CN109778250B - Method for preparing magnetic metal nanotube by controlling electrodeposition conditions - Google Patents
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Abstract
The invention relates to the field of nano materials, and discloses a method for preparing a magnetic metal nanotube by controlling electrodeposition conditions, which comprises the following steps: (a) preparing a template; (b) constant potential deposition of nanotubes: (b-1) preparation of salt bridges; (b-2) sputtering of conductive layer: sputtering a layer of copper film on the anodic aluminum oxide template; (b-3) potentiostatic electrodeposition: in a three-electrode system, an anodic aluminum oxide template sputtered with a copper film is used as a working electrode, a platinum sheet is used as a counter electrode, and a saturated calomel electrode is used as an auxiliary electrode; soaking the auxiliary electrode in a saturated KCl solution, and connecting the saturated KCl solution and an electrolyte by using a salt bridge; the deposition conditions were: the pH is 2-3, the deposition potential is-1 to-3V, and the deposition time is 300 to 600 s. (c) Releasing the magnetic metal nanotubes: soaking the anodic alumina template obtained in the step (b) in a post-treatment solution to remove the alumina template and the copper film.
Description
Technical Field
The invention relates to the field of nano materials, in particular to a method for preparing a magnetic metal nanotube by controlling electrodeposition conditions.
Background
Since the unexpected discovery of carbon nanotubes by the electron microscope expert Iijima, nanotubes have become a research hotspot in academia, and magnetic nanotubes are one-dimensional magnetic nanomaterials with hollow tubular structures. The magnetic nanotube as one member of nanotube family has the characteristics of nanotube such as low density, high surface energy, excellent adsorption performance, double-layer active surface inside and outside, and one-dimensional magnetic material characteristics such as excellent coercive force and remanence ratio, special magnetic inversion mode, small stable magnetic domain structure, no first-to-first connected domain wall of the magnetic nanotube, etc.
Due to various novel characteristics, magnetic nanotubes are gradually applied to the fields of in vivo diagnosis and biomedicine of drug carriers, chemical catalysis of sewage treatment, information technology of ultrahigh-density information storage, and the like. The Ni nanotube is used for diagnosing cells by utilizing the fluorescence effect of the Ni nanotube; the Ni nanotube is used for the catalytic decomposition application of AP (ammonium perchlorate) by utilizing the higher surface energy, the excellent adsorption property and the magnetic recovery characteristic of the Ni nanotube; carbon-coated Ni nanotubes are used as pure Doxorubicin (DOX) drug carriers and iron oxide nanotubes are used to achieve efficient administration of paclitaxel, and many unknown properties and applications of magnetic nanotubes are continuously explored by researchers. Therefore, the preparation and performance research of magnetic nanotubes are still required to be carried out deeply.
To date, various magnetic nanotubes have been prepared using various methods. The synthesis method of the magnetic metal nanotube mainly comprises chemical plating, Atomic Layer Deposition (ALD), sol-gel (sol-gel), template-electrodeposition and the like. Wherein, the chemical plating can only prepare metals with higher reduction potential and capable of being reduced by chemical reagents, such as Ni, Co and the like; ALD requires sophisticated instrumentation and is only suitable for the production of Fe3O4And oxides, etc.; the sol-gel method is simple and convenient, does not require any precise instrument, and can only prepare oxides. Moreover, none of the above three methods can adjust the properties of the nanotubes by controlling the length and diameter of the nanotubes.
The template-assisted electrochemical deposition is a method for synthesizing one-dimensional nano materials with different shapes by utilizing the confinement effect of the template and taking the template as a cathode, so that reduced atoms enter a pore channel by taking the template as a support and utilizing the constraint effect of the inner wall of the pore channel. The template-assisted electrochemical deposition has great advantages in the aspect of preparing the metal magnetic nanotube array, and has the advantages of convenient control of the components and the structure of the nanotubes, strong operability, simple experimental device and wide application range. Among them, the anodic alumina template (AAO) is one of the most commonly used templates in the template synthesis method due to its advantages of uniform pore diameter, ordered arrangement, high pore density, good thermal stability, controllable pore size, etc.
Tourilon et al use pulse electrodeposition method prepares Co, Fe nanotubes with polycarbonate template, Martin prepares Ni nanotubes with organic modified anodized aluminum template, Zuqin Liu et al prepares Fe with laser pulse deposition technology3O4A nanotube.
However, the series of metal nanotubes are prepared by a traditional electrochemical deposition method, and either the requirement on the conductive layer is high or impurities are introduced to seriously affect the performance of the material. And the metal nano tube prepared by the traditional electrochemical deposition method has poor regularity, uneven length and wall thickness and poor uniformity. Therefore, the research on a method which has low equipment requirement and can prepare the high-quality nanotube is of great significance.
Disclosure of Invention
In order to solve the technical problems, the invention provides a method for preparing the magnetic metal nano-tube by controlling the electrodeposition conditions, the method has low requirement on equipment, the magnetic metal nano-tube with different lengths can be obtained by controlling the process, and the prepared magnetic metal nano-tube has good regularity and good uniformity of length and wall thickness.
The specific technical scheme of the invention is as follows: a method for preparing magnetic metal nanotubes by controlling electrodeposition conditions, comprising the steps of:
(a) preparing a template: and preparing the anodic aluminum oxide template.
(b) The nanotubes are deposited at constant potential.
(b-1) preparation of salt bridge.
(b-2) sputtering of conductive layer: and sputtering a layer of copper film on the anodic aluminum oxide template.
(b-3) potentiostatic electrodeposition: in a three-electrode system, the anodic alumina template obtained in the step (b-2) is used as a working electrode, a platinum sheet is used as a counter electrode, and a saturated calomel electrode is used as an auxiliary electrode; soaking the auxiliary electrode in a saturated KCl solution, and connecting the saturated KCl solution and an electrolyte by using a salt bridge; the deposition conditions were: the pH value is 2-3, the deposition potential is-1 to-3V, and the deposition time is 300-600 s.
The electrolyte has a composition selected from any one of the following three compositions:
20～40g/L NiSO4·6H2O、45～60g/L NaCl、45～60g/L H3BO3；
20～40g/L CoSO4·6H2O、45～60g/L NaCl、45～60g/L H3BO3；
20～40g/L FeSO4·6H2o, 45-60 g/L NaCl, 15-30 g/L ascorbic acid, 45-60 g/LH3BO3。
(c) Releasing the magnetic metal nanotubes: and (c) soaking the anodic aluminum oxide template obtained in the step (b) in a post-treatment solution to remove the aluminum oxide template and the copper film, and obtaining the magnetic metal nanotube.
The invention adopts the form of constant potential electrodeposition matched with proper technological parameter adjustment, thereby being capable of preparing the magnetic metal nano-tube more simply, economically and rapidly and preparing the one-dimensional magnetic metal nano-tube with different lengths through technological control. The magnetic metal nanotube prepared by the method has good regularity and good uniformity of length and wall thickness.
Compared with the traditional direct current electrodeposition and pulse electrodeposition, the invention has the following differences: the principle of the invention is that the nanotube is prepared by relying on the formation of hydrogen, the traditional preparation principles of direct current deposition and pulse electrodeposition need to rely on the annular conductive electrode prepared by magnetron sputtering, and the preparation of the annular electrode has higher requirements on magnetron sputtering instruments and operating conditions.
In addition, the electrolyte of the present invention has a composition of plating metal salt much lower than the concentration of the conventional electrolyte, and additionally a strong electrolyte is added. The low concentration of the plating metal salt will reduce the metal deposition rate, and the strong electrolyte added can balance the charge of ions in the solution near the cathode, so that H+The ions continue to discharge at the cathode, thereby increasing the rate of hydrogen generation.
In addition, in (b-3), the deposition conditions are very important, and if the pH and deposition potential are not properly controlled, adverse consequences may occur. For example, too high a pH or too positive a deposition potential may inhibit the formation of hydrogen gas to obtain nanowires; while too low a pH or too negative a deposition potential results in too large a hydrogen formation rate to inhibit deposition of the metal such that nanotubes cannot be formed.
Preferably, in step (b-3), the deposition potential is-3V and the deposition time is 300 s.
Preferably, in the step (b-3), the composition of the electrolyte is selected from any one of the following three compositions:
27g/L NiSO4·6H2O、58g/L NaCl、45g/L H3BO3；
28g/L CoSO4·6H2O、58g/L NaCl、45g/L H3BO3；
28g/L FeSO4·6H2o, 58g/L NaCl, 10g/L ascorbic acid, 45g/L H3BO3。
The group of the invention finds that the electrolyte with the composition has the best effect through repeated experiments and a great deal of research.
Preferably, in step (a), the template preparation comprises:
(a-1) primary oxidation: placing the annealed and ultrasonically washed pretreated aluminum sheet in 0.3-0.5 mol/L oxalic acid aqueous solution, and carrying out electrochemical corrosion for 4-6 h under the conditions of 40-60V of voltage and 0-3 ℃ to obtain a primary aluminum oxide sheet;
(a-2) removing the primary oxide film: taking a primary oxidation aluminum sheet, soaking the primary oxidation aluminum sheet in a mixed aqueous solution of phosphoric acid and chromic acid at 50-70 ℃ for 12-16 h, and then cleaning the primary oxidation aluminum sheet with deionized water to obtain the aluminum sheet with the primary oxidation film removed;
in the mixed aqueous solution of phosphoric acid and chromic acid, the concentration of phosphoric acid is 3-6 wt%, and the concentration of chromic acid is 1-2 wt%;
(a-3) secondary oxidation: placing the aluminum sheet without the primary oxide film in 0.3-0.5 mol/L oxalic acid aqueous solution, electrochemically corroding for 6-8 h under the conditions of 80-90V voltage and 0-3 ℃ temperature, taking out, cleaning with deionized water, and placing in 1-3 mol/L CuCl2Soaking in the aqueous solution for 10-60 min, and then cleaning with deionized water to obtain an alumina template containing bi-pass nano-pores;
(a-4) reaming: placing an alumina template containing bi-pass nano-pores in 3-5 wt% of H at the temperature of 30-35 DEG C3PO4And (4) reaming the aqueous solution for 20-45 min to obtain the anodic aluminum oxide template.
Preferably, the aluminum sheet annealing and ultrasonic washing pretreatment method comprises the following steps: annealing the aluminum sheet at the temperature of 450-550 ℃ for 2-4 h, then carrying out ultrasonic treatment in acetone for 5-15min, then soaking in an alkaline solution for 5-10 min, and finally carrying out ultrasonic treatment in acetone for 3-5 min to finish the pretreatment. The alkaline solution can be 5wt% sodium hydroxide aqueous solution.
Preferably, the thickness of the aluminum sheet is 50-60 μm.
Preferably, in step (b-1), the preparation of the salt bridge comprises: adding 95-105 parts by weight of distilled water and 2.5-3.5 parts by weight of agar into a container, and heating in a water bath until the distilled water and the agar are completely dissolved; then adding 25-35 parts by weight of KCl to fully dissolve the mixture, finally pouring the mixture into a U-shaped thin glass tube while the mixture is hot, and obtaining a salt bridge after the agar is solidified.
Preferably, in the step (b-2), the conditions for sputtering the conductive layer are as follows: the flow rate of argon gas is 10-30 sccm, and the pressure is 3-5 × 10-4Pa, and a self-bias voltage of 150 to 200 Pa.
Preferably, in the step (c), the post-treatment solution contains 0.25 to 0.35mol/L of copper chloride, 0.25 to 0.35mol/L of chromic acid and 0.25 to 0.35mol/L of boric acid, and the soaking time is 50 to 70 min.
The copper chloride solution can conduct the copper film in solution under an acidic condition, and chromic acid can form an oxide film on the metal surface while boric acid dissolves the AAO template so as to protect the deposited nanotubes from being corroded, while the nanotubes can be corroded in a sodium hydroxide solution especially for cobalt metal.
Preferably, in the step (b-2), after the copper film is plated, the electrolyte and the anodized aluminum template are placed in a nitrogen atmosphere for 1-3h, and then a layer of Cu nanorods is deposited on the bottom pore channels of the anodized aluminum template in the Cu electrodeposition solution under the following deposition conditions: electric powerPressing at 0.7-0.9V for 8-12 min; the component concentration of the Cu electrodeposition solution is 12-18g/L CuSO4·5H2O，35-45g/L H3BO。
After the anodic aluminum oxide template is plated with the copper film, the anodic aluminum oxide template and the electrolyte are subjected to nitrogen treatment, so that the air in the anodic aluminum oxide template and the electrolyte can be exhausted, and the filling rate of deposition can be effectively improved. Then, a step of depositing Cu nano rods is added to the bottom of the template. The function is as follows: the invention (1) improves the adhesion strength of the copper film and the template so as to prevent the copper film from falling off in the deposition process, and 2) discovers that irregular-shaped pore channels or pore combination phenomena and the like generally exist at the bottom 1-5 um of the template after secondary oxidation under normal conditions, and influence is caused on the shape of the nanotube prepared subsequently. Therefore, the method deposits a layer of Cu nano-rods at the bottom of the template, and eliminates the influence of irregular pore canals at the bottom on the deposition process and the deposition product.
Compared with the prior art, the invention has the beneficial effects that: the invention adopts the form of constant potential electrodeposition matched with proper technological parameter adjustment, thereby being capable of preparing the magnetic metal nano-tube more simply, economically and rapidly and preparing the one-dimensional magnetic metal nano-tube with different lengths through technological control. The magnetic metal nanotube prepared by the method has good regularity and good uniformity of length and wall thickness.
Drawings
FIG. 1 is a schematic diagram of the formation of magnetic metal nanotubes according to the present invention;
FIG. 2 is a scanning electron microscope image of the magnetic metal Ni nanotube prepared in example 1 of the present invention;
FIG. 3 is a transmission electron microscope image of the magnetic metallic Ni nanotube prepared in example 1.
FIG. 4 is an SEM image of Ni nanotubes prepared in comparative example 1;
FIG. 5 is a TEM image of Ni nanotubes prepared in comparative example 2;
fig. 6 SEM image of Ni nanotubes prepared in comparative example 2.
Detailed Description
The present invention will be further described with reference to the following examples.
General examples
As shown in fig. 1, a method for preparing magnetic metal nanotubes by controlling electrodeposition conditions, comprising the steps of:
(a) template preparation
Annealing an aluminum sheet and carrying out ultrasonic washing pretreatment: annealing an aluminum sheet (with the thickness of 50-60 μm) at 550 ℃ for 2-4 h at 450-.
(a-1) primary oxidation: placing the annealed and ultrasonically washed pretreated aluminum sheet in 0.3-0.5 mol/L oxalic acid aqueous solution, and carrying out electrochemical corrosion for 4-6 h under the conditions of 40-60V of voltage and 0-3 ℃ to obtain a primary aluminum oxide sheet;
(a-2) removing the primary oxide film: taking a primary oxidation aluminum sheet, soaking the primary oxidation aluminum sheet in a mixed aqueous solution of phosphoric acid and chromic acid at 50-70 ℃ for 12-16 h, and then cleaning the primary oxidation aluminum sheet with deionized water to obtain the aluminum sheet with the primary oxidation film removed;
in the mixed aqueous solution of phosphoric acid and chromic acid, the concentration of phosphoric acid is 3-6 wt%, and the concentration of chromic acid is 1-2 wt%;
(a-3) secondary oxidation: placing the aluminum sheet without the primary oxide film in 0.3-0.5 mol/L oxalic acid aqueous solution, electrochemically corroding for 6-8 h under the conditions of 80-90V voltage and 0-3 ℃ temperature, taking out, cleaning with deionized water, and placing in 1-3 mol/L CuCl2Soaking in the aqueous solution for 10-60 min, and then cleaning with deionized water to obtain an alumina template containing bi-pass nano-pores;
(a-4) reaming: placing an alumina template containing bi-pass nano-pores in 3-5 wt% of H at the temperature of 30-35 DEG C3PO4And (4) reaming the aqueous solution for 20-45 min to obtain the anodic aluminum oxide template.
(b) The nanotubes are deposited at constant potential.
(b-1) preparation of salt bridge: adding 95-105 parts by weight of distilled water and 2.5-3.5 parts by weight of agar into a container, and heating in a water bath until the distilled water and the agar are completely dissolved; then adding 25-35 parts by weight of KCl to fully dissolve the mixture, finally pouring the mixture into a U-shaped thin glass tube while the mixture is hot, and obtaining a salt bridge after the agar is solidified.
(b-2) sputtering of conductive layer: sputtering a layer of copper film on the anodic aluminum oxide template: the conditions for sputtering the conductive layer are as follows: the flow rate of argon gas is 10-30 sccm, and the pressure is 3-5 × 10-4Pa, and a self-bias voltage of 150 to 200 Pa. After copper film plating, placing the electrolyte and the anodic alumina template in a nitrogen atmosphere for 1-3h, and then depositing a layer of Cu nano-rods at the pore canal at the bottom of the anodic alumina template in a Cu electrodeposition solution, wherein the deposition conditions are as follows: voltage is 0.7-0.9V, and time is 8-12 min; the component concentration of the Cu electrodeposition solution is 12-18g/L CuSO4·5H2O，35-45g/L H3BO。
(b-3) potentiostatic electrodeposition: in a three-electrode system, the anodic alumina template obtained in the step (b-2) is used as a working electrode, a platinum sheet is used as a counter electrode, and a saturated calomel electrode is used as an auxiliary electrode; soaking the auxiliary electrode in a saturated KC1 solution, and connecting the saturated KC1 solution and the electrolyte by using a salt bridge; the deposition conditions were: the pH value is 2-3, the deposition potential is-1 to-3V (preferably-3V), and the deposition time is 300s to 600s (preferably 300 s).
The electrolyte has a composition selected from any one of the following three compositions:
20～40g/L NiSO4·6H2O、45～60g/L NaCl、45～60g/L H3BO3；
20～40g/L CoSO4·6H2O、45～60g/L NaCl、45～60g/L H3BO3；
20～40g/L FeSO4·6H2o, 45-60 g/L NaCl, 15-30 g/L ascorbic acid, 45-60 g/LH3BO3。
Preferably, the composition of the electrolyte is selected from any one of the following three compositions:
27g/L NiSO4·6H2O、58g/L NaCl、45g/L H3BO3；
28g/L Co5O4·6H2O、58g/L NaCl、45g/L H3BO3；
28g/L FeSO4·6H2o, 58g/LNaCl, 10g/L ascorbic acid, 45g/L H3BO3。
(c) Releasing the magnetic metal nanotubes: and (c) soaking the anodized aluminum template obtained in the step (b) in a post-treatment solution (containing 0.25-0.35mol/L of copper chloride, 0.25-0.35mol/L of chromic acid and 0.25-0.35mol/L of boric acid, wherein the soaking time is 50-70 min., and the soaking time is 50-70min) to remove the anodized aluminum template, the copper film and the Cu nano-rods, so as to obtain the magnetic metal nano-tubes.
Example 1 (magnetic Metal Ni nanotubes)
(1) Template preparation
(1-1) selecting an aluminum sheet with high quality and high purity (the purity is 99.999 percent), annealing for 4 hours at 500 ℃, then carrying out ultrasonic treatment for 10 minutes in acetone, then soaking in 5 percent (wt) of sodium hydroxide for 5 minutes, and finally carrying out ultrasonic treatment for 3 minutes in acetone to finish the pretreatment of the aluminum sheet.
(1-2) first oxidation: corroding the pretreated aluminum sheet for 4 hours at the voltage of 40V and the temperature of 0 ℃, wherein the concentration of the electrolyte is 0.3mol/L oxalic acid.
(1-3) removing the primary oxide film: taking out, soaking in mixed solution of 6wt% phosphoric acid and 1.5 wt% chromic acid at 65 deg.C for 12 hr to remove primary oxide film, and cleaning with deionized water.
(1-4) second oxidation: and placing the aluminum sheet without the primary oxide film in 0.3mol/L oxalic acid aqueous solution, electrochemically corroding for 8 hours at the voltage of 80V and the temperature of 0 ℃, taking out, washing with deionized water, placing in 1mol/L CuCl2 aqueous solution, soaking for 30 minutes, and then washing with deionized water to obtain the alumina template with the two-way nano holes.
(1-5) reaming: placing the aluminum sheet at 35 ℃ in 5% (wt) H3PO4Reaming for 45min in the concentration to obtain the anodic aluminum oxide template.
(2) Constant potential deposition nanotubes
(2-1) preparation of salt bridge: 97ml of distilled water and 3g of agar were added to the beaker and heated in a water bath until complete dissolution. Then 30g of KCl is added to be fully dissolved, and finally the mixture is poured into a U-shaped thin glass tube while the mixture is hot, and the salt bridge is obtained after the agar is solidified.
(2-2) sputtering of conductive layer: fixing the anodic alumina template obtained in the step (a) in a magnetron sputtering fixtureThe argon flow rate is 20sccm, and the air pressure is 4 × 10-4Pa, sputtering a layer of copper film under the condition of self bias of 175 Pa. After copper film plating, placing the electrolyte and the anodic aluminum oxide template in a nitrogen atmosphere for 2h, and then depositing a layer of Cu nano rods at the pore canal at the bottom of the anodic aluminum oxide template in a Cu electrodeposition solution, wherein the deposition conditions are as follows: voltage is 0.8V, and time is 10 min; the component concentration of the Cu electrodeposition solution is 14g/L CuSO4·5H2O，10g/L H3BO。
(2-3) potentiostatic deposition: and (3) in a three-electrode system, taking the anodic alumina template obtained in the step (2-2) as a working electrode, a platinum sheet as a counter electrode, a saturated calomel electrode as an auxiliary electrode, soaking the auxiliary electrode in a saturated KCl solution, and connecting the saturated KCl solution and the electrolyte by using a salt bridge. The electrolyte comprises the following components: 27g/L NiSO4·6H2O、58g/L NaCl、45g/L H3BO3(ii) a pH2, deposition potential-3V, deposition time 300 s.
(3) Releasing the nanotubes:
and (3) soaking the anodized aluminum template subjected to the two-step electrodeposition in a post-treatment solution (containing 0.3mol/L of copper chloride, 0.3mol/L of chromic acid and 0.3mol/L of boric acid) for 1h, and sufficiently removing an oxidation film and a Cu nanorod aluminum substrate to obtain the magnetic metal Ni nanotube.
Example 2 (magnetic Metal Fe nanotubes)
(1) Template preparation
(1-1) selecting an aluminum sheet with high quality and high purity (the purity is 99.999 percent), annealing for 4 hours at 500 ℃, then carrying out ultrasonic treatment for 10 minutes in acetone, then soaking in 5 percent (wt) of sodium hydroxide for 5 minutes, and finally carrying out ultrasonic treatment for 3 minutes in acetone to finish the pretreatment of the aluminum sheet.
(1-2) first oxidation: corroding the pretreated aluminum sheet for 4 hours at the voltage of 40V and the temperature of 0 ℃, wherein the concentration of the electrolyte is 0.3mol/L oxalic acid.
(1-3) removing the primary oxide film: taking out, soaking in mixed solution of 6wt% phosphoric acid and 1.5 wt% chromic acid at 65 deg.C for 12 hr to remove primary oxide film, and cleaning with deionized water.
(1-4) second oxidation: aluminum sheet from which primary oxide film is to be removedPlacing in 0.3mol/L oxalic acid water solution, electrochemically corroding for 8h under the conditions of voltage 80V and temperature 0 ℃, taking out, cleaning with deionized water, and placing in 1mol/L CuCl2Soaking in the water solution for 30min, and then cleaning with deionized water to obtain the alumina template with bi-pass nano-pores.
(1-5) reaming: placing the aluminum sheet at 35 ℃ in 5% (wt) H3PO4Reaming for 45min in the concentration to obtain the anodic aluminum oxide template.
(2) Constant potential deposition nanotubes
(2-1) preparation of salt bridge: 97ml of distilled water and 3g of agar were added to the beaker and heated in a water bath until complete dissolution. Then 30g of KCl is added to be fully dissolved, and finally the mixture is poured into a U-shaped thin glass tube while the mixture is hot, and the salt bridge is obtained after the agar is solidified.
(2-2) sputtering of conductive layer: fixing the anodized aluminum template obtained in the step (a) in a magnetron sputtering fixture at an argon flow rate of 20sccm and a gas pressure of 4 × 10-4Pa, sputtering a layer of copper film under the condition of self bias of 175 Pa. After copper film plating, placing the electrolyte and the anodic aluminum oxide template in a nitrogen atmosphere for 1h, and then depositing a layer of Cu nano rods at the bottom pore canal of the anodic aluminum oxide template in a Cu electrodeposition solution, wherein the deposition conditions are as follows: voltage 0.7V, time 12 min: the component concentration of the Cu electrodeposition solution is 12g/L CuSO4·5H2O，45g/L H3BO。
(2-3) potentiostatic deposition: and (3) in a three-electrode system, taking the anodic alumina template obtained in the step (2-2) as a working electrode, a platinum sheet as a counter electrode, a saturated calomel electrode as an auxiliary electrode, soaking the auxiliary electrode in a saturated KCl solution, and connecting the saturated KCl solution and the electrolyte by using a salt bridge. The electrolyte comprises the following components: 28g/L FeSO4·6H2O、58g/L NaCl、45g/L H3BO3(ii) a pH2, deposition potential-3V, deposition time 300 s.
(3) Releasing nanotubes
And (3) soaking the anodized aluminum template subjected to the two-step electrodeposition in a post-treatment solution (containing 0.25mol/L of copper chloride, 0.35mol/L of chromic acid and 0.25mol/L of boric acid) for 1h, and sufficiently removing an oxide film, the Cu nano-rods and the aluminum substrate to obtain the magnetic metal Fe nano-tube.
Example 3 (magnetic Metal Co nanotubes)
(1) Template preparation
(1-1) selecting an aluminum sheet with high quality and high purity (the purity is 99.999 percent), annealing for 4 hours at 500 ℃, then carrying out ultrasonic treatment for 10 minutes in acetone, then soaking in 5 percent (wt) of sodium hydroxide for 5 minutes, and finally carrying out ultrasonic treatment for 3 minutes in acetone to finish the pretreatment of the aluminum sheet.
(1-2) first oxidation: corroding the pretreated aluminum sheet for 4 hours at the voltage of 40V and the temperature of 0 ℃, wherein the concentration of the electrolyte is 0.3mol/L oxalic acid.
(1-3) removing the primary oxide film: taking out, soaking in mixed solution of 6wt% phosphoric acid and 1.5 wt% chromic acid at 65 deg.C for 12 hr to remove primary oxide film, and cleaning with deionized water.
(1-4) second oxidation: placing the aluminum sheet without the primary oxide film in 0.3mol/L oxalic acid water solution, electrochemically corroding for 8 hours under the conditions of 80V voltage and 0 ℃, taking out, cleaning with deionized water, and placing in 1mol/L CuCl2Soaking in the water solution for 30min, and then cleaning with deionized water to obtain the alumina template with bi-pass nano-pores.
(1-5) reaming: placing the aluminum sheet at 35 ℃ in 5% (wt) H3PO4Reaming for 45min in concentration to obtain an anodic aluminum oxide template;
(2) constant potential deposition nanotubes
(2-1) preparation of salt bridge: 97ml of distilled water and 3g of agar were added to the beaker and heated in a water bath until complete dissolution. Then 30g of KCl is added to be fully dissolved, and finally the mixture is poured into a U-shaped thin glass tube while the mixture is hot, and the salt bridge is obtained after the agar is solidified.
(2-2) sputtering of conductive layer: fixing the anodized aluminum template obtained in the step (a) in a magnetron sputtering fixture at an argon flow rate of 20sccm and a gas pressure of 4 × 10-4Pa, sputtering a layer of copper film under the condition of self bias of 175 Pa. After copper film plating, placing the electrolyte and the anodic alumina template in a nitrogen atmosphere for 3h, and then depositing a layer of Cu nano-rods and depositing strips at the pore canal at the bottom of the anodic alumina template in a Cu electrodeposition solutionThe parts are as follows: voltage is 0.9V, and time is 8 min; the component concentration of the Cu electrodeposition solution is 12g/L CuSO4·5H2O，35g/L H3BO。
(2-3) potentiostatic deposition: and (3) in a three-electrode system, taking the template obtained in the step (2-2) as a working electrode, a platinum sheet as a counter electrode, a saturated calomel electrode as an auxiliary electrode, soaking the auxiliary electrode in a saturated KCl solution, and connecting the saturated KCl solution and the electrolyte by using a salt bridge. The electrolyte comprises the following components: 28g/L CoSO4·6H2O、58g/L NaCl、45g/L H3BO3(ii) a pH2, deposition potential-3V, deposition time 300 s.
(3) Releasing nanotubes
And (3) soaking the anodized aluminum template subjected to the two-step electrodeposition in a post-treatment solution (containing 0.35mol/L of copper chloride, 0.25mol/L of chromic acid and 0.35mol/L of boric acid) for 1h, and sufficiently removing an oxide film, the Cu nanorod and the aluminum substrate to obtain the magnetic metal Co nanotube.
Comparative example 1
Conventional electrodeposition process
(1) Sputtering a conductive layer: fixing the anodized aluminum template obtained in the step (a) in a magnetron sputtering fixture at an argon flow rate of 20sccm and a gas pressure of 3 × 10-4Pa, sputtering a 5nm gold film which can not completely block the bottom of the template under the condition of self bias voltage of 200Pa, and then sputtering a copper film with the thickness of 100nm under the same magnetron sputtering condition.
(2) Constant potential deposition: in a three-electrode system, an anodic aluminum oxide template sputtered with copper is used as a working electrode, a platinum sheet is used as a counter electrode, a saturated calomel electrode is used as an auxiliary electrode, the auxiliary electrode is soaked in a saturated KCl solution, and a salt bridge is used for connecting the saturated KCl solution and electrolyte. The electrolyte comprises the following components: 300g/LNiSO4·6H2O、40g/LH3BO3(ii) a pH2, deposition potential-3V, deposition time 300 s.
(3) Releasing the nanotubes:
and (3) soaking the anodized aluminum template subjected to the two-step electrodeposition in a post-treatment solution (1.5mol/L NaOH) for 1h, and sufficiently removing an oxide film to obtain the magnetic metal Ni nanotube.
Comparative example 2
Pulsed electrodeposition of nanotubes
(1) Sputtering a conductive layer: fixing the AAO template in a magnetron sputtering fixture at argon flow rate of 20sccm and air pressure of 4 × 10-4Pa, sputtering a layer of copper film under the condition of self bias of 175 Pa.
(2) Pulse electrodeposition: in a three-electrode system, an AAO template sputtered with copper is used as a working electrode, a platinum sheet is used as a counter electrode, a saturated calomel electrode is used as an auxiliary electrode, the auxiliary electrode is soaked in a saturated KCl solution, the counter electrode and the working electrode are soaked in an electrolyte, and the saturated KCl solution and the electrolyte are connected through a salt bridge. The electrolyte comprises the following components: 300g/L NiSO4·6H2O、45g/LNiCl2·6H2O、45g/L H3BO3(ii) a The pH was 3 and the deposition potential was a square wave pulse potential starting at 0V for 10s and then momentarily applying-3V for 1s for a total of 328 cycles of deposition for about 1 hour for 11s for one cycle, where a square wave potential was applied for one cycle as shown in FIG. 3.
(3) Releasing the nanotubes:
and soaking the deposited anodic alumina template in a 5% (wt) NaOH solution for 1.5h, and fully removing the alumina template to obtain the magnetic metal Ni nanotube.
FIG. 1 is a schematic diagram illustrating the formation of magnetic metal nanotubes according to the present invention; FIG. 2 shows a scanning electron microscope image of the magnetic Ni nanotube prepared in example 1 of the present invention; FIG. 3 shows a TEM image of the magnetic Ni nanotube prepared in example 1; FIG. 4 is an SEM photograph of a conventional Ni nanotube preparation method of comparative example 1; FIG. 5 is a TEM image of Ni nanotubes prepared by pulse deposition of comparative example 2; fig. 6 is an SEM image of Ni nanotubes prepared by the pulse deposition of comparative example 2. Compared with electron microscope images of the nanotubes prepared by traditional electrodeposition and pulse electrodeposition, the nanotubes prepared by the method have more uniform length and smoother and more uniform tube thickness, which shows that the method is an effective method for simply preparing high-quality nanotubes.
The raw materials and equipment used in the invention are common raw materials and equipment in the field if not specified; the methods used in the present invention are conventional in the art unless otherwise specified.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and all simple modifications, alterations and equivalents of the above embodiments according to the technical spirit of the present invention are still within the protection scope of the technical solution of the present invention.
Claims (9)
1. A method for preparing magnetic metal nanotubes by controlling electrodeposition conditions, characterized by comprising the steps of:
(a) preparing a template: preparing an anodic aluminum oxide template;
(b) constant potential deposition of nanotubes:
(b-1) preparation of salt bridges;
(b-2) sputtering of conductive layer: sputtering a layer of copper film on the anodic aluminum oxide template; after copper film plating, placing the electrolyte and the anodic alumina template in a nitrogen atmosphere for 1-3h, and then depositing a layer of Cu nano-rods at the pore canal at the bottom of the anodic alumina template in a Cu electrodeposition solution, wherein the deposition conditions are as follows: voltage is 0.7-0.9V, and time is 8-12 min; the component concentration of the Cu electrodeposition solution is 12-18g/L CuSO4·5H2O，35-45g/L H3BO；
(b-3) potentiostatic electrodeposition: in a three-electrode system, the anodic alumina template obtained in the step (b-2) is used as a working electrode, a platinum sheet is used as a counter electrode, and a saturated calomel electrode is used as an auxiliary electrode; soaking the auxiliary electrode in a saturated KCl solution, and connecting the saturated KCl solution and an electrolyte by using a salt bridge; the deposition conditions were: the pH is 2-3, the deposition potential is-1 to-3V, and the deposition time is 300 s-600 s;
the electrolyte has a composition selected from any one of the following three compositions:
20~40 g/L NiSO4•6H2O、45 ~60 g/L NaCl、45~60 g/L H3BO3；
20~40 g/L CoSO4•6H2O、45 ~60 g/L NaCl、45~60 g/L H3BO3；
20~40 g/L FeSO4•6H2o, 45-60 g/L NaCl, 15-30 g/L ascorbic acid, 45-60 g/L H3BO3；
(c) Releasing the magnetic metal nanotubes: and (c) soaking the anodic aluminum oxide template obtained in the step (b) in a post-treatment solution to remove the aluminum oxide template and the copper film, and obtaining the magnetic metal nanotube.
2. The method of claim 1, wherein the electrodeposition conditions are controlled to produce magnetic metal nanotubes, wherein: in the step (b-3), the deposition potential was-3V and the deposition time was 300 s.
3. A method for preparing magnetic metal nanotubes by controlling electrodeposition conditions as claimed in claim 1 or 2, wherein: in the step (b-3), the composition of the electrolyte is selected from any one of the following three compositions:
27 g/L NiSO4•6H2O、58 g/L NaCl、45 g/L H3BO3；
28 g/L CoSO4•6H2O、58 g/L NaCl、45 g/L H3BO3；
28 g/L FeSO4•6H2o, 58g/L NaCl, 10g/L ascorbic acid, 45g/L H3BO3。
4. The method of claim 1, wherein the template preparation in step (a) comprises:
(a-1) primary oxidation: placing the annealed and ultrasonically washed pretreated aluminum sheet in 0.3-0.5 mol/L oxalic acid aqueous solution, and carrying out electrochemical corrosion for 4-6 h under the conditions of 40-60V of voltage and 0-3 ℃ to obtain a primary aluminum oxide sheet;
(a-2) removing the primary oxide film: taking a primary oxidation aluminum sheet, soaking the primary oxidation aluminum sheet in a mixed aqueous solution of phosphoric acid and chromic acid at 50-70 ℃ for 12-16 h, and then cleaning the primary oxidation aluminum sheet with deionized water to obtain the aluminum sheet with the primary oxidation film removed;
in the mixed aqueous solution of phosphoric acid and chromic acid, the concentration of phosphoric acid is 3-6 wt%, and the concentration of chromic acid is 1-2 wt%;
(a-3) secondary oxidation: placing the aluminum sheet without the primary oxide film in 0.3-0.5 mol/L oxalic acid aqueous solution, electrochemically corroding for 6-8 h under the conditions of 80-90V voltage and 0-3 ℃ temperature, taking out, cleaning with deionized water, and placing in 1-3 mol/L CuCl2Soaking in the aqueous solution for 10-60 min, and then cleaning with deionized water to obtain an alumina template containing bi-pass nano-pores;
(a-4) reaming: placing an alumina template containing bi-pass nano-pores in 3-5 wt% of H at the temperature of 30-35 DEG C3PO4And (4) reaming the aqueous solution for 20-45 min to obtain the anodic aluminum oxide template.
5. The method for preparing magnetic metal nanotubes by controlling electrodeposition conditions as claimed in claim 4, wherein the aluminum sheet annealing and ultrasonic washing pretreatment method comprises: annealing the aluminum sheet at the temperature of 450-550 ℃ for 2-4 h, then carrying out ultrasonic treatment in acetone for 5-15min, then soaking in an alkaline solution for 5-10 min, and finally carrying out ultrasonic treatment in acetone for 3-5 min to finish the pretreatment.
6. The method for preparing magnetic metal nanotubes by controlling electrodeposition conditions as claimed in claim 4 or 5, wherein the thickness of the aluminum sheet is 50 to 60 μm.
7. The method for preparing magnetic metal nanotubes by controlling electrodeposition conditions as claimed in claim 1, wherein the preparation of the salt bridge in the step (b-1) comprises: adding 95-105 parts by weight of distilled water and 2.5-3.5 parts by weight of agar into a container, and heating in a water bath until the distilled water and the agar are completely dissolved; then adding 25-35 parts by weight of KCl to fully dissolve the mixture, finally pouring the mixture into a U-shaped thin glass tube while the mixture is hot, and obtaining a salt bridge after the agar is solidified.
8. The method for preparing magnetic metal nanotubes by controlling electrodeposition conditions as claimed in claim 1, wherein the step (b-2)In the method, the conditions for sputtering the conductive layer are as follows: the flow rate of argon gas is 10-30 sccm, and the pressure is 3-5 × 10-4Pa, and a self-bias voltage of 150 to 200 Pa.
9. The method for preparing magnetic metal nanotubes by controlling electrodeposition conditions as claimed in claim 1, wherein the post-treatment solution in the step (c) contains 0.25 to 0.35mol/L of copper chloride, 0.25 to 0.35mol/L of chromic acid and 0.25 to 0.35mol/L of boric acid for a soaking time of 50 to 70 min.
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