CN115893528B - Magnetic metal nanotube with controllable specific surface pipe diameter and preparation method and application thereof - Google Patents
Magnetic metal nanotube with controllable specific surface pipe diameter and preparation method and application thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 20
- 239000002184 metal Substances 0.000 title claims abstract description 20
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 81
- 239000002243 precursor Substances 0.000 claims abstract description 52
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 38
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims abstract description 35
- 229910000480 nickel oxide Inorganic materials 0.000 claims abstract description 33
- 238000009987 spinning Methods 0.000 claims abstract description 25
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims abstract description 24
- 150000002815 nickel Chemical class 0.000 claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 10
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 10
- 239000004745 nonwoven fabric Substances 0.000 claims abstract description 8
- 229920002239 polyacrylonitrile Polymers 0.000 claims abstract description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000010000 carbonizing Methods 0.000 claims abstract description 6
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 6
- 239000001301 oxygen Substances 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims description 10
- 238000004140 cleaning Methods 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 239000000835 fiber Substances 0.000 claims description 8
- 238000001291 vacuum drying Methods 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 239000000243 solution Substances 0.000 description 65
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 229910052759 nickel Inorganic materials 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 5
- 239000002041 carbon nanotube Substances 0.000 description 5
- 229910021393 carbon nanotube Inorganic materials 0.000 description 5
- 239000011259 mixed solution Substances 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- 238000005520 cutting process Methods 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
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- 239000000203 mixture Substances 0.000 description 4
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000002131 composite material Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000009713 electroplating Methods 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
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- GNMQOUGYKPVJRR-UHFFFAOYSA-N nickel(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ni+3].[Ni+3] GNMQOUGYKPVJRR-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
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- 229910021543 Nickel dioxide Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
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- 238000012377 drug delivery Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
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- 239000012528 membrane Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002073 nanorod Substances 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- MRHPUNCYMXRSMA-UHFFFAOYSA-N nickel(2+) oxygen(2-) Chemical compound [O--].[O--].[Ni++] MRHPUNCYMXRSMA-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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Abstract
The invention discloses a magnetic metal nanotube with controllable specific surface pipe diameter, and a preparation method and application thereof, and the method comprises the following steps: preparing methanol solutions of nickel salt and 2-methylimidazole respectively, and performing ultrasonic treatment for 30-60 minutes to prepare a precursor solution A; preparing spinning precursor solution by using polyacrylonitrile, carrying out electrostatic spinning, and tearing off an electrostatic spinning film from non-woven fabrics; placing the electrostatic spinning film into a methanol solution, placing the dried electrostatic spinning film into a prepared precursor solution A, performing ultrasonic treatment for 15-30 minutes to fully mix the electrostatic spinning film, and finally placing the electrostatic spinning film into a high-pressure reaction kettle to perform high-temperature high-pressure reaction to prepare a nanotube precursor film; and (3) carbonizing the nanotube precursor film in an oxygen atmosphere to prepare the nickel oxide nanotube, namely the magnetic metal nanotube. By adopting the scheme, the ultra-long magnetic metal nanotube can be manufactured, the specific surface area and the aperture of the nanotube can be controlled, and the manufacturing method is simple.
Description
Technical Field
The invention relates to the technical field of nano materials, in particular to a magnetic metal nano tube with a controllable specific surface tube diameter, a preparation method and application thereof.
Background
Since carbon nanotubes were found, hollow nanotubes have received much attention because of their important research significance and potential application value in the fields of nano devices, sensors, energy storage, energy conversion, etc. Among various hollow metal nanotube materials, noble metal nanotubes such as Au and Pt have been the first hot point of research because of their excellent properties such as conduction, electronics, optics, mechanics and catalysis, and scientists have conducted pioneering research in this field. Magnetic metal nanotubes such as nickel-based metal nanotubes have been increasingly becoming important research objects in metal nanotube systems for the twentieth century due to their unique magnetic properties, and have shown broader application prospects, such as perpendicular magnetic recording, high-density magnetic recording materials, cell separation, drug delivery, gene transfer, magnetic imaging, molecular motors, and the like. However, the synthesis of nanotubes is more challenging than other one-dimensional materials such as nanowires, nanorods, and the like, especially for structural control and performance research of nanotubes.
The common manufacturing methods of the nickel-based nanotubes include a template method and an electroplating method, wherein in the prior art, the template method commonly uses carbon nanotubes as templates to manufacture nickel oxide nanotubes, the manufacturing method is to compound nickel-containing element compounds on the surfaces of the carbon nanotubes and remove the carbon nanotubes, but the carbon nanotubes are difficult to remove and easy to agglomerate, the morphology of the manufactured nickel-based metal nanotubes is not uniform, the electroplating method also needs to select a proper template and is matched with an electrochemical instrument, and the method cannot be popularized because the preparation conditions are high and mass production cannot be realized. The nickel-based magnetic metal nano tube prepared by the method has uneven quality and low yield due to the reasons, and the tube wall thickness, the specific surface area, the tube diameter and the like of the nano tube are difficult to control, but the factors such as the tube wall thickness, the specific surface area, the tube diameter, the number of chemical active sites, the electron transmission rate and the like of the nickel-based nano tube are directly related, so that the optimization of the preparation method of the nano tube is a problem to be solved urgently.
Disclosure of Invention
The invention aims to solve the technical problem of providing a preparation method and application of a magnetic metal nanotube with controllable specific surface and tube diameter aiming at the defects in the prior art.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
the preparation process of magnetic metal nanotube with controllable specific surface and pipe diameter includes the following steps:
a1, respectively preparing methanol solutions of nickel salt and 2-methylimidazole according to a molar concentration ratio C Nickel salt ：C 2-methylimidazole =1: 2-8, uniformly mixing, and carrying out ultrasonic treatment for 30-60 minutes to prepare a precursor solution A;
a2, preparing spinning precursor solution by using polyacrylonitrile, carrying out electrostatic spinning, and tearing off an electrostatic spinning film from the non-woven fabric;
a3, cutting the electrostatic spinning film into small blocks, placing the small blocks into a methanol solution, ultrasonically cleaning the small blocks for 30-60 minutes, drying the small blocks in a vacuum drying oven at 60 ℃ for 24-48 hours to remove water, placing the dried electrostatic spinning film into a prepared precursor solution A, ultrasonically treating the small blocks for 15-30 minutes to fully mix the small blocks, and finally placing the small blocks into a high-pressure reaction kettle to perform high-temperature high-pressure reaction to prepare a nanotube precursor film;
a4, carbonizing the nanotube precursor film in an oxygen atmosphere at the reaction temperature of 400-700 ℃ for 0.5-3 h to prepare the nickel oxide nanotube, namely the magnetic metal nanotube.
According to the preparation method, the specific surface and the pipe diameter of the nanotube are controlled through the molar concentration ratio of the nickel salt to the 2-methylimidazole, and the larger the concentration of the 2-methylimidazole is, the smaller the specific surface and the outer diameter are;
the preparation method controls the inner diameter of the nanotube through the diameter of the electrostatic spinning membrane fiber; when the electrostatic spinning film is manufactured, the larger the concentration of the spinning precursor solution is, the smaller the spinning voltage is, the larger the fiber diameter is, and the larger the inner diameter of the manufactured nanotube is.
In the preparation method, in the step A2, a spinning precursor solution with the mass fraction of 7-14% is prepared by using polyacrylonitrile, stirring is carried out for 24 hours, the prepared spinning precursor solution is subjected to electrostatic spinning, the moving speed of a solvent box is 80-210mm/s, the voltage is 20kv-40kv, the spinning time is 45-120min, and an electrostatic spinning film is torn off from a non-woven fabric.
In the preparation method, in the step A4, the heating and cooling speed is 1 ℃/min-5 ℃/min.
In the preparation method, in the step A1, methanol solutions of nickel salt and 2-methylimidazole are respectively prepared according to the molar concentration ratio C Nickel salt ：C 2-methylimidazole =1: 2, uniformly mixing.
In the preparation method, in the step A4, the reaction temperature is 500 ℃ and the duration is 2 hours.
In the preparation method, in the step A4, the reaction temperature is 450 ℃ and the duration is 1.5h.
The magnetic metal nanotube prepared and obtained according to any one of the preparation methods.
The magnetic metal nanotube is applied to electrocatalysis, the prepared nickel oxide nanotube is used as an electrode for methanol decomposition electrocatalyst, and a three-electrode system is adopted.
Use of nickel oxide nanotubes in electrocatalysis:
the prepared nickel oxide nano tube is used for preparing an electrode by using a methanol decomposition electrocatalyst, a three-electrode system is adopted, and the concentration of an electrolyte solution is as follows: the molar concentration of methanol is 1mol/L, and the molar concentration of potassium hydroxide is 1mol/L;
the preparation method of the nickel oxide nanotube electrode comprises the following steps: weighing 5mg of nickel oxide nanotube, weighing 480 mu L of water, 480 mu L of ethanol and 40 mu L of naphthol solution, adding the four solutions into a sealed container at the same time, performing ultrasonic treatment for 30-60 minutes, fully mixing, and then dripping a certain amount of mixed solution on carbon paper to prepare the nickel oxide nanotube electrode.
By adopting the scheme, the ultra-long magnetic metal nanotube can be manufactured, the specific surface area and the aperture of the nanotube can be controlled, and the manufacturing method is simple.
Drawings
FIG. 1 is an electrospun fiber composite Ni-ZIF (C Nickel salt ：C 2-methylimidazole =1: 8) Scanning Electron Microscope (SEM) images of (a).
FIG. 2 shows a nickel oxide nanotube (C Nickel salt ：C 2-methylimidazole =1: 8) Scanning Electron Microscope (SEM) images of (a).
FIG. 3 is a close-up view of a nickel oxide nanotube orifice (C Nickel salt ：C 2-methylimidazole =1: 8) Scanning Electron Microscope (SEM)) A drawing.
FIG. 4 is an electrospun fiber composite Ni-ZIF (C Nickel salt ：C 2-methylimidazole =1: 4) Scanning Electron Microscope (SEM) images of (a).
FIG. 5 shows a nickel oxide nanotube (C Nickel salt ：C 2-methylimidazole =1: 4) Scanning Electron Microscope (SEM) images of (a).
FIG. 6 is a close-up view of a nickel oxide nanotube orifice (C Nickel salt ：C 2-methylimidazole =1: 4) Scanning Electron Microscope (SEM) images of (a).
Fig. 7 is an XRD pattern of nickel oxide nanotubes.
Fig. 8 is a graph of HER performance of nickel oxide nanotubes prepared in accordance with example one.
Fig. 9 is a graph of HER performance of nickel oxide nanotubes prepared in example two.
Detailed Description
The present invention will be described in detail with reference to specific examples.
Example preparation of nickel monoxide nanotubes:
preparing a methanol solution of nickel salt and 2-methylimidazole according to C Nickel salt ：C 2-methylimidazole =1: 8, uniformly mixing, and carrying out ultrasonic treatment for 30 minutes to prepare a precursor solution A;
preparing a D, D-dimethylformamide solution with the mass fraction of polyacrylonitrile of 7% into a spinning precursor solution, stirring for 24 hours, and using the prepared spinning precursor solution for electrostatic spinning, wherein the moving speed of a solvent box is 80mm/s, the voltage is 20kvkv, and the spinning time is 60 min; tearing off the electrostatic spinning film from the non-woven fabric after spinning is finished;
cutting an electrostatic spinning film into a size of 2cm multiplied by 4cm, placing the size into a methanol solution, ultrasonically cleaning the solution for 30min, drying the solution at 60 ℃ in a vacuum drying oven for 24h to remove residual solution, placing the dried electrostatic spinning film into a prepared precursor solution A, ultrasonically treating the solution for 15min to fully mix the solution, finally placing the solution into a high-pressure reaction kettle, reacting the solution at 140 ℃ for 12h to prepare a nanotube precursor film, compositing uniform Ni-ZIF particles on the surface of the electrostatic spinning film fiber, ultrasonically cleaning the nanotube precursor film with the methanol solution for 30min, fully expanding the nanotube precursor film, and drying the nanotube precursor film in the vacuum drying oven for 12h to remove residual solution;
carbonizing the dried nanotube precursor film for 2 hours at 500 ℃ in an oxygen atmosphere (the heating speed is 1 ℃/min-5 ℃/min) to prepare the nickel oxide nanotube. As shown in fig. 1, 2 and 3, the average outer diameter of the nanotubes is about 1 μm, the average inner diameter is about 800nm, the nanotubes are composed of particulate materials, the lengths of the nanotubes are distributed between 30 μm and 80 μm, and the wall thickness of the nanotubes is about 70nm. XRD testing was performed on the nanotubes thus prepared, and as shown in FIG. 7, the XRD spectrum of the nanotubes showed that the main component thereof was nickel oxide.
The nickel oxide nanotubes prepared in this example were used in methanol decomposition electrocatalysts, and the test method was as follows:
constructing a three-electrode system, wherein a counter electrode is a graphite electrode, a reference electrode is a saturated calomel electrode, a working electrode is a nickel oxide nanotube electrode, an electrolyte is a mixed solution of 1mol/L methanol solution and 1mol/L potassium hydroxide solution, and the adopted testing equipment is an electrochemical analyzer;
the manufacturing method of the nickel oxide nanotube electrode comprises the following steps: weighing 5mg of nickel oxide nanotube, weighing 480 mu L of water, 480 mu L of ethanol and 40 mu L of naphthol solution, adding the four solutions into a sealed container at the same time, performing ultrasonic treatment for 30-60 minutes, fully mixing, and then dripping a certain amount of mixed solution on carbon paper to prepare the nickel oxide nanotube electrode.
As shown in FIG. 8, the temperature was 10 mA.cm -2 The overpotential of the nickel oxide nanotube electrode prepared in this example was 305mV.
Example preparation of nickel dioxide nanotubes:
preparing a methanol solution of nickel salt and 2-methylimidazole according to C Nickel salt ：C 2-methylimidazole =1: 4, uniformly mixing, and carrying out ultrasonic treatment for 60 minutes to prepare a precursor solution A;
preparing a spinning precursor solution by preparing a D, D-dimethylformamide solution with the mass fraction of 14% of polyacrylonitrile, stirring for 24 hours, and using the prepared spinning precursor solution for electrostatic spinning, wherein the moving speed of a solvent box is 80mm/s, the voltage is 40kv, and the spinning time is 120min. Tearing off the electrostatic spinning film from the non-woven fabric after spinning is finished;
cutting an electrostatic spinning film into a size of 2cm multiplied by 4cm, placing the size into a methanol solution, ultrasonically cleaning the methanol solution for 60min, drying the methanol solution in a vacuum drying oven at 60 ℃ for 48h to remove residual solution, placing the dried electrostatic spinning film into a prepared precursor solution A, ultrasonically treating the precursor solution A for 30min to fully mix the precursor solution A, finally placing the precursor solution A into a high-pressure reaction kettle, reacting the precursor solution A at 140 ℃ for 12h to prepare a nanotube precursor film, compositing uniform Ni-ZIF sheets on the surface of the fiber of the electrostatic spinning film, ultrasonically cleaning the nanotube precursor film with the methanol solution for 30-60 min, fully expanding the nanotube precursor film, and then drying the nanotube precursor film in the vacuum drying oven for 12-24 h to remove residual solution;
carbonizing the dried nanotube precursor film for 1.5h (heating rate of 1 ℃/min-5 ℃/min) at 450 ℃ under the oxygen atmosphere to prepare the nickel oxide nanotube.
As shown in fig. 4, 5 and 6, the average outer diameter of the nanotubes is about 1.5 μm, the average inner diameter is about 800nm, the nanotubes are composed of a platelet-shaped substance, the length of the nanotubes is distributed between 30 μm and 80 μm, and the wall thickness of the nanotubes is about 600nm.
The nickel oxide nanotubes prepared in this example were used in methanol decomposition electrocatalysts, and the test method was as follows:
constructing a three-electrode system, wherein a counter electrode is a graphite electrode, a reference electrode is a saturated calomel electrode, a working electrode is a nickel oxide nanotube electrode, an electrolyte is a mixed solution of 1mol/L methanol solution and 1mol/L potassium hydroxide solution, and the adopted testing equipment is an electrochemical analyzer;
the manufacturing method of the nickel oxide nanotube electrode comprises the following steps: weighing 5mg of nickel oxide nanotube, weighing 480 mu L of water, 480 mu L of ethanol and 40 mu L of naphthol solution, adding the four solutions into a sealed container at the same time, performing ultrasonic treatment for 30-60 minutes, fully mixing, and then dripping a certain amount of mixed solution on carbon paper to prepare the nickel oxide nanotube electrode.
As shown in FIG. 9, the temperature was 10 mA.cm -2 The overpotential of the nickel oxide nanotube electrode made in this example was 250mV.
Example preparation of nickel trioxide nanotubes:
preparing a methanol solution of nickel salt and 2-methylimidazole according to C Nickel salt ：C 2-methyl esterRadical imidazole =1: 2, uniformly mixing, and carrying out ultrasonic treatment for 30 minutes to prepare a precursor solution A;
preparing a spinning precursor solution by preparing a D, D-dimethylformamide solution with the mass fraction of 14% of polyacrylonitrile, stirring for 24 hours, and using the prepared spinning precursor solution for electrostatic spinning, wherein the moving speed of a solvent box is 80mm/s, the voltage is 25kv, and the spinning time is 30min. Tearing off the electrostatic spinning film from the non-woven fabric after spinning is finished;
cutting an electrostatic spinning film into a size of 2cm multiplied by 4cm, placing the size into a methanol solution, ultrasonically cleaning the methanol solution for 30min, drying the solution in a vacuum drying oven at 60 ℃ for 48h to remove residual solution, placing the dried electrostatic spinning film into a prepared precursor solution A, ultrasonically treating the solution for 30min to fully mix the solution, finally placing the solution into a high-pressure reaction kettle, reacting the solution at 120 ℃ for 10h to prepare a nanotube precursor film, ultrasonically cleaning the nanotube precursor film with the methanol solution for 30min, fully expanding the nanotube precursor film, and drying the nanotube precursor film in the vacuum drying oven for 12h to remove residual solution;
carbonizing the dried nanotube precursor film for 2.5h (heating rate of 1 ℃/min-5 ℃/min) at 550 ℃ under oxygen atmosphere to prepare the nickel oxide nanotube.
It will be understood that modifications and variations will be apparent to those skilled in the art from the foregoing description, and it is intended that all such modifications and variations be included within the scope of the following claims.
Claims (4)
1. The preparation method of the magnetic metal nanotube with the controllable specific surface pipe diameter is characterized by comprising the following steps of:
a1, respectively preparing methanol solutions of nickel salt and 2-methylimidazole according to a molar concentration ratio C Nickel salt ：C 2-methylimidazole =1: 2-8, uniformly mixing, and carrying out ultrasonic treatment for 30-60 minutes to prepare a precursor solution A; controlling the specific surface area and the pipe diameter of the nanotube through the molar concentration ratio of the nickel salt and the 2-methylimidazole, wherein the larger the concentration of the 2-methylimidazole is, the smaller the specific surface area and the outer diameter are;
a2, preparing spinning precursor solution by using polyacrylonitrile, carrying out electrostatic spinning, and tearing off an electrostatic spinning film from the non-woven fabric; preparing a spinning precursor solution with the mass fraction of 7% -14% by using polyacrylonitrile, stirring for 24 hours, carrying out electrostatic spinning on the prepared spinning precursor solution, and tearing off an electrostatic spinning film from a non-woven fabric, wherein the moving speed of a solvent box is 80-210mm/s, the voltage is 20kv-40kv, and the spinning time is 45-120 min; controlling the inner diameter of the nanotube by the diameter of the fiber of the electrostatic spinning film; when the electrostatic spinning film is manufactured, the larger the concentration of the spinning precursor solution is, the smaller the spinning voltage is, the larger the fiber diameter is, and the larger the inner diameter of the manufactured nanotube is;
a3, placing the electrostatic spinning film into a methanol solution, ultrasonically cleaning for 30-60 minutes, drying at 60 ℃ in a vacuum drying oven for 24-48 hours to remove water, placing the dried electrostatic spinning film into the prepared precursor solution A, ultrasonically treating for 15-30 minutes to fully mix the electrostatic spinning film, and finally placing the electrostatic spinning film into a high-pressure reaction kettle to perform high-temperature high-pressure reaction to prepare a nanotube precursor film;
a4, carbonizing the nanotube precursor film in an oxygen atmosphere at the reaction temperature of 400-700 ℃ for 0.5-3 hours to prepare nickel oxide nanotubes, namely magnetic metal nanotubes; the temperature rise and fall speed is 1 ℃/min-5 ℃/min.
2. The method according to claim 1, wherein in the step A1, a methanol solution of nickel salt and 2-methylimidazole is prepared in a molar ratio C Nickel salt ：C 2-methylimidazole =1: 2, uniformly mixing.
3. The method according to claim 1, wherein in the step A4, the reaction temperature is 500 ℃ for a duration of 2 hours.
4. The method according to claim 1, wherein in the step A4, the reaction temperature is 450 ℃ for a duration of 1.5 hours.
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