CN109128138B - Magnetic fiber with core-shell heterostructure and preparation and application methods thereof - Google Patents

Magnetic fiber with core-shell heterostructure and preparation and application methods thereof Download PDF

Info

Publication number
CN109128138B
CN109128138B CN201811068449.6A CN201811068449A CN109128138B CN 109128138 B CN109128138 B CN 109128138B CN 201811068449 A CN201811068449 A CN 201811068449A CN 109128138 B CN109128138 B CN 109128138B
Authority
CN
China
Prior art keywords
fiber
core
shell
heterostructure
polypyrrole
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
CN201811068449.6A
Other languages
Chinese (zh)
Other versions
CN109128138A (en
Inventor
童国秀
何娜
童佳悦
杨晓晨
邵雯
施灵秀
董雯静
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 CN201811068449.6A priority Critical patent/CN109128138B/en
Publication of CN109128138A publication Critical patent/CN109128138A/en
Application granted granted Critical
Publication of CN109128138B publication Critical patent/CN109128138B/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
    • 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
    • B22F1/0547—Nanofibres or nanotubes
    • 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
    • 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
    • B22F9/20—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds
    • 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
    • B22F9/20—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds
    • B22F9/22—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds using gaseous reductors
    • 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

Abstract

The invention discloses a magnetic fiber with a core-shell heterostructure and a preparation method and an application method thereof. The fiber consists of Fe, Cu and C; fe. The atomic percentage contents of Cu and C elements are respectively 12.2-29.6%, 9.2-55.2% and 32.5-70.5%; the structure of the nano-fiber is Cu/Fe/C core-shell structure nano-fiber which consists of a Cu/Fe core and a C shell and has a hollow or porous structure, the length of the nano-fiber is 50 mu m, and the diameter of the nano-fiber is 70-380 nm; the saturation magnetization is 80.4-152.89 emu g–1. The fiber is prepared by adopting an in-situ carbothermic reduction-chemical vapor deposition method, namely: separately loading organic Polymer coated Cu with ceramic Canoe2And (3) placing the O core-shell heterogeneous nano-fibers and the iron pentacarbonyl into a tubular furnace, and roasting under the protection of inert gas. The method has the advantages of simple equipment, short period, good repeatability, large-scale production and the like, and has wide application prospect in the fields of electro-catalysis, microwave absorption, lithium ion batteries, surface enhanced Raman spectroscopy and the like.

Description

Magnetic fiber with core-shell heterostructure and preparation and application methods thereof
Technical Field
The invention relates to the technical field of nano materials, in particular to a simple method for preparing a Cu/Fe/C core-shell heterostructure magnetic fiber.
Background
The Cu and the Cu alloy fiber nanometer are applied to the fields of glass, ceramic coloring agent, paint crease resistance, automobile exhaust purification, super large scale integrated circuit, electric catalysis, lithium ion battery, surface enhanced Raman spectrum, microwave absorption and shielding and the like due to high specific surface area, good conductivity and high catalytic activity. At present, people synthesize Cu and alloy fibers thereof by a metal mechanical cutting method, an electrostatic spinning-carbonization method and the like. For example, patent document (CN 101104896a) discloses a fiber composite reinforced Cu-Fe-RE alloy and a method for preparing the same; patent document (CN 107988789a) discloses a composite conductive fiber composed of a plurality of metals; chinese patent document (CN 10436860B) discloses an antibacterial and antistatic composite copper fiber-copper fiber filter screen loaded with photocatalyst; chinese patent document (CN105442134A) discloses an antibacterial antistatic composite copper fiber; chinese patent literature (cn200610124078.x, CN103264162A, CN201410637659.8) discloses a copper fiber sintered felt and a method for producing the same. However, no report is found about the Cu/Fe/C core-shell heterostructure nanofiber. The above patent documents disclose that the copper fiber is mainly prepared by a metal mechanical cutting method, wherein the electrospinning-carbonizing method requires high temperature and special equipment, and has low yield, high energy consumption and high cost, thereby limiting the wide use thereof; the fibers prepared by the metal mechanical cutting method are thick, and uniform nano-scale fibers cannot be obtained. Therefore, a new method for preparing the Cu/Fe/C core-shell heterostructure fiber, which is relatively simple in process, low in cost, universal, green, environment-friendly and easy to industrialize, is urgently needed to be developed.
Disclosure of Invention
The invention aims to provide a Cu/Fe/C core-shell heterostructure magnetic fiber and a preparation method and a use method thereof. The provided precursor in-situ carbothermic reduction-chemical vapor deposition method has the advantages of simple equipment, short period, good repeatability, large-scale production and the like; the prepared Cu/Fe/C core-shell heterostructure fiber has the characteristics of novel structure, good dispersibility and uniformity, adjustable size and composition and the like, 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.
The invention adopts the following technical scheme for solving the technical problems:
the heterostructure magnetic fiber provided by the invention comprises Fe, C and Cu; fe. Atomic percent of Cu and C elementsThe amount of the additive is 12.2-29.6%, 9.2-55.2%, 32.5-70.5%; the structure of the nano-fiber is a hollow or porous Cu/Fe/C core-shell structure nano-fiber consisting of a Cu/Fe core and a C shell, the length of the fiber can reach 50 mu m, and the diameter of the fiber is 70-380 nm; the saturation magnetization is 80.4-152.89 emu g–1。
The heterostructure magnetic fiber is prepared by adopting an in-situ carbothermic reduction-chemical vapor deposition method, namely: with polypyrrole/Cu2The O core-shell heterogeneous fiber is used as a template and a precursor, and polypyrrole is pyrolyzed to obtain C; fe (CO)5Thermally decomposing to obtain Fe and CO, and reacting Cu with CO and C2And reducing O into Cu, depositing Fe nanocrystalline on the surface of the Cu, and finally obtaining the Cu/Fe/C core-shell heterostructure fiber.
The in-situ carbothermic reduction-chemical vapor deposition method for preparing the heterostructure magnetic fiber comprises the following steps: mixing polypyrrole/Cu2O fiber and Fe (CO)5Loading the fiber by using a ceramic square boat according to the mass and volume ratio of 0.05-0.017 g/mL, placing the fiber in a single-temperature tube furnace, reacting at a certain temperature under the protection of high-purity argon or high-purity nitrogen, and cooling the fiber to room temperature along with the furnace to finally obtain the heterostructure magnetic fiber.
In the method, the heating rate is 0.5-5 ℃/min; the flow rate of the inert gas is 0.5 to 1L/min.
In the method, the reaction temperature is 550-650 ℃; the reaction time is 1-3 hours.
In the above method, the polypyrrole/Cu2The O fiber is prepared by a hydrothermal oxidation method, and specifically comprises the following steps: sequentially transferring a pyrrole aqueous solution and a copper acetate solution with certain concentrations into a liner of a reaction kettle, magnetically stirring for 30-60 minutes to obtain a mixed solution, then placing the liner into the reaction kettle, sealing, and reacting in an oven at 140-200 ℃ for 5-20 hours; cooling to room temperature, washing the lower precipitate with ethanol for several times, decanting to separate, and drying to obtain polypyrrole/Cu2O core-shell heterogeneous fiber.
In the method, the dosage relation of the reagents is as follows: the concentration of copper acetate is 25-150 millimoles per liter; the concentration of pyrrole is 8.3-200 millimoles per liter; the ratio of the amount of pyrrole to the amount of copper acetate is 12 to 0.5.
In the above method, the polypyrrole/Cu2The O fiber is polypyrrole shell and Cu2The length of the core-shell heterostructure fiber consisting of the O core can reach 50 micrometers, the diameter of the fiber is 79-330, and the thickness of the polypyrrole shell is 3-10 nm.
The heterostructure fiber provided by the invention has excellent light weight, wide frequency and high microwave electromagnetic absorption property, the maximum effective bandwidth of the reflectivity less than or equal to-10 dB is 2.48-3.82 GHz, and the maximum absorption is-34.71-44.41 dB; the frequency band range with the reflectivity less than-20 dB is within 1.6-12.81 GHz; the mass fraction of the heterostructure magnetic fibers in the composite with the matrix is 25-30%.
The heterostructure magnetic fiber provided by the invention is applied to the fields of photocatalysis, piezoelectric effect, microwave absorption, optoelectronics, photoelectric conversion or gas sensitivity.
In the invention, an in-situ carbothermic reduction-chemical vapor deposition method is adopted, and the contents of Fe, Cu and C and the shape and structure of the core-shell heterogeneous fiber are regulated and controlled by changing the size of a precursor, the content of an organic carbon source, the heating rate, the roasting temperature and the amount of iron pentacarbonyl. The Cu/Fe/C core-shell heterostructure fiber has the characteristics of good dispersibility and uniformity, adjustable size and composition, good microwave absorption property and the like, and the method has the advantages of simple equipment, short period, good repeatability, large-scale production and the like, and the materials have wide application prospects in the fields of electro-catalysis, lithium ion batteries, surface-enhanced Raman spectroscopy, microwave absorption and shielding and the like.
Because the technical scheme of the in-situ carbothermic reduction-chemical vapor deposition method is adopted, compared with the prior methods of metal mechanical cutting, electrostatic spinning-carbonization and the like, the method has the following advantages and positive effects:
(1) the production equipment is simple, green and environment-friendly, and has good repeatability;
(2) the structure, the composition and the forming mechanism are novel, and the light broadband high-absorption microwave electromagnetic property is excellent;
(3) the composition and the size of the heterostructure fiber are easy to regulate, and the atomic percentage content of Fe, Cu and C elements is 12.2-29.6 percent respectively; 9.2-55.2%; 32.5-70.5%; the fiber has a hollow or porous structure, the fiber size is smaller, the range is wider (the length can reach 50 mu m, and the diameter is smaller by 70-380 nm);
(4) the raw materials are cheap and easy to obtain, the preparation cost is low, the efficiency is high, and the large-scale production can be realized.
Drawings
FIGS. 1 to 5 are respectively an XRD phase structure spectrum, a structure, a morphology and a core-shell structure observed under an infrared spectrometer, a scanning electron microscope, a transmission electron microscope and selective area electron diffraction of the product obtained in example 1.
FIGS. 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, and 16 are the morphologies observed under a scanning electron microscope for the products obtained in examples 2 to 12, respectively.
FIGS. 17 to 21 are the radiation diagrams of the product obtained in example 13, which are observed under an energy spectrometer, a scanning electron microscope, a transmission electron microscope and selected electron diffraction, and which show the composition, morphology, microstructure and product mass fraction of 30%.
FIGS. 22 to 25 are the radiation diagrams of the product obtained in example 14, which are observed under an energy spectrometer, an XRD diffractometer and a scanning electron microscope, and which have a composition, a phase structure, a morphology and a product mass fraction of 30%.
FIGS. 26 to 28 show compositions, phase structures, and morphologies of the products obtained in example 15 observed by an energy spectrometer, an XRD diffractometer, and a scanning electron microscope.
FIGS. 29 to 32 show compositions, morphologies, and structures of the products obtained in example 16 observed under an energy spectrometer, a scanning electron microscope, selective electron diffraction, and a transmission electron microscope.
FIGS. 33 to 35 are diagrams of the compositions, morphologies, and mass fractions of the products obtained in example 17, which were observed with an energy spectrometer and a scanning electron microscope, showing a reflection ray.
FIGS. 36 to 37 are graphs of the morphology of the product obtained in example 18 observed under a scanning electron microscope and the reflection ray when the mass fraction of the product is 25%.
Detailed Description
The invention discloses a core-shell heterogeneous materialStructural nanofibers and their preparation and use. The composition of the core-shell heterostructure nanofiber is C, Fe and Cu; fe. The atomic percentage contents of Cu and C elements are respectively 12.2-29.6%, 9.2-55.2% and 32.5-70.5%; the structure of the nano fiber is Cu/Fe/C core-shell structure nano fiber consisting of a Cu/Fe core and a C shell, the diameter is 70-380 nm, and the length can reach 50 microns. The core-shell heterostructure nanofiber is prepared by adopting an in-situ carbothermic reduction-chemical vapor deposition method, namely: separately loading organic Polymer coated Cu with ceramic Canoe2And (3) placing the O core-shell heterogeneous nano-fibers and the iron pentacarbonyl into a tubular furnace, and roasting under the protection of inert gas. The fiber has excellent microwave absorption characteristics: the maximum effective bandwidth of the reflectivity less than or equal to-10 dB is 2.48-3.82 GHz, and the maximum absorption is-34.71-44.41 dB. The method has the advantages of simple equipment, short period, good repeatability, large-scale production and the like, and has wide application prospect in the fields of electro-catalysis, microwave absorption, lithium ion batteries, surface enhanced Raman spectroscopy and the like.
In order to better understand the present invention, the following examples are further provided to illustrate the present invention, but the present invention is not limited to the following examples.
Example 1
Firstly, preparing 20 ml of 50 mmol/l copper acetate solution (0.2 g) and 60 ml of 16.7 mmol/l pyrrole aqueous solution (the amount ratio of pyrrole to copper acetate is 2:1), then transferring the prepared pyrrole aqueous solution and copper acetate solution into a 100 ml reaction kettle lining, magnetically stirring for 60 minutes to obtain a mixed solution, then placing the lining into the reaction kettle for sealing, and reacting in a drying oven at 140 ℃ for 10 hours; dispersing the lower precipitate in ethanol at room temperature, precipitating and separating for several times to obtain pure precipitate, and drying to obtain polypyrrole/Cu2O core-shell heterogeneous fiber.
The obtained product is green, and the phase, structure, morphology, microstructure and selected area electron diffraction patterns observed under an XRD diffractometer, an infrared spectrometer, a scanning electron microscope and a transmission electron microscope are respectively shown in figures 1-5. The product was found to be polypyrrole/Cu2O core-shell heterofiber with fiber diameter of 90-190 nm, a length of 50 μm, and a polypyrrole shell thickness of 5-6 nm.
Example 2
The procedure of example 1 was followed except that the ratio of the amount of pyrrole to the amount of copper acetate species was 0.5:1 and the concentration of pyrrole was 8.3 mmoles per liter. The appearance of the obtained product observed under a scanning electron microscope is shown in figure 6. As can be seen, the product is polypyrrole/Cu with smooth surface and uniform thickness2The O core-shell heterogeneous fiber has the diameter of 100-200 nm. The reaction ratio is reduced and the diameter is enlarged.
Example 3
The procedure of example 1 was followed except that the amount of pyrrole to copper acetate species was 2:0.5 and the copper salt concentration was 25 mmoles per liter. The appearance of the obtained product observed under a scanning electron microscope is shown in figure 7. As can be seen, the product was a uniform, uniform-thickness polypyrrole/Cu film2The O core-shell heterogeneous fiber has the diameter of 110-200 nm.
Example 4
The procedure of example 1 was followed except that the amount of pyrrole to copper acetate species was 12:1 and the copper salt concentration was 0.5 mmole per liter. The appearance of the obtained product observed under a scanning electron microscope is shown in figure 8. As can be seen, the product was a homogeneous, monodisperse polypyrrole/Cu2The O core-shell heterogeneous fiber is smooth in surface, uniform in thickness and 79-98 nm in diameter.
Example 5
The procedure of example 1 was followed, except that the reaction temperature was 180 ℃. The appearance of the obtained product observed under a scanning electron microscope is shown in figure 9. As can be seen, the product was a homogeneous, monodisperse polypyrrole/Cu2The O core-shell heterogeneous fiber has a fiber diameter of 110-200 nm.
Example 6
The procedure of example 1 was followed, except that the reaction temperature was 200 ℃ and the reaction time was 5 hours. The appearance of the obtained product observed under a scanning electron microscope is shown in figure 10. As can be seen, the product was a uniform-sized, monodisperse polypyrrole/Cu2The O core-shell heterogeneous fiber is in a locally hollow pod-shaped structure, and the diameter of the O core-shell heterogeneous fiber is 100-170 nm. A significant decrease in nanofiber diameter is seen with increasing temperature.
Example 7
The procedure of example 1 was followed except that the ratio of the amount of pyrrole to the amount of copper acetate species was 3:1 and the concentration of pyrrole was 50 mmoles per liter. The morphology of the obtained product observed under a scanning electron microscope is shown in fig. 11. As can be seen, the product was a uniform-sized, monodisperse polypyrrole/Cu2The O core-shell heterogeneous fiber has the diameter of 120-250 nm.
Example 8
The procedure of example 1 was followed except that the ratio of pyrrole to copper acetate species was 4:1 and the pyrrole concentration was 66.7 mmoles per liter. The appearance of the obtained product observed under a scanning electron microscope is shown in figure 12. As can be seen, the product was a uniform-sized, monodisperse polypyrrole/Cu2And in the O core-shell heterogeneous fiber, granular polypyrrole is deposited on the surface, so that the surface is rough, and the diameter of the fiber is 120-220 nm.
Example 9
The procedure of example 1 was followed, except that the reaction temperature was 160 ℃ and the reaction time was 15 hours. The appearance of the obtained product observed under a scanning electron microscope is shown in figure 13. As can be seen, the product was a uniform-sized, monodisperse polypyrrole/Cu2And (3) the O core-shell heterogeneous fiber, wherein granular polypyrrole is deposited on the surface, so that the surface is rough, and the diameter of the fiber is 110-330 nm.
Example 10
The procedure is as in example 1, but the reaction temperature is 200 ℃ and the reaction time is 5h, and the pyrrole concentration is 133.4 mmol per liter. The morphology of the obtained product observed under a scanning electron microscope is shown in fig. 14. As can be seen, the product was a uniform-sized, monodisperse polypyrrole/Cu2The O core-shell heterogeneous fiber is in a locally hollow pod-shaped structure, granular polypyrrole is deposited on the surface, the surface becomes rough, and the diameter of the fiber is 90-130 nm.
Example 11
The procedure of example 1 was followed, except that the reaction temperature was 200 ℃ and the reaction time was 10 hours. The morphology of the obtained product observed under a scanning electron microscope is shown in fig. 15. As can be seen, the product was a uniform-sized, monodisperse polypyrrole/Cu2O core-shell heterogeneous fiber, part of the structure is in the shape of a locally hollow pod, granular polypyrrole is deposited on the surface, the surface becomes rough,the diameter of the fiber is 100-170 nm.
Example 12
The procedure of example 1 was followed, except that the reaction temperature was 200 ℃ and the reaction time was 20 hours. The morphology of the obtained product observed under a scanning electron microscope is shown in fig. 16. As can be seen, the product was a uniform-sized, monodisperse polypyrrole/Cu2The O core-shell heterogeneous fiber is in a locally hollow pod-shaped structure, and the diameter of the fiber is 90-170 nm.
Example 13
0.1g of polypyrrole/Cu with the diameter of 80-130 nm2O fiber and 2mL Fe (CO)5Respectively loaded by a ceramic ark, placed in a single-temperature tube furnace, calcined for 120 minutes at 600 ℃ under the protection of high-purity nitrogen, and the reaction temperature rise rate is 5 ℃/min. The composition, surface morphology and microstructure of the obtained product observed under an energy spectrometer, a scanning electron microscope and a transmission electron microscope are respectively shown in FIGS. 17-20. Therefore, the product is uniform and monodisperse Cu/Fe/CC nuclear shell structure nanofiber. The diameter is 150-170 nm, the wall thickness is 25-50 nm, the length can reach 50 μm, and the Cu/Fe/C atomic ratio is 1:0.85: 3.70.
The heterogeneous material is filled in a paraffin base by 30 percent of mass fraction, and the reflectivity is measured as shown in figure 21, wherein the maximum effective bandwidth range of the reflectivity of less than or equal to-10 dB is 3.5GHz, the frequency range of the reflectivity of less than or equal to-20 dB is 11.7GHz, and the maximum reflection loss is-44.41 dB.
Example 14
The same procedure as in example 13, but at 550 deg.C, the composition, phase and surface morphology of the obtained product observed under energy spectrometer, XRD diffractometer and scanning electron microscope are shown in FIGS. 22-24 respectively. Therefore, the product is uniform and monodisperse Cu/Fe/C core-shell heterostructure nanofiber. The diameter is 130-180 nm, the wall thickness is 25-37 nm, the length is about 10-50 μm, and the Cu/Fe/C atomic ratio is: 1:0.76:4.20.
The heterogeneous material was filled in a paraffin base at a mass fraction of 30%, and the measured reflectance was as shown in fig. 25, in which the maximum effective bandwidth of-10 dB reflectance or less was 3.52GHz, the frequency range of-20 dB reflectance or less was 2.24GHz, and the maximum reflection loss was-42.16 dB.
Example 15
The procedure is as in example 13, but the temperature is 650 ℃. The composition, phase and morphology of the obtained product observed under an energy spectrometer, an XRD diffractometer and a scanning electron microscope are respectively shown in figures 26-28. Therefore, the product is uniform and monodisperse Cu/Fe/C core-shell heterostructure nanofiber, the diameter is 190-380 nm, the length can reach 50 mu m, and the atomic ratio of Cu/Fe/C is 1:1.85: 3.40.
Example 16
Same procedure as in example 13, but polypyrrole/Cu2The diameter of the O precursor is 170-230 nm, and the composition, the surface morphology and the structure of the obtained product observed under an energy spectrometer, a scanning electron microscope and a transmission electron microscope are respectively shown in FIGS. 29-32. Therefore, the product is uniform and monodisperse Cu/Fe/C core-shell heterostructure nanofiber, the diameter is 140-220 nm, the wall thickness is 42-79 nm, the length can reach 50 mu m, and the Cu/Fe/C atomic ratio is as follows: 1:0.22:0.59.
Example 17
Same procedure as in example 13, but with the addition of 4mL of Fe (CO)5. The composition and morphology of the obtained product observed under an energy spectrometer and a scanning electron microscope are respectively shown in FIGS. 33-34. The product is uniform and monodisperse Cu/Fe/C core-shell heterostructure nanofiber, the diameter is 160-200 nm, the wall thickness is 20-50 nm, the length can reach 50 mu m, and the Cu/Fe/C atomic ratio is as follows: 1:3.07:6.76.
The heterogeneous material was filled in a paraffin base at a mass fraction of 30%, and the measured reflectance was as shown in fig. 35, in which the effective bandwidth was 3.82GHz at the maximum effective bandwidth of-10 dB or less, the frequency range of-20 dB or less reflectance was 12.81GHz, and the maximum reflection loss was-43.1 dB.
Example 18
Same procedure as in example 13, but adding 6mL of Fe (CO) to the reaction5. The shapes of the obtained products observed under a scanning electron microscope are respectively shown in fig. 36. Therefore, the product is uniform and monodisperse Cu/Fe/C core-shell heterostructure nanofiber, the diameter is 250-380 nm, the length can reach 50 mu m, and the Cu/Fe/C atomic ratio is as follows: 1:1.52:5.54.
The heterogeneous material is filled in a paraffin base by 25 percent of mass fraction, and the measured reflectivity is shown in figure 37, wherein the maximum effective bandwidth of the reflectivity of less than or equal to-10 dB is 3.69GHz, the frequency range of the reflectivity of less than or equal to-20 dB is 3.79GHz, and the maximum reflection loss is-42.8 dB.

Claims (8)

1. A magnetic fiber with a core-shell heterostructure is characterized in that the magnetic fiber comprises Fe, Cu and C; fe. The atomic percentage contents of Cu and C elements are respectively 12.2-29.6%, 9.2-55.2% and 32.5-70.5%; the structure of the nano-fiber is Cu/Fe/C core-shell structure nano-fiber which consists of a Cu/Fe core and a C shell and has a hollow or porous structure, the length of the nano-fiber is 50 mu m, and the diameter of the nano-fiber is 70-380 nm; the saturation magnetization is 80.4-152.89 emu g–1。
2. The core-shell heterostructure magnetic fiber of claim 1, wherein the material has light weight, wide frequency, microwave electromagnetic absorption, effective bandwidth of-10 dB reflectivity or less of 2.48 to 3.82GHz, absorption of-34.71 to-44.41 dB; the frequency band range with the reflectivity less than-20 dB is within 1.6-12.81 GHz; the mass fraction of the core-shell heterostructure magnetic fibers and a matrix composite is 25-30%, and the matrix composite is a paraffin base.
3. A preparation method of magnetic fiber with a core-shell heterostructure is characterized by adopting an in-situ carbothermic reduction-chemical vapor deposition method, namely: with polypyrrole/Cu2The O core-shell heterogeneous fiber is used as a template and a precursor, and polypyrrole is pyrolyzed to obtain C; fe (CO)5Thermally decomposing to obtain Fe and CO, and reacting Cu with CO and C2Reducing O into Cu, depositing Fe nanocrystalline on the surface of Cu, and finally obtaining Cu/Fe/C core-shell heterostructure fiber;
polypyrrole/Cu2The O core-shell heterogeneous fiber is prepared by a hydrothermal oxidation method, and specifically comprises the following steps: sequentially transferring the pyrrole aqueous solution and the copper acetate solution into a liner of a reaction kettle, stirring for 30-60 minutes to obtain a mixed solution, then placing the liner into the reaction kettle, sealing, and reacting in an oven at 140-200 ℃ for 5-20 hours; is cooled toWashing the lower precipitate with ethanol several times at room temperature, and separating by decantation; finally drying to obtain polypyrrole/Cu2O core-shell heterogeneous fibers;
mixing polypyrrole/Cu2O fiber and Fe (CO)5Loading the fiber by using a ceramic square boat according to the mass and volume ratio of 0.05-0.017 g/mL, placing the fiber in a single-temperature tube furnace, reacting at a certain temperature under the protection of high-purity argon or high-purity nitrogen, cooling the fiber to room temperature along with the furnace, and recovering to obtain the heterostructure magnetic fiber.
4. A method of making core-shell heterostructure magnetic fibers of claim 3, employing the following reagents: the concentration of copper acetate is 25-150 millimoles per liter; the concentration of pyrrole is 8.3-200 millimoles per liter; the ratio of the amount of pyrrole to the amount of copper acetate is 12 to 0.5.
5. The preparation method of the core-shell heterostructure magnetic fiber according to claim 3, characterized in that the reaction temperature is 550 to 650 ℃; the reaction time is 1-3 hours; the flow rate of the high-purity argon or the high-purity nitrogen is 0.5-1L/min.
6. The preparation method of the core-shell heterostructure magnetic fiber according to claim 3, wherein the temperature rise rate is 0.5 to 5 ℃/min.
7. The method for preparing core-shell heterostructure magnetic fibers of claim 3, wherein the polypyrrole/Cu is present2The O fiber is polypyrrole shell and Cu2The length of the core-shell heterostructure fiber consisting of the O core is 50 microns, the fiber diameter is 79-330 mm, and the thickness of the polypyrrole shell is 3-10 nm.
8. Core-shell heterostructure magnetic fibers prepared by the process according to any of claims 3 to 7, for applications in the fields of catalysis, piezoelectric effect, microwave absorption, optoelectronics, photoelectric conversion or gas sensing.
CN201811068449.6A 2018-09-13 2018-09-13 Magnetic fiber with core-shell heterostructure and preparation and application methods thereof Active CN109128138B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201811068449.6A CN109128138B (en) 2018-09-13 2018-09-13 Magnetic fiber with core-shell heterostructure and preparation and application methods thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201811068449.6A CN109128138B (en) 2018-09-13 2018-09-13 Magnetic fiber with core-shell heterostructure and preparation and application methods thereof

Publications (2)

Publication Number Publication Date
CN109128138A CN109128138A (en) 2019-01-04
CN109128138B true CN109128138B (en) 2020-08-25

Family

ID=64825242

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201811068449.6A Active CN109128138B (en) 2018-09-13 2018-09-13 Magnetic fiber with core-shell heterostructure and preparation and application methods thereof

Country Status (1)

Country Link
CN (1) CN109128138B (en)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI686309B (en) * 2019-01-09 2020-03-01 可成科技股份有限公司 Heat-dissipating structure and manufacturing method thereof
CN110071300B (en) * 2019-04-28 2021-10-01 三峡大学 Preparation method of transition metal/nitrogen-doped carbon fiber electrocatalyst
CN111014649B (en) * 2019-10-31 2021-09-21 浙江师范大学 Magnetic hollow micro-nano material and preparation method and application thereof
CN113289619B (en) * 2021-04-30 2022-08-16 西北有色金属研究院 Preparation method of flexible carbon fiber loaded gold electrocatalyst

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005268509A (en) * 2004-03-18 2005-09-29 Magu Style:Kk Sheet-shaped bond magnet and its manufacturing method
EP2249964A1 (en) * 2008-02-27 2010-11-17 Basf Se Method for the production of iron-doped carbons
CN101898749B (en) * 2010-08-02 2014-07-02 武汉理工大学 Method for preparing metal oxide hollow particles or fibers
KR101331782B1 (en) * 2012-02-07 2013-11-28 공주대학교 산학협력단 Ag Nanowire Having Titanium Oxide Shell and the Fabrication Method Thereof
CN104034775B (en) * 2014-06-27 2016-03-30 安徽师范大学 A kind of polypyrrole/silver-colored silver chloride nuclear shell structure nano line, preparation method and application thereof
CN104927760B (en) * 2015-04-30 2017-04-05 浙江师范大学 A kind of magnetic heterojunction structure fiber and preparation method and application

Also Published As

Publication number Publication date
CN109128138A (en) 2019-01-04

Similar Documents

Publication Publication Date Title
Wang et al. Hierarchical nest-like structure of Co/Fe MOF derived CoFe@ C composite as wide-bandwidth microwave absorber
CN109128138B (en) Magnetic fiber with core-shell heterostructure and preparation and application methods thereof
Chen et al. Bimetallic CoFe-MOF@ Ti3C2Tx MXene derived composites for broadband microwave absorption
Kong et al. Construction of metal-organic framework derived Co/ZnO/Ti3C2Tx composites for excellent microwave absorption
Wang et al. A review on carbon/magnetic metal composites for microwave absorption
Yi et al. Regulating pyrolysis strategy to construct CNTs-linked porous cubic Prussian blue analogue derivatives for lightweight and broadband microwave absorption
Chai et al. Tunable defects and interfaces of hierarchical dandelion-like NiCo2O4 via Ostwald ripening process for high-efficiency electromagnetic wave absorption
Peng et al. Microcapsule MOFs@ MOFs derived porous “nut-bread” composites with broadband microwave absorption
Zhang et al. Designable synthesis of reduced graphene oxide modified using CoFe2O4 nanospheres with tunable enhanced microwave absorption performances between the whole X and Ku bands
Gao et al. Strategies for electromagnetic wave absorbers derived from zeolite imidazole framework (ZIF-67) with ferrocene containing polymers
Fan et al. Facile fabrication hierarchical urchin-like C/NiCo2O4/ZnO composites as excellent microwave absorbers
Li et al. In situ synthesis of CoFe2O4 nanocrystals decorated in mesoporous carbon nanofibers with enhanced electromagnetic performance
Zhou et al. Multi-dimensional ordered mesoporous carbon/silica@ Ni composite with hierarchical nanostructure for strong and broadband microwave absorption
Wu et al. Three-dimensional FeMZn (M= Co or Ni) MOFs: Ions coordinated self-assembling processes and boosting microwave absorption
Li et al. Micro-nanospheres assembled with helically coiled nitrogen-doped carbon nanotubes: fabrication and microwave absorption properties
Yao et al. Facile synthesis of La2O3/Co@ N-doped carbon nanotubes via Prussian blue analogues toward strong microwave absorption
Wang et al. Construction of string-bead-like spatial conductive network derived from CoFe Prussian blue analogue and carbon nanotube composite for excellent electromagnetic wave absorption
Ding et al. Novel ternary Co3O4/CeO2/CNTs composites for high-performance broadband electromagnetic wave absorption
Liu et al. Governing the Ni content and size of 2D layered C/Ni nanoparticle composites for enhanced electromagnetic wave absorption
CN115491177B (en) MOF-derived carbon-based magnetic nano composite electromagnetic wave absorbing material and preparation method thereof
Ma et al. Ti3C2Tx MXene@ NiFe layered double hydroxide derived multiple interfacial composites with efficient microwave absorption
Hou et al. Designing flower-like MOFs-derived N-doped carbon nanotubes encapsulated magnetic NiCo composites with multi-heterointerfaces for efficient electromagnetic wave absorption
Zhou et al. Multiple interfacial polarization from 3D net-like ZnO@ MWCNTs@ NiFe2O4 nanocomposites as broadband microwave absorbers
Zheng et al. Flower-like bimetal-organic framework derived composites with tunable structures for high-efficiency electromagnetic wave absorption
Lv et al. Ti3C2Tx/Co-MOF derived TiO2/Co/C composites for broadband and high absorption of electromagnetic wave

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