase degassing treating processes among the step c can repeat for several times.
5. preparation method according to claim 1 is characterized in that, the centrifugal layering of solution after the organic phase degassing among the step c is handled.
6. preparation method according to claim 1 is characterized in that, the substrate in the steps d comprises: anodic oxidation aluminium formwork, polycarbonate template or various kapillary.
7. preparation method according to claim 1 is characterized in that, the back taking-up is soaked in the substrate in the steps d, uses ultrasonic cleaning, then seasoning.
8. claim 1 or 7 described preparation methods is characterized in that, the product of steps d was cooled to room temperature, to remove template in 350-400 ℃ of constant temperature 1-2 hour.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101618854B (en) * | 2009-05-22 | 2012-02-01 | 哈尔滨工程大学 | Preparation method of one-dimensional MnO2 nanometer array structure |
| CN102660734A (en) * | 2012-05-18 | 2012-09-12 | 中国科学院上海硅酸盐研究所 | Method for preparing porous nanometer metal film and porous nanometer metal film prepared by same |
| CN104016299A (en) * | 2014-06-12 | 2014-09-03 | 中国科学院化学研究所 | Micro-nanotube and preparation method and application thereof |
| CN105014064A (en) * | 2015-07-22 | 2015-11-04 | 常州市好利莱光电科技有限公司 | Method for manufacturing nanofiber material by means of iron-nickel alloy pipe |
| CN111617516A (en) * | 2020-07-10 | 2020-09-04 | 安徽师范大学 | Silica gel integral open-tube capillary column with metal wire as template and preparation method thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100455297B1 (en) * | 2002-06-19 | 2004-11-06 | 삼성전자주식회사 | Manufacturing method of inorganic nano tube |
| CN1155522C (en) * | 2002-11-27 | 2004-06-30 | 南开大学 | Transition metal sulfied nano-pipe and preparation process and its application |
-
2004
- 2004-11-01 CN CNB2004100887261A patent/CN100491589C/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101618854B (en) * | 2009-05-22 | 2012-02-01 | 哈尔滨工程大学 | Preparation method of one-dimensional MnO2 nanometer array structure |
| CN102660734A (en) * | 2012-05-18 | 2012-09-12 | 中国科学院上海硅酸盐研究所 | Method for preparing porous nanometer metal film and porous nanometer metal film prepared by same |
| CN102660734B (en) * | 2012-05-18 | 2014-11-05 | 中国科学院上海硅酸盐研究所 | Method for preparing porous nanometer metal film and porous nanometer metal film prepared by same |
| CN104016299A (en) * | 2014-06-12 | 2014-09-03 | 中国科学院化学研究所 | Micro-nanotube and preparation method and application thereof |
| CN104016299B (en) * | 2014-06-12 | 2016-03-23 | 中国科学院化学研究所 | A kind of micro-nano mitron and preparation method thereof and application |
| CN105014064A (en) * | 2015-07-22 | 2015-11-04 | 常州市好利莱光电科技有限公司 | Method for manufacturing nanofiber material by means of iron-nickel alloy pipe |
| CN111617516A (en) * | 2020-07-10 | 2020-09-04 | 安徽师范大学 | Silica gel integral open-tube capillary column with metal wire as template and preparation method thereof |
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| CN100491589C (en) | 2009-05-27 |
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