CN112296350A - Magnetic hollow microsphere and preparation method and application thereof - Google Patents

Magnetic hollow microsphere and preparation method and application thereof Download PDF

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CN112296350A
CN112296350A CN202011033245.6A CN202011033245A CN112296350A CN 112296350 A CN112296350 A CN 112296350A CN 202011033245 A CN202011033245 A CN 202011033245A CN 112296350 A CN112296350 A CN 112296350A
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magnetic hollow
hollow microsphere
stirring
magnetic
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CN112296350B (en
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童国秀
刘敏敏
范宝新
季然
吴丽珊
兰应棋
吴文华
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Zhejiang Normal University CJNU
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    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/16—Making metallic powder or suspensions thereof using chemical processes
    • B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
    • B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/05—Metallic powder characterised by the size or surface area of the particles
    • B22F1/054—Nanosized particles
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    • B22—CASTING; POWDER METALLURGY
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    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/06—Metallic powder characterised by the shape of the particles
    • B22F1/065—Spherical particles
    • B22F1/0655—Hollow particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
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    • B82—NANOTECHNOLOGY
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    • B82Y25/00—Nanomagnetism, e.g. magnetoimpedance, anisotropic magnetoresistance, giant magnetoresistance or tunneling magnetoresistance
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    • B82—NANOTECHNOLOGY
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Abstract

The invention discloses a magnetic hollow microsphere and a preparation method and application thereof, belonging to the technical field of nano materials. The magnetic hollow microsphere prepared by the one-step hydrothermal method has novel structure and formation mechanism, the content of Cu and Co in a product and the composition, morphology and structure of the magnetic hollow microsphere can be regulated and controlled by changing reaction temperature, time, the ratio of surfactant, the mass ratio of copper salt and cobalt salt and the concentration of reactants, and the diameter of the prepared magnetic hollow microsphere is 2.2-10.2 mu m, and the magnetic hollow microsphere is widely applied to the fields of microwave absorption and shielding, electrocatalysis, lithium ion batteries, surface enhanced Raman spectroscopy and the like because the magnetic hollow microsphere has good dispersibility and uniformity and good microwave absorption characteristics. The preparation method disclosed by the invention is simple to operate, green and environment-friendly, has good industrial application potential, and is suitable for market popularization and application.

Description

Magnetic hollow microsphere and preparation method and application thereof
Technical Field
The invention belongs to the technical field of nano materials, and relates to a simple method for preparing magnetic hollow microspheres; more particularly, relates to a magnetic hollow microsphere, a preparation method and an application thereof.
Background
In recent years, magnetic metal and alloy nano materials have great application prospects in the aspects of ultrahigh-density information storage, catalysis, giant magneto-impedance, magneto-optical materials, microwave absorption materials, ferrofluids, biomedicine and the like due to excellent electric, magnetic and catalytic properties.
Because the appearance is an important factor for determining the performance, the hollow nano material has an important application prospect in the fields of nano devices, sensors, energy storage, energy conversion and the like due to the unique internal and external double-layer active surface, high surface energy, large surface-to-volume ratio, low density and excellent adsorption performance. The main technologies for preparing magnetic hollow microspheres at present include an in-situ codeposition method, a template method and the like, and for example, Chinese patent document (CN110508259A) discloses a method for preparing copper ion imprinted composite magnetic hollow microspheres by a microsphere template method; chinese patent document (CN108745217A) discloses a method for preparing multi-shell hollow magnetic microspheres by adopting a template method and an in-situ codeposition method, and a related one-step hydrothermal method is not reported yet.
Although the magnetic hollow microspheres can be prepared mainly by using the template-assisted method disclosed in the patent documents, the preparation method has strong dependence on the template, complicated steps, severe requirements on the accuracy of the instrument and long time consumption, and is not suitable for industrial production and application.
Therefore, how to develop a magnetic hollow micro-nano material with simple and convenient process, easy industrialization, controllable size and good microwave absorption characteristic is a technical problem to be solved urgently by technical personnel in the field.
Disclosure of Invention
In view of the above, the present invention provides a magnetic hollow microsphere with simple process and controllable size, which is directed to the problems in the prior art.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a magnetic hollow microsphere, which is prepared by a one-step hydrothermal method; the magnetic hollow microspheres are composed of Cu and Co, the atomic ratio of Cu to Co is 0.012-0.498, and the diameter of the magnetic hollow microspheres is 2.2-10.2 mu m; and the magnetic hollow microspheres are formed by self-assembling flower-shaped Co/Cu nano structures.
Preferably, the one-step hydrothermal method is as follows: and taking the Cu nanocrystalline obtained by reduction as a core, radially growing a Co nanorod on the surface of the Cu nanocrystalline to obtain a flower-shaped Co/Cu nanostructure, and then further self-assembling the flower-shaped Co/Cu nanostructure to obtain the magnetic hollow microsphere.
The invention adopts a one-step hydrothermal method to prepare the magnetic hollow microspheres, and compared with the existing method, the method has the advantages of simple steps, no need of depending on a template, simple operation, low requirement on instrument precision and great advantages.
The invention discloses a magnetic hollow microsphere, which is prepared by a one-step hydrothermal method, so that the magnetic hollow microsphere has the advantages of simple and convenient process, short production period, good repeatability and large-scale production; the magnetic hollow microsphere prepared by the method has the characteristics of novel structure, good dispersibility and uniformity, adjustable size and composition and good microwave absorption property, and has wide application prospect in the fields of electrode materials, electrocatalysis, surface-enhanced Raman spectroscopy, microwave absorption and shielding, photoelectric conversion or gas sensitivity.
Exemplarily, referring to the attached drawings of the relevant specification, the invention respectively observes the composition, phase and morphology of the prepared magnetic hollow microsphere through energy spectrum, XRD and scanning electron microscope, and monitors the static magnetic performance of the magnetic hollow microsphere through VSM; the magnetic hollow microsphere is filled in a paraffin substrate by the mass fraction of 25-30%, wherein the effective bandwidth of the reflectivity of less than or equal to-10 dB is 5.66-9.80 GHz, the effective bandwidth of the reflectivity of less than or equal to-5 dB can reach 9.11-11.52 GHz, and the maximum reflection loss is-38.04-39.42 dB, so that the magnetic hollow microsphere prepared by the method disclosed by the invention has excellent light broadband low-frequency microwave absorption characteristics, and can be applied to the fields of microwave absorption and shielding, electrocatalysis, lithium ion batteries and surface enhanced Raman spectroscopy.
The invention also aims to provide a preparation method of the magnetic hollow microsphere which is green, environment-friendly and suitable for industrial production.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of magnetic hollow microspheres specifically comprises the following steps:
(1) adding a surfactant and cobalt salt into a solvent, and stirring to obtain a solution A;
(2) adding Cu salt into a solvent, and stirring to obtain a solution B;
(3) adding the solution B into the solution A, uniformly stirring, and carrying out hydrothermal reaction to obtain a crude product;
(4) and washing and vacuum drying the crude product for many times to finally obtain the magnetic hollow microsphere.
By adopting the technical scheme, the invention has the following beneficial effects:
the preparation method disclosed by the invention has the advantages of simple production equipment, simplicity and convenience in operation, short production period, greenness and environmental friendliness, and is suitable for industrial mass production.
Preferably, the stirring temperature in the step (1) is 75 ℃, and the stirring time is 1-1.5 h; the stirring temperature in the step (2) is 60 ℃, and the stirring time is 30 min.
Preferably, in the step (3), the stirring time is 5-10 min, the reaction temperature is 160-220 ℃, and the reaction time is 2.5-20 h.
More preferably, the solvent is at least one of 1, 2-propylene glycol, ethylene glycol and glycerol.
More preferably, the mass ratio of the copper salt to the cobalt salt is (1-40): 100, respectively; the Co salt concentration is 0.0188-0.2258 mol/L, and the Cu salt concentration is 1.174 multiplied by 10-3～1.409×10-2mol/L。
More preferably, the surfactant is formed by mixing stearic acid and hexadecylamine according to the mass ratio of 1 (0.5-12), and the concentration of the surfactant is 1.925-16.625 g/L.
The invention also aims to provide the application of the magnetic hollow microsphere in microwave absorption and shielding, electrocatalysis, lithium ion batteries and surface enhanced Raman spectroscopy.
According to the technical scheme, compared with the prior art, the magnetic hollow microsphere and the preparation method and application thereof provided by the invention have the following excellent effects:
1) the magnetic hollow microsphere prepared by the one-step hydrothermal method has a novel structure and a novel formation mechanism, the contents of Cu and Co in a product and the composition, morphology and structure of the magnetic hollow microsphere can be regulated and controlled by changing the reaction temperature, the reaction time, the ratio of the surfactant, the mass ratio of copper salt to cobalt salt and the concentration of reactants, and the diameter of the finally prepared magnetic hollow microsphere is 2.2-10.2 mu m.
2) The invention discloses a preparation method of the magnetic hollow microsphere, which is simple to operate, green and environment-friendly and has good industrial application potential.
3) The invention discloses application of the magnetic hollow microsphere, and the material has wide application prospects in the fields of electrode materials, electrocatalysis, surface-enhanced Raman spectroscopy, microwave absorption and shielding, photoelectric conversion or gas sensitivity.
Therefore, in conclusion, the magnetic hollow microsphere disclosed and protected by the invention and the preparation method thereof have great market popularization and application values.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts.
Fig. 1 to 3 show the composition, phase and morphology of the product obtained in example 1 of the present invention under the conditions of energy spectrum, XRD and scanning electron microscope, respectively.
FIGS. 4 to 5 are graphs of the product static magnetic properties observed at VSM and the reflectance curve at a mass fraction of 25% for the product obtained in example 1 of the present invention, respectively.
Fig. 6 to 8 show the composition, phase and morphology of the product obtained in example 2 of the present invention under an energy spectrum, XRD and scanning electron microscope, respectively.
Fig. 9 to 11 show the composition, phase and morphology of the product obtained in example 3 of the present invention under the conditions of energy spectrum, XRD and scanning electron microscope, respectively.
Fig. 12 to 14 show the composition, phase and morphology of the product obtained in example 4 of the present invention under energy spectrum, XRD and scanning electron microscope, respectively.
FIGS. 15 to 16 are graphs of the product static magnetic properties observed at VSM and the reflectance curve at a mass fraction of 25% for the product obtained in example 4 of the present invention, respectively.
Fig. 17 to 19 show the composition, phase and morphology of the product obtained in example 5 of the present invention under energy spectrum, XRD and scanning electron microscope, respectively.
FIGS. 20 to 22 show the composition, phase and morphology of the product obtained in example 6 of the present invention under the conditions of energy spectrum, XRD and scanning electron microscope, respectively.
Fig. 23 to 25 show the composition, phase and morphology of the product obtained in example 7 of the present invention under an energy spectrum, XRD and scanning electron microscope, respectively.
FIGS. 26 to 27 are respectively the morphologies of the product obtained in example 8 of the present invention measured by scanning electron microscopy.
FIGS. 28 to 29 are respectively the morphologies of the product obtained in example 9 of the present invention measured by scanning electron microscopy.
Fig. 30 to 32 show the composition, phase and morphology of the product obtained in example 10 of the present invention under energy spectrum, XRD and scanning electron microscope, respectively.
FIGS. 33 to 34 are graphs of the product static magnetic properties observed at VSM and the reflectance curve at a product mass fraction of 30% for the product obtained in example 10 of the present invention, respectively.
Fig. 35 to 37 are compositions, phases and morphologies of the product obtained in example 11 of the present invention measured by energy spectrum, XRD and scanning electron microscopy, respectively.
FIG. 38 shows the morphology of the product obtained in example 12 under the scanning electron microscope.
FIGS. 39 to 40 are respectively the reflectance curves of the product obtained in experiment 1 of the present invention measured under a scanning electron microscope with a morphology and a product mass fraction of 30%.
FIGS. 41 to 42 are respectively the profile of the product obtained in experiment 2 of the present invention measured under a scanning electron microscope and the reflectance curve when the mass fraction of the product is 30%.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The embodiment of the invention discloses a magnetic hollow microsphere with simple and convenient process, controllable size and good microwave absorption characteristic, and a preparation method and application thereof.
The present invention will be further specifically illustrated by the following examples for better understanding, but the present invention is not to be construed as being limited thereto, and certain insubstantial modifications and adaptations of the invention by those skilled in the art based on the foregoing disclosure are intended to be included within the scope of the invention.
The technical solution of the present invention will be further described with reference to the following specific examples.
Example 1
A preparation method of magnetic hollow microspheres specifically comprises the following steps:
1.065g stearic acid, 1.05g hexadecylamine were dissolved in 70mL 1, 2-propanediol, stirred at 75 ℃ for 1h, and then 0.75g Co (OAc) was added2·4H2O, continuously stirring for 30min to form a purple solution A; then 0.375g Cu (OAc)2·H2Dissolving O in 10mL of 1, 2-propylene glycol, and stirring at 60 ℃ for 30min to form a blue solution B; and then adding the solution B into the solution A, stirring for 5min, transferring into a 100mL polytetrafluoroethylene-lined reaction kettle, heating to react for 15h at 200 ℃, naturally cooling to room temperature, washing for 3 times by using absolute ethyl alcohol, and drying in a vacuum drying oven at 60 ℃ to finally obtain the magnetic hollow microspheres.
The composition, phase, morphology and magnetostatic performance of the obtained product measured under energy spectrum, XRD, scanning electron microscope and VSM are respectively shown in figures 1-4.
From the above analysis, the product was a uniform, monodisperse hollow microsphere. Wherein the diameter of the hollow microsphere is 4.3-7.1 μm, and the Cu/Co atomic ratio is 0.019.
The heterogeneous material is filled in a paraffin base by 25 percent of mass fraction, and the measured reflectivity is shown in figure 5, wherein the effective bandwidth range of the reflectivity less than or equal to-10 dB is 5.29-5.66 GHz, the effective bandwidth range of the reflectivity less than or equal to-5 dB is 7.88-9.11 GHz, and the maximum reflection loss is-39.42 dB.
Example 2:
the only difference compared to the preparation procedure disclosed in example 1 is only that: reaction of Co (OAc) added2·4H2O、Cu(OAc)2·H2The mass ratio of O is half of that in example 1, and the rest of the preparation steps and process parameters are the same.
The composition, phase and morphology of the obtained product measured under an energy spectrum, XRD and scanning electron microscope are respectively shown in figures 6-8. Analysis shows that the product is a uniform and monodisperse flower-shaped Co/Cu nano structure. Wherein the tattoo length of the flower-shaped Co/Cu nano structure is about 67-238 nm, and the Cu/Ni atomic ratio is 0.023.
Example 3:
the only difference compared to the preparation procedure disclosed in example 1 is only that: reaction of Co (OAc) added2·4H2O、Cu(OAc)2·H2The mass ratio of O is 6 times of that in example 1, and the rest of the preparation steps and the process parameters are the same.
The composition, phase and morphology of the obtained product measured under an energy spectrum, XRD and scanning electron microscope are respectively shown in figures 9-11. The analysis shows that the product is uniform and monodisperse hollow microspheres. Wherein the diameter of the hollow microsphere is 2.2-4.1 μm, and the Cu/Ni atomic ratio is 0.030.
Example 4:
the only difference compared to the preparation procedure disclosed in example 1 is only that: the reaction temperature is 160 ℃, and the rest preparation steps and process parameters are the same.
The composition, phase, morphology and magnetostatic performance of the obtained product measured under energy spectrum, XRD, scanning electron microscope and VSM are respectively shown in FIGS. 12-15. Analysis shows that the product is in a small part of a uniform and monodisperse flower-shaped Co/Cu nano structure. Wherein the stabbing length of the flower-shaped Co/Cu nano structure is about 107-388 nm, and the Cu/Co atomic ratio is 0.043.
The heterogeneous material is filled in a paraffin base by 25% mass fraction, and the reflectivity is measured as shown in figure 16, wherein the effective bandwidth range of the reflectivity less than or equal to-10 dB is 1.26-6.10 GHz, the effective bandwidth range of the reflectivity less than or equal to-5 dB is 1.88-9.76 GHz, and the maximum reflection loss is-39.31 dB.
Example 5:
the only difference compared to the preparation procedure disclosed in example 1 is only that: the reaction temperature is 220 ℃, and the other preparation steps and process parameters are the same.
The composition, phase and morphology of the obtained product measured under an energy spectrum, XRD and scanning electron microscope are respectively shown in figures 17-19. Analysis shows that the product is a small part of uniform and monodisperse hollow microspheres. Wherein the diameter of the hollow microsphere is 2.8-4 μm, and the Cu/Co atomic ratio is 0.039.
Example 6:
the only difference compared to the preparation procedure disclosed in example 1 is only that: the reaction time is 2.5h, and the other preparation steps and the technological parameters are the same.
The composition, phase and morphology of the obtained product measured under an energy spectrum, XRD and scanning electron microscope are respectively shown in figures 20-22. Analysis shows that the product is a small part of uniform and monodisperse hollow microspheres. Wherein the diameter of the hollow microsphere is 2.9-4.6 μm, and the Cu/Co atomic ratio is 0.050.
Example 7:
the only difference compared to the preparation procedure disclosed in example 1 is only that: the reaction time is 20h, and the rest preparation steps and technological parameters are the same.
The composition, phase and morphology of the obtained product measured under an energy spectrum, XRD and scanning electron microscope are respectively shown in figures 23-25. Analysis shows that the product is a small part of uniform and monodisperse hollow microspheres. Wherein the diameter of the hollow microsphere is 3.4-5 μm, and the Cu/Co atomic ratio is 0.024.
Example 8:
the only difference compared to the preparation procedure disclosed in example 1 is only that: the mass ratio of stearic acid and hexadecylamine serving as surfactants used in the reaction is changed from 1:1 to 1:0.5, and the rest preparation steps and process parameters are the same.
The appearance of the obtained product measured under a scanning electron microscope is shown in FIGS. 26-27. Analysis shows that the product is a small part of uniform and monodisperse hollow microspheres. Wherein the diameter of the hollow microsphere is 4-7 μm.
Example 9:
the only difference compared to the preparation procedure disclosed in example 1 is only that: the mass ratio of stearic acid and hexadecylamine serving as surfactants used in the reaction is changed from 1:1 to 1:12, and the rest preparation steps and process parameters are the same.
The appearance of the obtained product measured under a scanning electron microscope is shown in FIGS. 28-29. Analysis shows that the product is a small part of uniform and monodisperse hollow microspheres. Wherein the diameter of the hollow microsphere is 3.3-5.2 μm.
Example 10:
the only difference compared to the preparation procedure disclosed in example 1 is only that: reaction of Cu (OAc) addition2·H2The mass of O is 0.0075g, and the rest preparation steps and process parameters are the same.
The composition, phase, morphology and magnetostatic performance of the obtained product measured under energy spectrum, XRD, scanning electron microscope and VSM are respectively shown in figures 30-33. The analysis shows that the product is uniform and monodisperse hollow microspheres. Wherein the diameter of the hollow microsphere is 5.2-10.2 mu m, and the Cu/Co atomic ratio is 0.010.
The heterogeneous material is filled in a paraffin base by 30% mass fraction, and the reflectivity is measured as shown in figure 34, wherein the effective bandwidth range of the reflectivity less than or equal to-10 dB is 2.46-9.80 GHz, the effective bandwidth range of the reflectivity less than or equal to-5 dB is 11.52-12.00 GHz, and the maximum reflection loss is-38.04 dB.
Example 11:
the only difference compared to the preparation procedure disclosed in example 1 is only that: reaction of Cu (OAc) addition2·H2The mass of O is 0.30g, and the rest preparation steps and process parameters are the same.
The composition, phase and morphology of the obtained product measured under an energy spectrum, XRD and scanning electron microscope are respectively shown in figures 35-37. Analysis shows that the product is uniform and monodisperse hollow microsphere, and the stabbing body on the microsphere is relatively coarse and short. Wherein the diameter of the hollow microsphere is 2.2-10.1 μm, and the atomic ratio of Cu/Co is 0.395.
Example 12:
the only difference compared to the preparation procedure disclosed in example 1 is only that: the solvent of the reaction is changed from 1, 2-propylene glycol to ethylene glycol, and the rest preparation steps and technological parameters are the same.
The morphology of the obtained product measured under a scanning electron microscope is shown in fig. 38. The analysis shows that the product is uniform and monodisperse hollow microspheres. Wherein the diameter of the hollow microsphere is 6.0-8.1 μm.
The embodiments in the present description are described in a progressive manner, each embodiment focuses on differences from other embodiments, and the same and similar parts among the embodiments are referred to each other.
The inventive content is not limited to the content of the above-mentioned embodiments, wherein combinations of one or several of the embodiments may also achieve the object of the invention.
To further verify the excellent effects of the present invention, the inventors also conducted the following experiments:
experiment 1:
1.065g stearic acid, 1.05g hexadecylamine were dissolved in 80mL 1, 2-propanediol, stirred at 75 ℃ for 1h, and then 0.75g Co (OAc) was added2·4H2And O, continuously stirring for 30min to form a purple solution, transferring the purple solution into a 100mL polytetrafluoroethylene lining reaction kettle, heating the solution at 200 ℃ for reaction for 15h, naturally cooling the reaction product to room temperature, washing the reaction product for 3 times by using absolute ethyl alcohol, and drying the reaction product in a vacuum drying oven at 60 ℃ to obtain a uniform and monodisperse flower-shaped product.
The morphology of the obtained product under a scanning electron microscope is shown in figure 39, the heterogeneous material is filled in a paraffin base by 30% of mass fraction, the measured reflectivity is shown in figure 40, wherein the effective bandwidth range of the reflectivity less than or equal to-10 dB is 1.18-1.76 GHz, the effective bandwidth range of the reflectivity less than or equal to-5 dB is 2.09-4.76 GHz, and the maximum reflection loss is-38.46 dB.
Experiment 2:
1.065g stearic acid, 1.05g hexadecylamine were dissolved in 80mL 1, 2-propanediol, stirred at 75 ℃ for 1h, and then 0.75g Cu (OAc) was added2·H2And O, continuously stirring for 30min to form a blue solution, transferring the blue solution into a 100mL reaction kettle with a polytetrafluoroethylene lining, heating the solution to react for 15h at 200 ℃, naturally cooling the solution to room temperature, washing the solution for 3 times by using absolute ethyl alcohol, and drying the solution in a vacuum drying oven at 60 ℃ to obtain uniform and monodisperse granular products.
The morphology of the obtained product under a scanning electron microscope is shown in figure 41, the heterogeneous material is filled in a paraffin base by 30% of mass fraction, and the reflectivity of the heterogeneous material is shown in figure 42, wherein the effective bandwidth range of the reflectivity less than or equal to-10 dB is 0.97-1.77 GHz, the effective bandwidth range of the reflectivity less than or equal to-5 dB is 4.26-4.84 GHz, and the maximum reflection loss is-39.97 dB.
Compared with materials obtained from pure copper and pure cobalt, the copper-cobalt magnetic hollow microsphere disclosed by the invention has excellent light broadband low-frequency microwave absorption characteristics.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims (9)

1. The magnetic hollow microsphere is characterized by being prepared by a one-step hydrothermal method; the magnetic hollow microspheres are composed of Cu and Co, the atomic ratio of Cu to Co is 0.012-0.498, and the magnetic hollow microspheres are formed by self-assembling flower-shaped Co/Cu nano structures.
2. The magnetic hollow microsphere according to claim 1, wherein the one-step hydrothermal method is to prepare: and taking the Cu nanocrystalline obtained by reduction as a core, radially growing a Co nanorod on the surface of the Cu nanocrystalline to obtain a flower-shaped Co/Cu nanostructure, and then further self-assembling the flower-shaped Co/Cu nanostructure to obtain the magnetic hollow microsphere.
3. The method for preparing magnetic hollow microspheres according to claim 1 or 2, wherein the method comprises the following steps:
(1) adding a surfactant and cobalt salt into a solvent, and stirring to obtain a solution A;
(2) adding Cu salt into a solvent, and stirring to obtain a solution B;
(3) adding the solution B into the solution A, uniformly stirring, and carrying out hydrothermal reaction to obtain a crude product;
(4) and washing and vacuum drying the crude product for many times to finally obtain the magnetic hollow microsphere.
4. The preparation method of the magnetic hollow microsphere according to claim 3, wherein the stirring temperature in the step (1) is 75 ℃, and the stirring time is 1-1.5 h; the stirring temperature in the step (2) is 60 ℃, and the stirring time is 30 min.
5. The preparation method of the magnetic hollow microsphere according to claim 3, wherein in the step (3), the stirring time is 5-10 min, the reaction temperature is 160-220 ℃, and the reaction time is 2.5-20 h.
6. The method for preparing magnetic hollow microspheres according to any one of claims 3 to 5, wherein the solvent is at least one of 1, 2-propanediol, ethylene glycol and glycerol.
7. The method for preparing magnetic hollow microspheres according to any one of claims 3 to 5, wherein the mass ratio of the added copper salt to the added cobalt salt is (1-40): 100, respectively; the Co salt concentration is 0.0188-0.2258 mol/L, and the Cu salt concentration is 1.174 multiplied by 10-3～1.409×10-2mol/L。
8. The method for preparing magnetic hollow microspheres according to any one of claims 3 to 5, wherein the surfactant is formed by mixing stearic acid and hexadecylamine according to a mass ratio of 1 (0.5-12), and the concentration of the surfactant is 1.925-16.625 g/L.
9. Use of the magnetic hollow microsphere according to claim 1 or 2 or the magnetic hollow microsphere prepared by the method according to any one of claims 3 to 8 in microwave absorption and shielding, electrocatalysis, lithium ion batteries and surface enhanced raman spectroscopy.
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