CN112296350B - Magnetic hollow microsphere and preparation method and application thereof - Google Patents

Magnetic hollow microsphere and preparation method and application thereof Download PDF

Info

Publication number
CN112296350B
CN112296350B CN202011033245.6A CN202011033245A CN112296350B CN 112296350 B CN112296350 B CN 112296350B CN 202011033245 A CN202011033245 A CN 202011033245A CN 112296350 B CN112296350 B CN 112296350B
Authority
CN
China
Prior art keywords
hollow microsphere
magnetic hollow
stirring
magnetic
preparing
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202011033245.6A
Other languages
Chinese (zh)
Other versions
CN112296350A (en
Inventor
童国秀
刘敏敏
范宝新
季然
吴丽珊
兰应棋
吴文华
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Zhejiang Normal University CJNU
Original Assignee
Zhejiang Normal University CJNU
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Zhejiang Normal University CJNU filed Critical Zhejiang Normal University CJNU
Priority to CN202011033245.6A priority Critical patent/CN112296350B/en
Publication of CN112296350A publication Critical patent/CN112296350A/en
Application granted granted Critical
Publication of CN112296350B publication Critical patent/CN112296350B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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
    • 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
    • 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
    • B22F1/0553—Complex form nanoparticles, e.g. prism, pyramid, octahedron
    • 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
    • B22F1/06—Metallic powder characterised by the shape of the particles
    • B22F1/065—Spherical particles
    • B22F1/0655—Hollow particles
    • 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
    • B22F1/07—Metallic powder characterised by particles having a nanoscale microstructure
    • 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
    • B22F1/17—Metallic particles coated with metal
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y25/00—Nanomagnetism, e.g. magnetoimpedance, anisotropic magnetoresistance, giant magnetoresistance or tunneling magnetoresistance
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Nanotechnology (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Manufacturing & Machinery (AREA)
  • Composite Materials (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacturing Of Micro-Capsules (AREA)

Abstract

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

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 and a preparation method and application thereof.
Background
In recent years, the magnetic metal and alloy nano-materials have great application prospects in the aspects of ultra-high density information storage, catalysis, giant magneto impedance, magneto-optical materials, microwave absorbing materials, ferrofluid, biomedicine and the like due to excellent electric, magnetic, catalytic and other performances.
Because the morphology is an important factor for determining the performance, the hollow nano material has important application prospect in the fields of nano devices, sensors, energy storage, energy conversion and the like because of having unique inner and outer double-layer active surfaces, high surface energy, large surface volume ratio, low density and excellent adsorption performance. The main technologies for preparing the magnetic hollow microspheres at present include an in-situ codeposition method, a template method and the like, and for example, chinese patent literature (CN 110508259A) discloses a method for preparing copper ion imprinting composite magnetic hollow microspheres by a microsphere template method; chinese patent literature (CN 108745217A) discloses a method for preparing multi-shell hollow magnetic microspheres by adopting a template method and an in-situ codeposition method, and a one-step hydrothermal method has not been reported yet.
Although the magnetic hollow microsphere can be prepared by mainly adopting a template auxiliary method disclosed in the patent document, the preparation method has strong template dependence, complicated steps, strict requirement on instrument accuracy 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 property is a technical problem to be solved by the technicians in the field.
Disclosure of Invention
In view of the above, the present invention aims to solve the problems in the prior art, and provides a magnetic hollow microsphere with simple process and controllable size.
In order to achieve the above object, the technical scheme of the present invention is as follows:
a magnetic hollow microsphere prepared by a one-step hydrothermal method; the composition of the magnetic hollow microsphere is Cu and Co, the atomic ratio of Cu to Co is 0.012-0.498, and the diameter of the magnetic hollow microsphere is 2.2-10.2 mu m; and the magnetic hollow microsphere is formed by self-assembly of a flower-shaped Co/Cu nano structure.
Preferably, the one-step hydrothermal method comprises the following steps: and (3) taking the Cu nanocrystalline obtained by reduction as a core, radially growing Co nanorods 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 microsphere, and has the advantages of simple steps, no need of depending on templates, simple operation, low requirement on instrument precision and great advantage compared with the existing method.
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 advantages 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 spectrum, microwave absorption and shielding, photoelectric conversion or gas sensitivity.
The composition, the phase and the morphology of the prepared magnetic hollow microsphere are observed through an energy spectrum, XRD and a scanning electron microscope respectively, and the magnetostatic performance of the magnetic hollow microsphere is monitored through VSM; the magnetic hollow microsphere is filled in a paraffin substrate in a 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 is 9.11-11.52 GHz, and the maximum reflection loss is-38.04 to-39.42 dB, so that the magnetic hollow microsphere prepared by the method 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 environment-friendly and suitable for industrial production.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
the preparation method of the magnetic hollow microsphere 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 performing hydrothermal reaction to obtain a crude product;
(4) And washing the crude product for multiple times, and drying in vacuum 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, environment friendliness and suitability 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 30min.
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.
Further preferably, the solvent is at least one of 1, 2-propanediol, ethylene glycol, and glycerol.
Further preferably, the mass ratio of the copper salt to the cobalt salt is (1-40): 100; and the Co salt concentration is 0.0188-0.2258 mol/L and Cu salt concentration is 1.174 ×10 -3 ～1.409×10 -2 mol/L。
Further preferably, 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.
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.
Compared with the prior art, the magnetic hollow microsphere provided by the invention, and the preparation method and application thereof have the following excellent effects:
1) The magnetic hollow microsphere prepared by the one-step hydrothermal method has novel structure and forming mechanism, the content of Cu and Co in the product and the composition, morphology and structure of the magnetic hollow microsphere can be regulated and controlled by changing the reaction temperature, time, the ratio of the surfactant, the mass ratio of the copper salt to the cobalt salt and the concentration of the reactant, 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 summary, the magnetic hollow microsphere and the preparation method thereof disclosed by the invention have great popularization and application values in the market.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required to be used in the embodiments or the description of the prior art will be briefly described below, and it is obvious that the drawings in the following description are only embodiments of the present invention, and that other drawings can be obtained according to the provided drawings without inventive effort for a person skilled in the art.
Fig. 1 to 3 are respectively the composition, phase and morphology of the product obtained in example 1 of the present invention measured by energy spectrum, XRD and scanning electron microscope.
FIGS. 4 to 5 are, respectively, a static magnetic property profile of the product obtained in example 1 of the present invention observed under VSM and a reflectance curve at 25% by mass of the product.
Fig. 6 to 8 are respectively the composition, phase and morphology of the product obtained in example 2 according to the present invention measured by energy spectrum, XRD and scanning electron microscope.
Fig. 9 to 11 are respectively the composition, phase and morphology of the product obtained in example 3 of the present invention measured by energy spectrum, XRD and scanning electron microscope.
Fig. 12 to 14 are the composition, phase and morphology of the product obtained in example 4 according to the present invention, respectively, measured by energy spectrum, XRD and scanning electron microscope.
FIGS. 15 to 16 are, respectively, a static magnetic property profile of the product obtained in example 4 of the present invention observed under VSM and a reflectance curve at 25% by mass of the product.
Fig. 17 to 19 are the composition, phase and morphology of the product obtained in example 5 of the present invention measured by energy spectrum, XRD and scanning electron microscope, respectively.
Fig. 20 to 22 show the composition, phase and morphology of the product obtained in example 6 according to the present invention, respectively, measured by energy spectrum, XRD and scanning electron microscope.
FIGS. 23 to 25 show the composition, phase and morphology of the product obtained in example 7 according to the present invention, respectively, measured by energy spectrum, XRD and scanning electron microscope.
FIGS. 26 to 27 are graphs showing the morphology of the product obtained in example 8 of the present invention under a scanning electron microscope.
FIGS. 28 to 29 are graphs showing the morphology of the product obtained in example 9 of the present invention under a scanning electron microscope.
FIGS. 30 to 32 show the composition, phase and morphology of the product obtained in example 10 according to the present invention, respectively, measured by energy spectrum, XRD and scanning electron microscope.
FIGS. 33 to 34 are, respectively, a static magnetic property profile of the product obtained in example 10 of the present invention and a reflectance curve at a mass fraction of 30% of the product observed under VSM.
Fig. 35 to 37 are the composition, phase and morphology of the product obtained in example 11 according to the present invention, respectively, measured by energy spectrum, XRD and scanning electron microscope.
FIG. 38 is a graph showing the morphology of the product obtained in example 12 of the present invention under a scanning electron microscope.
Fig. 39 to 40 are graphs showing the morphology of the product obtained in experiment 1 according to the present invention and the reflectance when the mass fraction of the product is 30% by scanning electron microscopy, respectively.
Fig. 41 to 42 are graphs showing the morphology of the product obtained in experiment 2 according to the present invention and the reflectivity of the product with a mass fraction of 30% measured by a scanning electron microscope, respectively.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the 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, which are not to be construed as limiting the invention, but rather as falling within the scope of the present invention, for some non-essential modifications and adaptations of the invention that are apparent to those skilled in the art based on the foregoing disclosure.
The technical scheme of the invention will be further described below with reference to specific embodiments.
Example 1
The preparation method of the magnetic hollow microsphere specifically comprises the following steps:
1.065g of stearic acid, 1.05g of hexadecylamine were dissolved in 70mL of 1, 2-propanediol, and after stirring at 75℃for 1 hour, 0.75g of Co (OAc) was added 2 ·4H 2 O, stirring continuously for 30min to form a purple solution A; then 0.375g Cu (OAc) 2 ·H 2 O is dissolved in 10mL of 1, 2-propylene glycol and stirred for 30min at 60 ℃ to form blue solution B; and then adding the solution B into the solution A, stirring for 5min, transferring into a 100mL polytetrafluoroethylene lining reaction kettle, heating at 200 ℃ for reaction for 15h, naturally cooling to room temperature, washing with absolute ethyl alcohol for 3 times, 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 under the conditions of energy spectrum, XRD, scanning electron microscope and VSM are shown in figures 1-4 respectively.
From the above analysis, the product was a uniform, monodisperse hollow microsphere. Wherein the diameter of the hollow microsphere is 4.3-7.1 mu m, and the Cu/Co atomic ratio is 0.019.
The heterogeneous material is filled in a paraffin substrate with the mass fraction of 25%, the reflectivity is measured as shown in figure 5, wherein the effective bandwidth range of the reflectivity of less than or equal to-10 dB is 5.29-5.66 GHz, the effective bandwidth range of the reflectivity of 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 that: co (OAc) added by reaction 2 ·4H 2 O、Cu(OAc) 2 ·H 2 The mass ratio of O is half that of example 1, and the rest preparation steps and process parameters are the same.
The composition, phase and morphology of the obtained product are respectively shown in figures 6-8 under the conditions of energy spectrum, XRD and scanning electron microscope. Analysis shows that the product is a uniform and monodisperse flower-like Co/Cu nanostructure. Wherein the tattooing length of the flower-shaped Co/Cu nano structure is about 67-238 nm, and the atomic ratio of Cu/Ni is 0.023.
Example 3:
the only difference compared to the preparation procedure disclosed in example 1 is that: co (OAc) added by reaction 2 ·4H 2 O、Cu(OAc) 2 ·H 2 The mass ratio of O is 6 times that of the example 1, and the rest preparation steps and process parameters are the same.
The composition, phase and morphology of the obtained product are respectively shown in figures 9-11 under the conditions of energy spectrum, XRD and scanning electron microscope. Analysis revealed that the product was a uniform, monodisperse hollow microsphere. Wherein the diameter of the hollow microsphere is 2.2-4.1 mu m, and the Cu/Ni atomic ratio is 0.030.
Example 4:
the only difference compared to the preparation procedure disclosed in example 1 is that: the reaction temperature is 160 ℃, and the other preparation steps and the process parameters are the same.
The composition, phase, morphology and magnetostatic performance of the obtained product under the conditions of energy spectrum, XRD, scanning electron microscope and VSM are shown in figures 12-15 respectively. Analysis revealed that a small portion of the product was a uniform, monodisperse flower-like Co/Cu nanostructure. Wherein the tattooing length of the flower-shaped Co/Cu nano structure is about 107-388 nm, and the atomic ratio of Cu/Co is 0.043.
The heterogeneous material is filled in a paraffin substrate with a mass fraction of 25%, and the reflectivity is measured as shown in figure 16, wherein the effective bandwidth range of the reflectivity of less than or equal to-10 dB is 1.26-6.10 GHz, the effective bandwidth range of the reflectivity of 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 that: the reaction temperature is 220 ℃, and the other preparation steps and the process parameters are the same.
The composition, phase and morphology of the obtained product are respectively shown in figures 17-19 under the conditions of energy spectrum, XRD and scanning electron microscope. Analysis revealed that a small portion of the product was homogeneous, monodisperse hollow microspheres. Wherein the diameter of the hollow microsphere is 2.8-4 mu m, and the atomic ratio of Cu/Co is 0.039.
Example 6:
the only difference compared to the preparation procedure disclosed in example 1 is that: the reaction time is 2.5h, and the other preparation steps and process parameters are the same.
The composition, phase and morphology of the obtained product are respectively shown in figures 20-22 under the conditions of energy spectrum, XRD and scanning electron microscope. Analysis revealed that a small portion of the product was homogeneous, monodisperse hollow microspheres. Wherein the diameter of the hollow microsphere is 2.9-4.6 mu m, and the Cu/Co atomic ratio is 0.050.
Example 7:
the only difference compared to the preparation procedure disclosed in example 1 is that: the reaction time is 20h, and the other preparation steps and process parameters are the same.
The composition, phase and morphology of the obtained product are respectively shown in figures 23-25 under the conditions of energy spectrum, XRD and scanning electron microscope. Analysis revealed that a small portion of the product was homogeneous, monodisperse hollow microspheres. Wherein the diameter of the hollow microsphere is 3.4-5 mu m, and the atomic ratio of Cu/Co is 0.024.
Example 8:
the only difference compared to the preparation procedure disclosed in example 1 is that: the mass ratio of the stearic acid serving as a surfactant to the hexadecylamine is changed from 1:1 to 1:0.5, and the rest preparation steps and process parameters are the same.
The morphology of the obtained product measured by a scanning electron microscope is shown in figures 26-27. Analysis revealed that a small portion of the product was homogeneous, monodisperse hollow microspheres. Wherein the hollow microsphere has a diameter of 4-7 μm.
Example 9:
the only difference compared to the preparation procedure disclosed in example 1 is that: the mass ratio of the stearic acid serving as a surfactant to the hexadecylamine is changed from 1:1 to 1:12, and the rest preparation steps and process parameters are the same.
The morphology of the obtained product measured by a scanning electron microscope is shown in figures 28-29. Analysis revealed that a small portion of the product was homogeneous, monodisperse hollow microspheres. Wherein the diameter of the hollow microsphere is 3.3-5.2 mu m.
Example 10:
the only difference compared to the preparation procedure disclosed in example 1 is that: cu (OAc) added by reaction 2 ·H 2 The 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 under the conditions of energy spectrum, XRD, scanning electron microscope and VSM are shown in figures 30-33 respectively. Analysis revealed that the product was a uniform, monodisperse hollow microsphere. 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 substrate with the mass fraction of 30%, the reflectivity of the heterogeneous material is shown in a graph 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 that: cu (OAc) added by reaction 2 ·H 2 The 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 are respectively shown in figures 35-37 under the conditions of energy spectrum, XRD and scanning electron microscope. Analysis shows that the product is a uniform and monodisperse hollow microsphere, and the puncture on the microsphere is thicker and shorter. Wherein the diameter of the hollow microsphere is 2.2-10.1 mu m, 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 that: the solvent of the reaction is changed from 1, 2-propylene glycol to ethylene glycol, and the rest preparation steps and process parameters are the same.
The morphology of the obtained product measured by a scanning electron microscope is shown in fig. 38. Analysis revealed that the product was a uniform, monodisperse hollow microsphere. Wherein the diameter of the hollow microsphere is 6.0-8.1 mu m.
In the present specification, each embodiment is described in a progressive manner, and each embodiment is mainly described in a different point from other embodiments, and identical and similar parts between the embodiments are all enough to refer to each other.
The present invention is not limited to the above embodiments, but one or a combination of several embodiments can achieve the object of the present invention as well.
To further verify the excellent effects of the present invention, the inventors have also conducted the following experiments:
experiment 1:
1.065g of stearic acid, 1.05g of hexadecylamine were dissolved in 80mL of 1, 2-propanediol, and after stirring at 75℃for 1 hour, 0.75g of Co (OAc) was added 2 ·4H 2 O, stirring for 30min to form purple solution, transferring into a 100mL polytetrafluoroethylene lining reaction kettle, heating at 200deg.C for reaction for 15h, naturally cooling to room temperature, and washing with absolute ethanol for 3 timesDrying in a vacuum drying oven at 60 ℃ to obtain uniform and monodisperse flower-like products.
The morphology of the obtained product under a scanning electron microscope is shown in figure 39, the heterogeneous material is filled in a paraffin substrate at a mass fraction of 30%, the 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 of stearic acid, 1.05g of hexadecylamine were dissolved in 80mL of 1, 2-propanediol, and after stirring at 75℃for 1 hour, 0.75g of Cu (OAc) was added 2 ·H 2 O, stirring continuously for 30min to form a blue solution, transferring into a 100mL polytetrafluoroethylene lining reaction kettle, heating at 200 ℃ for reaction for 15h, naturally cooling to room temperature, washing with absolute ethyl alcohol for 3 times, and drying in a vacuum drying oven at 60 ℃ to obtain a uniform and monodisperse granular product.
The morphology of the obtained product under a scanning electron microscope is shown as figure 41, the heterogeneous material is filled in a paraffin substrate at a mass fraction of 30%, the reflectivity is shown as 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 the materials obtained by pure copper and pure cobalt, the copper-cobalt magnetic hollow microsphere prepared by the method 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 (8)

1. The magnetic hollow microsphere is characterized by being prepared by a one-step hydrothermal method; the magnetic hollow microsphere comprises Cu and Co, wherein the atomic ratio of Cu to Co is 0.012-0.498, and the magnetic hollow microsphere is formed by self-assembly of flower-shaped Co/Cu nano structures;
the one-step hydrothermal method comprises the following steps: and (3) taking the Cu nanocrystalline obtained by reduction as a core, radially growing Co nanorods 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.
2. A method for preparing the magnetic hollow microsphere according to claim 1, wherein the method 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 performing hydrothermal reaction to obtain a crude product;
(4) And washing the crude product for multiple times, and drying in vacuum to finally obtain the magnetic hollow microsphere.
3. The method for preparing the magnetic hollow microsphere according to claim 2, 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 30min.
4. The method for preparing magnetic hollow microspheres according to claim 2, 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.
5. The method for preparing a magnetic hollow microsphere according to any one of claims 2 to 4, wherein the solvent is at least one of 1, 2-propanediol, ethylene glycol, and glycerol.
6. The method for preparing a magnetic hollow microsphere according to any one of claims 2 to 4, wherein the mass ratio of the copper salt to the cobalt salt is (1 to 40): 100; and the Co salt concentration is 0.0188-0.2258 mol/L and Cu salt concentration is 1.174 ×10 -3 ～1.409×10 -2 mol/L。
7. The method for preparing a magnetic hollow microsphere according to any one of claims 2 to 4, wherein the surfactant is prepared by mixing stearic acid and hexadecylamine according to a mass ratio of 1 (0.5 to 12), and the concentration of the surfactant is 1.925 to 16.625g/L.
8. Use of the magnetic hollow microsphere according to claim 1 or the magnetic hollow microsphere prepared by the method according to any one of claims 2 to 7 in microwave absorption and shielding, electrocatalysis, lithium ion batteries and surface enhanced raman spectroscopy.
CN202011033245.6A 2020-09-27 2020-09-27 Magnetic hollow microsphere and preparation method and application thereof Active CN112296350B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202011033245.6A CN112296350B (en) 2020-09-27 2020-09-27 Magnetic hollow microsphere and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202011033245.6A CN112296350B (en) 2020-09-27 2020-09-27 Magnetic hollow microsphere and preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN112296350A CN112296350A (en) 2021-02-02
CN112296350B true CN112296350B (en) 2023-04-25

Family

ID=74488128

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202011033245.6A Active CN112296350B (en) 2020-09-27 2020-09-27 Magnetic hollow microsphere and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN112296350B (en)

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000077222A (en) * 1998-09-02 2000-03-14 Hitachi Metals Ltd Porous composite magnetic body and manufacture of the same
US8137759B2 (en) * 2006-04-07 2012-03-20 The Regents Of The University Of California Gold nanostructures and methods of use
CN101619135A (en) * 2008-07-02 2010-01-06 中国科学院研究生院 Magnetic hollow compound microstructure preparation method
CN102923791B (en) * 2012-10-29 2014-07-30 江苏大学 Method for preparing multi-tunnel cobaltosic oxide flower-like microspheres by solvothermal method
CN104360064A (en) * 2014-10-24 2015-02-18 东南大学 Monodisperse hollow gold nanosphere and preparation method and application thereof
CN108124413B (en) * 2017-12-26 2019-08-06 山东大学 Porous hollow iron nanometer spherical electromagnetic wave absorbent material and preparation method and application
CN108526482B (en) * 2018-04-11 2021-05-04 浙江师范大学 Magnetic alloy hollow microsphere and preparation method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
张丽惠 ; .纳米棒和纳米片构建的CuO空心微球可控合成及其形貌依赖的声催化活性.化学研究与应用.2016,(第09期),第56-62页. *

Also Published As

Publication number Publication date
CN112296350A (en) 2021-02-02

Similar Documents

Publication Publication Date Title
Yi et al. Regulating pyrolysis strategy to construct CNTs-linked porous cubic Prussian blue analogue derivatives for lightweight and broadband microwave absorption
Wen et al. Controlling the heterogeneous interfaces of S, Co co-doped porous carbon nanosheets for enhancing the electromagnetic wave absorption
CN112961650B (en) Three-metal organic framework derived iron-nickel alloy/porous carbon ultrathin wave absorber and preparation method thereof
Zheng et al. Customized dielectric-magnetic balance enhanced electromagnetic wave absorption performance in CuxS/CoFe2O4 composites
CN104610913B (en) A kind of preparation method of the microwave absorbing material with MOFs molecular structure as template
CN109607625B (en) Core-shell nickel-cobalt-manganese ternary sulfide hollow spherical electrode material and preparation method thereof
Wei et al. Rational construction of magnetic core-shell structural carbon Nanotubes@ Mesoporous N-doped carbon nanofibers for efficient microwave absorption
CN113745009B (en) Binary nanocomposite Co 3 S 4 /NiCo 2 S 4 Preparation method and application of the electrode in super capacitor
Zhou et al. Facile synthesis of ZIF-67 derived dodecahedral C/NiCO 2 S 4 with broadband microwave absorption performance
Li et al. Metal-organic framework-derived Co/CoO nanoparticles with tunable particle size for strong low-frequency microwave absorption in the S and C bands
Jia et al. Nanostructure-modified in-situ synthesis of nitrogen-doped porous carbon microspheres (NPCM) loaded with FeTe2 nanocrystals and NPCM as superior anodes to construct high-performance lithium-ion capacitors
Wang et al. Recent progress of one-dimensional nanomaterials for microwave absorption: a review
CN113285243A (en) Covalent organic framework composite material and preparation method and application thereof
Feng et al. Fabrication of hollow Ni/NiO/C/MnO2@ polypyrrole core-shell structures for high-performance electromagnetic wave absorption
He et al. A control strategy for microwave absorption performance on a two-dimensional scale
Chen et al. Carbon doped with binary heteroatoms (N, X–C, where X= P, B, or S) derived from polypyrrole for enhanced electromagnetic wave absorption at microwave frequencies
CN112296350B (en) Magnetic hollow microsphere and preparation method and application thereof
Lv et al. MXene/bimetallic CoNi-MOF derived magnetic-dielectric balanced composites with multiple heterogeneous interfaces for excellent microwave absorption
CN107511478B (en) Graphite wraps up the alloy cpd Fe that Haas strangles (Heusler) and N doping3Si Nano capsule
CN109231270B (en) Preparation method of lead molybdate dendritic crystal
CN111014649B (en) Magnetic hollow micro-nano material and preparation method and application thereof
Li et al. Facile Synthesis of Metal Oxide Decorated Carbonized Bamboo Fibers with Wideband Microwave Absorption
Wang et al. Enhanced microwave absorption capacity of hierarchical structural MnO 2@ NiMoO 4 composites
CN114411132A (en) Preparation method of cobalt-nickel alloy particle hydrophilic carbon cloth composite material with corn cob-like heterostructure
CN114206091A (en) CoFe/C-CNT wave-absorbing material and preparation process and application thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant