CN101590531B - Method for preparing metal/organic small molecular core/shell type one-dimensional nano-composite material - Google Patents
Method for preparing metal/organic small molecular core/shell type one-dimensional nano-composite material Download PDFInfo
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- CN101590531B CN101590531B CN2009100881910A CN200910088191A CN101590531B CN 101590531 B CN101590531 B CN 101590531B CN 2009100881910 A CN2009100881910 A CN 2009100881910A CN 200910088191 A CN200910088191 A CN 200910088191A CN 101590531 B CN101590531 B CN 101590531B
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Abstract
The invention relates to a method for preparing a metal/organic small molecular core/shell type one-dimensional nano-composite material. The metal/organic small molecular core/shell type one-dimensional nano-composite material is prepared by the steps of: 1) preparing organic small molecular nano-tubes in an inorganic porous template by adopting a solution wetting method; and 2) taking the organic small molecular nano-tubes as a secondary template, and preparing the metal/organic small molecular core/shell type one-dimensional nano-composite material by introducing oxidant and reductant solutions into channels of the organic small molecular nano-tubes. The method is simple and practicable; and the prepared metal/organic small molecular core/shell type one-dimensional nano-composite material has regular morphology as well as uniform and controllable dimension.
Description
Technical field
The present invention relates to a kind of method for preparing metal/organic small molecular core/shell type one-dimensional nano-composite material.
Background technology
The material of one-dimensional nano structure because they at electricity, magnetic, the potential using value in aspects such as optics and micro mechanical device has caused people's extensive studies interest.Wherein, no matter metal nanometer line is angle or following application facet from basic research, especially many concerns have all been received.Metal nanometer line is very responsive to air and steam, and this character that will reduce itself reaches the performance of relevant nano-device.Therefore on the basis that successfully prepares a series of metal nano wires, the preparation of the nano wire of multi-layer compound structure and sign have caused widely to be paid close attention to.The core/shell type nano composite material can show and both be different from nuclear material, is different from the special performance of shell material again, and this makes this class material have very high scientific research meaning and using value.So far, the research of metal nanometer composite material mainly concentrates on the metal/oxide and the metal/polymer of nuclear/shell nanostructured.By contrast, the metal nanometer composite material with organic molecule shell does not but cause the attention that people are enough.Many as organic molecule in existing report with the surface of granular adsorption at silver, and it is also rare to form the core/shell type structure at the outer introducing of nano silver wire one deck organic molecule.
For the preparation of monodimension nanometer material, template synthesis method has following advantage than other method: experimental implementation is simple, the gained nano material is arranged in order, can be by the template that adopts different size the size of nano material be regulated and control etc.Traditional template synthesis method mainly is that technology such as combined with electrochemical technology, sol-gel deposit required nano material in the template hole of porous, and this conventional method has higher requirement to experimental implementation condition and technical ability.
Summary of the invention
The purpose of this invention is to provide a kind of simple method for preparing metal/organic small molecular core/shell type one-dimensional nano-composite material.
The method for preparing metal/organic small molecular core/shell type one-dimensional nano-composite material provided by the present invention may further comprise the steps:
1) preparation organic molecule nanotube in inorganic porous template:
1. preliminary treatment: inorganic porous template is immersed in water, ethanol, acetone and the chloroform behind the ultrasonic processing 10-20min successively, dry;
2. under the normal temperature and pressure, behind 1-2min in the saturated solution in the organic solvent of pretreated inorganic porous template immersion organic molecule, place air to dry;
3. repeating step is 2. 5-10 time;
4. after removing the organic molecule of inorganic porous template surface absorption, inorganic porous template is carried out slaking in the organic solvent atmosphere, curing temperature is 50-60 ℃, and the curing time is 10-12 hour, after the cooling, removes the organic molecule of inorganic porous template surface;
2) in inorganic porous template, prepare metal/organic small molecular core/shell type one-dimensional nano-composite material, this process is finished in a U type reaction unit, described U type reaction unit is made up of two L type pipes and a support ring, the end of two L type pipes is connected by support ring, forms U type reaction unit; Concrete steps are:
1. the inorganic porous template with the 4. middle preparation organic molecule of step 1) nanotube is positioned in the support ring, the plane of inorganic porous template parallels with the end face of L type pipe, the area of inorganic porous mould is identical with the cross-sectional area of support ring, and inorganic porous template is divided into two parts with U type reaction unit;
2. add aqueous oxidizing agent solution in one of them L type pipe, add the reducing agent aqueous solution in another L type pipe, the mol ratio of oxidant and reducing agent is 1: 1, and keeps two liquid levels in the L type pipe identical, reacts at normal temperatures 2-4 hour;
Oxidizing and Reducing Agents enters respectively in the little molecule nano pipe of machine in inorganic porous template duct with current under the effect of hydraulic pressure, redox reaction takes place generate metal nanometer line.
3) remove inorganic porous template: with step 2) 2. in preparation have the inorganic porous template of metal/organic small molecular core/shell type one-dimensional nano-composite material to immerse in the sodium hydroxide solution of 2-6M to remove inorganic porous template, obtain metal/organic small molecular core/shell type one-dimensional nano-composite material.
Wherein, the inorganic porous template of step 1) described in 1. is porous alumina formwork or CNT; The aperture of described inorganic porous template is 100nm or 200nm.The organic molecule of step 1) described in 2. is selected from rubrene or 2,4, a kind of in 5-triphenyl imidazoles or the pyrene.Step 1) 2. and the organic solvent 4. be chloroform or oxolane.Step 2) oxidant described in 2. is a silver nitrate; The concentration of described aqueous oxidizing agent solution is 2 * 10
-3M.Step 2) reducing agent described in 2. is an ascorbic acid; The concentration of the described reducing agent aqueous solution is 2 * 10
-3M.
The present invention has following advantage:
1) method provided by the present invention is simple, directly utilizes the organic molecule nanotube in the inorganic porous template to be the secondary template, directly generates metal/organic small molecular core/shell type one-dimensional nano-composite material by simple liquid phase oxidation reduction reaction; And traditional template synthesis method needs combined with electrochemical method or sol-gel technique etc., and experimental implementation condition and technical ability are had relatively high expectations.
2) can effectively regulate and control the size of prepared core/shell type composite nano materials by the template that adopts different aperture sizes and thickness.
3) can obtain different metal/organic small molecular core/shell type one-dimensional nano-composite materials with the redox reaction thing by providing for simple replacement of organic micromolecule compound.
Description of drawings
Fig. 1, U type reaction unit structural representation, among the figure, 1 is L type pipe; 2 is support ring; 3 is inorganic porous template.
Field emission scanning electron microscope (SEM) image of the silver/rubrene nuclear/shell one-dimensional nano-composite material of Fig. 2, embodiment 1 preparation.
Field emission scanning electron microscope (SEM) image of the silver/rubrene nuclear/shell one-dimensional nano-composite material of Fig. 3, embodiment 1 preparation, enlarged drawing.
Transmission electron microscope (TEM) image of the silver/rubrene nuclear/shell one-dimensional nano-composite material of Fig. 4, embodiment 1 preparation.
Elementary analysis power spectrum (EDX) figure of the silver/rubrene nuclear/shell one-dimensional nano-composite material of Fig. 5, embodiment 1 preparation.
Field emission scanning electron microscope (SEM) image of the silver/pyrene nuclear/shell one-dimensional nano-composite material of Fig. 6, embodiment 2 preparations.
Transmission electron microscope (TEM) image of the silver/pyrene nuclear/shell one-dimensional nano-composite material of Fig. 7, embodiment 2 preparations.
Silver/2,4 of Fig. 8, embodiment 4 preparations, field emission scanning electron microscope (SEM) image of 5-triphenyl imidazole nucleus/shell one-dimensional nano-composite material.
Silver/2,4 of Fig. 9, embodiment 4 preparations, transmission electron microscope (TEM) image of 5-triphenyl imidazole nucleus/shell one-dimensional nano-composite material.
The invention will be further described below in conjunction with the drawings and specific embodiments, but protection scope of the present invention is not limited to following examples.
The specific embodiment
Employed U type device as shown in fig. 1 among the following embodiment.
The preparation of silver/rubrene nuclear/shell one-dimensional nano-composite material
1) preparation rubrene nanotube:
1. porous alumina formwork (aperture is 200nm) is immersed successively in water, ethanol, acetone and the chloroform behind the ultrasonic processing 15min, dry;
2. under the normal temperature and pressure, after 2min makes abundant absorption in the chloroform saturated solution of pretreated porous alumina formwork immersion rubrene, dry;
3. repeating step is 2. 10 times, dries;
4. after removing the organic molecule of porous alumina formwork surface absorption with 1500 purpose sand paperings, be positioned in the closed container that contains 2ml chloroform solvent porous alumina formwork is unsettled, slaking is 12 hours under 60 ℃ of conditions, after the cooling, remove the organic molecule on porous alumina formwork surface once more with 1500 purpose sand paperings;
2) preparation silver/rubrene nuclear/shell one-dimensional nano-composite material:
1. the porous alumina formwork with the 4. middle preparation rubrene of step 1) nanotube is fixed in the support ring 2, the plane of inorganic porous template parallels with the end face of L type pipe 1, the area of inorganic porous mould is identical with the cross-sectional area of support ring 2, and inorganic porous template is divided into two parts with U type reaction unit;
2. in the L on left side type pipe 1, add 200ml AgNO
3The aqueous solution (2 * 10
-3M), add 200ml aqueous ascorbic acid (2 * 10 in the L type pipe 1 on the right
-3M), react 2 hours at normal temperatures;
3) with step 2) 2. in preparation have the inorganic porous template of silver/rubrene core/shell type one-dimensional nano-composite material to immerse in the sodium hydroxide solution of 6M to remove inorganic porous template, obtain silver/rubrene core/shell type one-dimensional nano-composite material.
Be washed to the pH value be neutral and drying after, carry out electron microscope observation, scanning electron microscope image is shown among Fig. 2 and Fig. 3, transmission electron microscope image is shown among Fig. 4, energy dispersion energy spectrogram picture is in Fig. 5.By Fig. 2-5 as seen, silver/rubrene nuclear/shell one-dimensional nano-composite material output is big, and pattern is regular, the size homogeneous.
The preparation of silver/pyrene nuclear/shell one-dimensional nano-composite material
1) preparation pyrene nanotube:
1. 1. with the step 1) among the embodiment 1;
2. under the normal temperature and pressure, after 2min makes abundant absorption in the oxolane saturated solution of pretreated porous alumina formwork immersion pyrene, dry;
3. 3. with the step 1) among the embodiment 1;
4. 4. with the step 1) among the embodiment 1;
2) preparation silver/pyrene nuclear/shell one-dimensional nano-composite material:
1. the porous alumina formwork with the 4. middle preparation pyrene of step 1) nanotube is fixed in the support ring 2, the plane of inorganic porous template parallels with the end face of L type pipe 1, the area of inorganic porous mould is identical with the cross-sectional area of support ring 2, and inorganic porous template is divided into two parts with U type reaction unit;
2. with the step 2 among the embodiment 1) 2.;
3) with step 2) 2. in preparation have the inorganic porous template of silver/pyrene core/shell type one-dimensional nano-composite material to immerse in the sodium hydroxide solution of 6M to remove inorganic porous template, obtain silver/pyrene core/shell type one-dimensional nano-composite material.
Be washed to the pH value be neutral and drying after, carry out electron microscope observation, scanning electron microscope image is shown among Fig. 6, transmission electron microscope image is shown among Fig. 7.By Fig. 6-7 as seen, silver/pyrene nuclear/shell one-dimensional nano-composite material output is big, and pattern is regular, the size homogeneous.
The preparation of silver/pyrene nuclear/shell one-dimensional nano-composite material
1) preparation pyrene nanotube:
1. porous alumina formwork (aperture is 100nm) is immersed successively in water, ethanol, acetone and the chloroform behind the ultrasonic processing 15min, dry;
2.-4. with the step 1) among the embodiment 2 2.-4.;
2) with the step 2 among the embodiment 2);
3), obtain silver/pyrene nuclear/shell one-dimensional nano-composite material with the step 3) among the embodiment 2.
Silver/pyrene nuclear/shell one-dimensional nano-composite material output is big, and pattern is regular, the size homogeneous.
Embodiment 4
Silver/2,4, the preparation of 5-triphenyl imidazole nucleus/shell one-dimensional nano-composite material
1) preparation 2,4,5-triphenyl imidazoles nanotube:
1. with embodiment 1) in step 1) 1.;
2. under the normal temperature and pressure, pretreated porous alumina formwork is immersed 2,4, after 2min makes abundant absorption in the oxolane saturated solution of 5-triphenyl imidazoles, dry;
3. with embodiment 1) in step 1) 3.;
4. with embodiment 1) in step 1) 4.;
2) preparation silver/2,4,5-triphenyl imidazole nucleus/shell one-dimensional nano-composite material:
1. with the 4. middle preparation 2 of step 1), 4, the porous alumina formwork of 5-triphenyl imidazoles nanotube is fixed in the support ring 2, the plane of inorganic porous template parallels with the end face of L type pipe 1, the area of inorganic porous mould is identical with the cross-sectional area of support ring 2, and inorganic porous template is divided into two parts with U type reaction unit;
2. with the step 2 among the embodiment 1) 2.;
3) with step 2) 2. middle the preparation silver/2 are arranged, 4, remove inorganic porous template in the sodium hydroxide solution of the inorganic porous template immersion 6M of 5-triphenyl imidazole nucleus/shell type one-dimensional nano-composite material, obtain silver/2,4,5-triphenyl imidazole nucleus/shell type one-dimensional nano-composite material.
Be washed to the pH value be neutral and drying after, carry out electron microscope observation, scanning electron microscope image is shown among Fig. 8, transmission electron microscope image is shown among Fig. 9.By Fig. 8-9 as seen, silver/2,4,5-triphenyl imidazole nucleus/shell one-dimensional nano-composite material output is big, and pattern is regular, the size homogeneous.
Embodiment 5
Silver/2,4, the preparation of 5-triphenyl imidazole nucleus/shell one-dimensional nano-composite material
1) preparation 2,4,5-triphenyl imidazoles nanotube:
1. porous alumina formwork (aperture is 100nm) is immersed successively in water, ethanol, acetone and the chloroform behind the ultrasonic processing 15min, dry;
2.-4. with the step 1) among the embodiment 4 2.-4.;
2) with the step 2 among the embodiment 4)
3), obtain silver/2,4,5-triphenyl imidazole nucleus/shell one-dimensional nano-composite material with the step 3) among the embodiment 4.
Silver/2,4,5-triphenyl imidazole nucleus/shell one-dimensional nano-composite material output is big, and pattern is regular, the size homogeneous.
Claims (7)
1. a method for preparing metal/organic small molecular core/shell type one-dimensional nano-composite material is characterized in that, may further comprise the steps:
1) preparation organic molecule nanotube in inorganic porous template:
1. inorganic porous template is immersed successively in water, ethanol, acetone and the chloroform behind the ultrasonic processing 10-20min, dry;
2. under the normal temperature and pressure, behind 1-2min in the saturated solution in the organic solvent of pretreated inorganic porous template immersion organic molecule, place air to dry;
3. repeating step is 2. 5-10 time;
4. after removing the organic molecule of inorganic porous template surface absorption, inorganic porous template is carried out slaking in the organic solvent atmosphere, curing temperature is 50-60 ℃, and the curing time is 10-12 hour, after the cooling, removes the organic molecule of inorganic porous template surface;
2) in inorganic porous template, prepare metal/organic small molecular core/shell type one-dimensional nano-composite material, this process is finished in a U type reaction unit, described U type reaction unit is made up of two L type pipes (1) and a support ring (2), the end of two L type pipes (1) is connected by support ring (2), forms U type reaction unit; Concrete steps are:
1. the inorganic porous template with the 4. middle preparation organic molecule of step 1) nanotube is positioned in the support ring (2), and the plane of inorganic porous template parallels with the end face of L type pipe (1), and inorganic porous template is divided into two parts with U type reaction unit;
2. in one of them L type pipe (1), add aqueous oxidizing agent solution, in another L type pipe (1), add the reducing agent aqueous solution, the mol ratio of oxidant and reducing agent is 1: 1, and keeps the liquid level in two L type pipes (1) identical, reacts at normal temperatures 2-4 hour;
3) remove inorganic porous template: with step 2) 2. in preparation have the inorganic porous template of metal/organic small molecular core/shell type one-dimensional nano-composite material to immerse in the sodium hydroxide solution of 2-6M to remove inorganic porous template, obtain metal/organic small molecular core/shell type one-dimensional nano-composite material;
Described organic molecule is selected from rubrene or 2,4, a kind of in 5-triphenyl imidazoles or the pyrene;
Organic solvent described in the step 1) is chloroform or oxolane.
2. method according to claim 1 is characterized in that, the inorganic porous template of step 1) described in 1. is porous alumina formwork or CNT.
3. method according to claim 1 and 2 is characterized in that, the aperture of described inorganic porous template is 100nm or 200nm.
4. method according to claim 1 is characterized in that step 2) oxidant described in 2. is silver nitrate.
5. method according to claim 1 is characterized in that step 2) concentration of the aqueous oxidizing agent solution described in 2. is 2 * 10
-3M.
6. method according to claim 1 is characterized in that step 2) reducing agent described in 2. is ascorbic acid.
7. method according to claim 1 is characterized in that step 2) concentration of the reducing agent aqueous solution described in 2. is 2 * 10
-3M.
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| CN102528021A (en) * | 2011-12-27 | 2012-07-04 | 北京化工大学 | Method for preparing precious metal/organic functional small molecule core-shell structure nano particles |
| CN103752850B (en) * | 2014-02-18 | 2015-08-26 | 南京瑞盈环保科技有限公司 | A kind of method utilizing alumina formwork to prepare nano silver wire |
| CN104368822B (en) * | 2014-10-09 | 2016-03-16 | 哈尔滨工业大学宜兴环保研究院 | Utilize phosphatide pipe as the method for Template preparation metal nano-tube |
| CN107552806B (en) * | 2016-06-30 | 2020-01-21 | 郑州科斗科技有限公司 | Preparation method of Fe3O4@ Au core @ shell structure nanorod with controllable size and dispersity in large-scale preparation |
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| CN101208605A (en) * | 2005-05-04 | 2008-06-25 | 新加坡科技研究局 | New type water-solubility nanocrystalline containing low molecular weight coating agent and preparation method thereof |
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