CN108277462B - method for preparing magnetic metal nano-tube by pulse electrodeposition - Google Patents
method for preparing magnetic metal nano-tube by pulse electrodeposition Download PDFInfo
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- 239000002071 nanotube Substances 0.000 title claims abstract description 94
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 65
- 239000002184 metal Substances 0.000 title claims abstract description 65
- 238000004070 electrodeposition Methods 0.000 title claims abstract description 64
- 238000000034 method Methods 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 claims abstract description 13
- 229910052782 aluminium Inorganic materials 0.000 claims description 54
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 54
- 239000007864 aqueous solution Substances 0.000 claims description 49
- 238000002791 soaking Methods 0.000 claims description 44
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 42
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 42
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 32
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 32
- 238000000151 deposition Methods 0.000 claims description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 29
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 28
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical class [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 28
- 239000008367 deionised water Substances 0.000 claims description 28
- 229910021641 deionized water Inorganic materials 0.000 claims description 28
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 26
- 239000010949 copper Substances 0.000 claims description 25
- 239000012266 salt solution Substances 0.000 claims description 24
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 23
- 229910052802 copper Inorganic materials 0.000 claims description 23
- 239000003792 electrolyte Substances 0.000 claims description 21
- 230000003647 oxidation Effects 0.000 claims description 20
- 238000007254 oxidation reaction Methods 0.000 claims description 20
- 239000011148 porous material Substances 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 17
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 16
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 claims description 16
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 claims description 16
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 16
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 14
- 238000004140 cleaning Methods 0.000 claims description 14
- 235000006408 oxalic acid Nutrition 0.000 claims description 14
- 238000004544 sputter deposition Methods 0.000 claims description 14
- 238000009210 therapy by ultrasound Methods 0.000 claims description 14
- 230000008021 deposition Effects 0.000 claims description 13
- 238000000137 annealing Methods 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 8
- 239000012670 alkaline solution Substances 0.000 claims description 8
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 claims description 8
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 8
- 150000002815 nickel Chemical class 0.000 claims description 8
- 229910052697 platinum Inorganic materials 0.000 claims description 8
- 229920001817 Agar Polymers 0.000 claims description 7
- 239000008272 agar Substances 0.000 claims description 7
- 229910052786 argon Inorganic materials 0.000 claims description 7
- 150000001868 cobalt Chemical class 0.000 claims description 7
- 238000005137 deposition process Methods 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 7
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 7
- 239000001103 potassium chloride Substances 0.000 claims description 7
- 235000011164 potassium chloride Nutrition 0.000 claims description 7
- 238000006056 electrooxidation reaction Methods 0.000 claims description 6
- 229960005070 ascorbic acid Drugs 0.000 claims description 4
- 239000002211 L-ascorbic acid Substances 0.000 claims description 3
- 235000000069 L-ascorbic acid Nutrition 0.000 claims description 3
- 241000080590 Niso Species 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 claims description 2
- 229910021577 Iron(II) chloride Inorganic materials 0.000 claims description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 7
- 230000008859 change Effects 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 230000002349 favourable effect Effects 0.000 abstract description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 238000000231 atomic layer deposition Methods 0.000 description 3
- 239000002041 carbon nanotube Substances 0.000 description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 description 3
- 238000001465 metallisation Methods 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
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- 229910021389 graphene Inorganic materials 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 239000002082 metal nanoparticle Substances 0.000 description 2
- 239000011800 void material Substances 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000007772 electroless plating Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- WHQSYGRFZMUQGQ-UHFFFAOYSA-N n,n-dimethylformamide;hydrate Chemical compound O.CN(C)C=O WHQSYGRFZMUQGQ-UHFFFAOYSA-N 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/3485—Sputtering using pulsed power to the target
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/0005—Separation of the coating from the substrate
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- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/02—Pretreatment of the material to be coated
- C23C14/024—Deposition of sublayers, e.g. to promote adhesion of the coating
- C23C14/025—Metallic sublayers
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- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/14—Metallic material, boron or silicon
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- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
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Abstract
The invention relates to methods for preparing magnetic metal nanotubes by pulse electrodeposition, which have great potential application prospects in the aspect of magnetic recording materials, the method has the advantages of simplicity, convenience and strong operability, can effectively control the length and the diameter of the prepared magnetic metal nanotubes, has low cost, has low requirement on the precision of required instruments and strong applicability, can prepare various magnetic metal nanotubes, is not limited to preparing single magnetic metal nanotubes, does not obviously change the process steps, and is favorable for mass production and preparation.
Description
Technical Field
The invention relates to the field of metal nanotube preparation methods, in particular to methods for preparing magnetic metal nanotubes by pulse electrodeposition, which have great potential application prospects in the aspect of magnetic recording materials.
Background
At present, the synthesis methods of magnetic metal nanotubes mainly include electroless plating, Atomic Layer Deposition (ALD), sol-gel (sol-gel), 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. In addition, none of the above methods can adjust the properties of the nanotubes by controlling the length and diameter of the nanotubes.
The template-assisted electrochemical deposition has great advantages in the preparation of metal magnetic nanotube arrays, can conveniently control the components and the structure of the nanotubes, and has strong operability, simplicity and convenience, so far, series metal nanotube arrays are prepared by the traditional electrochemical deposition method, but the aspect has higher requirements on a conductive layer, and in addition, the aspect introduces impurities to seriously affect the performance of the material.
The patent office in china discloses patent grant of a method for preparing a metal nanoparticle/graphene/carbon nanotube material on 6.13.2017, and publication number CN105251979B provides technical methods for preparing a metal nanoparticle/graphene/carbon nanotube nanocomposite material with low infrared emissivity by dispersing a metal salt solution, graphite oxide and a carbon nanotube in water, ethanol and N, N-dimethylformamide lamp solvent for irradiation, which can prepare a composite nanotube material with specific properties, but compared with a conventional method , the method has the problems that the length and diameter of the nanotube cannot be controlled, the preparation of a high-quality magnetic metal nanotube cannot be performed, the cost is too high, and only a specific kind of nanotube can be prepared by a single method.
Disclosure of Invention
In order to solve the problems that the length and the diameter of a nanotube cannot be controlled, high cost cannot be realized for preparing a high-quality magnetic metal nanotube, only a specific type of nanotube can be prepared by a single method and the like in the prior art, methods for preparing the magnetic metal nanotube by pulse electrodeposition are provided, wherein the methods can control the length and the diameter of the nanotube, and have the advantages of low cost, simple process and application range.
In order to achieve the purpose, the invention adopts the following technical scheme:
A method for preparing magnetic metal nanotubes by pulse electrodeposition, the method for preparing magnetic metal nanotubes by pulse electrodeposition comprises the following steps:
(a) template preparation
(a-1) times of oxidation, namely placing the annealed and ultrasonically washed pretreated aluminum sheet in 0.3-0.5 mol/L oxalic acid aqueous solution, and electrochemically corroding the aluminum sheet for 4-6 hours under the conditions of 40-60V of voltage and 0-3 ℃ to obtain a times of oxidized aluminum sheet;
(a-2) removing times of oxide films, namely, placing the times of aluminum oxide sheets prepared in the step (a-1) in a mixed aqueous solution of phosphoric acid and chromic acid at 50-70 ℃ for soaking for 12-16 h, and then cleaning the aluminum sheets by using deionized water to obtain aluminum sheets from which times of oxide films are removed;
(a-3) secondary oxidation, namely placing the aluminum sheet obtained in the step (a-2) and subjected to times of oxide film removal in 0.3-0.5 mol/L oxalic acid aqueous solution, electrochemically corroding for 6-8 hours under the conditions of 80-90V voltage and 0-3 ℃, taking out, washing with deionized water, and placing in 1-3 mol/LCuCl2Soaking 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 the alumina template containing the bi-pass nano-pores obtained in the step (a-3) in 3-5 wt% of H at the temperature of 30-35 DEG C3PO4Reaming in the aqueous solution for 20-45 min to obtain an anodic aluminum oxide template;
(b) pulsed electrodeposition of nanotubes
(b-1) sputtering of conductive layer: fixing the anodized aluminum template obtained in the step (a-4) in a magnetron sputtering fixture at an argon flow rate of 10-30 sccm and a gas pressure of 3-5 × 10-4Pa, sputtering layers of copper films under the condition of self bias of 150-200 Pa;
(b-2) pulse electrodeposition, namely constructing a three-electrode system, taking the anodic aluminum oxide template sputtered with the copper film obtained in the step (b-1) as a working electrode, a platinum sheet as a counter electrode and a saturated calomel electrode as an auxiliary electrode, soaking the auxiliary electrode in a saturated KCl solution, soaking the counter electrode and the working electrode in an electrolyte, connecting the saturated KCl solution and the electrolyte by a salt bridge for electrodeposition, wherein the deposition potential is square-wave pulse potential, firstly depositing at 0V for 10-15 s, then depositing at-3V for 1-3 s, and taking cycles as the deposition process, and totally performing 164-492 cycles;
(c) releasing nanotubes
And (b-2) soaking the electrodeposited anodic alumina template in an alkaline solution to remove the alumina template and the copper film, and obtaining the magnetic metal nanotube.
Preferably, the aluminum sheet annealing and ultrasonic washing pretreatment in the step (a-1) is as follows: annealing an aluminum sheet at 500 ℃ for 2-4 h, performing ultrasonic treatment in acetone for 10min, soaking in an alkaline solution for 5-10 min, and performing ultrasonic treatment in acetone for 3-5 min, wherein the aluminum sheet is a 50-60 mu m thick sheet.
Preferably, the alkaline solution in the pretreatment is a 5wt% aqueous sodium hydroxide solution.
Preferably, the phosphoric acid and chromic acid mixed aqueous solution in the step (a-2) has a phosphoric acid concentration of 3 to 6wt% and a chromic acid concentration of 1 to 2 wt%.
Preferably, the salt bridge in the step (b-2) contains the following raw materials in parts by weight: 0.95-1.0 part of agar, 8-12 parts of potassium chloride and 25-35 parts of deionized water.
Preferably, the electrolyte in step (b-2) includes, but is not limited to: nickel salt solution, cobalt salt solution and ferrous salt solution.
Preferably, the nickel salt solution is dissolved with 300-400 g/L NiSO4•6H2O、45～60g/L NiCl2•6H2O and 45-60 g/L H3BO3The pH value of the nickel salt solution is 3-5.
Preferably, the cobalt salt solution is dissolved with 300-400 g/L CoSO4•6H2O、45～60 g/L CoCl2•6H2O and 45-60 g/L H3BO3The pH value of the cobalt salt solution is 3-5.
Preferably, the ferrous salt solution is dissolved with 300-400 g/LFeSO4•6H2O、45～60 g/L FeCl2•6H2O, 15-30 g/L ascorbic acid and 45-60 g/L H3BO3The pH value of the ferrous salt solution is 3-5.
Preferably, the alkaline solution in step (c) is a 5wt% sodium hydroxide aqueous solution, and the soaking time is 0.5-2 h.
Pulse electrodeposition is novel electroplating processes developed in recent years, the relaxation of current or voltage pulses can increase the activation polarization of a cathode and reduce the concentration change of the cathode, the purity, density and uniformity of a deposition layer are improved, the void ratio of the deposition layer is reduced, the quality of the deposition layer is improved, compared with common electrodeposition in the prior art, the prepared nanotube has higher purity and fewer voids, and the quality of the nanotube is improved.
The basic template is removed by adopting twice oxidation for times, and a reaming process is carried out, so that high-quality anode templates are provided for preparing the magnetic metal nanotubes by the subsequent pulse electrodeposition, and favorable preconditions are provided for preparing the high-quality magnetic metal nanotubes subsequently.
The sputtered copper film provides a conductive layer, is convenient to remove, greatly reduces the impurity content in the prepared magnetic nano tube, and can relatively improve the performance of the prepared magnetic metal nano tube material.
The three-electrode system provides complete and stable electrodeposition environments, and a pulse electrodeposition mode is adopted, so that the purity, the density and the uniformity of the prepared magnetic metal deposition layer are greatly improved, the void ratio of the magnetic metal deposition layer is reduced, and the quality of the magnetic metal deposition layer is improved.
The invention has the beneficial effects that:
1) the method for preparing the magnetic metal nanotube by pulse electrodeposition has the advantages of simplicity, convenience and strong operability;
2) the method provided by the invention can effectively control the length and the diameter of the prepared magnetic metal nanotube;
3) the method provided by the invention has the advantages of low cost, low requirement on the precision of the required instrument and strong applicability;
4) the method provided by the invention can be used for preparing various magnetic metal nanotubes, is not limited to the preparation of the magnetic metal nanotube of the single , does not obviously change the process steps, and is beneficial to mass production and preparation.
Drawings
FIG. 1 is a schematic view of an apparatus of the present invention;
FIG. 2 is a schematic diagram of nanotube formation;
FIG. 3 is a schematic diagram of square wave potential applied for cycles during pulsed electrodeposition;
FIG. 4 is a scanning electron microscope image of the surface of a template prepared according to the present invention;
FIG. 5 is a scanning electron microscope image of a cross section of a template prepared according to the present invention;
FIG. 6 is a projection electron microscope image of the magnetic metal Ni nanotube prepared by the present invention;
in the figure, 1 saturated calomel electrode, 2 platinum sheet electrodes, 3 anodic alumina template sputtered with copper film, 4 salt bridge, 5 electrochemical work stations.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below with reference to the embodiments of the present invention and the drawings attached to the specification, and it is obvious that the described embodiments are only partial embodiments of of the present invention, rather than all embodiments.
The apparatus is constructed according to FIG. 1, as described in FIG. 1
Example 1
A method for preparing magnetic metal nanotubes by pulse electrodeposition, the method for preparing magnetic metal nanotubes by pulse electrodeposition comprises the following steps:
(a) template preparation
(a-1) times of oxidation, namely, placing the aluminum sheet at 500 ℃ for annealing for 4h, then carrying out ultrasonic treatment in acetone for 10min, then soaking in 5wt% of sodium hydroxide aqueous solution for 5min, carrying out ultrasonic treatment in acetone for 3min, then placing the pretreated aluminum sheet in 0.3mol/L oxalic acid aqueous solution, and carrying out electrochemical corrosion for 4h at the voltage of 40V and the temperature of 0 ℃ to obtain an aluminum oxide sheet times;
(a-2) removing times of oxide films, namely, taking times of aluminum oxide sheets prepared in the step (a-1), soaking the aluminum sheets in a mixed aqueous solution of phosphoric acid and chromic acid with the phosphoric acid concentration of 6wt% and the chromic acid concentration of 1.5wt% at 65 ℃ for 12 hours, and then cleaning the aluminum sheets with deionized water to obtain the aluminum sheets with times of oxide films removed;
(a-3) Secondary Oxidation the times oxidized film-removed aluminum sheet obtained in step (a-2) was placed in 0.3mol/L oxalic acid aqueous solution at 80V voltage and temperatureElectrochemically corroding at 0 deg.C for 8h, taking out, washing with deionized water, and placing in 1mol/LCuCl2Soaking in the aqueous solution for 30min, and then cleaning with deionized water to obtain an alumina template with bi-pass nano-pores;
(a-4) reaming: placing the alumina template containing double-pass nano-pores obtained in the step (a-3) in 5wt% of H at the temperature of 35 DEG C3PO4Reaming for 45min in the aqueous solution to obtain an anodic aluminum oxide template;
(b) pulsed electrodeposition of nanotubes
(b-1) sputtering of conductive layer: fixing the anodized aluminum template obtained in the step (a-4) in a magnetron sputtering fixture at an argon flow rate of 20sccm and a gas pressure of 4 × 10-4Pa, sputtering layers of copper films under the condition of self bias of 175 Pa;
(b-2) pulse electrodeposition, namely constructing a three-electrode system, taking the anodic aluminum oxide template sputtered with the copper film obtained in the step (b-1) as a working electrode, taking a platinum sheet as a counter electrode and taking a saturated calomel electrode as an auxiliary electrode, soaking the auxiliary electrode in a saturated KCl solution, soaking the counter electrode and the working electrode in an electrolyte, connecting the saturated KCl solution and the electrolyte by a salt bridge for electrodeposition, wherein the deposition potential is square-wave pulse potential, firstly depositing for 10s at 0V, then depositing for 1s at-3V, and taking cycles, and the deposition process is totally carried out for 328 cycles, wherein square-wave potentials added in cycles are shown in figure 3;
(c) releasing nanotubes
And (b-2) soaking the anode alumina template subjected to electrodeposition in a 5wt% sodium hydroxide aqueous solution for 1.5h, and removing the alumina template and the copper film to obtain the magnetic metal nanotube.
In the embodiment, an aluminum sheet with the thickness of 50 μm is selected; the salt bridge contains 1.0 part of agar, 10 parts of potassium chloride and 29 parts of deionized water; the electrolyte used in step (b-2) of this example was NiSO at 300g/L4•6H2O、45g/LNiCl2•6H2O and 45g/L H3BO3The pH value of the nickel salt solution is 3; the prepared magnetic metal nanotube is a magnetic metal Ni nanotube.
Example 2
A method for preparing magnetic metal nanotubes by pulse electrodeposition, the method for preparing magnetic metal nanotubes by pulse electrodeposition comprises the following steps:
(a) template preparation
(a-1) times of oxidation, namely, placing the aluminum sheet at 500 ℃ for annealing for 4h, then carrying out ultrasonic treatment in acetone for 10min, then soaking in 5wt% of sodium hydroxide aqueous solution for 5min, carrying out ultrasonic treatment in acetone for 3min, then placing the pretreated aluminum sheet in 0.3mol/L oxalic acid aqueous solution, and carrying out electrochemical corrosion for 4h at the voltage of 40V and the temperature of 0 ℃ to obtain an aluminum oxide sheet times;
(a-2) removing times of oxide films, namely, taking times of aluminum oxide sheets prepared in the step (a-1), soaking the aluminum sheets in a mixed aqueous solution of phosphoric acid and chromic acid with the phosphoric acid concentration of 6wt% and the chromic acid concentration of 1.5wt% at 65 ℃ for 12 hours, and then cleaning the aluminum sheets with deionized water to obtain the aluminum sheets with times of oxide films removed;
(a-3) secondary oxidation, namely placing the aluminum sheet obtained in the step (a-2) and removed with the times oxidation film in 0.5mol/L oxalic acid aqueous solution, electrochemically corroding for 8 hours under the conditions of 80V voltage and 0 ℃, taking out, washing with deionized water, and placing in 1mol/LCuCl2Soaking in the aqueous solution for 30min, and then cleaning with deionized water to obtain an alumina template with bi-pass nano-pores;
(a-4) reaming: placing the alumina template containing double-pass nano-pores obtained in the step (a-3) in 5wt% of H at the temperature of 35 DEG C3PO4Reaming for 45min in the aqueous solution to obtain an anodic aluminum oxide template;
(b) pulsed electrodeposition of nanotubes
(b-1) sputtering of conductive layer: fixing the anodized aluminum template obtained in the step (a-4) in a magnetron sputtering fixture at an argon flow rate of 10sccm and a gas pressure of 3X 10-4Pa, sputtering layers of copper films under the condition of self bias of 150 Pa;
(b-2) pulse electrodeposition, namely constructing a three-electrode system, taking the anodic aluminum oxide template sputtered with the copper film obtained in the step (b-1) as a working electrode, taking a platinum sheet as a counter electrode and taking a saturated calomel electrode as an auxiliary electrode, soaking the auxiliary electrode in a saturated KCl solution, soaking the counter electrode and the working electrode in an electrolyte, connecting the saturated KCl solution and the electrolyte by a salt bridge for electrodeposition, wherein the deposition potential is square-wave pulse potential, firstly depositing for 10s at 0V, then depositing for 1s at-3V, and taking cycles, and the deposition process is totally carried out for 328 cycles, wherein square-wave potentials added in cycles are shown in figure 3;
(c) releasing nanotubes
And (b-2) soaking the anode alumina template subjected to electrodeposition in a 5wt% sodium hydroxide aqueous solution for 1.5h, and removing the alumina template and the copper film to obtain the magnetic metal nanotube.
In the embodiment, an aluminum sheet with the thickness of 60 mu m is selected; the salt bridge contains 1.0 part of agar, 10 parts of potassium chloride and 29 parts of deionized water; the electrolyte used in step (b-2) of this example was FeSO at 300g/L4•6H2O、45 g/LFeCl2•6H2O、45g/L H3BO3And 15g/L ferrous salt solution of ascorbic acid, pH 3; the prepared magnetic metal nanotube is a magnetic metal Fe nanotube.
Example 3
A method for preparing magnetic metal nanotubes by pulse electrodeposition, the method for preparing magnetic metal nanotubes by pulse electrodeposition comprises the following steps:
(a) template preparation
(a-1) times of oxidation, namely, placing the aluminum sheet at 500 ℃ for annealing for 4h, then carrying out ultrasonic treatment in acetone for 10min, then soaking in 5wt% of sodium hydroxide aqueous solution for 5min, carrying out ultrasonic treatment in acetone for 3min, then placing the pretreated aluminum sheet in 0.3mol/L oxalic acid aqueous solution, and carrying out electrochemical corrosion for 4h at the voltage of 40V and the temperature of 0 ℃ to obtain an aluminum oxide sheet times;
(a-2) removing times of oxide films, namely, taking times of aluminum oxide sheets prepared in the step (a-1), soaking the aluminum sheets in a mixed aqueous solution of phosphoric acid and chromic acid with the phosphoric acid concentration of 6wt% and the chromic acid concentration of 1.5wt% at 65 ℃ for 12 hours, and then cleaning the aluminum sheets with deionized water to obtain the aluminum sheets with times of oxide films removed;
(a-3) secondary oxidation, namely placing the aluminum sheet obtained in the step (a-2) and removed with the times oxidation film in 0.5mol/L oxalic acid aqueous solution, electrochemically corroding for 8 hours under the conditions of 80V voltage and 0 ℃, taking out, washing with deionized water, and placing in 1mol/LCuCl2Soaking in the aqueous solution for 30min, and then cleaning with deionized water to obtain an alumina template with bi-pass nano-pores;
(a-4) reaming: placing the alumina template containing double-pass nano-pores obtained in the step (a-3) in 5wt% of H at the temperature of 35 DEG C3PO4Reaming for 45min in the aqueous solution to obtain an anodic aluminum oxide template;
(b) pulsed electrodeposition of nanotubes
(b-1) sputtering of conductive layer: fixing the anodic alumina template obtained in the step (a-4) in a magnetron sputtering fixture at an argon flow rate of 30sccm and a gas pressure of 5 × 10-4Pa, sputtering layers of copper films under the condition of self bias voltage of 200 Pa;
(b-2) pulse electrodeposition, namely constructing a three-electrode system, taking the anodic aluminum oxide template sputtered with the copper film obtained in the step (b-1) as a working electrode, taking a platinum sheet as a counter electrode and taking a saturated calomel electrode as an auxiliary electrode, soaking the auxiliary electrode in a saturated KCl solution, soaking the counter electrode and the working electrode in an electrolyte, connecting the saturated KCl solution and the electrolyte by a salt bridge for electrodeposition, wherein the deposition potential is square-wave pulse potential, firstly depositing for 10s at 0V, then depositing for 1s at-3V, and taking cycles, and the deposition process is totally carried out for 328 cycles, wherein square-wave potentials added in cycles are shown in figure 3;
(c) releasing nanotubes
And (b-2) soaking the anode alumina template subjected to electrodeposition in a 5wt% sodium hydroxide aqueous solution for 1.5h, and removing the alumina template and the copper film to obtain the magnetic metal nanotube.
In the embodiment, an aluminum sheet with the thickness of 60 mu m is selected; the salt bridge contains 1.0 part of agar, 10 parts of potassium chloride and 29 parts of deionized water; the electrolyte used in step (b-2) of this example was CoSO at 300g/L4•6H2O、45 g/LCoCl2•6H2O and 45g/L H3BO3The cobalt salt solution of (3), pH value; the prepared magnetic metal nanotube is a magnetic metal Co nanotube.
Example 4
A method for preparing magnetic metal nanotubes by pulse electrodeposition, the method for preparing magnetic metal nanotubes by pulse electrodeposition comprises the following steps:
(a) template preparation
(a-1) times of oxidation, namely, placing the aluminum sheet at 500 ℃ for annealing for 2h, then carrying out ultrasonic treatment in acetone for 10min, then soaking in 5wt% of sodium hydroxide aqueous solution for 5min, carrying out ultrasonic treatment in acetone for 3min, then placing the pretreated aluminum sheet in 0.3mol/L oxalic acid aqueous solution, and carrying out electrochemical corrosion for 4h at the voltage of 40V and the temperature of 0 ℃ to obtain an aluminum oxide sheet times;
(a-2) removing times of oxide films, namely, placing the times of aluminum oxide sheets prepared in the step (a-1) in a mixed aqueous solution of phosphoric acid and chromic acid with the phosphoric acid concentration of 3wt% and the chromic acid concentration of 1wt% at 50 ℃ for soaking for 12 hours, and then, cleaning the aluminum sheets with deionized water to obtain the aluminum sheets with the times of oxide films removed;
(a-3) secondary oxidation, namely placing the aluminum sheet obtained in the step (a-2) and removed with the times oxidation film in 0.3mol/L oxalic acid aqueous solution, electrochemically corroding for 6 hours under the conditions of 80V voltage and 0 ℃, taking out, washing with deionized water, and placing in 1mol/LCuCl2Soaking in the aqueous solution for 10min, and then cleaning with deionized water to obtain an alumina template with bi-pass nano-pores;
(a-4) reaming: placing the alumina template containing double-pass nano-pores obtained in the step (a-3) in 3wt% of H at the temperature of 30 DEG C3PO4Reaming in the aqueous solution for 20min to obtain an anodic aluminum oxide template;
(b) pulsed electrodeposition of nanotubes
(b-1) sputtering of conductive layer: fixing the anodized aluminum template obtained in the step (a-4) in a magnetron sputtering fixture at an argon flow rate of 10sccm and a gas pressure of 3X 10-4Pa, sputtering layers of copper films under the condition of self bias of 150 Pa;
(b-2) pulse electrodeposition, namely constructing a three-electrode system, taking the anodic aluminum oxide template sputtered with the copper film obtained in the step (b-1) as a working electrode, a platinum sheet as a counter electrode and a saturated calomel electrode as an auxiliary electrode, soaking the auxiliary electrode in a saturated KCl solution, soaking the counter electrode and the working electrode in an electrolyte, connecting the saturated KCl solution and the electrolyte by a salt bridge for electrodeposition, wherein the deposition potential is square-wave pulse potential, firstly depositing for 10s at 0V, then depositing for 1s at-3V, and taking cycles as the basis, wherein the deposition process is totally carried out for 164 cycles;
(c) releasing nanotubes
And (b-2) soaking the anode alumina template subjected to electrodeposition in a 5wt% sodium hydroxide aqueous solution for 0.5h, and removing the alumina template and the copper film to obtain the magnetic metal nanotube.
In the embodiment, an aluminum sheet with the thickness of 50 μm is selected; the salt bridge contains raw materials of 0.95 parts of agar, 8 parts of potassium chloride and 25 parts of deionized water; the electrolyte used in step (b-2) of this example was NiSO at 400g/L4•6H2O、60g/LNiCl2•6H2O and 60g/L H3BO3The pH value of the nickel salt solution is 5; the prepared magnetic metal nanotube is a magnetic metal Ni nanotube.
Example 5
A method for preparing magnetic metal nanotubes by pulse electrodeposition, the method for preparing magnetic metal nanotubes by pulse electrodeposition comprises the following steps:
(a) template preparation
(a-1) times of oxidation, namely, placing the aluminum sheet at 500 ℃ for annealing for 4h, then carrying out ultrasonic treatment in acetone for 10min, then soaking in a 5wt% sodium hydroxide aqueous solution for 10min, carrying out ultrasonic treatment in acetone for 5min, then placing the pretreated aluminum sheet in a 0.5mol/L oxalic acid aqueous solution, and carrying out electrochemical corrosion at the voltage of 60V and the temperature of 3 ℃ for 6h to obtain an aluminum oxide sheet times;
(a-2) removing times of oxide films, namely, placing the times of aluminum oxide sheets prepared in the step (a-1) in a mixed aqueous solution of phosphoric acid and chromic acid with the phosphoric acid concentration of 6wt% and the chromic acid concentration of 2wt% at 70 ℃ for soaking for 16h, and then cleaning the aluminum sheets with deionized water to obtain the aluminum sheets with the times of oxide films removed;
(a-3) secondary oxidation, namely placing the aluminum sheet obtained in the step (a-2) and removed with the times oxidation film in 0.5mol/L oxalic acid aqueous solution, electrochemically corroding for 8 hours under the conditions of 90V voltage and 3 ℃, taking out, washing with deionized water, and placing in 3mol/LCuCl2Soaking in the aqueous solution for 60min, and then cleaning with deionized water to obtain an alumina template with bi-pass nano-pores;
(a-4) reaming: placing the alumina template containing double-pass nano-pores obtained in the step (a-3) in 5wt% of H at the temperature of 35 DEG C3PO4Reaming for 45min in the aqueous solution to obtain an anodic aluminum oxide template;
(b) pulsed electrodeposition of nanotubes
(b-1) sputtering of conductive layer: fixing the anodic alumina template obtained in the step (a-4) in a magnetron sputtering fixture at an argon flow rate of 30sccm and a gas pressure of 5 × 10-4Pa, sputtering layers of copper films under the condition of self bias voltage of 200 Pa;
(b-2) pulse electrodeposition, namely constructing a three-electrode system, taking the anodic aluminum oxide template sputtered with the copper film obtained in the step (b-1) as a working electrode, a platinum sheet as a counter electrode and a saturated calomel electrode as an auxiliary electrode, soaking the auxiliary electrode in a saturated KCl solution, soaking the counter electrode and the working electrode in an electrolyte, connecting the saturated KCl solution and the electrolyte by a salt bridge for electrodeposition, wherein the deposition potential is square-wave pulse potential, firstly depositing for 15s at 0V, then depositing for 3s at-3V, and taking cycles as the basis, wherein the deposition process is totally 492 cycles;
(c) releasing nanotubes
And (b-2) soaking the electrodeposited anodic alumina template in a 5wt% sodium hydroxide aqueous solution for 2 hours, and removing the alumina template and the copper film to obtain the magnetic metal nanotube.
In the embodiment, an aluminum sheet with the thickness of 60 mu m is selected; the salt bridge contains 1.0 part of agar, 12 parts of potassium chloride and 35 parts of deionized water; the electrolyte used in step (b-2) of this example was FeSO at 400g/L4•6H2O、60 g/LFeCl2•6H2O, 30 g/L ascorbic acid and 60g/L H3BO3The pH value of the ferrous salt solution is 5; the prepared magnetic metal nanotube is a magnetic metal Fe nanotube.
Comparative example
Depositing high-purity Al on an n-type silicon substrate, then obtaining a PAA/Si porous membrane through anodic oxidation, and synthesizing the Ni nanotube with high filling rate by taking the PAA/Si porous membrane as a template when the potential is more negative.
Mechanism research shows that the electrodeposition is realized through electric breakdown of the template, the more negative the potential is, the higher the charge of the pore wall is, so that the electrodeposition is preferentially carried out on the pore wall, and the pore openings of the template are closed before the pore channels are completely filled, so that the tubular structure is ensured to be formed.
The method used by the comparative example takes Al as a conductive substrate, and the conductivity is not high enough than Cu, so the deposition rate of the nanotube is not high enough; secondly, the point location of the method is not well controlled and is difficult to operate, and the template is easy to puncture if the point location is over negative, so that the template is damaged.
Compared with the existing nanotube deposition method, the method has the advantages of simple operation, good point control, no influence on the template, good conductivity of the Cu substrate, and high deposition rate of the nanotube, and can be used for carrying out scanning electron microscope detection on the surface and the cross section of the template used in the embodiment 1 and carrying out scanning electron microscope detection on the magnetic metal Ni nanotube prepared in the embodiment 1, and the result is shown as a scanning electron microscope picture of the surface of the template in fig. 4, a scanning electron microscope picture of the cross section of the template in fig. 5, and a scanning electron microscope picture of the magnetic metal Ni nanotube prepared in the embodiment 1 in fig. 6.
Claims (10)
1, methods for preparing magnetic metal nanotubes by pulse electrodeposition, which is characterized by comprising the following steps:
(a) template preparation
(a-1) times of oxidation, namely placing the annealed and ultrasonically washed pretreated aluminum sheet in 0.3-0.5 mol/L oxalic acid aqueous solution, and electrochemically corroding for 4-6 hours to obtain times of aluminum oxide sheet;
(a-2) removing times of oxide films, namely, placing the times of aluminum oxide sheets prepared in the step (a-1) in a mixed aqueous solution of phosphoric acid and chromic acid at 50-70 ℃ for soaking for 12-16 h, and then cleaning the aluminum sheets by using deionized water to obtain aluminum sheets from which times of oxide films are removed;
(a-3) secondary oxidation, namely placing the aluminum sheet obtained in the step (a-2) and subjected to times of oxide film removal in 0.3-0.5 mol/L oxalic acid aqueous solution, electrochemically corroding for 6-8 hours under the conditions of 80-90V voltage and 0-3 ℃, taking out, washing with deionized water, and placing in 1-3 mol/LCuCl2Soaking 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 the alumina template containing the bi-pass nano-pores obtained in the step (a-3) in 3-5 wt% of H at the temperature of 30-35 DEG C3PO4Reaming in the aqueous solution for 20-45 min to obtain an anodic aluminum oxide template;
(b) pulsed electrodeposition of nanotubes
(b-1) sputtering of conductive layer: fixing the anodized aluminum template obtained in the step (a-4) in a magnetron sputtering fixture at an argon flow rate of 10-30 sccm and a gas pressure of 3-5 × 10-4Pa, sputtering layers of copper films under the condition of self bias of 150-200 Pa;
(b-2) pulse electrodeposition, namely constructing a three-electrode system, wherein the deposition potential is square-wave pulse potential, depositing for 10-15 s at 0V, then depositing for 1-3 s at-3V, and performing cycles with the deposition potential as well as 164-492 cycles in total in the deposition process;
(c) releasing nanotubes
And (b-2) soaking the electrodeposited anodic alumina template in an alkaline solution to remove the alumina template and the copper film, and obtaining the magnetic metal nanotube.
2. The method for preparing magnetic metal nanotubes by pulse electrodeposition according to claim 1, wherein the annealing and ultrasonic washing pretreatment of the aluminum sheet in step (a-1) comprises annealing the aluminum sheet at 500 ℃ for 2-4 h, performing ultrasonic treatment in acetone for 10min, soaking in alkaline solution for 5-10 min, and performing ultrasonic treatment in acetone for 3-5 min, wherein the aluminum sheet is a thin sheet with a thickness of 50-60 μm, and the electrochemical corrosion is performed at a voltage of 40-60V and a temperature of 0-3 ℃.
3. The method for preparing magnetic metal nanotubes by pulse electrodeposition as claimed in claim 2, wherein the alkaline solution in the pretreatment is a 5wt% aqueous solution of sodium hydroxide.
4. The method of kinds of pulse electrodeposition for producing magnetic metal nanotubes as claimed in claim 1 or 2, wherein the phosphoric acid and chromic acid mixed aqueous solution in the step (a-2) has a phosphoric acid concentration of 3 to 6wt% and a chromic acid concentration of 1 to 2 wt%.
5. The method for preparing magnetic metal nanotubes by pulse electrodeposition according to claim 1 or 2, wherein the three-electrode system constructed in step (b-2) comprises the steps of using the anodic alumina template of the sputtered copper film obtained in step (b-1) as a working electrode, using a platinum sheet as a counter electrode, using a saturated calomel electrode as an auxiliary electrode, soaking the auxiliary electrode in a saturated KCl solution, soaking the counter electrode and the working electrode in an electrolyte, and then connecting the saturated KCl solution and the electrolyte by a salt bridge for electrodeposition, wherein the salt bridge comprises the following raw materials, by weight, 0.95-1.0 part of agar, 8-12 parts of potassium chloride and 25-35 parts of deionized water.
6. The method for preparing magnetic metal nanotubes by pulse electrodeposition as claimed in claim 1 or 2, wherein the electrolyte in step (b-2) includes but is not limited to nickel salt solution, cobalt salt solution and ferrous salt solution.
7. The method for preparing magnetic metal nanotubes by pulse electrodeposition according to claim 6, wherein the nickel salt solution is NiSO dissolved with 300-400 g/L4•6H2O、45～60g/L NiCl2•6H2O and 45-60 g/L H3BO3The pH value of the nickel salt solution is 3-5.
8. The method for preparing magnetic metal nanotubes by pulse electrodeposition according to claim 6, wherein the cobalt salt solution is CoSO dissolved in 300-400 g/L4•6H2O、45～60 g/L CoCl2•6H2O and 45-60 g/L H3BO3The pH value of the cobalt salt solution is 3-5.
9. The method for preparing magnetic metal nanotubes by pulse electrodeposition as claimed in claim 6, wherein the ferrous salt solution is FeSO dissolved with 300-400 g/L4•6H2O、45～60 g/L FeCl2•6H2O, 15-30 g/L ascorbic acid and 45-60 g/L H3BO3The pH value of the ferrous salt solution is 3-5.
10. The kinds of pulse electrodeposition method for preparing magnetic metal nanotubes of claim 1 or 2, wherein the alkaline solution in step (c) is 5wt% aqueous sodium hydroxide solution, and the soaking time is 0.5-2 h.
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