CN117758396A - Copper-based metal organic framework derived carbon composite nanofiber as well as preparation method and application thereof - Google Patents
Copper-based metal organic framework derived carbon composite nanofiber as well as preparation method and application thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 76
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 68
- 239000002131 composite material Substances 0.000 title claims abstract description 59
- 239000002121 nanofiber Substances 0.000 title claims abstract description 56
- 239000013084 copper-based metal-organic framework Substances 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000010949 copper Substances 0.000 claims abstract description 54
- 239000000835 fiber Substances 0.000 claims abstract description 26
- 239000002105 nanoparticle Substances 0.000 claims abstract description 23
- 239000002245 particle Substances 0.000 claims abstract description 11
- 229920000049 Carbon (fiber) Polymers 0.000 claims abstract description 10
- 239000004917 carbon fiber Substances 0.000 claims abstract description 10
- 239000011159 matrix material Substances 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 20
- 238000001354 calcination Methods 0.000 claims description 19
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 17
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 12
- 238000001523 electrospinning Methods 0.000 claims description 10
- 239000013148 Cu-BTC MOF Substances 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 7
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 6
- 239000012298 atmosphere Substances 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
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- 230000003647 oxidation Effects 0.000 claims description 4
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
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- 239000013110 organic ligand Substances 0.000 claims description 3
- 230000001590 oxidative effect Effects 0.000 claims description 3
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 2
- 229910001431 copper ion Inorganic materials 0.000 claims description 2
- 229910021392 nanocarbon Inorganic materials 0.000 claims description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 239000011358 absorbing material Substances 0.000 abstract description 21
- 239000012621 metal-organic framework Substances 0.000 abstract description 20
- 238000010521 absorption reaction Methods 0.000 abstract description 17
- 238000011049 filling Methods 0.000 abstract description 3
- 239000006096 absorbing agent Substances 0.000 description 18
- 239000000463 material Substances 0.000 description 16
- 239000012188 paraffin wax Substances 0.000 description 10
- YIWGJFPJRAEKMK-UHFFFAOYSA-N 1-(2H-benzotriazol-5-yl)-3-methyl-8-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carbonyl]-1,3,8-triazaspiro[4.5]decane-2,4-dione Chemical compound CN1C(=O)N(c2ccc3n[nH]nc3c2)C2(CCN(CC2)C(=O)c2cnc(NCc3cccc(OC(F)(F)F)c3)nc2)C1=O YIWGJFPJRAEKMK-UHFFFAOYSA-N 0.000 description 9
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Abstract
The invention discloses a copper-based metal organic framework derived carbon composite nanofiber, and a preparation method and application thereof, wherein the composite nanofiber comprises a three-dimensional network structure matrix formed by stacking one-dimensional carbon fibers and octahedral Cu which is monodisperse in the one-dimensional carbon fibers and on the inner part and the surface of the one-dimensional carbon fibers 9 S 5 and/C nanoparticles. The invention leads MOF to be derived from Cu 9 S 5 the/C nanoparticles are dispersed within the carbonaceous fibers, and the carbonaceous fibers are utilized to construct a conductive network between MOF-derived particles. Prepared hierarchical Cu 9 S 5 The carbon composite nanofiber electromagnetic wave absorbing material has the characteristics of high absorption intensity, wide absorption frequency band, thin matching thickness, low filling amount and the like, and meanwhile, the preparation method is simple and feasible, has low cost and has great industrial application prospect.
Description
Technical Field
The invention belongs to the field of electromagnetic wave absorbing materials, and particularly relates to a copper-based metal-organic framework derived carbon composite nanofiber as well as a preparation method and application thereof.
Background
The statements herein merely provide background information related to the present disclosure and may not necessarily constitute prior art.
The vigorous development of the fifth generation mobile communication technology predicts the arrival of the global intelligent era, and the consequent electromagnetic wave pollution is attracting public attention. The ubiquitous electromagnetic radiation places higher demands on electromagnetic wave absorbing materials: the electromagnetic wave absorbing material needs to realize high absorption strength, light weight, thin thickness and wide absorption bandwidth at the same time. Metal Organic Framework (MOF) -derived carbon-based composite materials are considered as one of the powerful candidates for achieving high absorption strength, thin thickness, and wide absorption bandwidth due to their diverse defects, optional components, and rich interfaces. At the same time, transition metal sulfides have received great attention as a second component of MOF-derived carbon-based composites because of their higher chemical stability than metals and richer loss pathways than metal oxides.
However, MOF-derived carbon-based composite materials have a problem that the filling rate is generally more than 40wt%, which is contrary to the purpose of weight reduction of electromagnetic wave absorbing materials. This phenomenon can be attributed to the discontinuity of the conductive path caused by the separability of the MOF-derived particles, resulting in an increase in the percolation threshold of the wave-absorbing body. Currently, various improvement strategies are applied to optimize conductivity, for example, to increase carbonization temperature, or to optimize component selection, or to complex with highly conductive materials (e.g., graphene, carbon nanotubes). However, the former two methods have problems that the structure is easily collapsed and the conductivity is not sufficiently improved, respectively. For the composition of MOF-derived carbon-based particles and graphene or carbon nanotubes, the current widely applied methods (direct loading method and in-situ growth method) cannot realize the precise loading and stable dispersion of MOF particles at the same time, which limits the breakthrough of electromagnetic wave absorption performance and the design of efficient electromagnetic wave absorbers in the future.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention aims to provide copper-based metal organic framework derived carbon composite nanofiber as well as a preparation method and application thereof. The invention leads MOF to be derived from Cu 9 S 5 the/C nanoparticles are dispersed within the carbonaceous fibers, and the carbonaceous fibers are utilized to construct a conductive network between MOF-derived particles. Prepared hierarchical Cu 9 S 5 The carbon composite nanofiber electromagnetic wave absorbing material has the characteristics of high absorption intensity, wide absorption frequency band, thin matching thickness, low filling amount and the like, and meanwhile, the preparation method is simple and feasible, has low cost and has great industrial application prospect.
In order to achieve the above object, the present invention is realized by the following technical scheme:
in a first aspect, the invention provides a copper-based metal-organic framework-derived carbon composite nanofiber, comprising a three-dimensional network structure matrix formed by stacking one-dimensional carbonaceous fibers and octahedral Cu monodisperse in and on the one-dimensional carbonaceous fibers 9 S 5 and/C nanoparticles.
Copper-based MOF-derived octahedral Cu 9 S 5 the/C nano particles are monodisperse in the one-dimensional carbonaceous fibers, and a conductive network is constructed among MOF derived particles through the carbonaceous fibers, so that the improvement of conductivity, the optimization of impedance matching and the synergistic effect of various loss mechanisms are realized. First, the unique hierarchy and selection of reasonable MOF loadings results in optimization of electromagnetic parameters to achieve optimal impedance matching characteristics. Second, N, O, S doping atoms and Cu in carbon 9 S 5 The inherent defect in (a) can act as a polarization center, trapping unpaired electrons, causing dipole polarization effects. Third, a special layered carbon structure and rich Cu 9 S 5 the-C interface results in higher interface polarization losses. Finally, three-dimensional guideThe electrical network provides a channel for carrier migration and hopping in the MOF-derived composite particles, forming a microcurrent amplifier, facilitating conduction losses.
In some embodiments, the one-dimensional carbonaceous fibers have a diameter of 100-500nm.
In some embodiments, octahedral Cu 9 S 5 The average particle diameter of the/C nano-particles is 500-600nm.
Preferably, cu 9 S 5 The average diameter of the particles is 80-120nm.
In some embodiments, octahedral Cu 9 S 5 The mass percentage of the C nano particles in the composite nano fiber is 0-50 wt% and is not 0;
preferably, octahedral Cu 9 S 5 The mass percentage of the/C nano particles in the composite nano fiber is 5-40 wt%.
Further preferred, octahedral Cu 9 S 5 The mass percentage of the/C nano particles in the composite nano fiber is 10-40 wt%.
In a second aspect, the invention provides a preparation method of the copper-based metal organic framework derived carbon composite nanofiber, which comprises the following steps:
preparing a viscous electrospinning solution from copper-based MOF powder and a carbon source, then carrying out electrostatic spinning to obtain nanofibers, drying and pre-oxidizing the nanofibers, wherein the copper-based MOF is HKUST-1 or Cu-BDC;
calcining the pre-oxidized nanofiber in an inert atmosphere for one time to reduce copper ions into copper, converting an organic ligand into an octahedral carbon skeleton, and converting a carbon source fiber matrix into nano-carbon fibers;
and (3) co-calcining the calcined nanofiber with thiourea in an inert atmosphere to obtain the nano-fiber.
The invention prepares the hierarchical carbon nanofiber with a one-dimensional microstructure by high-voltage electrostatic spinning, and the three-dimensional network structure is formed by stacking the fibers, so that the conductivity of the composite material is improved, and meanwhile, the hierarchical structure brings optimization of impedance matching; h produced by decomposition of thiourea during calcination 2 S converts elemental copper into Cu 9 S 5 Simultaneously, sulfur doping in the carbonaceous fibers is caused, organic ligands of PVP and MOF are used as organic carbon sources, a large amount of N, O elements are contained, and N, O elements remain in the carbonaceous fibers during calcination to form nitrogen and oxygen doping.
In some embodiments, the viscous electrospinning solution comprises polyvinylpyrrolidone as the carbon source and N, N-Dimethylformamide (DMF) as the solvent.
Preferably, in the viscous electrospinning solution, the addition ratio of the copper-based MOF, the carbon source and the DMF is 3.5-1.4:1-2:5-20, and g is g to mL;
further preferably, in the viscous electrospinning solution, the addition ratio of the copper-based MOF, the carbon source and the DMF is 6-12:1.4:6-10, and g is g to mL;
still more preferably, the addition ratio of copper-based MOF, carbon source and DMF in the viscous electrospinning solution is 0.933:1.4:7.05, g: mL.
In some embodiments, the drying is at a temperature of 45-60 ℃ for a period of 12-24 hours.
In some embodiments, the method of pre-oxidizing is: and (3) preserving the heat of the dried nanofiber for 2-3 hours at the temperature of 150-200 ℃. The pre-oxidation can lead the organic carbon chain to initially form an annular structure, so that the organic carbon chain is not cracked in the subsequent carbonization process, and the collapse of the structure is avoided.
In some embodiments, the temperature of the primary calcination is 600-900 ℃ and the calcination time is 0.5-5 hours.
Preferably, the temperature of the primary calcination is 650-800 ℃ and the calcination time is 1-2h.
In some embodiments, the temperature of co-calcination with thiourea is 400-500 ℃ and the calcination time is 0.2-0.5h.
In a third aspect, the invention provides an application of the copper-based metal-organic framework derived carbon composite nanofiber in preparing an electromagnetic wave absorbing device.
The beneficial effects achieved by one or more embodiments of the present invention described above are as follows:
(1) The copper-based MOF-derived hierarchical Cu prepared by the invention 9 S 5 Carbon composite nanofiber electromagnetic wave absorbing material, produced byThe carbon fiber constructs a conductive network of the MOF, so that the conductivity of the composite material is improved and the electromagnetic parameters are adjusted.
(2) The copper-based MOF-derived hierarchical Cu prepared by the invention 9 S 5 The carbon composite nanofiber electromagnetic wave absorbing material realizes the optimization of impedance matching through a layering structure, and can realize a wide impedance matching frequency band below 2 mm thickness.
(3) The copper-based MOF-derived hierarchical Cu prepared by the invention 9 S 5 The carbon composite nanofiber electromagnetic wave absorbing material realizes the synergistic effect of various loss paths. Doping atoms in carbon and Cu 9 S 5 The inherent defect in (a) can act as a polarization center, trapping unpaired electrons, causing dipole polarization effects. Special layered carbon structure and rich Cu 9 S 5 The carbon interface results in a relatively rich loss of interfacial polarization. The three-dimensional conductive network is carbon and Cu 9 S 5 The carrier migration and hopping in (a) provides a channel, forming a micro-current amplifier, facilitating conduction losses.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention.
FIG. 1 is a copper-based MOF-derived layered Cu prepared in example 1 9 S 5 SEM image of carbon composite nanofiber electromagnetic wave absorbing material.
FIG. 2 is a copper-based MOF-derived layered Cu prepared in example 1 9 S 5 -TEM images of carbon composite nanofiber electromagnetic wave absorbing material.
FIG. 3 is a copper-based MOF-derived layered Cu prepared in example 1 9 S 5 XRD pattern of carbon composite nanofiber electromagnetic wave absorbing material.
FIG. 4 is a copper-based MOF-derived layered Cu prepared in example 1 9 S 5 -XPS spectra of carbon composite nanofiber electromagnetic wave absorbing material; 4a is a full spectrum containing C, N, O, cu, S element, 4b is a C element partial amplified spectrum, and 4C is NElement partial amplification energy spectrum, 4d is Cu element partial amplification energy spectrum, and 4e is S element partial amplification energy spectrum.
Fig. 5 is an electromagnetic parameter chart of the wave absorbers prepared in example 2, example 3, example 4, example 5 and example 6.
Detailed Description
It should be noted that the following detailed description is illustrative and is intended to provide further explanation of the invention. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
The invention is further illustrated below with reference to examples.
Example 1
Copper-based MOF-derived layered Cu 9 S 5 -a method for preparing a carbon composite nanofiber electromagnetic wave absorbing material, comprising the steps of:
(1) 0.933g HKUST-1 powder is dissolved in 7.05ml DMF, 1.4g PVP is added after ultrasonic dispersion, and the uniform viscous solution is obtained by vigorous stirring;
(2) Spinning the viscous solution in the step (1) by using a high-voltage electrostatic spinning process under a 12kV high-voltage electrostatic condition to obtain organic fibers, drying the organic fibers at 50 ℃ for 12 hours, and then preserving heat at 180 ℃ for 3 hours to perform pre-oxidation treatment;
(3) And (3) placing the product subjected to the pre-oxidation treatment in the step (2) in a closed tubular furnace, and carrying out high-temperature calcination treatment at 700 ℃ for 2 hours in a nitrogen atmosphere.
(4) Placing the product after the calcination treatment in the step (3) in a closed tubular furnace, placing excessive thiourea on the upstream of the tubular furnace and placing the product on the downstream of the tubular furnace, and carrying out high-temperature calcination treatment at 450 ℃ for 0.5h to obtain the copper-based MOF-derived hierarchical Cu 9 S 5 -carbon composite nanofiber electromagnetic wave absorbing material.
FIG. 1 is a copper-based MOF-derived layered Cu prepared in example 1 9 S 5 SEM images of carbon composite nanofibrous material, from which it can be seen that the material prepared is provided with "stringsBeaded "profiled fibers with irregular nanoparticles embedded in the fibers. The carbon-based fibers with high aspect ratio are mutually piled to form a three-dimensional network structure.
FIG. 2 is a copper-based MOF-derived layered Cu prepared in example 1 9 S 5 -TEM images of carbon composite nanofiber material. There are a large number of cavities in the fiber matrix, with a diameter of about 150nm, and these cavities are always accompanied by nanoparticles. While there is a distinct layered interface structure within the fiber.
FIG. 3 is a copper-based MOF-derived layered Cu prepared in example 1 9 S 5 XRD patterns of carbon composite nanofiber materials, indicating that the composite material synthesized contains Cu 9 S 5 And C, XRD spectrum line and standard diffraction pattern Cu 9 S 5 (JCPDS No. 47-1748) has better anastomosis degree. The amorphous carbon peak intensity in the XRD spectrum is low and not sharp, because of its poor crystallinity.
FIG. 4 is a copper-based MOF-derived layered Cu prepared in example 1 9 S 5 XPS (x-ray image) of carbon composite nanofiber material, from which Cu can be seen 9 S 5 The ions in (a) are composed of multiple valence states, and a large amount of N, S, O is doped in the carbonaceous fibers.
Example 2
Hierarchical Cu derived from copper-based MOF prepared in example 1 9 S 5 Performing wave-absorbing performance test on the carbon composite nanofiber material to obtain copper-based MOF-derived hierarchical Cu 9 S 5 The carbon composite nanofiber material and paraffin wax are mixed at 50 ℃ to obtain the electromagnetic wave absorber. Copper-based MOF-derived layered Cu 9 S 5 The mass ratio of the carbon composite nanofiber material to the paraffin is 1:4.
Table 1 shows the minimum reflection loss at a typical thickness for the absorber prepared in example 2. At 3.18mm, the strongest absorption performance was-69.6 dB.
TABLE 1
Example 3
Cu derived from copper-based MOF 9 S 5 The method for preparing the carbon composite nanoparticle electromagnetic wave absorbing material is different from the first embodiment in that the steps (1) and (2) are not needed, and the HKUST-1 powder is directly used for the subsequent steps.
The obtained copper-based MOF-derived Cu 9 S 5 The carbon composite nanoparticle material is mixed with paraffin wax at 50 ℃ to obtain the electromagnetic wave absorber. Copper-based MOF-derived Cu 9 S 5 The mass ratio of the carbon composite nanoparticle material to the paraffin wax is 1:4.
Table 2 is the minimum value of reflection loss at a typical thickness of the absorber prepared in example 3. The strongest absorption performance was-1.2 dB when the absorber thickness was 2.59 mm.
TABLE 2
Example 4
A method for preparing a carbonaceous fiber electromagnetic wave absorbing material, which is different from the first embodiment in that the powder added amount of HKUST-1 in the step (1) is 0g.
The obtained carbonaceous fiber electromagnetic wave absorbing material was mixed with paraffin wax at 50 ℃ to obtain an electromagnetic wave absorber. The mass ratio of the carbon fiber electromagnetic wave absorbing material to the paraffin is 1:4.
Table 3 shows the minimum reflection loss at typical thickness for the absorber prepared in example 4. The strongest absorption performance was-20.3 dB when the absorber thickness was 1.55 mm.
TABLE 3 Table 3
Example 5
Copper-based MOF-derived layered Cu 9 S 5 The process for preparing the electromagnetic wave absorbing material of the carbon composite nanofiber material is different from the first embodiment in that the powder of HKUST-1 is added in the step (1)The amount was 0.35g.
The obtained copper-based MOF-derived Cu 9 S 5 The carbon composite nanoparticle material is mixed with paraffin wax at 50 ℃ to obtain the electromagnetic wave absorber. Copper-based MOF-derived Cu 9 S 5 The mass ratio of the carbon composite nanoparticle material to the paraffin wax is 1:4.
Table 4 shows the minimum reflection loss at typical thickness for the absorber prepared in example 5. The strongest absorption performance was-13.6 dB when the absorber thickness was 5.00 mm.
TABLE 4 Table 4
Example 6
Copper-based MOF-derived layered Cu 9 S 5 The process for preparing the electromagnetic wave absorbing material of carbon composite nanofiber material is different from the first example in that the powder added amount of HKUST-1 in the step (1) is 1.4g.
The obtained copper-based MOF-derived Cu 9 S 5 The carbon composite nanoparticle material is mixed with paraffin wax at 50 ℃ to obtain the electromagnetic wave absorber. Copper-based MOF-derived Cu 9 S 5 The mass ratio of the carbon composite nanoparticle material to the paraffin wax is 1:4.
Table 5 shows the minimum reflection loss at typical thickness for the absorber prepared in example 6. The strongest absorption performance was-9.1 dB when the absorber thickness was 1.25 mm.
TABLE 5
Comparison of the reflection loss values of example 3, example 4, example 5 and example 6 and the reflection loss value of example 2 shows that the construction of the conductive network and the adjustment of the MOF loading can affect the absorption effect. The absorption effect of example 2 was better than that of examples 3, 4, 5 and 6. Table 6 is the electrical conductivity of the wave absorbers prepared in example 2, example 3, example 4, example 5 and example 6. As can be seen from table 6, the amplification of conductivity can be achieved by constructing the conductive network of MOF-derived particles from carbonaceous fibers, and the regulation of conductivity can be achieved by adjusting the MOF loading.
TABLE 6
Fig. 5 is an electromagnetic parameter chart of the wave absorbers prepared in example 2, example 3, example 4, example 5 and example 6. As can be seen from fig. 5, the adjustment of the electromagnetic parameters of the composite material was achieved by adjusting the MOF loading, which is also the reason for the improved absorption performance of example 2.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A copper-based metal organic framework-derived carbon composite nanofiber, characterized by: comprises a three-dimensional network structure matrix formed by stacking one-dimensional carbon fibers and octahedral Cu which is monodisperse in the one-dimensional carbon fibers and on the surfaces of the one-dimensional carbon fibers 9 S 5 and/C nanoparticles.
2. The copper-based metal organic framework-derived carbon composite nanofiber according to claim 1, characterized in that: the diameter of the one-dimensional carbonaceous fiber is 100-500nm.
3. The copper-based metal organic framework-derived carbon composite nanofiber according to claim 1, characterized in that: octahedral Cu 9 S 5 The average particle diameter of the/C nano particles is 500-600nm;
preferably, cu 9 S 5 The average diameter of the particles is 80-120nm.
4. The copper-based metal organic framework-derived carbon composite nanofiber according to claim 1, characterized in that: octahedral Cu 9 S 5 The mass percentage of the C nano particles in the composite nano fiber is 0-50 wt% and is not 0;
preferably, octahedral Cu 9 S 5 The mass percentage of the C nano particles in the composite nano fiber is 5-40 percent;
further preferred, octahedral Cu 9 S 5 The mass percentage of the/C nano particles in the composite nano fiber is 10-40 wt%.
5. The method for preparing the copper-based metal organic framework-derived carbon composite nanofiber according to any one of claims 1 to 4, which is characterized in that: the method comprises the following steps:
preparing a viscous electrospinning solution from copper-based MOF powder and a carbon source, then carrying out electrostatic spinning to obtain nanofibers, drying and pre-oxidizing the nanofibers, wherein the copper-based MOF is HKUST-1 or Cu-BDC;
calcining the pre-oxidized nanofiber in an inert atmosphere for one time to reduce copper ions into copper, converting an organic ligand into an octahedral carbon skeleton, and converting a carbon source fiber matrix into nano-carbon fibers;
and (3) co-calcining the calcined nanofiber with thiourea in an inert atmosphere to obtain the nano-fiber.
6. The method for preparing the copper-based metal organic framework-derived carbon composite nanofiber according to claim 5, wherein the method comprises the following steps: in the viscous electrospinning solution, the carbon source is polyvinylpyrrolidone, and the solvent is N, N-dimethylformamide.
7. The method for preparing the copper-based metal organic framework-derived carbon composite nanofiber according to claim 5, wherein the method comprises the following steps: in the viscous electrospinning solution, the addition ratio of the copper-based MOF, the carbon source and the DMF is 3.5-1.4:1-2:5-20, and g is g to mL;
preferably, in the viscous electrospinning solution, the addition ratio of the copper-based MOF, the carbon source and the DMF is 6-12:1.4:6-10, and g is g to mL;
preferably, the addition ratio of copper-based MOF, carbon source and DMF in the viscous electrospinning solution is 0.933:1.4:7.05, g: mL.
8. The method for preparing the copper-based metal organic framework-derived carbon composite nanofiber according to claim 5, wherein the method comprises the following steps: the pre-oxidation method comprises the following steps: and (3) preserving the heat of the dried nanofiber for 2-3 hours at the temperature of 150-200 ℃.
9. The method for preparing the copper-based metal organic framework-derived carbon composite nanofiber according to claim 5, wherein the method comprises the following steps: the temperature of the primary calcination is 600-900 ℃ and the calcination time is 0.5-5h;
preferably, the temperature of the primary calcination is 650-800 ℃ and the calcination time is 1-2h;
or the temperature of co-calcination with thiourea is 400-500 ℃ and the calcination time is 0.2-0.5h.
10. Use of the copper-based metal-organic framework-derived carbon composite nanofiber according to any one of claims 1 to 4 for the preparation of electromagnetic wave absorbing devices.
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