CN102021654B - A kind of preparation method of magnetic nanotube - Google Patents

Abstract

The invention discloses a method for preparing magnetic nanotubes, comprising the following steps: placing an aluminum oxide film with a pore size of 100-200nm in the middle of two quartz reaction pools, injecting a monovalent or divalent iron-based metal ion plating solution with a total concentration of 0.02-0.1mol/L into one quartz reaction pool, injecting a 5-15g/L sodium borohydride aqueous solution into the other quartz reaction pool, standing for 2-20 minutes at room temperature, removing the black nanotube/aluminum oxide composite film, dissolving it with a 1-2mol/L NaOH solution for no less than 5 minutes, washing the dissolved nanotubes with distilled water and anhydrous ethanol for several times, and drying them at room temperature in vacuum to constant weight. Compared with the prior art, the present invention synthesizes nanotubes in a one-step method, has a very simple synthesis device, and a short preparation cycle. The prepared magnetic nanotubes have a porous structure that can provide a good loading function, thereby also providing magnetic raw materials for drug loading and targeted transportation.

Description

A kind of preparation method of magnetic nanotube

Technical field:

The invention relates to a method for preparing nanometer materials, in particular to a method for preparing magnetic nanotubes.

Background technique:

At present, the synthesis method of magnetic nanotubes is not very mature, and the template electrochemical deposition method is more reported. However, this method of synthesizing magnetic nanotubes usually requires vacuum spraying conductive film or electroplating on one side of the alumina template. Electrochemical operations can be performed only when the conductive layer is made by coating conductive adhesive. This method has problems such as high equipment requirements, poor practicability, and troublesome post-processing of the obtained materials. At the same time, in order to obtain the tubular structure, some special synthesis techniques and strategies are usually used, which can only be obtained after multi-step synthesis. For example, it is necessary to carry out chemical modification pretreatment on alumina templates, use molecular anchors or precursors for inductive synthesis, use multilayer template replication technology, and partially spray gold on templates to form ring-shaped electrode substrates, etc. This method is generally not well controlled in the synthesis of nanotubes.

Invention content:

The technical problem to be solved by the invention is to provide a simple and controllable method for preparing magnetic nanotubes.

The technical scheme for solving technical problems of the present invention is: a kind of preparation method of magnetic nanotube, comprises following operation:

Put the aluminum oxide film with a pore size of 100-200nm in the middle of two quartz reaction pools. One quartz reaction pool is injected with a total concentration of 0.02-0.1mol/L mono- or binary iron-based metal ion plating solution, and the other quartz reaction pool is injected 5-15g/L sodium borohydride aqueous solution, let it stand at room temperature for 2-20 minutes, remove the black nanotube/alumina composite film, dissolve it with 1-2mol/L NaOH solution for no less than 5 minutes, and dissolve the dissolved nanotubes The tube was washed several times with distilled water and absolute ethanol, and dried in vacuum at room temperature to constant weight to obtain amorphous magnetic nanotubes.

In order to obtain crystalline nanotubes, the corresponding amorphous nanotubes are heated and annealed in vacuum at 300-500° C. for 30-100 minutes, and the vacuum degree is greater than 0.995 bar.

The iron series metal ions are divalent iron ions, divalent cobalt ions and divalent nickel ions.

In order to obtain magnetic oxide nanotubes, the amorphous iron nanotubes are heated in air at 300-500° C. for 60-100 minutes.

As shown in Figure 2, the present invention uses the nano-holes of the porous aluminum oxide film as a microreactor, wherein the aluminum oxide film acts as a hard template; sodium borohydride molecules and reduced metal ions enter the holes from both sides of the template respectively, and When they meet in the pores of the template, the redox reaction occurs immediately and a large amount of gas is released. Since the pore size of the template is small, the generated gas preferentially moves and is discharged from the axis of the hole with less resistance, so that the reduced ions can only be released in Deposition and attachment on the hole wall; the metal or alloy particles deposited on the template hole wall can be used as new growth points, and the activity of the template hole wall is very high, and other ions continue to grow along the tube wall on these growth points , forming nanotubes.

One of the advantages of the method of the present invention is that it realizes a simple method for synthesizing nanotubes in one step, the synthesis device is very simple, the preparation period is very short, it can be efficiently utilized, and it has good promotion and application value.

The second advantage of the method of the present invention is that it expands the technique of synthesizing one-dimensional nanometer materials by template method, and the appearance of the synthesized magnetic nanotubes is controllable and has good array property.

The third advantage of the method of the present invention is that it solves a new method for synthesizing magnetic metals, magnetic alloys and ferrite nanotubes, and provides a research means for the research of magnetic materials.

The fourth advantage of the method of the present invention is that it provides a method for synthesizing amorphous magnetic nanotubes.

The fifth advantage of the method of the present invention is that the corresponding crystalline magnetic nanotubes can be obtained by further annealing the target amorphous magnetic nanotubes, thereby also providing a simple synthesis technique for crystalline magnetic nanotubes.

The sixth advantage of the method of the present invention is that the porous structure of the magnetic nanotubes synthesized by this technology can provide a good loading function, so that it can also provide magnetic materials for drug loading and targeted transport.

Description of drawings

Fig. 1 is a device schematic diagram of the present invention;

Figure 2 is a schematic diagram of the formation of nanotubes in the present invention;

Fig. 3 is the scanning electron micrograph of cobalt nanotube;

Fig. 4 is the scanning electron micrograph of nickel nanotube;

Fig. 5 is the scanning electron micrograph of iron nanotube;

Fig. 6 is the scanning electron micrograph of cobalt-nickel nanotube;

Fig. 7 is the scanning electron micrograph of cobalt-iron nanotube;

Fig. 8 is a scanning electron micrograph of iron-nickel nanotubes.

In Fig. 1, 1 is a quartz reaction cell, 2 is a plating solution, 3 is an aluminum oxide film, and 4 is an aqueous solution of sodium borohydride.

Detailed ways:

Below in conjunction with embodiment the present invention is described in detail.

Example 1

Take a purchased 200nm aluminum oxide film 3 and place it in the middle of two quartz reaction tanks 1. One quartz reaction tank is injected with a concentration of 0.08mol/L CoSO ₄ solution 2, and the other quartz reaction tank is injected with 10g/L sodium borohydride aqueous solution 4 , stand at room temperature for 8 minutes, remove the black nanotube/alumina composite film, wash the composite film with distilled water and absolute ethanol for 3-4 times, put it in a vacuum drying oven at room temperature and dry to constant weight, and use 2mol /L NaOH partially dissolved can be used to detect the topography of the nanotube array with a scanning electron microscope (Figure 3); immerse in 2mol/L NaOH for 48 hours until the aluminum oxide film is completely dissolved, then centrifuge and wash with distilled water until the pH is neutral, and finally use Rinse twice with water and ethanol, put into a vacuum drying oven at room temperature and dry to constant weight to obtain amorphous magnetic cobalt nanotubes. The obtained magnetic cobalt nanotubes are heated and annealed in vacuum at 380° C. for 80 minutes, and the vacuum degree is greater than 0.995 bar, and corresponding crystalline cobalt nanotubes can be obtained.

Example 2

Take a purchased 200nm aluminum oxide film and place it in the middle of two quartz reaction cells. One quartz reaction cell is injected with a concentration of 0.06mol/L NiSO ₄ solution, and the other quartz reaction cell is injected with 8g/L sodium borohydride aqueous solution. Leave it for 10 minutes, remove the black nanotube/alumina composite film, wash the composite film 3-4 times with distilled water and absolute ethanol respectively, put it in a vacuum drying oven at room temperature and dry to constant weight, and partially dissolve it with 2mol/L NaOH Scanning electron microscopy can be used to detect the topography of nanotube arrays (Figure 4); soak in 2mol/L NaOH for 48 hours until the aluminum oxide film is completely dissolved, then centrifugally wash with distilled water until the pH is neutral, and finally rinse twice with absolute ethanol placed in a vacuum oven at room temperature and dried to constant weight to obtain amorphous magnetic nickel nanotubes.

The obtained magnetic nickel nanotubes are heated and annealed in vacuum at 420° C. for 100 minutes, and the vacuum degree is greater than 0.995 bar, and corresponding crystalline nickel nanotubes can be obtained.

Example 3

Take a purchased 200nm aluminum oxide film and place it in the middle of two quartz reaction tanks. One quartz reaction tank is injected with a concentration of 0.05mol/L FeSO _solution , and the other quartz reaction tank is injected with 5g/L sodium borohydride aqueous solution. Set aside for 12 minutes, remove the black nanotube/alumina composite film, wash the composite film 3-4 times with distilled water and absolute ethanol respectively, put it in a vacuum drying oven at room temperature and dry to constant weight, and partially dissolve it with 2mol/L NaOH Scanning electron microscopy can be used to detect the topography of nanotube arrays (Figure 5); soak in 2mol/L NaOH for 48 hours until the aluminum oxide film is completely dissolved, then centrifugally wash with distilled water until the pH is neutral, and finally rinse twice with absolute ethanol , placed in a vacuum drying oven at room temperature and dried to constant weight to obtain amorphous magnetic iron nanotubes.

The obtained amorphous magnetic iron nanotube is heated and annealed in vacuum at 350° C. for 80 minutes, and the vacuum degree is greater than 0.995 bar, so that the corresponding crystalline iron nanotube can be obtained.

The obtained amorphous magnetic iron nanotubes are heated in air at 350° C. for 60 minutes to obtain magnetic iron oxide nanotubes.

Example 4

Take a purchased 200nm aluminum oxide film and place it in the middle of two quartz reaction cells. One quartz reaction cell is injected with a concentration of 0.06mol/L CoSO ₄ and 0.02mol/L NiSO ₄ solution, and the other quartz reaction cell is injected with 10g/L boron Sodium hydride aqueous solution, let stand at room temperature for 10 minutes, remove the black nanotube/alumina composite film, then wash the composite film with distilled water and absolute ethanol for 3-4 times, put it in a vacuum drying oven at room temperature and dry to constant weight , Partially dissolved with 2mol/L NaOH, the topography of the nanotube array can be detected by scanning electron microscopy (Figure 6); immersed in 2mol/L NaOH for 48 hours until the aluminum oxide film is completely dissolved, and then centrifuged with distilled water until the pH is neutral. Finally, rinse twice with absolute ethanol, put into a vacuum drying oven at room temperature and dry to constant weight to obtain amorphous magnetic cobalt-nickel nanotubes.

The obtained magnetic cobalt-nickel nanotubes are heated and annealed in vacuum at 380° C. for 80 minutes, and the vacuum degree is greater than 0.995 bar, and corresponding crystalline nanotubes can be obtained.

Example 5

Take a purchased 200nm aluminum oxide film and place it in the middle of two quartz reaction cells. One quartz reaction cell is injected with a concentration of 0.05mol/L CoSO ₄ and 0.03mol/L FeSO ₄ solution, and the other quartz reaction cell is injected with 7g/L boron Sodium hydride aqueous solution, let stand at room temperature for 8 minutes, remove the black nanotube/alumina composite film, then wash the composite film with distilled water and absolute ethanol for 3-4 times, put it in a vacuum drying oven at room temperature and dry to constant weight , Partially dissolved with 2mol/L NaOH can be used to detect the topography of the nanotube array with a scanning electron microscope (Figure 7); soak in 2mol/L NaOH for 48 hours until the aluminum oxide film is completely dissolved, and then centrifuged with distilled water until the pH is neutral. Finally, it was rinsed twice with absolute ethanol, put into a vacuum drying oven at room temperature and dried to constant weight to obtain amorphous magnetic cobalt-iron nanotubes.

The obtained magnetic cobalt-iron nanotubes are heated and annealed in vacuum at 400° C. for 80 minutes, and the vacuum degree is greater than 0.995 bar, and corresponding crystalline nanotubes can be obtained.

Example 6

Take a piece of purchased 200nm aluminum oxide film and place it in the middle of two quartz reaction cells. One quartz reaction cell is injected with a concentration of 0.04mol/L NiSO ₄ and 0.02mol/L FeSO ₄ solution, and the other quartz reaction cell is injected with 5g/L boron Sodium hydride aqueous solution, let stand at room temperature for 12 minutes, remove the black nanotube/alumina composite film, then wash the composite film with distilled water and absolute ethanol for 3-4 times, put it in a vacuum drying oven at room temperature and dry to constant weight , Partially dissolved with 2mol/L NaOH can be used to detect the topography of the nanotube array with a scanning electron microscope (Figure 8); soak in 2mol/L NaOH for 48 hours until the aluminum oxide film is completely dissolved, and then centrifuged with distilled water until the pH is neutral. Finally, it was rinsed twice with absolute ethanol, put into a vacuum drying oven at room temperature and dried to constant weight to obtain amorphous magnetic nickel-iron nanotubes.

The obtained magnetic nickel-iron nanotubes are heated and annealed in vacuum at 400° C. for 100 minutes, and the vacuum degree is greater than 0.995 bar, so that corresponding crystalline nanotubes can be obtained.

Claims (3)

1. the preparation method of a Magnetic nano-pipe is characterized in that: comprise following operation:

With aperture 100-200nm pellumina; Be placed on the centre in two quartz reaction ponds, it is 0.02-0.1mol/L monobasic or binary Ferrious material ion plating bath that total concn is injected in a quartz reaction pond, and the 5-15g/L sodium borohydride aqueous solution is injected in another quartz reaction pond; Left standstill under the room temperature 2-20 minute; Take off black nano pipe/aluminum oxide composite package, be no less than 5 minutes with 1-2mol/L NaOH solution dissolving, with the nanotube that is dissolved out again through zero(ppm) water and absolute ethyl alcohol cleaning many times; The vacuum room temperature is dried to constant weight, obtains amorphous Magnetic nano-pipe;

Described Ferrious material ion is ferrous ion, divalent cobalt ion, bivalent nickel ion.

2. the preparation method of a kind of Magnetic nano-pipe according to claim 1 is characterized in that: in 300-500 ℃ of heating under vacuum annealing 30-100 minute, vacuum tightness can obtain the Magnetic nano-pipe of crystalline state greater than 0.995 crust with amorphous nanotube.

3. the preparation method of a kind of Magnetic nano-pipe according to claim 1 is characterized in that: with 300-500 ℃ of heating 60-100 minute in air of amorphous iron nanotube, can obtain the oxide magnetic nanotube.

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